Base Metals and Base-Metal Family Groups: Metallurgical Reactions

CHAPTER 4
Base Metals and Base-Metal

Family Groups
THIS CHAPTER BEGINS by describing the requirements of the base metal in the brazement,
general metallurgical considerations related to the effect of the brazing cycle on the base metal
the selection of different base metals. The re- and the final joint strength must be considered.
mainder of the chapter is devoted to describing Cold-worked-strengthened base metals are
specific considerations related to the groups of annealed and the joint strength reduced when
alloys that are most commonly joined by brazing. the brazing process temperature and time are in
the annealing range of the base metal being
processed. Hot-cold-worked heat-resistant base
Metallurgical Reactions metals can also be brazed; however, only the
annealed physical properties are available in the
Some metals and alloys exhibit metallurgical final brazement.
phenomena that influence the behavior of The brazing cycle, by its very nature, usually
brazed joints and base-metal properties and, in anneals the cold-worked base metal, unless the
some cases, necessitate special procedures. brazing temperature is very low and the time at
These phenomena may be classified as: heat is very short. It is not practical to cold work
• Base-metal effects, including carbide precip- the base metal after the brazing operation.
itation When a brazement must have strength after
• Hydrogen embrittlement brazing that is above the annealed properties of
• Heat-affected zone and oxide stability the base metal, a heat treatable base metal
• Sulfur embrittlement should be selected. The base metal can be an oil-
• Filler-metal effects, such as vapor pressure quench type, an air-quench type that can be
• Base-metal/filler-metal interactions, includ- brazed and hardened in the same or a separate
ing alloying operation, or a precipitation-hardening type that
• Phosphorus embrittlement can be brazed and solution treated in a com-
• Stress cracking bined cycle. Parts already hardened may be
brazed with a low-temperature filler metal,
Other factors that cause interactions between using short times at temperature to maintain the
base metals and filler metals include postbraz- mechanical properties.
ing thermal treatments, corrosion resistance, The strength of the base metal has a profound
and dissimilar-metal combinations. effect on the strength of the brazed joint; thus,
The extent of interaction varies greatly, de- this property must be clearly kept in mind when
pending on compositions (base metal and filler designing the joint for specific properties. Some
metal) and the duration and extent of the thermal base metals also are easier to braze than others,
cycles in the processing. There is always some particularly by specific brazing processes.
interaction, except when mutual insolubility per- Carbide Precipitation. If stainless steels
mits practically no metallurgical interaction. are heated to temperatures from 425 to 815 °C
In addition to the base-metal effects men- (800 to 1500 °F), the carbon in the base metal
tioned previously and the normal mechanical combines preferentially with chromium to form
64 / Brazing, Second Edition
chromium carbide, usually at the grain bound- Alternatively, corrosion resistance can be
aries. This chromium depletion reduces the cor- restored by diffusing chromium back into the
rosion resistance of the stainless steel. This con- depleted area around the carbide precipitates.
dition has been defined as sensitization by some Two hours at 870 °C is the recommended ho-
investigators. In certain corrosive environments, mogenizing heat treatment.
the mechanical properties may be impaired, with Hydrogen Embrittlement. Hydrogen can
little or no apparent surface attack. A short braz- also be a source of trouble. Because of its small
ing cycle keeps the chromium carbide precipita- atomic size, it is able to diffuse quite rapidly
tion to a negligible level with normal types of through many metals, and the rate of diffusion
stainless steels. When this is not possible, one of increases with temperature. When hydrogen dif-
the special grades of stainless steel may have to fuses into a metal that has not been completely
be used if its corrosion resistance is to be pre- deoxidized, it may reduce the oxide of the metal,
served after brazing. if the temperature is high enough. Metallic
Precipitated carbides in stainless steels may sponge and water vapor are the end products of
be redissolved by heat treating at 1010 to 1120 this reaction.
°C (1850 to 2050 °F), followed by rapid cooling. Once hydrogen has diffused into the metal,
Another stabilizing treatment that disperses the several things can happen. If oxygen is present,
unprecipitated chromium uniformly throughout the hydrogen may combine with it to produce
the structure consists of heating to 870 °C (1600 water vapor. The water-vapor molecule, unlike
°F) for 2 h, followed by furnace cooling to 540 the hydrogen molecule, is too large to diffuse
°C (1000 °F) and subsequent air cooling. out of the metal, and the high vapor pressures
If the cooling from the brazing temperature is that develop can literally tear the metal apart by
rapid, no appreciable amount of carbides is pre- starting many fissures and blisters, mainly at the
cipitated. Where this cannot be done due to mass grain boundaries. The ultimate result is hydro-
and it is necessary to braze stainless steels for gen embrittlement. It commonly occurs in cop-
corrosive service, one of the stabilized composi- per and copper-base alloys that have not been
tions, such as type 347 or 321, or an extra-low- deoxidized. Pressures developed for tough pitch
carbon grade, such as 304L, should be used. copper have been calculated to be as high as 620
There are several ways to prevent or mini- MPa (90 ksi).
mize the deleterious effects of carbide precipita- Electrolytic tough pitch copper, silver, and
tion. First, because the reaction is time depen- palladium, when they contain oxygen, are sub-
dent, keeping the brazing thermal cycle as short ject to hydrogen embrittlement if heated in the
as possible can minimize carbide precipitation. presence of hydrogen. If tough pitch copper is to
With short cycle times, such as would result be brazed without embrittlement, hydrogen
from torch or induction brazing of small parts, must not be present in the heating atmosphere.
even the unstabilized grades can be brazed with- A better practice is to use deoxidized copper or
out severe losses in corrosion resistance. oxygen-free copper where brazing is to be per-
The susceptibility to carbide precipitation formed. Oxygen-free copper, if improperly
also depends on carbon content. Thus, type 304 heated, may also be oxidized and become sub-
is less susceptible than type 302, and the extra- ject to hydrogen embrittlement. It is impractical
low-carbon grades, such as type 304L, are rela- to salvage hydrogen-embrittled copper.
tively insensitive to carbide precipitation. A recently completed study (Ref 1) examined
For critical applications, type 347, the nio- several commercial filler metals containing
bium-stabilized grade, is recommended. It has zinc, cadmium, or phosphorus that were found
good high-temperature strength and can be to cause embrittlement by migration of (copper)
brazed without danger of impaired corrosion oxide to the grain boundaries, causing void for-
resistance. Type 321 is also a stabilized grade, mation and rupture of grain boundaries. (Oxides
but it has slightly lower general corrosion do not migrate as such but rather dissolve in the
resistance than type 347 and is more difficult to grains. The oxygen diffuses to the grain bound-
braze, because titanium is used as the carbide- aries, where it recombines, forming less-
stabilizing element. stressed particles.) The brazing was performed
When high-melting-point filler metals are both by the conventional fluxed and fluxless
used, precipitated carbides can be redissolved methods without the presence of any source of
by heat treatment after brazing. hydrogen; however, this still resulted in the
Chapter 4: Base Metals and Base-Metal Family Groups / 65
same embrittlement. Therefore, it was con- nism for hydrogen embrittlement. In this type,
cluded that the influence of flux is insignificant, hydrogen diffuses into the steel as atomic hydro-
because embrittlement also persisted in joints gen in the same manner as it diffuses into copper,
brazed without flux under argon. but it tends to accumulate in small voids, such as
To narrow the possibilities of embrittlement, a those around nonmetallic inclusions and at grain
72Ag-28Cu eutectic filler metal was used to fill boundaries. Water vapor is not formed, as in
several joints, and there was no such embrittle- copper, but the hydrogen atoms combine to form
ment, even in the most drastic brazing conditions hydrogen molecules, which are less mobile and
employed. In comparing this filler metal with the remain trapped at the discontinuities and, as a
others, the only difference was in the composi- result, increase the concentration of molecular
tion. While BAg-8 contains silver as the only hydrogen, increase the vapor pressure, and
addition to copper, the other filler metals are a lower the ductility of steel when stressed.
ternary or quaternary formulation, containing However, steel and other ferrous alloys may
additions of zinc, cadmium, and phosphorus. be salvaged by allowing the hydrogen to diffuse
The difference between silver and these other out by baking at slightly elevated temperatures
alloying additions is in their ability to reduce (95 to 205 °C, or 200 to 400 °F) or by permitting
copper oxide; silver cannot act as a reducing the steel to stand for long periods of time until
agent. This indicates that embrittlement occurs the ductility is regained.
as a result of the interaction of the other alloying A third type of embrittlement can occur when
elements with the copper base metal and not hydrogen combines with the metal to form
directly because of other factors, such as flux, hydride. The hydride lowers the notch tough-
atmosphere, and the time-temperature cycle. ness and affects the strain rate of the metal. Tita-
These parameters were identical for all the filler nium, zirconium, niobium, tantalum, and their
metals, and their influences were as expected; alloys are subject to this form of hydrogen
that is, the embrittlement was enhanced when embrittlement. Ductility can be restored if
more drastic conditions were employed. proper thermal treatments are followed after
Furthermore, embrittlement occurred only in brazing; however, an inert or vacuum atmos-
tough pitch copper (containing oxygen as Cu2O phere should be used for brazing to avoid any
precipitates) but not in phosphorus-deoxidized embrittlement. Most other metals and alloys
copper, which is completely free of oxides. As a whose oxides may be reduced by hydrogen con-
consequence, the coexistence of the additional tain an excess of deoxidizing elements and are
alloying elements of zinc, cadmium, and phos- not subject to hydrogen embrittlement.
phorus, together with oxygen in the substrate, is Heat-Affected Zone. The heating of base
the necessary prerequisite for embrittlement. metals may cause changes in their properties,
The results indicate that the responsible ele- particularly if the metals are heated above their
ments are those that are capable of reducing annealing temperatures. Base metals whose
copper oxide by a mechanism analogous to the mechanical properties were obtained by cold
hydrogen embrittlement of tough pitch copper. working (hard tempers) may soften or undergo
It seems quite certain that the thermodynamic an increase in grain size if the brazing tempera-
activity of zinc, cadmium, and phosphorus is ture is above the recrystallization temperature.
sufficiently high to cause the following reaction Where mechanical properties are obtained by
to take place: thermal treatment, they may be altered by the
brazing operation. Materials in the annealed
CuO + (X) 3 Cu + XO condition generally experience no appreciable
change due to brazing.
where X stands for one of these elements in the The width of the zone through which these
filler metal. changes may occur varies with the process used.
The mechanism suggested by this study is If the heating is localized, as in torch or induc-
embrittlement induced by the coexistence of tion brazing, the effects are confined to a narrow
copper oxides in the base material together with zone. If the whole assembly is heated, as in fur-
certain alloying additions in the filler metal, nace brazing, the entire assembly is affected. In
such as cadmium, zinc, or phosphorus, capable general, the heat-affected zone produced during
of reducing the copper oxides. brazing is wider and less sharply defined than
Steel is especially prone to another mecha- those resulting from other welding processes.
Oxide Stability and Formation. When of this interaction aids in wetting the base metal,
clean metals are heated to brazing temperature, other detrimental effects may occur. Such
their surfaces may form metal oxides if the effects include:
atmosphere around the part contains oxygen.
Oxidized metal surfaces are usually difficult to • Formation of brittle intermetallic compounds
wet with most filler metals. Fluxes and special that lower joint strength
atmospheres are designed to prevent oxide for- • Diffusion of the filler metal into the base
mation or to reduce at elevated temperature any metal to produce color changes
oxidation that occurs during initial heating (Ref • Creation of a new alloy—with a higher melt-
2). Chromium, aluminum, titanium, silicon, ing point than that of the original filler
magnesium, manganese, and beryllium all have metal—that chokes off the flow of the filler
oxides that are difficult to remove, and, there- metal
fore, these metals usually require special prepa-
ration (Ref 2). Fluoride-bearing fluxes can re- Researchers (Ref 3–6) have reported on their
duce some oxides; hydrogen gas of sufficient work whereby modified brazing processes for
purity can reduce them above certain tempera- nickel-base materials were used to reduce the
tures, and techniques such as vacuum brazing formation of brittle phases in the braze joint and
may have to be used. Ideally, oxide formation also to speed the joining operation.
should be prevented by brazing in low-dew- The three modified brazing processes devel-
point or vacuum atmospheres. oped by the researchers included:
Sulfur Embrittlement. Nickel and certain
alloys containing appreciable amounts of • Brazing under defined load
nickel, if heated in the presence of sulfur or • High-speed brazing
compounds containing sulfur, may become • Application of mechanical-excitation brazing
embrittled. This occurs when a low-melting
nickel sulfide is formed preferentially at the Additives (silicon, boride) used to reduce the
grain boundaries; this sulfide, being brittle and melting point of nickel-base materials brazed
weak, cracks if subsequently stressed. Material with nickel filler metals cause brittle phases,
so embrittled is usually scrapped, because the which exert a negative influence on the mechan-
damage that has occurred cannot be salvaged. ical properties of the brazed joints. Diffusion
Nickel and nickel-copper alloys are most sus- annealing and subsequent aging merge the brit-
ceptible to this attack, whereas alloys containing tle phases in the braze joint, whereas the aging
chromium are less susceptible. It is important causes hardening of the base material. After
that alloys in which nickel is the major compo- this, the mechanical properties of the joint are
nent be clean and free of sulfur-containing mate- comparable to those of the base material. How-
rials (such as oil, grease, paint, and drawing ever, applying this heat treatment may cause the
lubricants) prior to heating and that heating be formation of coarse grains.
done in relatively sulfur-free atmospheres. Brazing under defined load pressures differs
Vapor Pressure. Every metal is in equilib- from conventional brazing in that a previously
rium with its vapor pressure; some amount of defined load is set up quickly after the brazing
the metal is present in the gaseous state. For temperature is reached. Brazing temperatures of
most metals, at normal temperatures, this vapor 1150 and 1180 °C (2100 and 2150 °F) with tem-
pressure is so small as to be considered nonex- perature retention times of 1 and 10 min, respec-
istent. For vacuum-tube applications, some met- tively, have proved to be the best parameter
als, such as zinc and cadmium, have relatively combination.
high vapor pressures, give off undesirable gases This type of pressure-brazed joint with a
at normal brazing temperatures, and therefore more homogeneous microstructure produces
cannot be permitted as constituents of the filler good strength properties. Brazing time is of lit-
metal. Accordingly, special vacuum-tube-grade tle significance; in contrast, the brazing temper-
filler metals have become commercially avail- ature is of great importance to the strength prop-
able (see Chapter 5, “Brazing Filler Metals”), erties. However, strength values that can be
and special fluxes are used in some situations. attained without diffusion annealing are compa-
Base-Metal/Filler-Metal Interactions. rable with those of conventionally brazed spec-
There are always some interactions between the imens using cost-intensive and time-consuming
filler metal and the base metal. Although some heat treatments.
The formation of brittle phases can be influ- melting complex can cause joint degradation.
enced or even avoided by combining a consid- This effect is particularly damaging if the base
erable reduction of the brazing time with a metal is thin, as in the case of brazed honeycomb
simultaneous increase in the brazing pressure. sandwich panels. Producers and experienced
The only useful method to achieve the required users of high-temperature filler metals should be
high gradient of temperature is a conductive consulted during the design of parts for which
heat treatment technique. the use of these filler metals is anticipated.
Another method to prevent the formation of Formation of intermetallic compounds as a
brittle phases is by the mechanical excitation of result of interactions between constituents of
the components during the brazing process. the base and filler metals can occur, and these
While brazing, a transducer directly connected compounds are usually brittle. Whether or not
to one specimen transfers high-frequency ener- such compounds form depends on base-metal
gy into the brazing couple. and filler-metal compositions, time, and temper-
Using ultrasonic vibrations of approximately ature, and just because intermetallic compounds
30 kHz (amplitude of approximately 2 µm in do form, it does not necessarily follow that the
the longitudinal direction of the specimens), the joint is so embrittled as to lose engineering util-
accumulation of brittle phases is prevented. The ity. This depends on the nature of the specific
wetting of the base metal with filler metal is compound, its quantity, and its distribution.
improved, because the ultrasonic vibrations Phosphorus Embrittlement. Phosphorus
destroy any existing surface oxides. The super- combines with many metals to form brittle
position of mechanical excitation produces compounds known as phosphides. For this rea-
seams of a quality comparable with those joints son, copper-phosphorus filler metals are not
heat treated (1100 °C, or 2010 °F, for 20 h) after usually used with iron- or nickel-base alloys;
conventional brazing. however, two nickel-base filler metals—10 to
Alloying is one of the significant base- 12 P, 0.10 maximum C, balance Ni; and 13 to 15
metal/filler-metal interactions that can deter- Cr, 9.7 to 10.5 P, 0.08 maximum C, balance
mine the behavior of brazed joints. The extent Ni—have been used in some applications for
of interaction varies greatly, depending on the brazing heat-resisting alloys. The first filler
compositions of the base metal and the filler metal is extremely free flowing, exhibits a min-
metal and on thermal cycles. There is always imum amount of erosion with most nickel- and
some interaction, except where mutual insolu- iron-base alloys, and is good for use in exother-
bility permits practically none. mic atmospheres. The second is used for braz-
The term alloying is a general term covering ing of honeycomb structures, thin-wall tube
practically every aspect of interaction. Some of assemblies, and other structures that are used at
these aspects are as follows. high temperatures. Erosion can be controlled
First, the molten filler metal can dissolve the because of low solubility with iron- and nickel-
base metal. Second, constituents of the filler base alloys, and this filler metal produces
metal can diffuse into the base metal, either strong, leakproof joints with heat-resistant base
through the bulk of the grains or along the grain metals at relatively low brazing temperatures.
boundaries, or can penetrate the grain bound- Furthermore, it is recommended for nuclear
aries as a liquid. The results of such base-metal applications where boron cannot be used.
dissolution or filler-metal diffusion may be to Stress Cracking. There are many high-
raise or lower the liquidus or solidus tempera- strength materials, such as stainless steels,
ture of the filler-metal layer, depending on com- nickel alloys, and copper-nickel alloys, that
position and thermal cycle. have a tendency to crack during brazing when in
Examples include nickel, cupronickel, or a highly stressed condition and in contact with
Monel joined with pure copper filler metal; molten filler metal. Materials with high anneal-
enough dissolution and diffusion occur so that ing temperatures—and particularly those that
the solidus of the copper filler metal is increased are age hardenable—are susceptible to this phe-
and flow is terminated. This also means that the nomenon. Such cracking occurs almost instan-
remelt temperature of the filler-metal layer is taneously during the brazing operation and is
higher than its original solidus temperature. usually readily visible, because the molten filler
In brazing of ferrous-base high-temperature metal follows the crack and completely fills it.
alloys with filler metals containing boron, grain- This process has been described as stress-cor-
boundary penetration of the base metal by a low- rosion cracking (SCC), where the molten filler
metal is considered to be the corrosion medium. by cold work prior to brazing or by an externally
Cracking of stressed steel in a caustic solution applied stress from mechanical or thermal
or stressed brass in an ammonia solution are sources during the brazing operation.
widely known examples of SCC. Sufficient When stress is encountered, its cause can usu-
stress to cause stress cracking can be produced ally be determined from a critical analysis of the
Fig. 4.1 Thermal expansion curves for some common materials. These nomographs assume a case wherein α1 exceeds α2, so that
scale value for (α1 – α2) is negative. Resultant values of ∆CD are therefore also negative, signifying that the joint gap is
reduced on heating. Where (α2 – α1) is positive, values of ∆CD are read as positive, signifying enlargement of the joint gap on heating.
Clearance to promote filler-metal flow must be provided at brazing temperature. D, nominal diameter of joint, mm (in.); ∆CD, change
in clearance, mm (in.); ∆T, brazing temperature minus room temperature, °C (°F); α1, mean coefficient of thermal expansion, male
member, mm/mm · °C (in./in. · °F); α2, mean coefficient of thermal expansion, female member, mm/mm · °C (in./in. · °F). Source: Ref
7, 8
brazing procedure. The usual remedy is to re- • Redesigning parts or revising joint design
move the source of stress. Stress cracking has • Heating at a lower rate
been eliminated by: • Heating the fluxed and assembled parts in a
torch brazing application to a temperature
• Using annealed-temper rather than hard-tem-
high enough to effect stress relief, cooling to
per material
the brazing temperature, and then hand feed-
• Annealing cold-worked parts prior to brazing
ing the filler metal
• Removing the source of externally applied
stress, such as improper fit of parts or jigs that The age-hardenable high-nickel alloys are
exert stress on the parts very susceptible to SCC. These alloys should be
Fig. 4.1 (continued)

brazed in the annealed or solution-treated con- usually best to prepare preproduction samples
dition with a relatively high-melting filler metal to establish ideal clearances.
(preferably above 870 °C, or 1600 °F) that has A technique often used in brazing of material
sufficient strength to withstand handling during with different coefficients of expansion is sand-
the age-hardening treatment. wich brazing. A common application of this
Postbrazing Thermal Treatments. A post- technique is the manufacture of carbide-tipped
brazing thermal treatment to improve mechani- metal cutting tools. A relatively ductile metal is
cal properties in brazed assemblies is frequently coated on each side with the filler metal, and the
desired. In ferrous alloys, this treatment entails composite is used in the joint. This places a third
quenching from an elevated temperature, fol- material in the joint that creeps during cooling
lowed by tempering at some lower temperature. and reduces the stresses caused by differential
In other alloys, such as beryllium copper, 17-7 contraction. In some variations of the technique,
PH, Inconel X, and some Monels, the treatment wire mesh is used in place of the foil.
consists of heating to some intermediate temper- There are other factors that also must be con-
ature, followed by a controlled rate of cooling. sidered for successful brazing of dissimilar met-
When a thermal treatment is performed sub- als. The filler metal must be compatible with
sequent to brazing, it is important that the fil- both the base metals. Wide differences in base-
ler metal selected have sufficient strength at metal melting points must be considered when
the thermal treatment temperatures to withstand choosing the filler metal (Ref 7, 8). Where cor-
the necessary handling. It is also important rosion or oxidation resistance is needed, the
for the base metal, filler metal, and postbrazing filler metal should have properties at least equal
thermal treatment to be compatible relative to to the poorest of the two metals being brazed. In
temperatures in heating and cooling. Postbraz- addition, under conditions of the application,
ing thermal treatments may generate residual galvanic couplers that may promote crevice cor-
stresses in brazed joints and may result in low- rosion should be avoided. Filler metals that
ered joint strength. form low-melting phases with the base metals
Dissimilar-Metal Combinations. There are are not recommended unless, as in some special
many dissimilar-metal combinations that may cases, techniques are used to form the final filler
be brazed. In fact, brazing can often be used metal in situ.
where metallurgical incompatibility precludes The metallurgical reactions that occur during
the use of other joining processes. brazing or subsequent thermal treatments be-
One of the most important factors to consider tween the filler metal and the base metal are
in brazing dissimilar metals is rate of thermal important. One example is brazing of aluminum
expansion. If a metal having high thermal ex- to copper. The copper reacts with the aluminum
pansion surrounds a low-expansion metal, to form a low-melting brittle compound. Such
clearances that are satisfactory for promotion of problems can be overcome by coating one of the
capillary flow at room temperature are exces- base metals with a compatible metal. In the case
sive at brazing temperature. Conversely, if the of aluminum to copper, the copper can be
low-expansion metal surrounds the high-expan- coated with silver or a high-silver alloy and then
sion metal, no clearance may exist at brazing the joints made with a standard aluminum filler
temperature. For example, in brazing of a metal.
molybdenum plug in a copper block, the parts
must be press fitted at room temperature. How-
ever, if a copper plug is to be brazed in a molyb- Base-Metal Family Groups
denum block, a properly centered loose fit at
room temperature is required (Ref 7–9). Figure In the ensuing list of base-metal groups, it is
4.1 shows thermal expansion of copper, molyb- apparent that prerequisites for ductile joint
denum, and other common materials. behavior include freedom from related hard
Nomographs have been developed that are phase bands in the brazed joint and a matching
useful for learning the actual changes in clear- of elastic-plastic behavior in the brazed joint
ance in ring-and-plug joints between dissimilar and base material. It thus follows that not only
metals (Fig. 4.2). The equation may be used in is the optimal structural development required
cases where more accuracy is important or for a joint capable of deformation, but also the
where one of the variables is off the nomograph elastic-plastic behavior of the whole system of
scale. In more complex joint configurations, it is filler metal and base metal must be considered
(Ref 10–12). This results in a ductile behavior in alloys have manganese or magnesium as major
the brazed joint and an elastic and plastic behav- alloying elements. Some alloys contain only
ior in the base metal. When the elastic and plas- one alloying element; others contain several.
tic properties of the brazed joint and base metal The alloys with higher magnesium contents are
are well matched, this leads to the demand for more difficult to braze by the usual flux methods
filler metals whose mechanical properties in the because of poor wetting by the filler metal and
joint are well matched to those of the base met- excessive penetration into the base metal. Filler
als (Ref 13). metals are available that melt below the solidus
temperatures of most commercial non-heat-
Aluminum and Aluminum Alloys treatable wrought alloys.
The non-heat-treatable wrought aluminum The heat-treatable wrought alloys most com-
alloys that are brazed most successfully are the monly brazed are the ASTM 6xxx series (6151,
ASTM 1xxx and 3xxx series (e.g., 1350, 1100, 6951, 6053, 6061, 6063). The ASTM 2xxx and
3003, 3004, 3005) and low-magnesium alloys 7xxx series of aluminum alloys are low melting
of the ASTM 5xxx series (e.g., 5005, 5050, and, therefore, not normally brazeable, with the
5052). Available filler metals melt below the exception of the 7072 and 7075 alloys.
solidus temperatures of all commercial wrought The rest of the wrought aluminum alloys can
non-heat-treatable alloys. be strengthened by heat treatment and, to a
The non-heat-treatable wrought aluminum much smaller degree, by cold working. They are
mm D (in.) Nomograph for equation

∆ C = D∆ T (α – α )
D 2 1
150 6
125 5
(α – α )
2 1
6 6
10 mm/mm/°C (10 in./in./°F)
100 4 ∆C
mm D (in.) –16 –9
–15
–1.20 –0.050 –14 –8
3 –1.00 –0.040 –13
75 ∆ T –7
–0.80 –12
°C (°F) –0.030
–11 –6
1800 –0.60
–10
950 –0.50
–0.020
1700 –0.40 –9 –5
2 900
50 –0.015
1600 –0.30 –8
850
–0.010 –7 –4
1500
800 –0.20 Solution to
sample problem
–6
Ind 1400
ex 750 –3
line Index lin
1 –0.005 e2
–5
700 1300 –0.10
1 –0.08
25
650 –0.06 –4
1200 –2
20 600 –0.04
0.75 1100 –3
–0.03
–0.001
550
15 1000
0.50 500
–2
900 –1
10 Sample problem
Given: D = 50 mm
∆ T = 680°C
–6
(α – α ) = –5X = –5 x 10 mm/mm/°C
2 1
7 ∆
Solution: C = –0.17 mm
D
0.25
Fig. 4.2 Nomograph for determining changes in diametral clearance caused by heating of dissimilar-metal joints. Source: Ref 7, 8
called heat treatable alloys. The heat treatable melting temperatures than those of commer-
alloys generally contain magnesium and silicon. cially available filler metals. Some experimen-
These alloys, because of their higher total alloy tal lower-melting filler metals have been pro-
content, begin to melt at lower temperatures duced that can be used for successful brazing of
than higher-purity aluminum alloys and conse- the not-readily-brazeable alloys 2024, 2219,
quently are generally brazed at lower tempera- and 7075. Low-melting filler metals contain
tures than the non-heat-treatable alloys. The zinc, copper, or other metal with or without sil-
heat treatable alloys, which include the com- icon alloyed with aluminum. Although some of
monly used 6061 alloy, are thermally treated these combinations have been used success-
during fabrication or after brazing to attain their fully, none has been developed with adequate
high mechanical properties. corrosion resistance to be recommended for
Both groups of alloys lose strength at increas- commercial use. Therefore, the 2xxx and 7xxx
ingly rapid rates as they are heated. At their series of aluminum alloys are not normally
respective annealing temperatures, they exhibit brazeable, with the exception of 7072 (used as a
distinctly different behavior. The non-heat- cladding material only) and 7005.
treatable alloys soften and return immediately All commercial filler metals for brazing of
to the O temper. The heat treatable alloys must aluminum alloys are aluminum-base alloys
be held at annealing temperature for a minimum themselves. These filler metals are available as
of 20 min before an appreciable portion of their wire or shim stock. A convenient method of pre-
temper disappears. The heat treatable alloys can placing filler metal is to use brazing sheet,
be returned to temper by heat treatment and which is an aluminum alloy base metal that is
aging. The non-heat-treatable alloys must be coated with a filler metal. Brazing sheet is
cold worked to be tempered. coated on one or both sides. Core alloys 3003
Aluminum is brazed at temperatures between and 6951 (a heat treatable alloy) are generally
555 and 645 °C (1030 and 1195 °F). Obviously, used. A third method of applying filler metal is
a certain amount of annealing cannot be avoided to use a paste mixture of flux and filler-metal
during brazing. powder. Common aluminum filler metals con-
Aluminum alloys that have solidus tempera- tain silicon as the melting-point depressant with
tures above 590 °C (1090 °F) are easily brazed or without additions of zinc, copper, and mag-
with commercial binary aluminum-silicon filler nesium.
metals. Stronger, lower-melting alloys can be Commercial filler metals for brazing of alu-
brazed with proper attention to filler-metal minum are aluminum-silicon alloys containing
selection and temperature control, but the braz- 7 to 12% Si. Lower melting points are attained,
ing cycle must be short to minimize penetration with some sacrifice in resistance to corrosion,
by the molten filler metal. High-quality castings by adding copper and zinc. Filler metals for vac-
are no more difficult to braze than equally mas- uum brazing of aluminum usually contain mag-
sive wrought alloys. Aluminum sand and per- nesium. More information on filler metals is
manent mold casting alloys with high solidus presented in Chapter 5, “Brazing Filler Metals.”
temperatures are brazeable; brazeable alu- The optimal brazing temperature range for an
minum casting alloys include 443.0, 356.0, 406, aluminum-base filler metal is not only deter-
710, 711, and 850.0. Alloys 443.0, 356.0, and mined by the melting range of the filler metal
406 are used for both sand and permanent mold and the amount of molten filler metal needed to
casting. Alloy A710.0 is primarily a sand cast- fill the joint but is also limited by the mutual sol-
ing metal. Alloys 711 and 850.0 are used for ubility of the filler metal and the base metal
permanent mold casting. Alloys 443.0, 356.0, being brazed. The brazing temperature ranges
and 710.0 are the casting alloys most frequently of some filler metals are related to those of some
brazed. Die casting alloys are difficult to braze; base metals.
the castings are not easily wetted by the molten Aluminum can be brazed by most of the stan-
filler metal and tend to blister when brought to dard practices. Most aluminum brazing is done
brazing temperature because of their high gas by the torch, dip, or furnace process. Furnace
content and entrapped lubricants. brazing may be done in air or controlled atmos-
Not all aluminum alloys can be brazed. The phere, including vacuum. Other methods, in-
high-strength wrought aluminum alloys and cluding induction, infrared, and resistance braz-
certain casting alloys contain high amounts of ing, are used for specific applications, usually of
alloying ingredients. These alloys have lower the readily brazeable aluminum alloys. Regard-
less of the process, the temperature must be filler metal is required, 4004 in wire or sheet
closely controlled for successful brazing. form can be introduced. The joint designs used
With dip or furnace brazing, automatic pro- for brazing with flux can also be used for flux-
portioning temperature-control devices are less vacuum brazing.
available that can maintain the flux bath within The diffusion brazing process (Ref 14),
±3 °C (±5 °F) and the furnace atmosphere within which uses diffusion between the base metal
±6 °C (±11 °F) of the desired brazing tempera- and the filler metal, has been tried for joining
ture. In manual torch, induction, or resistance aluminum-silicon alloy castings.
brazing, operator skill and judgment are used to The diffusion brazing process with a copper
maintain the required temperature range for or brass preform, described in Ref 14, can apply
brazing based on flux color and on melting and for all hypoeutectic, eutectic, and hypereutectic
flow of the filler metal. Automated torch and in- alloys of aluminum-silicon system castings; the
duction brazing utilize paste filler metals and minimum temperature where the braze interface
preforms or wire with dispensable fluxes. showed a liquid phase structure was 530 °C
On the increase is the use of vacuum furnace (990 °F) for the copper preform and 510 °C (950
brazing for aluminum fabrication. Because it is °F) for the brass preform. The shear strength of
done without flux, the joints are free from the the diffusion-brazed joint was dependent on the
corrosion problems commonly associated with chemical compositions of the base metal, the
residual or entrapped flux. Moreover, brazed type of material for the preform, and the brazing
assemblies containing inaccessible recesses can temperature and time. The maximum strength
be fabricated efficiently. Furnaces operating in of the diffused-brazed joint under optimal con-
the 0.0013 Pa (10–5 torr) range are used. The ditions was 130 to 150 MPa (19 to 22 ksi) for
success of the operation depends on the use of the base metal of both Al-7Si and Al-12Si alloy
magnesium vapor as a getter of oxygen on the castings and 100 to 130 MPa (15 to 19 ksi) for
aluminum surface and magnesium alloyed in the base metal of Al-20Si alloy casting. The
the filler-metal (aluminum-silicon) coating. effect of brazing time on the strength of the
Most furnace brazing of aluminum is done in brazed joint varied depending on the type of
air, but some benefits can be gained by braz- preform. The strength of the joint with the cop-
ing in a controlled atmosphere; by controlling per preform was determined by the characteris-
moisture in the furnace at low levels, less flux tics of the braze interface structure. With the
is needed to achieve brazing (Nocolok pro- brass preform, the strength was controlled by
cess; Nocolok is a trademark of Solvay Fluor the growth of silicon grains in the braze inter-
GmbH). New types of brazing sheet designed face structure.
for fluxless brazing require nitrogen or other Figure 4.3 shows the effect of brazing tem-
inert atmospheres. perature and time on the strength of the diffu-
Furnaces operating at 0.0013 Pa have been sion-brazed joints of various aluminum-silicon
used, and the success has stemmed from the use system alloy castings.
of magnesium as vapor, which acts as a getter of The 8019 (Al-8.3Fe-4.0Ce) aluminum alloy,
oxide on the aluminum brazing surface. Work a high-performance alloy, was weld brazed by
has shown that magnesium in the parent alu- researchers (Ref 15), and the work indicated
minum alloy and in the brazing sheet can pro- that no thermal degradation was observed in
duce satisfactory brazed joints. Aluminum alloy 8019 after 450 °C (840 °F) for up to 4 h;
alloys are sometimes brazed to ferrous materi- however, clear degradation could be found at
als; in such cases, a nonoxidizing atmosphere is 500 °C (930 °F) after only 100 s. The joining
used to protect the ferrous material. temperature for alloy 8019 was kept below 450
Even though dip brazing of aluminum is still °C. Weld brazing is an innovative new approach
a popular and successful process, the search for that combines brazing with welding to provide
improved methods of brazing complex alu- synergistic benefits. The results of preliminary
minum structures, such as heat exchangers, that studies on 6061-T6 alloys showed that the tech-
eliminate or minimize flux removal and corro- nique could improve tensile-shear, tensile-frac-
sive residue problems has continued for many ture, and fatigue strengths.
years. Aluminum alloys of the 1xxx, 3xxx, 5xxx, The new generation of aluminum alloys con-
6xxx, and 7xxx series can be vacuum brazed taining lithium exhibit improved specific stiff-
using No. 7, 8, 13, or 14 brazing sheet that is ness and strength compared with conventional
clad with 4004 filler metal. When additional aluminum-copper (2000-series) and Al-Zn-Mg
(7000-series) alloys. Such alloys are therefore niques (Ref 16). The strengths are much greater
of particular interest to the aerospace industry, than values for adhesive-bonded joints, and in
where weight reduction is a major requirement. the solid state, the bond microstructure and cor-
The compositions of some important alloys are rosion resistance are expected to be similar to
given in Table 4.1. those of the base metal.
High-strength diffusion-bonded joints have The highest shear and peel strengths and min-
been obtained in aluminum-lithium alloy sheet imum variability have been obtained for joints
using both solid-state and liquid phase tech- fabricated under very clean conditions in vac-
uum, and diffusion bonding followed by super-
plastic forming has been demonstrated for alu-
minum-lithium 8090 alloy (Ref 16).
200 30 In another study (Ref 17), diffusion bonds
Insert metal: Cu were produced between sheets of an Al-Li-Cu-
Mg-Zr alloy using Al-4%Cu vapor-deposited
metallic interlayers. The joining was performed
at a bonding temperature of 530 °C (990 °F), a
100 15 pressure of 4 to 5.5 MPa (0.6 to 0.8 ksi), times
500 °C 530 °C 540 °C
7 % Si in the range of 10 to 30 min, and a bonding
12 % Si atmosphere with partial oxygen pressure lower
20 % Si
than 2 × 10–3 Pa (3 × 10–7 psi).
Shear strength, MPa
Shear strength, ksi
Microstructural changes were analyzed that

0
occurred both in the parent alloy and in the bond
200
500 °C 530 °C 540 °C
30 interface after diffusion-bonding cycles and
Insert metal:
Cu - 30% Zn 7 % Si postbonding heat treatments.
12 % Si For previous bonding conditions, elimination
20 % Si
of the continuous interfacial oxide layer is pos-
sible, and only discrete oxide particles (proba-
100 15 bly lithium-rich spinels) were detected in the
bond interface. This oxide elimination is accel-
erated if the bonding surfaces are chemically
cleaned with a commercial deoxidant.
In spite of the stability and high resistance to
0
migration of the bonding interface, it is possible
0 5 10 15 20 to obtain zones of local recrystallization, espe-
Brazing time, min
cially in superplastic joined sheets. It is proba-
bly due to mechanisms of local dynamic recrys-
Fig. 4.3 Effects of brazing time and temperature on the shear
tallization associated with highly deformed
strength of diffusion-brazed joints in relation to the
types of preforms and aluminum-silicon alloy castings used zones.
Table 4.1 Compositions and densities of some important aluminum-lithium alloys

Composition, wt%
Production route Alloy Li Cu Mg Si Fe Zr Density, 103 kg/m3
Ingot 8090 (U.K.) 2.1–2.7 1.0–1.6 0.6–1.3 0.2 0.3 0.04–0.16 2.53
8091 (U.K.) 2.4–2.8 1.8–2.2 0.5–1.2 0.3 0.5 0.08–0.16 2.54
2090 (U.S.) 1.9–2.6 2.4–3.0 0.25 0.1 0.12 0.08–0.15 2.60
2091 (France) 1.7–2.3 1.8–2.5 1.1–1.9 0.2 0.3 0.04–0.10 2.58
Weldalite 049 (U.S.) 1.3 4.5–6.3 0.4 ... ... 0.14 2.73
1420 (Russia) 1.5–2.6 ... 4.0–7.0 ... ... 0.05–0.3 2.50
Melt spun 678 (U.S.) 3.22 0.54 3.07 ... ... 0.83 ...
Powder atomized . . . (U.S.) 4.1 ... 1.0 ... ... 0.2 ...
Cospray (U.K.) 4.33 ... ... ... ... 0.11 2.41
Mechanically IN 905 XL (U.S.) 1.5 ... 4.0 ... ... ... 2.58
alloyed
Source: Ref 16
The thermal bonding cycles applied to the (~660 °C, or 1220 °F). Joining is carried out in
alloys do not cause serious surface oxidation the presence of a noncorrosive flux, such as a
problems, although surface lithium depletion fluoroaluminate salt (Ref 23, 24), to remove
occurs by sublimation. In addition, the grain native surface oxide films from the contacting
size of the superplastic alloy is kept in the range aluminum surfaces. Oxide removal enhances
necessary for superplastic behavior. wetting by the molten aluminum-silicon eutec-
Diffusion-bonding trials were carried out tic alloy at the brazing temperature and eases
using the same alloy (AA8090), both in the non- liquid metal penetration of the joint.
superplastic (T6) and superplastic conditions. The present brazing technique uses the eutec-
The liquid phase bonding in air of unrein- tic bonding approach described in earlier publi-
forced and SiC-fiber-reinforced aluminum cations (Ref 25, 26) but avoids the need to coat
using interlayers of copper-silver alloy was the base-metal surface with an intimately adher-
investigated (Ref 18). The bond strengths were ing layer of the eutectic-forming metal by elec-
measured using a simple shear jig, and the asso- troplating or vacuum deposition. In the present
ciated microstructures were characterized by technique, at least one of the aluminum surfaces
electron microscopy and electron probe micro-
analysis. A shear strength of 65 MPa (9.4 ksi)
was achieved when bonding unreinforced alu- Al Al
minum at 510 °C (950 °F) using a 50 µm thick FeAlx Ag - Al
alloy interlayer and a pressure of 10 MPa (1.5 Cu - Al

Cu - Ag
Cu - Ag
ksi) for 30 min; the bonded region covered Cu - Al
~85% of the area of the joint. With reinforced Ag - Al
Al Al
aluminum, a bonding pressure of 20 MPa (3 ksi) 50 µm
(a) (b)
was required to achieve sufficient contact and a
Al
similar area of bond; after application of pres- Al
sure for 30 min at 510 °C, shear strength of 54 Al - Cu - Ag

MPa (8 ksi) was developed at the joint. A mech- Al - Cu - Ag
liquid
liquid
anism for bonding that reflects diffusion behav-

ior and interphase reactions is shown in Fig. 4.4. Ag2Al Al
Ag2Al
Al
A novel brazing technique (a simplified and (c) (d)
cost-effective method) using an alloy powder
Al
mixture instead of a clad surface has been devel- Al
oped for brazing aluminum, copper, and brass Al - Cu - Ag Al - Cu - Ag

liquid
(Ref 19, 20). liquid
In these applications, at least one of the alu- Ag2Al Al

Ag2Al
Al
minum components is clad with filler metal con- (e) (f)
sisting of an aluminum-silicon alloy of near-
eutectic composition, such as AA4045,
AA4047, or AA4343 (Table 4.2) (Ref 21). Fig. 4.4 Proposed mechanism for aluminum bonded with
copper-silver alloy interlayer. (a) Start of process,
These alloys contain 9 to 13 wt% Si and are 490 °C (915 °F). (b) Solid-state interdiffusion, 0 to 5 min. (c) For-
characterized by a melting temperature (in a mation of Al-Cu-Ag liquid, 5 min, 502 °C (935 °F). (d) Expulsion
of liquid, 5 to 10 min, 510 °C (950 °F). (e) Further reaction, 5 to
narrow range near 577 °C, or 1071 °F) (Ref 22) 15 min, 510 °C (950 °F). (f ) Isothermal solidification, >15 min,
considerably lower than that of the core alloy 510 °C (950 °F)
Table 4.2 Composition limits for selected aluminum alloys

Content, wt%
Aluminum alloy Si Fe Cu Mn Mg Zn Cr Ti Others
1050 0.25 0.4 0.05 0.05 0.05 0.05 ... 0.03 ...
1100 0.95 Si+Fe 0.05–0.2 0.05 ... 0.1 ... ... 0.15
3003 0.6 0.7 0.05–0.2 .1.0–1.5 ... 0.1 ... ... 0.15
3102 0.4 0.7 0.1 0.05–0.4 ... 0.3 ... 0.1 0.15
4045 9–11 0.8 0.3 0.05 0.05 0.1 ... 0.2 0.15
6061 0.4–0.8 0.7 0.15–0.4 0.15 0.8–1.2 0.25 0.04–0.35 0.15 0.15
X-800 0.05 0.19 0.31 1.11 0.27 ... ... 0.008 0.15
is coated with a thin layer of a powder mix con- interface cause the aluminum and silicon to in-
sisting of an element capable of forming a low- terdiffuse (Fig. 4.5c). At temperatures ex-
temperature eutectic with aluminum (e.g., sili- ceeding 577 °C (1071 °F), it is found that the sil-
con, copper, germanium, zinc) and a flux icon particles diffuse rapidly into the aluminum
capable of dissolving surface oxide films (Ref surface and generate in situ a layer of alu-
27), as illustrated in Fig. 4.5(a). A commonly minum-silicon liquid alloy of near-eutectic
available noncorrosive flux (Ref 24) was used in composition (Fig. 4.5d). The filler metal pene-
the present work. This flux consists of a mixture trates the joint of interest by capillary action and
of KAlF4 and K2AlF5 · H2O powders in a molar forms a fillet, thus producing a metallurgical
ratio of the respective salts of approximately 13 bond on cooling. Any unused filler metal
to 1 (Ref 28), with a particle dimension of the remains on the aluminum surface to form a layer
order of 1 µm. of aluminum-silicon alloy of near-eutectic com-
Brazing is carried out by heating the joint at position (Fig. 4.5e).
approximately 600 °C (1110 °F) in nitrogen gas In this process, only one of the joined surfaces
at near-atmospheric pressure for a few minutes. need be covered with the silicon-flux mix,
During temperature ramp-up, the flux melts at because the molten flux spreads rapidly across
~562 °C (1044 °F) and dissolves the surface the joint to remove surface oxide films from the
oxide layers on the aluminum, as illustrated in mating surfaces. The quantity of filler material
Fig. 4.5(b). Sufficient flux must always be pres- formed from one coated surface is generally suf-
ent to remove these oxides. Oxide dissolution ficient to yield a good metallurgical bond.
must occur more rapidly than reoxidation of the Because fillets are formed through capillary flow
aluminum surface, allowing the silicon particles of the filler metal, brazing requires only minimal
to come into intimate contact with the bare contact force at the joint interface (Ref 29).
metal. At this juncture, the large, elemental con- In recent years, the use of rapid-solidification
centration gradients at the aluminum-silicon powder metallurgy has made it possible to
Fig. 4.5 Successive steps in the novel brazing process. (a) Deposition of a silicon-flux powder mix on the aluminum surface. The
silicon particle dimensions range from ~1 to 100 µm; the flux particle dimensions do not exceed 1 µm. (b) Melting of the
flux at 562 °C (1044 °F) and dissolution of surface oxide films. (c) At 562 °C <T <577 °C (1044 °F <T <1070 °F), solid-state interdiffu-
sion of silicon and aluminum. (d) At T >577 °C (1070 °F), rapid dissolution of silicon to form localized pools of filler metal of near-
eutectic composition, followed by coalescence of liquid metal pools. (e) End of filler-metal generation and solidification
develop a new family of aluminum alloys process of grain erosion and coarsening can be
exhibiting unique properties. One of these mate- controlled by restricting the supply of the filler
rials, dispersion-strengthened aluminum, de- metal so that only a small metal volume is
rives its high strength from nanoscale AlN par- exposed to erosion. In addition, there is a great
ticles embedded in an aluminum matrix. Unlike potential for reducing the thermodynamic driv-
precipitate particles in conventional aluminum ing force of the erosion reaction by proper
alloys, these ceramic particles resist dissolution adjustments of the filler-metal composition and/
and/or coarsening during thermal treatment; or the brazing temperature (Ref 33). Still, grain-
therefore, the material is capable of maintaining boundary liquidation may be a problem, which,
much of its strength at high temperatures (Ref in turn, may require additions of surface-active
30–32). Due to these properties, dispersion- elements to the filler metal to control the wetting
strengthened aluminum is expected to be well behavior (Ref 39).
suited as construction material for high-temper-
ature applications where weight reductions are
of particular concern. Beryllium and Beryllium Alloys
Two different brazing filler metals, based on Joint design, filler-metal selection, and a
the aluminum-silicon system, were investigated choice of brazing cycle are complicated by the
with regard to the brazeability of dispersion- low ductility of beryllium as well as its re-
strengthened aluminum (Ref 33). One of the activity with many of the filler metals used for
filler metals was a commercial type with eutec- brazing. The low ductility of beryllium is aggra-
tic aluminum-silicon composition, whereas the vated by the presence of structural discontinu-
other one was especially made for the present ities, such as surface scratches, notches, and
investigation (Table 4.3). The alloy was made asymmetrical stress patterns produced by sin-
with an addition of 1% Mg, which has been gle-lapped joints. Beryllium parts must be han-
reported in numerous papers to have a beneficial dled carefully, and joint configurations such as
effect on the wetting behavior of the filler met- butt, scarf, step, and double-lapped joints
als in vacuum (Ref 34–38). During brazing, should be considered when beryllium structures
magnesium evaporates and has a gettering ef- are designed.
fect on the residual gas contaminants in the fur- Because beryllium reacts with the con-
nace atmosphere. This reduces the oxidation of stituents of most filler metals, brazing should be
aluminum and simultaneously breaks up the done under conditions that minimize the forma-
surface oxide layer through precipitation of tion of intermetallic compounds: rapid heating
indigenous MgO crystallites. and cooling cycles, low brazing temperatures,
The results on the wetting behavior of disper- minimum time at brazing temperature, and min-
sion-strengthened aluminum under conditions imum amounts of filler metal. However, these
applicable to brazing showed that a eutectic alu- procedures are not always practical, because
minum-silicon filler metal completely wets the many filler metals do not wet or flow well on
base metal both under high-vacuum conditions beryllium surfaces. As a result, filler metal fre-
and in controlled argon atmospheres, provided quently must be preplaced between the joint
that the partial pressure of oxygen is sufficiently members in amounts sufficient to produce the
low. The main problem appears to be the stabil- brazed joint. Longer brazing times than desired
ity of the matrix grain structure. In general, the may be needed to ensure wetting and flow of the
Table 4.3 Compositions of filler metals investigated for brazing of dispersion-strengthened

aluminum
Content, wt%
Filler metal Si Mg Ti Br Mn Zn Cu Fe Al
No. 1 11–13 0.03 ... ... 0.07–0.2 0.05 0.05 0.4 bal
No. 2 11 1 0.2 0.04 ... ... ... ... bal
Source: Ref 33
filler metal; under such conditions, the diffusion (2.5 ksi) at 425 °C (800 °F), indicating mod-
that occurs between the base metal and the filler erate temperature applications.
metal may tend to adversely affect the joint • Sophisticated equipment was not required.
properties.
Brazing is the preferred method for metallur- Aluminum and aluminum-silicon filler met-
gically joining beryllium. From a stiffness/ als that contain 7 to 12% Si can provide high-
weight standpoint, beryllium is unexcelled by strength brazed joints for service at tempera-
any bulk metal or alloy in existence. However, tures up to 150 °C (300 °F). These filler metals
due to its chemical and metallurgical reactivity, have been used widely in high-strength wrought
braze-joining techniques must be highly spe- beryllium assemblies, because joining is per-
cialized, and suitable filler-metal systems and formed well below the base-metal recrystalliza-
brazing temperature ranges include: tion temperature. Fluxless brazing requires
stringent processing but has been used effec-
• Zinc (427 to 454 °C, or 801 to 849 °F) tively. A significant advantage of aluminum-
• Aluminum-silicon (566 to 605 °C, or 1051 to base versus silver-base filler metals is that met-
1120 °F) allurgical interaction is minimal. This is of
• Aluminum (645 to 655 °C, or 1195 to 1210 prime concern when thin beryllium sections or
°F) foils are to be joined.
• Silver-copper (640 to 904 °C, or 1185 to 1659 When beryllium assemblies are brazed using
°F) the aluminum-silicon-type filler metal, by virtue
• Silver (882 to 954 °C, or 1620 to 1749 °F) of the low furnace brazing temperature (605 °C,
or 1120 °F), the wrought sheet beryllium base
properties do not deteriorate but maintain the
Strictly speaking, zinc, with a melting point desirable isotropic mechanical properties of
of 420 °C (788 °F), does not quite meet the beryllium.
accepted definition for liquidus temperature for Silver and silver-base filler metals, such as
a filler metal (425 °C, or 800 °F). Nevertheless, Si-7Cu-0.2Li, find use particularly in structures
it is generally accepted as the lowest-melting exposed to elevated temperatures. An added
filler metal for brazing of beryllium. advantage with these systems is that atmosphere
Using rather specialized techniques, zinc brazing is used and may be performed in inert-
brazing of beryllium has found important appli- gas atmospheres or vacuum. The lithium is
cations. Its successful use was demonstrated in added to improve wettability. Silver interacts
production joining of over 2000 fuselage favorably with beryllium, in that hard or brittle
longeron components for the beryllium spacer intermetallics do not remain on cooling. Braz-
for an intercontinental ballistic missile. Brazing ing temperatures vary, depending on the mass
was selected as the joining process for the of the parts to be joined, joint precision, and
longeron assembly because the brazed design pressure applied to the components. Both the
had the lowest cost, the least weight, and it min- silver-base and aluminum-silicon filler metals,
imized clearance problems in the assembly (Ref however, exhibit poor capillary flow, and pre-
40). Zinc was selected as the filler metal placement is recommended. The use of the 7%
because it caused no detrimental reaction with Cu-0.2%Li sterling silver filler metal markedly
the beryllium base material. The dip brazing of improves the ability of the filler metal to make
beryllium with zinc filler metal offered the fol- well-defined fillets and to bridge gaps of several
lowing advantages: mils. Copper beryllides, which generally form
at the faying surfaces, inhibit rapid penetration
• Zinc has no undesirable reaction with beryl- of silver into the beryllium components, and,
lium. hence, a more stable liquid phase is present at
• The brazing temperature was low enough that the brazing temperature. Properly executed
no recrystallization effects took place in beryllium brazements may be made to exhibit
beryllium sheet. useful strengths at temperatures up to approxi-
• Shear strength at room temperature was con- mately 870 °C (1600 °F) (Ref 40, 41).
sistent and high (128 MPa, or 19 ksi). Research on brazing beryllium to a CuCrZr
• Shear strength at room temperature decreased vabotron element (Ref 42) found that beryllium
linearly to a value of approximately 17 MPa forms brittle intermetallic compounds with most
other metals; however, beryllium and copper some alloys, however, difficulties may be
form a eutectic at ~850 °C (1560 °F), and beryl- encountered. For example, some lead-contain-
lium recrystallizes above 730 °C (1350 °F). ing alloys can form dross that interferes with
The alloy CuCrZr is precipitation hardenable, wetting, and tin-containing alloys, if not stress
requiring annealing (>900 °C, or 1650 °F) and relieved before brazing, may crack when sub-
hardening at ~500 °C (930 °F) for optimal jected to rapid localized heating.
strength, while beryllium forms an oxide layer Softening of the base metal frequently occurs
on its surface. during brazing, because many copper-base
The use of BAg-18 (Ag-30Cu-10Sn) as a alloys derive their properties as a result of heat
filler metal was successful in joining the beryl- treatment at relatively low temperatures, cold
lium component at 650 to 680 °C (1200 to 1255 work, or both. The degree of softening increases
°F) for 10 to 45 min under a pressure of ~0.3 with higher temperatures and longer times of
MPa (0.04 ksi). Also used was the Incusil active exposure to elevated temperatures. Softening of
brazing alloy (ABA) filler metal (Wesgo Met- areas in proximity to the braze can be mini-
als) with vacuum induction brazing at 720 °C mized by cooling the assembly, except for the
(1330 °F) for 30 s to 3 min at a pressure of 0.4 area to be brazed, by immersion in water, pack-
MPa (0.06 ksi). ing with wet rags or wet asbestos, or otherwise
providing a heat sink to keep the overall tem-
perature of the part as low as possible. In all
Copper and Copper Alloys cases, brazing with a low-melting filler metal
The copper alloy base metals include copper- for a minimum time reduces softening. The
zinc alloys (brass), copper-silicon alloys (sili- importance of uniform and controlled heating
con bronze), copper-aluminum alloys (alu- cannot be overemphasized, especially when
minum bronze), copper-tin alloys (phosphor dealing with brasses, cold-worked phosphor
bronze), copper-nickel alloys, and several oth- bronzes, and cold-worked silicon bronzes. They
ers. The previously mentioned alloys are com- are especially susceptible to cracking.
monly brazed with copper- and silver-base filler Tough pitch coppers are subject to embrittle-
metals (Table 4.4). ment when heated in reducing atmospheres
The brazeability of copper and its alloys is containing hydrogen. Consequently, although
generally rated from good to excellent. With tough pitch coppers are generally rated as hav-
Table 4.4 Filler metals and other parameters for brazing of copper alloys
Base material Filler metal Atmosphere Flux Notes
Coppers BCuP-2, BCuP-5 None None Do not braze oxygen-containing

C10100 to 14200 BCuZn; BAg-1, -1a, 1, 2, 5 FB3A, C, D, alloys in hydrogen atmospheres.
-2, -5, -6, -18 E, I, J
High coppers BAg-8, -1 ... FB3A
C15000 to 19400
Red brasses BAg-1, -1a, -2, -5, -6; 1, 2, 5 FB3 A, C, D,
C20500 to 24000 BCuP-5, -3; BCuZn E, I, J
Yellow brasses BCuP-3, -4, -5; 3, 4, 5 FB3A, C, E Braze cycle should be short to avoid
C25000 to 29800 BAg-1, -1a, -5, -6 softening
Leaded brasses BAg-1, -1a, -2, -7, 3, 4, 5 FB3A, C, E Short braze cycle. Stress relieve prior
C31000 to 38500 -18; BCuP-5 to brazing
Tin brasses BAg-1, -1a, -2, -5, -6; 3, 4, 5 FB3A, C, E ...
C40500 to 45500 BCuP-5, -3
Phosphor bronzes BAg-1, -1a, -2 None None Stress relieve prior to brazing
C50200 to 52900 BCuP-3, -5; BAg-5, -6 1, 2, 5 FB3A, C, E
Aluminum bronzes BAg-1, -1a, -2, -3 4, 5 FB4A Apply flux with furnace brazing
C60600 to 64200
Silicon bronzes BAg-1, -1a, -2 4, 5 FB3A, C, E Clean surface well. Stress relieve
C64700 to 66100 prior to brazing
Copper nickel BAg-1, -1a, -2, -5, -18; 1, 2, 5 FB3A, C, E Stress relieve prior to brazing
C70100 to 82000 BCuP-3, -5
Nickel silver BAg-1, -1a, -2, -5, -6; 3, 4, 5 FB3A, C, E, Stress relieve prior to brazing
C73200 to 79800 BCuP-3, -5
Note: For information about brazing copper alloys under Atmosphere, see Table 3.4; under fluxes, see Chapter 6, “Fluxes and Atmospheres.”
ing good to excellent brazeability, they should The chromium-coppers are brazed with sil-
not be brazed in a furnace that contains hydro- ver-base filler metal and fluoride flux and simul-
gen with a reducing potential, such as dissoci- taneously solution treated at 900 to 1010 °C
ated ammonia, or in an exothermic-based or en- (1650 to 1850 °F) and cold worked; aging can
dothermic-based atmosphere. Heating by open take place as a subsequent operation to develop
flame or by torch also may result in hydrogen improved mechanical properties. This is not the
diffusion and embrittlement. case with zirconium coppers. They do not pre-
Phosphorus-deoxidized and oxygen-free cop- cipitation harden without the benefit of prior
pers can be brazed without flux in hydrogen- cold working, a sequence that is incompatible
containing atmospheres without risk of embrit- with brazing. In the absence of cold working,
tlement, provided that self-fluxing filler metals the strength of zirconium coppers is not
(copper-phosphorus) are used. The use of flux is improved by aging treatments.
required, however, when silver-base filler met- Brasses. The copper-zinc alloys (brasses)
als that contain additives such as zinc, cad- are produced with varying ratios of the two ele-
mium, or lithium are used to braze these coppers ments to provide desired properties and casting
to each other or to copper alloys or other metals. characteristics. Other elements occasionally are
The coppers, including those that contain added to enhance particular mechanical or cor-
small additions of silver, lead, tellurium, sele- rosion properties; these special brasses are iden-
nium, or sulfur (generally no more than 1%), are tified by the added element—for instance, lead,
readily brazed with the self-fluxing copper- which gives leaded brass. Additions of man-
phosphorus filler metals, but wetting action is ganese, tin, iron, silicon, lead, and aluminum,
improved when a flux is used and when a slid- either singly or collectively, rarely exceed 4%.
ing motion between components is provided Red brasses (low) contain up to 20% Zn and
while the filler metal is molten. are readily brazed with a variety of filler metals.
Another copper group includes those with Flux is normally required for best results, espe-
enhanced mechanical properties due to the addi- cially when the zinc content is above 15%. All
tion of small amounts of alloying elements. the brasses can be brazed with the silver and
These precipitation-hardenable copper alloys copper-phosphorus filler metals, and the higher-
contain beryllium, chromium, or zirconium and melting-point (low-zinc) brasses can also be
form oxide films that impede the flow of filler brazed with the copper-zinc filler metal.
metal. To ensure proper wetting action of the It is recommended that protective atmos-
joint surface by the filler metal, beryllium-cop- pheres be used in furnace brazing of brasses;
per alloys should be freshly machined or me- however, even in a protective atmosphere, flux
chanically abraded before being brazed. Re- should be used to promote good wetting by the
moval of beryllium oxide from joint surfaces filler metal and to reduce zinc fuming. When
requires the use of a high-fluoride-content flux. heated above 400 °C (750 °F), brass tends to lose
Brazing precipitation-hardenable coppers in zinc by vaporization. This loss can be reduced by
the aged condition reduces their mechanical fluxing the parts during furnace brazing or by
properties. The high-strength beryllium-copper using an oxidizing flame during torch brazing.
alloys (2% Be) can be furnace brazed and simul- Brasses are also subject to cracking and should
taneously solution treated at 790 °C (1455 °F). therefore be heated carefully and uniformly.
The temperature is lowered to 760 °C (1400 °F) Yellow brasses (high) contain 25 to 40% Zn
to solidify the filler metal, and then the assem- and are readily brazed, but low-melting filler
bly is rapidly quenched in water and aged at 315 metals should be used to avoid dezincification
to 345 °C (600 to 655 °F), which develops ade- of the base metal.
quate hardness in the base material. The 72Ag- Leaded brasses are formed when lead is added
28Cu eutectic filler metal is generally used with to red or yellow brass in amounts up to 5%.
flux. When the sections to be brazed are thin and Alloys containing more than 5% Pb are usually
can be cooled very rapidly, solution heat treated not brazed. The lead forms dross on heating that
beryllium-copper may be brazed in the temper- can seriously impede wetting and the flow of the
ature range of 620 to 650 °C (1150 to 1200 °F). filler metal. Consequently, in brazing of leaded
Other beryllium-copper alloys (0.5% Be) can be brasses, the use of a flux is mandatory to prevent
silver brazed rapidly with filler metals contain- dross formation in the joint area.
ing 45 to 50% Ag, 15% Cu, 16% Zn, and 18 to Naval brass, leaded naval brass, and admiralty
24% Cd. brass contain up to 1% Sn and may contain other
alloying elements such as lead, manganese, stress cracking by molten filler metal and should
arsenic, nickel, and aluminum. Except for the be well fixtured during heating and brazing to
aluminum-containing alloys, these brasses are prevent excessive stressing. To avoid cracking,
readily brazed; they have greater resistance to these alloys should be stress relieved at approx-
thermal shock and are less susceptible to hot imately 290 to 345 °C (555 to 655 °F) before
cracking than the high-lead brasses. For proper brazing. For best brazing results, joint surfaces
wetting, brasses that contain aluminum require a of copper-silicon alloys should be freshly
special flux. machined, cleaned, and flux coated or copper
Bronzes. Alloys of copper and tin are prop- plated before brazing to prevent the formation
erly termed tin bronzes. However, these copper- of refractory silicon oxide. Mechanical cleaning
tin alloys contain small amounts of phosphorus is recommended, or, for light oxide, the material
(up to 0.25%) added as a deoxidizer. The tin can be pickled. Silver-bearing filler metals and
bronzes have come to be known commercially flux generally are used.
as phosphor bronzes. Although susceptible to Other Copper Alloys. Commercially avail-
hot cracking in the cold-worked condition, able copper nickels may contain from 5 to 40%
phosphor bronzes have good brazeability and Ni and are susceptible to both hot cracking and
are adaptable to brazing with any of the com- stress cracking by molten filler metal. To pre-
mon filler metals that have melting tempera- vent cracking, copper-nickel alloys should be
tures lower than that of the base metal. To avoid stress relieved before brazing. Stresses should
cracking, phosphor bronzes should be stress not be introduced during brazing. The Ag-Cu-
relieved at 290 to 345 °C (555 to 655 °F) before Zn-Cd filler metals and flux are preferred for
brazing. After this stress relief or anneal, the brazing the copper nickels.
parts should be supported in a stress-free condi- Nickel silvers, which are brasses (Cu-Zn-Ni)
tion during brazing, and slow heating cycles that contain up to approximately 20% Ni but do
should be used to avoid thermal shock. When not contain silver, are highly susceptible to hot
the tin content is high or when there are appre- cracking and should be stress relieved at
ciable lead additives, adequate flux protection approximately 290 °C (555 °F) before being
during brazing is necessary. All the phosphor brazed. The nickel silvers can be brazed readily
bronzes can be brazed with the Ag-Cu-Zn-Cd with the same procedures used for brazing
and copper-phosphorus filler metals. The cop- brass. When copper-zinc filler metals are used,
per-zinc filler metals are appropriate for brazing however, care is required because of the rela-
the low-tin varieties. tively high brazing temperatures.
Aluminum bronzes are copper-aluminum Brazing Processes for Copper Alloys. Typ-
alloys with high copper contents and 3 to 13% ical brazing processes used for copper and its
Al, with or without varying amounts of iron, alloys include torch, furnace, and induction. The
nickel, manganese, and silicon. Aluminum advantages of furnace brazing that are applicable
bronzes are generally considered difficult to to the joining of copper and copper alloys relate
braze because of their aluminum content, which to the furnace as a source of heat and to the cool-
results in the formation of refractory aluminum ing chamber that is provided on conveyor-belt
oxide at brazing temperature in alloys contain- furnaces as a means for cooling assemblies from
ing more than 8% Al. However, alloys contain- the brazing temperature to 150 °C (300 °F) or
ing 8% Al or less are brazeable, provided that below. To a lesser degree, the protective atmos-
appropriate fluxes are used to dissolve the alu- pheres used most conveniently in furnace braz-
minum oxide. The oxide, which inhibits the ing—notably, the exothermic-based and endo-
flow of filler metal, cannot be reduced in dry thermic-based atmospheres—constitute another
hydrogen. advantage of brazing deoxidized coppers and
Electroplating of copper on the surface to be copper alloys in a furnace. For copper alloys sus-
brazed is one technique used to enhance wetting ceptible to hot cracking, control of cooling rate
of the low-melting silver filler metal, while use in the cooling chambers of brazing furnaces is as
of flux and a protective atmosphere in a furnace important as control of the rate of heating to the
is a technique employed if unplated surfaces are brazing temperature.
used. Torch brazing of copper and its alloys is
Silicon bronzes that contain up to approxi- selected largely on the basis of feasibility and
mately 3.25% Si and are in a highly stressed cost. Torch brazing is often used when work-
condition are susceptible to hot shortness and piece limitations preclude the use of alternative
brazing processes. Low equipment cost is a dip brazing in molten salt. Because the effi-
major advantage in manual torch brazing, which ciency of heating copper and copper alloys by
is particularly useful for assemblies involving induction is generally low, costs to achieve
unequal masses. A brazer with moderate skill given production rates are high. The low long-
can adjust and apply the heating flame so that term operating and maintenance costs of induc-
unequal masses are brought uniformly to braz- tion units, however, may outweigh the higher
ing temperature. The brazer can also apply the initial costs.
heat selectively to the joints of assemblies in- Other general limitations of induction braz-
volving both large and small areas. The size of ing may relate to the size and shape of assem-
brazing flames may range from those of ex- blies that can be brazed, the design of inductors
tremely small torches the size of a hypodermic (cooling coils used to convey heat to the assem-
needle used for electronic leads up to those of bly), and the requirements for matching imped-
large torches used in brazing assemblies weigh- ances that apply to brazing of copper and copper
ing hundreds of kilograms. alloys.
Precautions should be taken in torch brazing In a recently completed study (Ref 43) on the
certain coppers and copper alloys. Where it is use of advanced particulate-reinforced compos-
necessary to braze oxide-containing coppers, a ites and dispersion-hardened materials as candi-
reducing atmosphere in the flame must be date materials to replace pure annealed copper
avoided, because it can promote hydrogen em- for the electromagnetic windings of the com-
brittlement. For these coppers, a neutral or pact ignition tokamak nuclear fusion reactor, it
slightly oxidizing flame and a short brazing cy- was found that direct brazing of such materials
cle are necessary. Brasses are subject to vol- may lead to brittle joints and that indirect braz-
atilization of zinc when overheated or when ing may need to be employed for joining such
held too long at brazing temperature. Applica- materials.
tion of flux suppresses zinc volatilization. As a result, 0.25 vol% alumina dispersion-
Alloys containing elements that readily form hardened copper (ADHC) was brazed satisfac-
refractory oxides (aluminum, beryllium, chro- torily using induction brazing in an argon
mium, and silicon) must be protected by flux atmosphere using 72Ag-28Cu eutectic and pure
and should not be exposed to an oxidizing silver electroplate as interlayer materials. Both
flame. interlayers completely wet ADHC. For both
The efficiency of heating by induction varies interlayers, the application of additional stress
directly with the electrical resistivity of the (20 MPa, or 3 ksi) on the joint improved the
alloy. Brass, because it has higher electrical joint quality. By plating a 17.5 µm layer of cop-
resistivity, can be heated more efficiently than per on the ADHC prior to brazing, other re-
copper; steel, which has even higher resistivity, searchers have obtained shear strengths as high
can be heated more efficiently than brass. In as 223 MPa (32 ksi).
terms of the high-frequency power input and the Resistance brazing is often used in joining
time required to heat 0.45 kg (1 lb) of metal in a copper conductors, terminals, and other parts in
joint assembly at a brazing temperature of 705 lap joints for electrical connections where heat-
°C (1300 °F) and a power input (450 kHz) of 15 ing must be localized and closely controlled
kW, steel required 16 s, whereas brass required during brazing and where the brazed joint must
30 s and copper approximately 55 s. The main have low electrical resistance. Generation of
advantages of induction brazing of copper and heat in the filler metal and nearly complete fill-
its alloys over torch brazing are minimized ing of the joint with a thin layer of the filler
warpage, reduced postbraze cleaning, and less metal help meet all these objectives. Normally,
required operator skill. Induction heating is the filler metal most frequently used is copper-
suited for mass producing brazed assemblies, phosphorus, which is used without a flux—
primarily because inductors can be designed especially in brazing of copper.
that heat a line of assemblies as they are carried The success of resistance brazing for joining
through the induction field by conveyor belt or small copper electrical conductors to massive
turntable. One of the general limitations of copper assemblies has led to the use of the
induction brazing is the cost of induction heat- process for attaching armature leads to commu-
ing equipment, which far exceeds the cost of tator bars on large electric motors and genera-
torch brazing equipment and usually exceeds tors. Joints made by this method provide a large
the cost of equipment for resistance brazing or conducting cross section that prevents signifi-
cant resistive heating at the connections in ser- large, two-layer structures consisting of a ribbed
vice. The joints are made at a much lower tem- wall and a smooth external jacket. They have
perature than would be possible by resistance the form of rotating bodies of complicated geo-
welding. metrical form with cooling circuits operating at
The use of conventional resistance welding high pressures. Therefore, special requirements
equipment and high-resistivity electrodes with on strength, corrosion resistance, and efficiency
specially contoured tips makes it possible to at high and low temperatures are imposed on
concentrate the heating at the joint, to keep the brazed joints.
heating time to a minimum, and to obtain effi- The design of sections requires the produc-
cient handling and comparatively high production of brazed joints in combinations of copper
tion rates. and creep-resisting alloys with steels.
Another use of portable resistance welding In producing brazed sections, the filler metals
machines for resistance brazing is in attaching are represented mainly by specially developed
copper bus-bar terminals or similar strip con- copper-manganese alloys of the PM17 type and
nectors to large electrical equipment that cannot nickel-manganese alloys of the G70NKh,
be brought to, or positioned for brazing in, a G40NKh, and so on types, produced in the form
conventional fixed-position resistance welding of strips and foils 0.1 to 0.3 mm (0.004 to 0.012
machine. Electrical connections to such equip- in.) thick. Their use ensures strength character-
ment can often be made more economically by istics and corrosion resistance of brazed joints
resistance brazing than by mechanical means close to those of the parent material (Ref 44).
and are made more readily by resistance brazing High-temperature brazing of sections is car-
than by arc welding. ried out in vacuum compression systems
Resistance brazing done with portable resis- (VCSs) using induction heating, with automatic
tance welding machines is a convenient and control of the temperature-time parameters of
economical way of interconnecting large copper brazing and rotation of the brazed section
electrical bus bars or of attaching either large or around the horizontal axis.
small copper bus bars to motor generators, Figure 4.6 shows the diagram of a VCS for
transformers, and other electrical equipment. brazing sections of engine systems in the hori-
The low melting temperature of the filler zontal position, with rotation and compression
metal helps to avoid overheating and excessive of the surfaces of components during heating
annealing of the work, and the usual selection of for brazing. The system consists of a brazing
self-fluxing copper-phosphorus filler metals chamber with an induction heater, a system for
avoids corrosion problems and the need for flux loading and unloading sections, a vacuum sys-
removal. tem, and a system for forced pressurizing and
In some applications, filler metal for resis-
tance brazing can be provided in the form of a
coating already present on one or both members
to be joined, eliminating not only the use of flux
but also the operation of placing filler metal at
the joint. This is done when copper wire is
joined by high-speed resistance brazing to cop-
per terminals clad with copper-phosphorus filler
metal.
Salt bath furnaces have been used for brazing
of copper and copper alloys with silver filler
metals. The same neutral salts, operating tem-
peratures, and brazing procedures used for steel
are used for dip brazing of most copper alloys.
Applications of dip brazing of copper alloys in
molten salt include waveguides and waveguide
hardware, flowmeter hardware, and capillary
tube and bellows assemblies.
Copper, Other Metals, and Composites.
Copper-steel and steel sections of engine sys- Fig. 4.6 Diagram of a vacuum compression system for braz-
ing sections of engine systems in the horizontal
tems produced by high-temperature brazing are position
cooling. Brazing of engine system sections is The optimal brazing conditions of steel sec-
carried out at 1000 to 1200 °C (1830 to 2190 °F) tions using a nickel-manganese coating as the
(depending on the grade of the alloy used) and filler metal include: thickness of the layer of the
with the pressure of the shielding gas up to 490 nickel coating deposited on each surface to be
kPa (71 psi). brazed, 10 to 15 µm; thickness of the layer of
However, when producing brazed sections the manganese coating deposited on one of the
with a small cross section of the channels, the brazed surfaces, 25 to 30 µm; brazing tempera-
use of filler metals in the form of strips, even ture, 1200 ± 10 °C (2190 ± 18 °F); holding time,
0.005 mm (0.0002 in.) thick, often leads to clog- 10 min; and residual pressure, 6.65 Pa (10–3
ging of the channels and unstable hydraulic psi). The tensile strength of the brazed joints is
resistance. In addition, the technology of 580 to 700 MPa (84 to 102 ksi).
depositing filler metals in the form of strips on Locomotives used in the channel tunnel con-
the brazed surfaces by resistance welding is necting Britain and France have a rotor made of
very complicated, laborious, and not always parallel copper bars held together by an end ring
efficient. Therefore, it is more efficient to de- (Fig. 4.7). This ring, which is made of Cr-Cu-Zr
posit metallic coatings, which are components material, is brazed at each end to the copper
of the filler metals, on the surfaces to be brazed. bars. This braze must withstand the stress of
In brazing, as a result of contact interaction of rotor speeds up to 6000 rpm. It was essential to
the metal of the coating with the parent material, develop a brazement that retains a high strength
a liquid phase with a lower melting point than in during the brazing process.
the brazed material forms and plays the role of Flame brazing was the method chosen, be-
the filler metal. cause it provided a uniform heat over and
This brazing method, the so-called resis- around irregular shapes. It was also thought to
tance-reactive brazing, is used widely for probe better for odd joint configurations. The gas
ducing sections where, in brazing, it is neces- chosen was an air-acetylene mixture. This mix-
sary to ensure accurate amounts of the filler ture gave the desired flame characteristics for
metal to obtain brazed joints of the required wraparound, depth of heating, and rate of heat-
quality. Metallic coatings can be deposited by ing. The number of heat devices varied depend-
electroplating or thermovacuum spraying on the ing on the size of the rotor being brazed; one
surfaces of the brazed components. setup had 42 and another had 64. Uniformity of
When brazing copper-steel sections of the heating was attained by rotating the rotor
engine systems, the main component of the filler assembly.
metal is manganese, which can also be deposited The part of the rotor that fit into the end ring
on the ribbed surface of the copper wall. was designed with a series of rectangular cavi-
The optimal conditions of brazing copper- ties adjacent to the joint area where the filler
steel sections through a manganese coating in-
clude: thickness of the deposited coating layer,
12 to 15 µm; brazing temperature, 1010 ± 10 °C
(1850 ± 18 °F); holding time, 10 min; and resid-
ual pressure, 6.65 Pa (10–3 psi). The tensile
strength of the brazed joints is 200 to 225 MPa
(29 to 33 ksi).
X-ray spectrum microanalysis of the distribu-
tion of elements in the brazed joint shows that
the composition of the brazed joint is identical
with that of brazed joints obtained when brazing
copper-steel sections with copper-manganese
filler metals in compact form (strips, foils).
Steel sections of engine systems are brazed
with alloys where the main components are
nickel and manganese, which are deposited in
layers on one of the components to be brazed. In
heating for brazing, manganese and nickel and
melted by resistance-reactive heating, and a liq-
uid phase forms. Fig. 4.7 Rotors made of copper bars
metal and flux could be placed. The filler metal low as 600 °C (1110 °F) and are self-fluxing in
was a silver alloy that melted at 620 °C (1150 an inert atmosphere, so no rinsing is required
°F). The foil form was cut into small segments after the brazing operation.
and placed at the joints. The flux was hand Reference 47 reports on an investigation into
brushed onto the braze area and filler metal. a composite carbon-fiber/copper matrix. This
Four pilot burners were used to ignite the type of composite manifests a number of advan-
flames in four quadrants around the ring. tages originating from the properties of the
Brazing time, on average, was 21/2 to 41/2 min, component materials, such as thermal and elec-
with the unit rotating at 1 rpm. The rotors were trical conductivity, which make it suitable for,
quenched in cold water after brazing. Hardness for example, resistance welding electrodes and
before brazing was 148 to 154 HV. After braz- electrical contacts or dilatation bases in semi-
ing, it was 135–143, which was within accept- conductor power elements. In order to make full
able limits (Ref 45). use of the advantages of this material, it is nec-
The first commercially available brazed cop- essary to join it to ceramics and to metals and
per-brass car and truck radiators have made alloys used in engineering.
their debut in the global automotive market. The research work examined the joining of
The design innovations and technological carbon-fiber/copper composite to molybdenum
advances of copper-brass (CuproBraze) radia- and to FeNi42 alloy. These two materials were
tors have shown that these radiators are 35 to selected in view of the potential future applica-
40% lower in weight compared to traditional tions of the resulting joints in the electronics
(nonoptimized) copper-brass radiators, because industry, namely, for power diodes and thyris-
they are designed and manufactured with far tors (joints involving molybdenum) and for
less materials in their fins and tubes. Also, the electrical contact pieces (joints involving
heavy lead-base solder traditionally used in FeNi42).
copper-brass radiators is replaced with a light- The filler metal used was 72.5Ag-19.5Cu-
weight filler metal. 5In-3Ti (wt%). The joints were made using the
Copper-brass radiators can be designed and diffusion-bonding method in a diffusion-bond-
manufactured to suit the diverse cooling ing press. In the bonding of the volumetric com-
requirements of the automakers of the world. posite carbon fiber/copper to molybdenum, the
They can be produced using the same furnaces following process parameters were used: tem-
as employed to braze aluminum radiators. Other perature, 950 °C (1740 °F); time, 30 min; pres-
advantages of copper-brass radiators include the sure, 50 MPa (7 ksi); and vacuum, 2.66 × 10–4
inherent superiority of copper over aluminum in Pa (3 × 10–8 psi). The laminar composites, con-
thermal conductivity, internal corrosion resis- sisting of carbon fiber in Ag-Cu-In-Ti alloy,
tance, durability, ease of fabrication, longer were bonded to FeNi42 alloy and to Al2O3
manufacturing tool life, and simpler joining ceramics under the following conditions: tem-
techniques. In laboratory performance tests, perature, 850 °C (1560 °F); pressure, 0.6 MPa
copper-brass radiator prototypes have lasted (0.09 ksi); time, 5 min; and vacuum, 2.66 × 10–4
8000 h without failure. This equals more than Pa (3 × 10–8 psi).
800,000 km (500,000 miles) of service (Ref 46). The experiments showed that it was possible
Chief among the technologies that provide to produce joints displaying good strength prop-
advantages in the manufacture of copper-brass erties of carbon-fiber/copper composites to
radiators are no-flux brazing and electrophoretic molybdenum and of carbon-fiber/AgCu alloy
coating. composites to FeNi42 alloy. In the examination
Newly designed materials and fluxless braz- of the microstructure, of the linear distribution
ing of radiator components develop superior of elements and of x-ray diffraction patterns, the
strength in fin, tube, and header joints and over- bond of the composite carbon-fiber/AgCu alloy
all strength of copper-brass radiators. They to molybdenum is likely to be of the diffusion
comprise thinner fin and tube material; brazed type, which results from diffusion of silver and
copper fins are 0.05 mm (0.002 in.) thick or less, titanium out of the composite as well as from
while brazed brass tubes are 0.127 mm (0.005 diffusion of iron and nickel in the opposite
in.) thick. A filler metal of a nontoxic, low-tem- direction. In the case of the composite carbon-
perature alloy (based on the Cu-Ni-Sn-P sys- fiber/copper bonding to molybdenum, the joint
tem) has been successfully employed. was formed mainly as an effect of nickel diffu-
These alloys have a melting temperature as sion into molybdenum.
tion is performed in a flux bath. Furnace brazing

Magnesium and Magnesium Alloys offers the greatest potential for magnesium com-
Brazing techniques similar to those used for bustion, because the entire structure is heated to
aluminum are used for magnesium alloys. Fur- the brazing temperature. However, because the
nace, torch, and dip brazing can be employed, M1A alloy, with its high solidus temperature
although dip brazing is the most widely used. (648 °C, or 1198 °F), is the only magnesium alloy
Magnesium alloys that are considered braze- suitable for furnace brazing, the risk of combus-
able, and recommended filler metals, are listed tion is minimal, provided that the furnace tem-
in Table 4.5. Furnace and torch brazing experi- perature is controlled within the prescribed limits
ence has been limited to the M1A alloy. Dip and that brazing time is the minimum necessary
brazing has been used successfully for AZ10A, to achieve filler-metal flow.
AZ31B, K1A, M1A, and ZK21A alloys. Other Electric or gas heating furnace equipment
magnesium alloys have not been brazed with with automatic temperature controls capable of
present filler metals and techniques developed, holding the furnace temperature within ±6 °C
due to their low solidus temperatures. (±10 °F) of the brazing temperature for magne-
The two filler metals AZ92A or BMg-1 (9% sium base metal should be used to minimize
Al, 2% Zn, 0.1% Mn, 0.00005% Be, balance incipient melting of the base metal and to reduce
Mg) and AZ125A or BMg-2 (12% Al, 0.5% Zn, the potential of a magnesium fire. The best
0.00005% Be, balance Mg) are both suitable for results in furnace brazing are obtained if dry
torch, dip, or furnace brazing. Because the powdered flux is sprinkled along the joint. Braz-
AZ125A filler metal has a lower melting range ing times depend somewhat on the thickness of
(Table 4.5), it is usually preferred in most braz- the materials used and the amount of fixturing
ing applications. necessary to position the parts.
The ease of ignition of magnesium depends Torch brazing is accomplished using a neu-
to a large extent on the size and shape of the tral oxyfuel or air-fuel gas flame. Because of the
material as well as on the size or intensity of the close proximity of the initial melting point
source of ignition. Fabricated assemblies, (solidus temperature) of the magnesium alloy
ingots, and castings are difficult to ignite, be- base metal and the flow point (liquidus temper-
cause heat is conducted rapidly away from the ature) of the filler metal, manual torch brazing is
source of ignition. generally preferred, using the AZ125A magne-
The probability of combustion occurring dur- sium filler metal. Natural gas is also well suited
ing torch brazing of magnesium is extremely for torch brazing, because its relatively low
remote, because only the joint area, and not the flame temperature reduces the danger of over-
entire structure, is heated, and because the fluxes heating.
used prevent burning in the heated area. The dip Dip brazing of magnesium alloys is accom-
brazing process presents no combustion prob- plished by immersing the assembly in a molten
lems with magnesium, because the entire opera- brazing flux and holding the parts and fixture at
Table 4.5 Brazeable magnesium alloys and recommended brazing filler metals
Solidus Liquidus Brazing range Suitable brazing filler metal
ASTM alloy
designation °C °F °C °F °C °F BMg-1 or AZ92A BMg-2 or AZ125A
Base metals
AZ10A 632 1170 643 1190 582–616 1080–1140 X X

AZ31B 566 1050 627 1160 582–593 1080–1100 ... X
K1A 649 1200 650 1202 582–616 1080–1140 X X
M1A 648 1198 650 1202 582–616 1080–1140 X X
ZK21A 626 1159 642 1187 582–616 1080–1140 X X
Brazing filler metals
AZ92A(a) 443 830 599 1110 604–616 1120–1140 ... ...

AZ125A(b) 410 770 566 1050 582–610 1080–1130 ... ...
(a) Available as wire or rod. (b) Available as wire, rod, strip, or powder
the desired brazing temperature. The flux serves Parts should, therefore, be annealed prior to
the dual function of heating and fluxing. The brazing to remove residual stresses or be care-
immersion time in the flux bath can vary from fully stress relieved during the brazing cycle.
30 to 45 s up to 1 to 3 min. Large assemblies In selection of a brazing process and a filler
with more metal mass and/or fixturing require metal for a nickel-base alloy, the characteristics
the longer times. Because of the large volume of of the alloy must be carefully considered.
flux and uniform heating, more consistent Nickel alloys differ significantly not only in
results are achieved with dip brazing than with physical metallurgy (precipitation strengthened
other brazing procedures. versus solid-solution strengthened) but also in
The corrosion resistance of brazed joints in process history (cast versus wrought). These
magnesium alloys depends primarily on the characteristics can have a profound effect on
thoroughness of flux removal and the adequacy brazeability.
of joint design to prevent flux entrapment. The filler metals normally used for ferrous
Because the filler metal is a magnesium-base metals are suitable for joining nickel and high-
alloy, the problem of galvanic corrosion is min- nickel alloys. It also is important to consider any
imized. Protection of magnesium alloys from heat treatments that may be required for the base
corrosion is provided by applying appropriate metal, because the brazed joint must withstand
chromate and other coatings. the temperatures involved. In corrosive envi-
Torch brazing has been used to join hydraulic ronments, high-silver filler metals are preferred,
lift floats, whereas dip brazing has been used to while cadmium-free filler metals are chosen to
produce battery containers and microwave avoid stress-corrosion cracking (SCC).
antennas. Most high-nickel alloys are capable of being
brazed with pure copper filler metal, which is
Nickel, Cobalt, and similar to the brazing of carbon and low-alloy
Heat-Resistant Alloys steel, except that the copper filler metal charac-
teristically alloys to a greater extent with nickel
Nickel and the high-nickel alloys may be than with iron. Alloying during brazing makes
divided into the following classes: capillary flow difficult. The copper does not
flow far before it has picked up enough nickel to
• Commercially pure nickel raise its liquidus and reduce its fluidity. To elim-
• Nickel-copper alloys inate this problem, the filler metal should be
• Nickel-chromium-iron alloys placed as close to the joint as possible, and there
• Nickel-chromium-molybdenum alloys should be a sufficient reservoir to fill the joint.
• Thorium-dispersed nickel alloys Secondly, the assembly should be heated as rap-
idly as practicable to the brazing temperature.
Commercially pure nickel and nickel-copper Phosphorus combines with many metals to
alloys are used primarily for applications where form brittle compounds known as phosphides.
corrosion resistance is important or where prod- For this reason, the copper-phosphorus filler
uct purity must be maintained. The other cate- metals usually are not used with any iron- or
gories of alloys also have good corrosion resis- nickel-base alloy; however, the BNi-6 and BNi-
tance in many media and, in addition, have high 7 filler metals are used for brazing nickel-base
strength and oxidation resistance at elevated alloys. Nickel-base filler metals offer the great-
temperatures. To use these properties, it is est corrosion and oxidation resistance and ele-
important to determine the effects of service vated-temperature strength.
conditions on the brazed joint. Nickel-base filler metals, containing palla-
Nickel and the high-nickel alloys are embrit- dium or platinum, and gold-base, palladium-
tled by sulfur and low-melting metals, such as base, and platinum-base filler metals have also
zinc, lead, bismuth, and antimony. Nickel and been used successfully to braze high-nickel
nickel alloy parts should be thoroughly cleaned alloys. These filler metals generally have good
prior to brazing to ensure the absence of sub- wetting and flow characteristics. They have a
stances that may contain any of these elements. low interaction rate with most nickel-base met-
Sulfur and sulfur compounds must also be als and are used to advantage in many special
excluded from the brazing atmosphere. applications where joints are required to have
Nickel and its alloys are subject to stress good ductility, high strength, and good oxida-
cracking in the presence of molten filler metals. tion resistance. Filler metals consisting of base
material plus additions of silicon and boron metal alloy systems most frequently used in
have been used successfully for brazing the pre- brazing nickel-base alloys—the Ni-Cr-Si and
cipitation-strengthened alloys of nickel. Ni-Cr-B systems.
When appreciable amounts of aluminum and It is significant to point out the effects of ther-
titanium appear (greater than 1%) in the precip- mal cycles on solid-solution-strengthened and
itation-strengthened nickel-base alloys, the precipitation-strengthened nickel-base alloys.
oxides of aluminum and titanium are almost An example of the former is Inconel 600, a
impossible to reduce in a controlled atmosphere high-temperature nickel-base alloy containing
(vacuum or hydrogen). Therefore, nickel plat- 15.5% Cr, 76% Ni-Co, and 8% Fe that resists
ing or the use of a flux is necessary to obtain a oxidation up to 1175 °C (2150 °F) and is used in
surface that allows wetting by the filler metal. furnace parts and fixtures, heat exchangers,
Most commercial brazing processes may be chemical-handling equipment, and turbine and
used on nickel and high-nickel alloys. The most reactor parts. This alloy may not be adversely
common of these are torch, furnace, induction, affected by nickel-base filler-metal brazing tem-
and resistance brazing; salt bath dip brazing has peratures of 1010 to 1230 °C (1850 to 2250 °F).
limited application. Whereas the silver-base An example of the latter is Inconel 718, a
filler metals may be used in torch brazing, the nickel-base superalloy containing 50 to 55% Ni,
copper and nickel filler metals are usually used 17 to 21% Cr, 4.75 to 5.5% Nb and Ta, 1% Co,
in controlled-atmosphere brazing. approximately 0.20% Fe, and greater than 2%
Attempting to braze over the refractory Al and Ti. This alloy is oxidation resistant up to
oxides of titanium and aluminum that may be 980 °C (1800 °F) and is used in aircraft turbine
present on precipitation-hardenable nickel-base parts, pumps, and rocket motors. This alloy
alloys must be avoided. Procedures to prevent may, however, display adverse property effects
or inhibit the formation of these oxides before when exposed to brazing cycles higher than its
and/or during brazing include special treatments normal solution heat treatment temperature.
of the surface to be joined, and brazing in a Inconel 718, for example, is solution heat
highly controlled atmosphere. Surface treat- treated at 955 °C (1750 °C) for optimal stress-
ments include electrolytic nickel plating and rupture life and ductility. Brazing temperatures
reduction of the oxides to metallic form. As of 1010 °C (1850 °F) or above result in grain
stated earlier, a typical practice is to nickel plate growth and an attendant decrease in stress-rup-
the joint surfaces of any alloy that contains alu- ture properties, which cannot be recovered by
minum and/or titanium. For vacuum brazing, subsequent heat treatment.
when aluminum and titanium are present in The applicability of the transient liquid phase
trace amounts, plating 0.01 mm (0.0004 in.) (TLP) metallic bonding method for joining fine-
thick is considered optional. Alloys with up to grained Inconel 718SPF superalloy sheets by
4% Al and/or Ti require plating 0.015 mm inserting a nickel-phosphorus or a Ni-Cr-P
(0.0006 in.) thick, whereas alloys with alu- amorphous interlayer has shown that a joint
minum and/or titanium contents greater than with uniform chemical composition could be
4% require plating 0.02 to 0.03 mm (0.0008 to obtained for the Inconel 718SPF superalloy
0.0012 in.) thick. When brazing is done in a with a nickel-phosphorus interlayer at 1100 °C
pure dry hydrogen atmosphere, thicker plating (2010 °F) for 8 h. When a Ni-Cr-P interlayer
(0.03 to 0.04 mm, or 0.0012 to 0.0016 in.) is was used under the same metallic bonding con-
desirable for alloys with greater than 4% Al ditions, the concentrations of nickel, iron, and
and/or Ti contents. niobium in the bond region and in the base
Brazing of base materials containing more metal had a difference of more than 2 wt%. This
than a few percent of aluminum, titanium, zir- means that longer bonding time was required to
conium, or other elements that form very stable homogenize the chemical compositions of
oxides requires vacuums of 0.13 Pa (2 × 10–5 bonds with a Ni-Cr-P interlayer.
psi) or lower. Vacuum furnaces for this type of The shear strength of the TLP bonds with a
brazing usually employ a diffusion pump nickel-phosphorus interlayer indicated higher
backed by a mechanical pump. bond strengths than did that with the Ni-Cr-P
Consideration must be given to the effect of interlayer under the same bonding conditions.
the brazing thermal cycle on the base metal. The second phases, which existed at the grain
Filler metals that are suitable for brazing nickel- boundaries, retarded grain growth in the bonding
base alloys may require relatively high thermal region. Homogenization during the TLP metal-
cycles. This is particularly true for the filler- lic bonding process was thus limited (Ref 48).
Consideration of base-metal property re- structures. After brazing, a diffusion cycle was
quirements for service enables selection of an used to raise the brazed-joint remelt tempera-
appropriate filler metal. For lower melting tem- ture to 1260 to 1315 °C (2300 to 2400 °F).
peratures (below 1040 °C, or 1900 °F), filler Additionally, it may be desirable to heat treat
metals are available within the nickel-base the brazement after brazing to attain optimal
filler-metal family and within other filler-metal base-metal properties. The BCo-1 filler metal
systems (Tables 4.6, 4.7) (Ref 49–51). (Table 4.7) appears to offer a good combination
Brazing is one of the preferred methods for of strength, oxidation resistance, and remelt
joining dispersion-strengthened nickel alloys temperature for use on cobalt-base alloy foil
that must function at elevated temperatures. (Haynes 25) (Ref 53).
High-strength brazements have been made with Cobalt alloys, much like nickel alloys, can be
special nickel-base filler metals tested up to subject to liquid metal embrittlement or SCC
1315 °C (2400 °F). when brazed under residual or dynamic stresses.
Procedures have been developed for brazing This frequently is observed when silver or sil-
of thoria-dispersed nickel and thoria-dispersed ver-copper filler metals are used. Liquid metal
NiCr foils for high-temperature service using embrittlement of cobalt-base alloys by copper
the candidate filler metals shown in Table 4.8 filler metals occurs with or without the applica-
(Ref 49, 51). tions of stress; therefore, copper filler metals
Heat-resistant alloys are suitable for use should be avoided in brazing of cobalt-base
under moderate to high loading in the tempera- alloys.
ture range from 540 to 1100 °C (1000 to 2010 Superalloys can be subdivided into two cat-
°F). These metals are complex austenitic alloys egories: conventional cast and wrought alloys,
based on nickel, cobalt, or both. They have and powder metallurgy (P/M) products. Powder
often been termed superalloys. Their greatest metallurgy products may be produced in con-
use is in the construction of gas turbine engines ventional alloy compositions and oxide-disper-
and hot airframe components. sion-strengthened (ODS) alloys.
Heat-resistant alloys are generally brazed in Oxide-dispersion-strengthened alloys are
hydrogen-atmosphere or high-vacuum furnaces P/M alloys that contain stable oxide evenly dis-
with nickel-base or special filler metals. Be- tributed throughout the matrix. The oxide does
cause the brazing temperatures are high, the not go into the solution in the alloy even at the
effect of the brazing thermal cycle on the base liquidus temperature of the matrix. However,
metals should be taken into account. The non- the oxide is usually rejected from the matrix on
heat-treatable alloys suffer moderate strength melting of the matrix, which occurs during
losses due to grain growth during brazing. Cold- fusion welding, and cannot be redistributed in
worked alloys should not be brazed unless the the matrix on solidification; therefore, these
severe loss in strength from annealing during alloys are usually joined by brazing. There are
brazing is considered in the design. two commercial alloy classes of ODS alloys:
Brazing of cobalt-base alloys is readily the dispersion-strengthened nickel-chromium
accomplished by the same techniques used for and dispersion-strengthened nickel, discussed
nickel-base alloys. Because most of the popular previously, and the mechanically alloyed (MA)
cobalt-base alloys do not contain appreciable alloys. An example is Inconel MA 754, a tur-
amounts of aluminum or titanium, brazing- bine vane material made from powder.
atmosphere requirements are less stringent. The material has extremely good creep and
These materials can be brazed in either a hydro- oxidation resistance at temperatures up to 1050
gen atmosphere or a vacuum. Filler metals are °C (1920 °F) and is used in gas turbines (vanes,
usually nickel- or cobalt-base alloys or gold- nozzle, burners, combustors), chemical plants
palladium compositions. Silver or copper filler (liners, heat exchangers, combustion cham-
metals may not have sufficient strength and oxi- bers), and so on. They owe their oxidation re-
dation resistance in many high-temperature sistance to a stable and tenacious oxide film, and
applications. Although cobalt-base alloys do their creep resistance to the combination of a
not contain appreciable amounts of aluminum large and directional grain structure plus a dis-
or titanium, an electroplate or flash of nickel is persion of submicron-sized particles consisting
often used to promote better wetting of the filler chiefly of yttrium oxide.
metal. Nickel-base filler metals such as BNi-3 There is no joining method that can preserve
(Table 4.7) have been used successfully on the coarse and elongated grain structure of the
cobalt-base alloys (Ref 51, 52) for honeycomb recrystallized parent metal across a joint line
Table 4.6 Commercially available nickel-base filler metals

Solidus Liquidus
Chemical composition, % (melting point) (flow point)
Ni Cr C P Fe B Si Co Mn Cu Other °C °F °C °F
99.26 0.04 0.04 0.30 ... ... ... ... ... ... ... 1082 1980 1121 2050
98.88 ... 0.015 1.10 ... ... ... ... ... ... ... 1038 1900 1204 2200
97.25 ... ... ... ... 0.75 2.00 ... ... ... ... 1021 1870 1066 1950
96.00 ... ... ... ... 1.50 2.50 ... ... ... ... 1010 1850 1066 1950
95.50 ... ... ... ... 1.50 3.00 ... ... ... ... 1010 1850 1066 1950
95.20 ... ... ... ... 1.80 3.00 ... ... ... ... 1004 1840 1066 1950
94.60 ... 0.03 ... ... 1.90 3.50 ... ... ... ... 982 1800 1066 1950
93.72 ... 0.03 ... 1.25 1.50 3.50 ... ... ... ... 982 1800 1066 1950
93.60 2.20 ... ... 1.00 1.60 2.60 ... ... ... ... 954 1750 1038 1900
92.80 2.30 ... ... 1.00 1.50 2.40 ... ... ... ... 954 1750 1038 1900
92.60 2.70 ... ... 1.10 1.90 2.80 ... ... ... ... 954 1750 1038 1900
92.54 ... 0.06 ... ... 2.90 4.50 ... ... ... ... 982 1800 1024 1875
92.40 2.90 ... ... 1.30 1.90 2.80 ... ... ... ... 954 1750 1038 1900
92.30 2.25 ... ... 1.00 1.70 2.75 ... ... ... ... 954 1750 1038 1900
91.70 2.30 ... ... 1.20 1.80 3.00 ... ... ... ... 954 1750 1038 1900
91.60 2.50 ... ... 1.10 1.80 3.00 ... ... ... ... 954 1750 1038 1900
91.30 2.70 ... ... 1.20 1.80 3.00 ... ... ... ... 954 1750 1038 1900
91.22 ... 0.03 ... 1.25 3.00 4.50 ... ... ... ... 954 1750 1024 1875
90.80 3.00 ... ... 1.30 1.90 3.00 ... ... ... ... 954 1750 1038 1900
90.66 0.20 0.14 ... 1.50 3.00 4.50 ... ... ... ... 982 1800 1038 1900
88.95 5.00 0.25 ... 1.00 1.80 3.00 ... ... ... ... 971 1780 1182 2160
88.80 3.80 ... ... 1.70 2.20 3.50 ... ... ... ... 954 1750 1038 1900
88.40 5.60 ... ... 2.40 2.80 3.20 ... ... ... ... 954 1750 1038 1900
87.10 5.00 ... 4.00 0.60 1.20 2.10 ... ... ... ... 954 1750 1038 1900
85.90 5.60 ... ... 2.40 2.50 3.60 ... ... ... ... 954 1750 1038 1900
84.39 9.00 0.35 ... 2.10 1.66 2.50 ... ... ... ... 1010 1850 1066 1950
84.08 5.50 0.12 1.50 2.50 2.50 3.80 ... ... ... ... 982 1800 1038 1900
83.40 8.00 ... 6.00 0.40 0.80 1.40 ... ... ... ... 982 1800 1049 1920
82.97 6.50 0.03 ... 3.00 3.00 4.50 ... ... ... ... 971 1780 999 1830
82.50 11.50 ... ... ... ... 6.00 ... ... ... ... 1082 1980 1138 2080
82.10 7.00 0.03 ... 3.00 2.90 5.00 ... ... ... ... 1038 1900 1065 1950
81.50 11.40 ... ... ... 0.30 6.80 ... ... ... ... 1082 1980 1138 2080
81.50 15.00 ... ... ... 3.50 ... ... ... ... ... 1054 1930 1054 1930
81.10 11.50 ... ... ... 0.40 7.00 ... ... ... ... 1082 1980 1138 2080
80.85 10.00 ... 7.50 0.25 0.50 0.90 ... ... ... ... 954 1750 1038 1900
79.25 11.00 0.50 ... 3.50 2.25 3.50 ... ... ... ... 971 1780 1160 2120
79.20 10.00 0.35 ... 4.00 2.10 4.35 ... ... ... ... 971 1780 1149 2100
78.87 13.30 ... ... ... 0.23 7.60 ... ... ... ... 1082 1980 1138 2080
78.65 13.00 ... ... ... 0.35 8.00 ... ... ... ... 1082 1980 1138 2080
78.40 13.00 0.70 ... 3.50 2.90 1.50 ... ... ... ... 1082 1980 1138 2080
77.00 15.00 ... ... ... ... 8.00 ... ... ... ... 1082 1980 1138 2080
76.80 15.20 ... ... ... ... 8.00 ... ... ... ... 1082 1980 1138 2080
76.30 7.00 ... ... 3.00 3.20 4.50 ... ... ... 6.00 W 977 1790 1038 1900
75.60 13.50 0.15 ... 3.50 3.25 4.00 ... ... ... ... 976 1789 1052 1925
74.85 ... 0.15 ... ... ... 8.00 ... 17.00 ... ... 1024 1875 1065 1950
74.60 ... ... ... ... 3.15 4.25 18.00 ... ... ... 982 1800 1024 1875
74.40 15.00 0.10 ... 3.00 3.00 4.50 ... ... ... ... 971 1780 1077 1970
73.90 14.80 0.70 ... 3.80 3.00 3.80 ... ... ... ... 977 1790 1038 1900
73.62 17.10 ... ... ... 0.08 9.20 ... ... ... ... 1082 1980 1138 2080
73.40 17.00 ... ... ... 0.10 9.50 ... ... ... ... 1082 1980 1138 2080
72.44 15.00 0.06 ... 4.00 3.50 5.00 ... ... ... ... 982 1800 1024 1875
72.20 ... ... ... ... 3.30 4.50 20.00 ... ... ... 982 1800 1024 1875
72.00 ... 0.03 ... ... 3.60 4.50 20.00 ... ... ... 982 1800 1024 1875
71.90 15.00 0.60 ... 4.00 3.50 5.00 ... ... ... ... 977 1790 1052 1925
70.00 16.00 ... ... 2.00 3.50 3.50 ... ... 2.50 2.50 Mo 1093 2000 1149 2100
69.20 17.50 0.80 ... 4.50 3.50 4.50 ... ... ... ... 949 1740 1065 1950
68.59 18.00 ... ... 4.50 ... 9.00 ... ... ... ... 1082 1980 1138 2080
68.10 10.00 0.40 ... 3.50 2.50 3.50 ... ... ... 12.00 W 971 1780 1093 2000
67.00 20.00 ... ... 3.00 ... 10.00 ... ... ... ... 1079 1975 1135 2075
66.85 19.00 0.15 ... 3.00 ... 10.00 0.50 0.50 ... ... 1082 1980 1138 2080
65.50 ... 0.01 ... ... ... 7.00 ... 23.00 4.50 ... 982 1800 1010 1850
65.00 ... 0.07 ... ... ... 7.00 ... 23.00 5.00 ... 982 1800 1010 1850
63.00 ... ... ... 5.00 2.00 ... ... ... ... 30.00 Mo 1066 1950 1138 2080
61.95 12.00 0.55 ... 3.50 2.50 3.50 ... ... ... 16.00 W 971 1780 1104 2020
61.50 19.00 ... ... 4.50 ... 9.80 5.20 ... ... ... 1082 1980 1138 2080
61.40 19.50 ... ... ... ... 9.60 ... 9.50 ... ... 1082 1980 1107 2025
60.35 11.50 0.55 ... 3.40 2.50 3.20 2.50 ... ... 16.00 W 1010 1850 1121 2050
59.15 19.50 ... ... 2.25 ... 9.50 ... 9.50 ... ... 1082 1980 1121 2050
57.10 3.50 ... ... 1.00 0.90 2.50 ... 35.00 ... ... 987 1800 1066 1950
(continued)
Table 4.6 (continued)

Solidus Liquidus
Chemical composition, % (melting point) (flow point)
Ni Cr C P Fe B Si Co Mn Cu Other °C °F °C °F
50.20 4.00 ... ... ... 0.80 ... ... 45.00 ... ... 996 1825 1079 1975
50.10 ... ... 3.50 30.00 ... 11.00 ... ... ... 5.40 Mo 954 1750 1001 1835
36.00 ... ... ... ... ... ... ... ... 59.00 5.00 In 1038 1900 1204 2200
17.00 21.00 0.80 ... ... 3.25 3.00 44.95 ... ... 10.00 W 1038 1900 1121 2050
17.00 19.00 0.40 ... ... 0.80 8.00 50.80 ... ... 4.00 W 1107 2025 1149 2100
16.00 ... ... ... ... 1.00 ... 16.00 67.00 ... ... 1004 1840 1021 1870
12.00 18.00 ... 0.10 66.90 ... 1.00 ... 2.00 ... ... 1121 2050 1163 2125
9.00 ... 0.03 ... ... ... ... ... 23.50 67.50 ... 910 1670 932 1710
9.00 ... ... ... ... ... ... ... 38.50 52.50 ... 880 1615 927 1700
9.00 ... 0.03 ... ... ... ... ... 37.00 52.00 ... 871 1600 927 1700
5.00 ... ... ... ... ... ... 10.00 22.00 63.00 ... 943 1730 957 1755
2.00 16.00 0.20 ... 81.80 ... ... ... ... ... ... 1149 2100 1204 2200
(Ref 54, 55). However, some sacrifice of the A second nickel-base ODS alloy is Inconel
maximum properties may be allowable if such a MA 6000. Like Inconel MA 754, it is γ strength-
joint were to be sited outside the area of maxi- ened. Inconel MA 6000 has a solidus tempera-
mum stress; alternatively, a joint parallel to the ture of 1300 °C (2370 °F); therefore, the brazing
major stresses might be acceptable in certain temperature should be no higher than 1250 °C
cases. (2280 °F). Nickel and cobalt filler metals have
Although brazing introduces a change in com- been used to join this alloy. Other mechanically
position across the joint line, and although it alloyed ODS alloys include iron-base creep-
does melt some of the parent metal and thus resistant MA 956, which was also recently
causes agglomeration of the dispersoid, never- examined (Ref 56). Although it was possible to
theless, these effects can be minimized by a suit- produce a reasonable brazed joint in MA 956 by
able choice of composition and by close control means of sputter-coated brazes based on the
of brazing and postbrazing conditions. Further- nickel filler metal BNi-la (72.5Ni-16.5Cr-4Fe-
more, brazing does not introduce mechanical 4Si-3B), an agglomeration of the dispersed
distortion, and it can be carried out at tempera- oxide at the braze interface was unavoidable.
tures well below the recrystallization range. Furthermore, as in the brazing of nickel-base
Inconel MA 754 is one of the easiest alloys to ODS alloys, the presence of boron in the braze
braze in the family of ODS alloys. Vacuum, causes local recrystallization of the parent mate-
hydrogen, or inert atmospheres can be used for rial. This has led to future work whereby diffu-
brazing. Prebraze cleaning consists of grinding sion bonding was to be examined as the only
or machining the faying surfaces and washing joining process that did not require either a for-
with a solvent that evaporates without leaving a eign material or a melted or disrupted region in
residue. Generally, brazing temperatures should the joint. Diffusion bonding therefore offered
not exceed 1315 °C (2400 °F) unless demanded the ability to form a bond in an iron-ODS alloy
by a specific application that has been well in which the massive grain structure continued
examined and tested. The filler metals for use unbroken across the bond.
with these ODS alloys usually are not classified To decrease the completion time during TLP
(Table 4.8); in most cases, they have brazing bonding, an iron-base filler metal, comprising
temperatures in excess of 1230 °C (2250 °F). MA 956 base metal containing 7% Si and 1% B
These include proprietary filler metals contain- (wt%), was developed to join MA 956 base
ing nickel, cobalt, gold, or palladium. material. Transient-liquid-phase-bonded joints
A series of filler-metal evaluation tests (Ref free of microvoids and bond line intermetallic
55) found that brazing fine-grained MA 754 at phases were obtained using a bonding tempera-
1200 °C (2190 °F) by induction heating for less ture of 1563 K, a holding time of 2 to 16 ks, and
than 30 s with a thin β-free coating equivalent to an applied pressure of 7.0 MPa (1 ksi). The
BNi-5 gave joints of excellent appearance and bond line region in the TLP-bonded MA 956
without recrystallization. base metal had a bamboolike microstructure,
Table 4.7 American Welding Society (AWS) brazing alloys for elevated-temperature service
Composition, wt %
Other Solidus Liquidus Brazing range

AWS elements
classification Cr B Si Fe C P S Al Ti Mn Cu Zr Ni total °C °F °C °F °C °F
Nickel-base alloy filler metals(a)
BNi-1 13.0–15.0 2.75–3.50 4.0–5.0 4.0–5.0 0.6–0.9 0.02 0.02 0.05 0.05 ... ... 0.05 bal 0.50 975 1790 975 1790 1065–1205 1950–2200
BNi-1a 13.0–15.0 2.75–3.50 4.0–5.0 4.0–5.0 0.06 0.02 0.02 0.05 0.05 ... ... 0.05 bal 0.50 975 1790 1075 1970 1075–1205 1970–2200
BNi-2 6.0–8.0 2.75–3.50 4.0–5.0 2.5–3.5 0.06 0.02 0.02 0.05 0.05 ... ... 0.05 bal 0.50 970 1780 1000 1830 1010–1175 1850–2150
BNi-3 ... 2.75–3.50 4.0–5.0 0.5 0.06 0.02 0.02 0.05 0.05 ... ... 0.05 bal 0.50 980 1800 1040 1900 1010–1175 1850–2150
BNi-4 ... 1.5–2.2 3.0–4.0 1.5 0.06 0.02 0.02 0.05 0.05 ... ... 0.05 bal 0.50 980 1800 1065 1950 1010–1175 1850–2150
BNi-5 18.5–19.5 0.03 9.75–10.50 . . . 0.10 0.02 0.02 0.05 0.05 ... ... 0.05 bal 0.50 1080 1975 1135 2075 1150–1205 2100–2200
BNi-6 ... ... ... ... 0.10 10.0–12.0 0.02 0.05 0.05 ... ... 0.05 bal 0.50 875 1610 875 1610 925–1095 1700–2000
BNi-7 13.0–15.0 0.01 0.10 0.2 0.08 9.7–10.5 0.02 0.05 0.05 0.04 ... 0.05 bal 0.50 890 1630 890 1630 925–1095 1700–2000
BNi-8 ... ... 6.0–8.0 ... 0.10 0.02 0.02 0.05 0.05 21.5–24.5 4.0–5.0 0.05 bal 0.50 980 1800 1010 1850 1010–1095 1850–2000
BNi-9 13.5–16.5 3.25–4.0 ... 1.5 0.06 0.02 0.02 0.05 0.05 ... ... 0.05 bal 0.50 1055 1930 1055 1930 1065–1205 1950–2200
Composition, wt %

AWS elements
classification Au Cu Pd Ni total °C °F °C °F °C °F
Precious metals
BAu-1 37.0–38.0 bal ... ... 0.15 990 1815 1015 1860 1015–1095 1860–2000
BAu-2 79.5–80.5 bal ... ... 0.15 890 1635 890 1635 890–1010 1635–1850
BAu-3 34.5–35.5 bal ... 2.5–3.5 0.15 975 1785 1030 1885 1030–1090 1885–1995
BAu-4 81.5–82.5 ... ... bal 0.15 950 1740 950 1740 950–1005 1740–1840
BAu-5 29.5–30.5 ... 33.5–34.5 35.5–36.5 0.15 1135 2075 1165 2130 1165–1230 2130–2250
Composition, wt %

AWS elements
classification Cr Ni Si W Fe B C P S Al Ti Zr Co total °C °F °C °F °C °F
Cobalt-base alloy filler metals
BCo-1 18.0–20.0 16.0–18.0 7.5–8.5 3.5–4.5 1.0 0.7–0.9 0.35–0.45 0.02 0.02 0.05 0.05 0.05 bal 0.50 1120 2050 1150 2100 1150–1230 2100–2250
(a) If determined, cobalt is 0.1% maximum unless otherwise specified. Source: AWS A5.8
which was considered to be peculiar to bonded energy efficiency. With this in mind, electric
ODS alloys. For this reason, the growth mecha- power systems combining gas and steam tur-
nism of the solid phase during isothermal solid- bines must be improved to increase the energy
ification was evaluated. During tensile testing at efficiency. A key requirement for land gas tur-
923 K, the joints TLP bonded at 1563 K for 2 to bines is that higher inlet gas temperatures can be
16 ks fractured in the base-metal zone, and con- applied. Single-crystal base material is one of
sequently, the mechanical properties of the joint the most suitable candidate materials for high-
region and the base metal were similar. The quality land gas turbines. Nickel-base single-
creep-rupture properties of the joint regions crystal superalloys possess the excellent me-
were close to the base-metal properties in the chanical properties at elevated temperatures
transverse direction. (because the melting temperature is increased
In order to produce complex and high-tem- when grain-boundary strengthening elements
perature-resistant components, diffusion bond- are not present). The elevated-temperature
ing/brazing has been investigated. The joining properties of single-crystal base material deteri-
of a new iron-base ODS alloy, PM2000, was orate when grain boundaries are formed in the
developed (Ref 57). joint region. Therefore, it is vital that single-
Oxide-dispersion-strengthened superalloys crystal base material is bonded without creating
are very promising metallic materials for differ- such a problem.
ent high-temperature-exposed components. The Bonding and the crystallization behavior of a
ferritic ODS material is especially interesting nickel-base single-crystal superalloy base mate-
and suitable for high-temperature-exposed sta- rial, CMSX-2, was investigated during TLP
tionary components in turbine and diesel engine bonding using MBF-80 insert metal (Ref 58).
constructions. The combination of excellent Joint strength was evaluated using tensile and
oxidation and corrosion resistance and the high creep-rupture testing at elevated temperature.
melting point (1480 °C, or 2700 °F) of the Fe- The TLP bonding of CMSX-2 was carried out at
Cr-Al alloy with a Y2O3-dispersion-strength- 1373 to 1548 K for 0 to 19.6 ks in vacuum
ened matrix permits higher operating tempera- (Table 4.9).
tures for the iron-base ODS alloy than ever Some of the conclusions include:
attainable with the nickel-base superalloys.
In iron-base Fe-Cr-Al ODS alloys, the Y2O3 • The dissolution width of the base metal
dispersoid does not coarsen and coagulate dur- increased when the bonding temperature and
ing the joining. holding time increased. Base-metal dissolu-
At room temperature, a bending strength of tion was consistent with a derivation based on
approximately 70% of base-material strength is the Nernst-Brunner theory.
attainable. A secondary recrystallization some- • Material grew epitaxially into the liquid
times occurs in the bonding zone. Generally, the phase from substrates during the isothermal
bond interface is formed as a straight grain solidification, and single-crystal properties
boundary, which can limit the strength of the were maintained in completed joints.
bond. • The elevated-temperature tensile properties
It is very important to develop high-quality of completed joints were almost identical to
electric power systems that have excellent those of base metal. The creep-rupture
Table 4.8 Filler metals for brazing thoria-dispersed (TD) nickel and TD-NiCr alloys
Brazing temperature
Base metal Brazing filler metal °C °F Nominal composition
TD-Ni TD-20 1302 2375 Ni-16Cr-25Mo-4Si-5W

TD-6 1302 2375 Ni-22Cr-17Mo-4Si-5W
J8600 1177 2150 Ni-33Cr-25Pd-4Si
Ni-Pd 1246 2275 Ni-60Pd
TD-NiCr Td-6 1302 2375 Ni-22Cr-17Mo-4Si-5W
CM50 1066–1121 1950–2050 Ni-3.5Si-1.9B
NX77 1177–1191 2150–2175 Ni-5Cr-7Si-1B-1W-4Co
NSB 1288 2350 Ni-2Si-0.8B
Source: Ref 51
strength and rupture lives of completed joints temperatures, high to very high densities, low
were also almost identical to those of the base specific heats, and low coefficients of thermal
metal. Joint fracture always occurred in the expansion. Mechanical strength and structural
base material (Fig. 4.8). integrity at high temperatures are excellent.
The mechanical properties of refractory met-
Molybdenum, Niobium, Tantalum, als are affected markedly by ductile-to-brittle
transition behavior, recrystallization tempera-
Tungsten, and Their Alloys ture, and reactions with carbon and various
The refractory metals have a history of use in gases. These characteristics must be considered
applications where structural integrity at high when brazing procedures are established.
temperatures is required. For example, the fila- Refractory metals, because of their body-cen-
ments for incandescent lamps are made from tered cubic structure, have a well-defined transi-
tungsten. This metal is used extensively in vac- tion from ductile to brittle behavior. With these
uum tubes for cathode structures. Similarly, metals, a large decrease in energy absorption
molybdenum is used for grids and supporting occurs over a narrow temperature range, and an
members in vacuum tubes and for lead wires in associated change in the type of fracture from
incandescent lamps. In current applications of tough to brittle is also evident. This temperature
the refractory metals in the aircraft, space, range is not a fixed property of the metal,
nuclear, and electronics industries, the joints because it varies with strain rate, alloying addi-
must be of significant dimensions, with proper- tion, impurities, heat treatment, and method of
ties that are adequate to meet exacting require- fabrication. The transition-temperature ranges
ments of strength, ductility, corrosion resis- for the pure refractory metals are as follows:
tance, and so on. Because of its limited effect on
base-metal properties, brazing has been • Niobium, –200 to –75 °C (–330 to –105 °F)
accepted widely as a method of joining assem- • Molybdenum, 150 to 260 °C (300 to 500 °F)
blies fabricated from refractory metals. The • Tantalum, <–195 °C (–320 °F)
characteristics that affect the brazeability of • Tungsten, 260 to 370 °C (500 to 700 °F)
refractory metals include ductile-to-brittle tran-
sition behavior, recrystallization temperature, Therefore, molybdenum and tungsten are
and reactivity with oxygen, nitrogen, hydrogen, brittle at room temperature and must be handled
and carbon. carefully to avoid damage. Also, these metals
The refractory metals include those metals must be brazed in a stress-free condition. The
that have melting points in excess of 2205 °C strength and ductility of refractory metals are
(4000 °F), that is, niobium, iridium, molybde- adversely affected by microstructural changes
num, tantalum, ruthenium, tungsten, osmium, that occur when the recrystallization tempera-
and rhenium. Sometimes vanadium, hafnium, tures of these metals are exceeded. Recrystal-
rhodium, and chromium are included in this lization-temperature range also varies with
group of metals. The most important refractory alloying additions, interstitial content, fabrica-
metals, from a structural standpoint, are molyb- tion method (including degree of cold working),
denum, tantalum, niobium, and tungsten. and time at temperature. Recrystallization-tem-
Niobium, molybdenum, tantalum, and tung- perature ranges for unalloyed refractory metals
sten have much in common; however, there are are:
differences that have a bearing on the manner in
which these metals are used and joined. All of • Niobium, 985 to 1150 °C (1805 to 2100 °F)
the refractory metals have a body-centered • Molybdenum, 1150 to 1200 °C (2100 to 2190
cubic crystal structure, with very high melting °F)
Table 4.9 Composition of materials used in brazing a nickel-base single-crystal superalloy

Composition, mass%
Ni B Cr Co Mo W Ti Al Ta
Base metal: CMSX-2 bal ... 8.0 4.6 0.6 8.0 1.0 5.6 6.0
Insert metal: MBF-80 bal 3.7 15.5 ... ... ... ... ... ...
Source: Ref 58
• Tantalum, 1100 to 1400 °C (2010 to 2550 °F) can be brazed in a hydrogen atmosphere. Moly-
• Tungsten, 1200 to 1650 °C (2190 to 3000 °F) bdenum, tantalum, and niobium are embrittled
by nitrogen at high temperatures.
Some applications permit brazing with filler All of the refractory metals form carbides in
metals that melt below the recrystallization- the presence of minute quantities of carbon and
temperature range. Other applications require its compounds.
the use of filler metals that melt above this tem- Based on the various characteristics of refrac-
perature range. The joint also must be designed tory metals, the following principles are appli-
to accommodate the loss in mechanical proper- cable to brazing of refractory metals:
ties associated with recrystallization.
Research has improved the high-temperature
• If maximum joint strength is required, refrac-
mechanical properties of the refractory metals
tory metals must be brazed at temperatures
and has led to an increase in recrystallization
below those at which recrystallization occurs.
temperatures through alloying. For example,
• However, brazing at much higher tempera-
titanium, zirconium, and hafnium can be used to
tures may be necessitated by service require-
strengthen molybdenum and increase its recrys-
ments, and some decrease in joint properties
tallization temperature. The recrystallization
must be anticipated.
temperature of unalloyed molybdenum is ap-
• All of the refractory metals can be brazed in a
proximately 1150 to 1200 °C (2100 to 2190 °F).
vacuum or in an argon or helium atmosphere
In contrast, the recrystallization temperature of
with a very low dewpoint.
Mo-0.5Ti-0.07Zr molybdenum alloy (TZM) is
• Graphite fixturing should not be used to posi-
approximately 1480 °C (2700 °F), and the stress-
tion refractory metal parts during brazing,
rupture strength of this alloy at 980 to 1095 °C
because these metals readily form carbides.
(1800 to 2000 °F) is several times that of unal-
However, graphite tooling may be acceptable
loyed molybdenum.
if coated with a refractory material.
The third consideration is reactions with
• Ceramics can also be used for fixturing, but
gases and carbon. The environment in which
care in their selection must be exercised.
refractory metals are brazed is determined by
Some ceramics cannot be used in a vacuum
the reactivity of these metals with oxygen,
because of outgassing, whereas others react
hydrogen, and nitrogen and the effects of these
with refractory metals at high temperatures.
elements on mechanical properties.
• Refractory metals with higher melting tem-
Tantalum and niobium are embrittled by the
peratures than the one being brazed also can
presence of hydrogen at relatively low tempera-
be used for fixturing.
tures. In contrast, molybdenum and tungsten
The filler metals used for brazing of refrac-

1000 (145)
tory metals must be selected on the basis of the
900 (131) Base metal CMSX-2 Joint service condition, the specific application, and
800 (116)
700 (102)
Insert metal MBF-80 1523 x 1.8ks (2.3MPa) their compatibility with the base metal and coat-
600 (87) ing (if a coating is used) (Table 4.10).
Stress (σ), MPa (ksi)
500 (73)
Molybdenum and Its Alloys. Copper- and
silver-base filler metals can be used to braze
400 (58)
molybdenum for low-temperature service. For
300 (44) high-temperature applications, molybdenum
can be brazed with gold, palladium, and plat-
inum filler metals, nickel-base filler metals,
200 (30)
Base metal
reactive metals, and refractory metals that melt
at lower temperatures than molybdenum.
Nickel-base filler metals have limited applica-
bility for high-temperature service, because
100 (15)
23 24 25 26 27 28 29 30 31 nickel and molybdenum form a low-melting
Larson–Miller parameter, T(20+Log t)x10–3 eutectic at approximately 1315 °C (2400 °F).
There are three basic limits on brazing of
Fig. 4.8 Creep-rupture strength of superalloy CMSX-2 joints. molybdenum and its alloys for use above 980
Source: Ref 58 °C (1800 °F):
• Recrystallization of molybdenum systems, and the best filler-metal base on over-

• Formation of intermetallics between refrac- all performance has been Fe-15Mo-5Ge-4C-1B
tory metals and filler metals (Ref 60, 61).
• Relative weakness of filler metals at elevated The molybdenum alloy TZM (0.5Ti-0.08Zr-
temperatures Mo) has also been brazed successfully at 1400
°C (2550 °F), with molybdenum powder added
The formation of intermetallics between to the Ti-8.5Si filler metal (Ref 59, 62); other
molybdenum and filler metals is detrimental to filler metals also can be used (Ref 63). A Ti-
joint soundness, because the intermetallics 25Cr-13Ni filler metal with a brazing tempera-
become brittle and may fracture at relatively ture of 1260 °C (2300 °F) has produced the
low loads when the joint is stressed. highest remelt temperature on TZM.
The relative weakness of filler metals at Remelt investigations conducted to develop
elevated temperatures limits the use of brazed vacuum brazements of molybdenum and tung-
molybdenum assemblies. Most of the nickel- sten that can be used in seal-joint applications
base elevated-temperature filler metals melt up to 1600 °C (2910 °F) were completed with
between 980 and 1150 °C (1800 and 2100 the following filler metals:
°F), where the superior elevated-temperature
strength of molybdenum begins to manifest • Ti-65 wire
itself. • Vanadium wire
Two binary filler metals, V-35Nb and Ti- • MoB-50MoC powder mixture
30V, have been evaluated for use with the Mo- • V-50Mo powder mixture
0.5Ti molybdenum base metal. Tee-joints were • Mo-15MoB2 powder mixture
brazed in a vacuum for 5 min at temperatures of • Mo-49V-15MoB2 powder mixture
1650 °C (3000 °F) for the Ti-30V filler metal
and 1870 °C (3400 °F) for the V-35Nb filler Brazing temperatures ranged from 1625 to
metal. The filler metals had excellent metallur- 2255 °C (2960 to 4095 °F). Molybdenum joints
gical compatibility with the molybdenum base made with Ti-65V, pure vanadium wire, V-
metal, and minimum erosion of the base metal 50Mo, and MoB-50MoC were as strong, or
occurred during brazing. stronger, than the base metal at elevated tem-
Brazements made on Mo-0.5Ti alloy with the perature. The most resistant joints tested were
diffusion-sink filler metal Ti-8.5Si, which melts brazed with Ti-65V, V-50Mo, and MoB-
at approximately 1330 °C (2425 °F), exhibited 50MoC. Without further testing, it probably
excellent filleting and wetting, joint ductility, would be best to limit the maximum service
and freedom from cracks. Specimens with temperature to 1395 °C (2545 °F).
molybdenum powder added to the filler-metal A more recently completed wettability study
powder were also evaluated and brazed at 1400 (Ref 64) found that:
°C (2550 °F) (Ref 59).
Because of its excellent high-temperature • Filler metals generally wet molybdenum sig-
properties and compatibility with certain envi- nificantly better than they wet TZM. This is
ronments, molybdenum is a prime candidate for seen in Tables 4.11 and 4.12. The wettability
use in isotopic power systems for components index shown for each filler metal indicates
of nuclear reactors and chemical-processing that indexes >0.05 are indicative of good per-
Table 4.10 Filler metals for brazing of graphite, ceramics, and refractory and reactive metals
Chemical composition, % Solidus (melting point) Liquidus (flow point)
Ti Zr Be Ni Al Cu °C °F °C °F
43 43 2 12 ... ... 799 1470 816 1500

45 45 2 8 ... ... 899 1650 899 1650
48 47 5 ... ... ... 893 1640 904 1660
43 47 5 ... 5 ... 927 1700 927 1700
70 ... ... 15 ... 15 950 1742 1000 1832
48 48 4 ... ... ... 1000 1832 1050 1922
formance during brazing, and wettability Niobium and Its Alloys. Niobium is used
indexes >0.10 are indicative of excellent per- mostly for nuclear and aerospace applications.
formance during brazing. One aerospace application required the develop-
• The decrease in wettability of the filler metals ment of manufacturing procedures for fab-
on TZM versus molybdenum is believed to ricating flat and curved niobium alloy sand-
be due to the presence of titanium in the oxide wich heatshield panels (Ref 59). Titanium
on the surface of TZM. and the titanium-base alloy Ti-11Cr-13V-3Al
• Some nickel-containing filler metals have (B120VCA) produced joints with excellent duc-
been shown to embrittle both molybdenum tility and less base-metal reaction (Ref 67, 68).
and TZM. Liquid metal embrittlement is The flow characteristics of the B120VCA
believed to be the mechanism by which this filler metal were more sluggish than those of
embrittlement occurs. pure titanium; as a result, the filler metal could
be used to bridge wide joint clearances. The pre-
Torches, controlled-atmosphere furnaces, vac- viously mentioned honeycomb sandwich panels
uum furnaces, and induction and resistance were successfully brazed with pure titanium at
heating equipment can be used to braze molyb- 1815 °C (3300 °F). Heat-shield panels have
denum with the variety of filler metals described been brazed with B120VCA filler metal at 1650
previously. °C (3000 °F) in the same vacuum brazing envi-
In a report (Ref 66) on the vacuum brazing of ronment. Simulated re-entry environment tests
P/M molybdenum TZM alloy plate and drawn have shown that the heatshield panel could be
molybdenum tubing assembly for spacecraft used at temperatures up to 1315 °C (2400 °F).
radiator panels, the full-scale test panel success- Room-temperature and elevated-temperature
fully passed a battery of tests, including heat tests of the structural honeycomb panel indi-
transport, thermal shock, and launchlike vibra- cated that it possessed useful properties up to
tion testing. 1260 °C (2300 °F) (Ref 59).
Brazing was successfully employed despite Other developments investigated and evalu-
the recrystallization of both the tubing and the ated the high-remelt-temperature brazing tech-
isogrid substrate panel. Platinum filler metal niques based on diffusion-sink and reactive
demonstrated its ability to obtain high-strength brazing concepts. The diffusion-sink technique
reliable joints. involves either permitting the filler metal to
Table 4.11 Wettability index values for commercial filler metals used in brazing of
molybdenum alloys
Temperature, °C (°F)
750 800 825 850 875 900 950 975 1000 1025 1050 1075
Filler metal (1380) (1470) (1520) (1560) (1610) (1650) (1740) (1790) (1830) (1880) (1920) (1970)
Palcusil 5 ... ... ... 0.012 ... 0.034 0.045 ... ... ... ... ...
Palcusil 10 ... ... ... 0.011 ... 0.030 0.045 ... ... ... ... ...
Palcusil 15 ... ... ... ... ... 0.044 0.045 0.152 ... ... ... ...
Palcusil 20 ... ... ... 0.015 ... 0.037 ... ... ... ... ... ...
Palcusil 25 ... ... ... ... ... ... 0.102 0.119 0.418 ... ... ...
Nicusil 3 ... 0 ... 0.024 ... 0.053 ... ... ... ... ... ...
Nicusil 8 ... ... ... 0.020 ... 0.052 0.096 ... ... ... ... ...
T50 ... ... ... 0.023 ... 0.052 0.069 ... ... ... ... ...
T51 ... 0 ... 0.023 ... 0.049 ... ... ... ... ... ...
T52 ... ... ... 0.024 ... 0.057 0.075 ... ... ... ... ...
Cusiltin 5 ... ... ... 0.008 0.012 0.057 ... ... ... ... ... ...
Cusiltin 10 ... ... 0.021 0.037 0.031 ... ... ... ... ... ... ...
Braze 580 0.030 0.037 ... 0.045 ... ... ... ... ... ... ... ...
Braze 630 ... ... 0 0.066 ... 0.080 ... ... ... ... ... ...
Braze 655 ... ... 0.061 0.075 0.069 ... ... ... ... ... ... ...
Nioro ... ... ... ... ... ... ... 0.158 ... ... ... ...
Nicoro 80 ... ... ... ... ... ... 0.024 ... ... 0.071 ... ...
Palniro 7 ... ... ... ... ... ... ... ... ... 0.023 0.119 0.102
Gapasil 9 ... ... ... ... ... 0.017 0.061 ... ... ... ... ...
Source: Ref 65
Table 4.12 Wettability index values for commercial filler metals used in brazing of molybdenum alloy TZM
Temperature, °C (°F)
750 800 825 850 875 900 925 950 975 1000 1025 1050 1075 1100 1125 1150 1175 1200 1225 1275 1300
Filler metal (1380) (1470) (1520) (1560) (1610) (1650) (1700) (1740) (1790) (1830) (1880) (1920) (1970) (2010) (2060) (2100) (2150) (2190) (2240) (2330) (2370)
580 ... 0.007 ... 0.009 0.018 ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ...
Nicusil 3 ... 0.008 ... 0.009 ... 0.015 ... 0.022 ... ... ... ... ... ... ... ... ... ... ... ... ...
T51 ... 0.007 ... 0.009 ... 0.010 0.020 0.018 ... ... ... ... ... ... ... ... ... ... ... ... ...
630 ... 0.015 ... 0.018 ... 0.016 ... ... ... ... ... ... ... ... ... ... ... ... ... ... ...
Cusiltin ... ... 0 0 0 0 ... ... ... ... ... ... ... ... ... ... ... ... ... ... ...
655 ... ... 0.009 0.009 0.025 ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ...
Palcusil 5 ... ... ... 0 ... 0.011 ... 0.027 ... ... ... ... ... ... ... ... ... ... ... ... ...
Palcusil 10 ... ... ... 0.007 ... 0.016 ... 0.028 ... ... ... ... ... ... ... ... ... ... ... ... ...
Nicusil 8 ... ... ... 0.008 ... 0.018 ... 0.024 ... ... ... ... ... ... ... ... ... ... ... ... ...
T50 ... ... ... 0.014 ... 0.020 ... 0.025 ... ... ... ... ... ... ... ... ... ... ... ... ...
T52 ... ... ... 0.016 ... 0.017 ... 0.026 ... ... ... ... ... ... ... ... ... ... ... ... ...
Cusiltin 5 ... ... ... 0 0 0 ... ... ... ... ... ... ... ... ... ... ... ... ... ... ...
Palcusil 20 ... ... ... ... 0.009 0.017 0.034 ... ... ... ... ... ... ... ... ... ... ... ... ... ...
Ticusil ... ... ... ... 0.024 0.101 ... ... ... ... ... ... ... ... ... ... ... ... ... ... ...
Cusil ... ... ... ... ... 0 0.009 0.009 ... ... ... ... ... ... ... ... ... ... ... ... ...
Palcusil 15 ... ... ... ... ... 0.023 ... 0.039 ... 0.50 ... ... ... ... ... ... ... ... ... ... ...
Gapasil 9 ... ... ... ... ... 0 ... 0.025 ... 0.041 ... ... ... ... ... ... ... ... ... ... ...
Silcoro 60 ... ... ... ... ... 0 0.020 0.023 ... ... ... ... ... ... ... ... ... ... ... ... ...
Palcusil 25 ... ... ... ... ... ... ... 0.096 0.105 0.204 ... ... ... ... ... ... ... ... ... ... ...
Nioro ... ... ... ... ... ... ... 0 0.070 0.225 ... ... ... ... ... ... ... ... ... ... ...
Nicoro 80 ... ... ... ... ... ... ... 0.020 ... 0.029 ... 0.049 ... ... ... ... ... ... ... ... ...
Ticuni ... ... ... ... ... ... ... 0.093 ... ... ... ... ... ... ... ... ... ... ... ... ...
Silver ... ... ... ... ... ... ... ... ... ... ... 0 0.013 0.013 ... ... ... ... ... ... ...
Incuro 60 ... ... ... ... ... ... ... ... 0.008 0.012 0.013 ... ... ... ... ... ... ... ... ... ...
Silcoro 75 ... ... ... ... ... ... ... ... 0 0 0 ... ... ... ... ... ... ... ... ... ...
Palnicusil ... ... ... ... ... ... ... ... 0.089 ... 0.318 ... ... ... ... ... ... ... ... ... ...
Altizirbe ... ... ... ... ... ... ... ... 0.034 ... ... ... ... ... ... ... ... ... ... ... ...
Palniro 7 ... ... ... ... ... ... ... ... ... ... 0 0.107 0.133 ... ... ... ... ... ... ... ...
Gold ... ... ... ... ... ... ... ... ... ... ... ... 0.088 0.107 ... ... ... ... ... ... ...
Palniro 1 ... ... ... ... ... ... ... ... ... ... ... ... ... ... 0.037 0.053 0.070 ... ... ... ...
Palniro 4 ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... 0.037 0.044 0.047 ... ...
Palco ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... ... 0.041 0.048
Source: Ref 65
react with the base metal under controlled con- 2095 °C (3800 °F) in tee and lap joints. Diffu-
ditions or adding base-metal powder to the sion-sink brazing with 33Zr-34Ti-33V filler
filler-metal powder. One diffusion-sink filler metal with a brazing temperature of 1425 °C
metal is Ti-33Cr, requiring brazing tempera- (2600 °F) has produced remelt temperatures
tures of 1455 to 1480 °C (2650 to 2700 °F) (Ref exceeding 1760 °C (3200 °F). Therefore, these
67). The other is a Ti-30V-4Be reactive filler remelt temperatures indicate that service tem-
metal that requires brazing temperatures of peratures could be 1925 °C (3500 °F) for the
1290 to 1315 °C (2350 to 2400 °F). titanium and Ti-30V filler metals and 1650 °C
Test results of Ti-33Cr brazed joints with D-36 (3000 °F) for the 33Zr-34Ti-33V filler metal.
niobium alloy indicate an increase in lap shear Most of the filler metals currently available
strength from approximately 17 MPa (2.5 ksi) to for tantalum are in powder form, which is diffi-
more than 31 MPa (4.5 ksi) at 1370 °C (2500 °F) cult to work with at elevated temperatures. New
and 7 MPa (1 ksi) at 1650 °C (3000 °F). powder filler metals, such as Hf-7Mo, Hf-40Ta,
Other niobium alloys—D43 (10W-1Zr-0.1C- and Hf-19Ta-12.5Mo, have been used success-
Nb), Nb-752 (10W-2.5Zr-Nb), and C-129Y fully but require further development and re-
(10W-11Hf-0.07Y-Nb)—have been brazed finement.
successfully with two filler metals, B120VCA Special techniques are necessary to braze tan-
and Ti-8.5Si, whose brazing temperature was talum satisfactorily. All gases that have any
1455 °C (2650 °F). reactivity must be removed. Oxygen and carbon
Tantalum and Its Alloys. The filler metals monoxide must be eliminated. Tantalum forms
for moderate-temperature applications of tanta- oxides, carbides, nitrides, and hydrides very
lum and its alloys are chosen on the basis of the readily with these gases. A loss of ductility
intended application. Nickel-base filler metals ensues. At high temperatures, tantalum should
(such as the Ni-Cr-Si filler metals) have been be protected from oxidation. One method is to
used in successful brazing of tantalum. These electroplate the surfaces with copper or nickel,
filler metals are satisfactory for service temper- in which case it is necessary for the filler metal
atures below 980 °C (1800 °F). Copper-gold to be compatible with the plating. Controlled-
alloys having less than 40% Au can also be used atmosphere and both hot- and cold-wall vacuum
as filler metals, but gold in amounts between 40 furnaces have been used for brazing tantalum
and 90% tends to form brittle, age-hardening and its alloys. Induction, resistance, and torch
compounds. Copper-tin, gold-nickel, and cop- brazing are not recommended.
per-titanium filler metals also have been used in Tungsten and Its Alloys. Tungsten has
brazing tantalum and its alloys. been successfully brazed in vacuum. Filler met-
Because most uses of tantalum and its alloys als that have been used to braze tungsten as well
are in elevated-temperature applications (at or as the other refractory metals are listed in Table
above 1650 °C, or 3000 °F), there is a lack of 4.10. These filler metals and pure metals having
high-temperature filler metals for use with tan- liquidus temperatures ranging from 650 to 1925
talum. Investigations have examined conven- °C (1200 to 3500 °F) are potentially useful for
tional brazing, reactive brazing, and diffusion- brazing.
sink brazing concepts for new tantalum filler Tungsten can be brazed in much the same
metals. The reactive brazing concept uses a manner as molybdenum and its alloys, using
filler metal containing a strong melt-tempera- many of the same filler metals. Brazing can be
ture depressant. The depressant is selected to accomplished in a vacuum or in a dry argon,
react with the base material or powder additions helium, or hydrogen atmosphere. To some ex-
to form a high-melting intermetallic compound tent, the selection of the brazing atmosphere
during a postbraze diffusion treatment. As the depends on the filler metal used. For example,
depressant diffuses into the base material, the filler metals that contain elements with high
joint remelt temperature is increased. Success- vapor pressures at the brazing temperature can-
ful application of this concept appears highly not be used effectively in a high vacuum.
dependent on controlling the intermetallic com- Care must be exercised in handling and fix-
pound reaction to form discrete particles. turing tungsten parts because of their inherent
Diffusion-sink brazing with titanium and Ti- brittleness; these parts should be assembled in a
30V filler metals, whose brazing temperatures stress-free condition. Contact between graphite
range from 1675 to 1760 °C (3050 to 3200 °F), fixtures and tungsten must be avoided to prevent
has produced remelt temperatures exceeding the formation of brittle tungsten carbides.
Although nickel-base filler metals have been ing portion of the electrode. Any of the silver-
used successfully to braze tungsten, a reaction copper and/or zinc series of filler metals are suit-
between nickel and tungsten that results in base- able for this application. Tungsten-copper tips
metal recrystallization can occur; this reaction usually are applied by induction or torch heating
can be minimized by short brazing cycles, min- in a neutral or reducing atmosphere. The most
imum brazing temperatures, and the use of suitable filler metal is 72Ag-28Cu. To hold parts
small quantities of filler metal. in alignment, pins are incorporated in the design,
Data on brazing of tungsten are more limited and the filler metal is preplaced in the form of
than data on brazing of other refractory metals. shim stock located between the mating parts.
Unalloyed tungsten has been vacuum brazed In brazing of resistance welding electrodes
with two experimental filler metals, Nb-2.2B with pure tungsten tips, precoating of the tung-
and Nb-20Ti. The lap shear strength of joints sten surface aids uniform flow of the filler metal
brazed with the Nb-2.2B filler metal was approx- between the faying surfaces of the joint. Usu-
imately 35 MPa (5 ksi) at 1650 °C (3000 °F) and ally, one of the silver-base filler metals is used
55.2 MPa (8 ksi) at 1370 °C (2500 °F). The as a precoating. Without pretreatment, poor
strength of joints brazed with Nb-20Ti was wetting of the tungsten by the filler metal often
somewhat lower, approximately 21 MPa (3 ksi) results, causing premature joint failure under
at both test temperatures. The flow of Nb-20Ti the high pressures and temperatures of resis-
filler metal was more sluggish than that obtained tance welding.
with Nb-2.2B.
Filler metals based on the platinum-boron and Cast Iron
iridium-boron systems were developed to braze Brazing of gray, ductile, and malleable cast
tungsten for service at 1925 °C (3500 °F). They irons differs from brazing of steel in two princi-
contained up to 4.5% B and could be used for pal respects: special precleaning methods are
brazing below the recrystallization temperature necessary to remove graphite from the surface
of tungsten. Tungsten lap joints were brazed and of the iron, and the brazing temperature is kept
diffusion treated in a vacuum at 1095 °C (2000 as low as feasible to avoid reduction in the hard-
°F) for 3 h. This cycle resulted in the production ness and strength of the iron.
of joints with remelt temperatures of approxi- The processes used for brazing of cast irons
mately 2040 °C (3700 °F). A slight increase in are the same as those used for brazing of steel,
joint remelt temperature was noted when tung- which include furnace, torch, induction, and dip
sten powder was added to the filler metal. The brazing. As with other metals, selection of the
highest remelt temperature of 2170 °C (3940 °F) brazing process depends largely on the size and
was obtained when joints were brazed with Pt- shape of the assembly, the quantity of assem-
3.6B plus 11 wt% W powder (Ref 69). blies to be brazed, and the equipment available.
Studies have been conducted to develop and In recent years, brazing of ordinary gray cast
evaluate filler metals that could be used to braze irons using silver-base filler metal has become
tungsten for nuclear reactor service at 2500 °C practical commercially; the development of a
(4530 °F) in hydrogen atmosphere. Butt joints satisfactory surface pretreatment has opened up
have been brazed using a gas tungsten arc as the many design possibilities. Intricate forms can be
heat source and the filler metals W-25Os, W- built from simple castings or by joining castings
50Mo-3Re, and Mo-5Os. to standard wrought forms, such as tubing and
Furnace brazing (inert-gas or reducing at- rolled shapes. Foundry work may be simplified
mosphere and vacuum), torch brazing, resis- by making intricate castings in several parts to
tance brazing, or induction brazing can be used reduce coring. Gray, ductile, and malleable
to braze tungsten. Furnace brazing operations irons commonly are brazed to steels or to other
usually are used when the parts are larger than cast irons.
those considered practical for the induction and In brazing of ductile or malleable irons, cer-
resistance processes. tain precautions are imperative. If ductile or
Tungsten-copper electrode tips are materials malleable irons are heated above 760 °C (1400
made by P/M processes. A normal analysis of °F), the metallurgical structure may be dam-
one of the materials is 80W-20Cu. These tips aged; brazing thus should be done below this
may be used for resistance welding electrodes temperature.
that are usually brazed to the copper-chromium The effects of graphite, which is present in all
alloys, which constitute the main current-carry- gray, ductile, and malleable cast irons, are sig-
nificant. Although gray, ductile, and malleable ical activity. This action is further enhanced in
irons all have lower brazeability than carbon or the cleaning operations by the introduction of
low-alloy steels, the three types of iron are not electrical energy. The effective use of these salts
equal in brazeability. and the removal of their by-products to produce
Malleable iron is generally considered the an excellent metallurgical surface has resulted
most brazeable of the three types of cast iron, in quality bonds and has permitted direct bab-
largely because the total carbon content is some- bitting of cast iron bearings and silver brazing
what lower (seldom over 2.70%), and, therefore, fittings to cast iron surfaces. With proper clean-
graphitization is lower. Brazeability is also ing and preparation of the cast iron, it has been
enhanced because the graphite occurs in the possible to produce a brazed bond between
form of approximately round nodules and thus is metal surfaces that exceeds the strength of the
easier to remove or cover up (as by abrasive parent metal.
blasting). Also, malleable iron is lower in silicon With proper surface preparation, the usual
than the other types of cast iron and thus is less variety of filler metals suitable for steel brazing
graphitized, which makes it better suited for is satisfactory for cast irons. In selection of the
brazing. filler metal, the metallurgical effects of the braz-
Ductile iron can have a composition nearly the ing cycle on the base-metal matrix (hardening,
same as gray iron, but the graphite particles are softening, etc.) should be considered. Various
spheroidal rather than flake-shaped. The spher- filler metals in the silver-copper series are com-
oidal shape is more favorable for brazing. Shot monly used. Copper filler metal has been used
or grit blasting is effective in rolling metal over successfully in furnace brazing. Some cast irons
graphite particles that are exposed at the surface. have low melting (solidus) temperatures, sug-
Gray iron, which is characterized by large gesting that care must be exercised to keep the
flakes of graphite, is the most difficult type of brazing temperature below 1120 °C (2050 °F).
cast iron to braze. Until the development of Brass filler metals (copper-zinc series) fre-
electrolytic salt bath cleaning, brazing of gray quently are used to braze cast irons, while the sil-
iron was considered impractical. ver-base filler metals have been used to join cop-
Abrasive blasting with steel shot or grit has per to cast iron.
proved reasonably successful for preparing sur- Most brazing of cast iron is performed to join
faces of ductile and malleable iron castings but assemblies at lower cost than is possible by
is seldom suitable for preparing surfaces of gray another process or to fabricate parts that are dif-
iron castings. Electrolytic treatment in a molten ficult to produce—one-piece castings, for ex-
salt bath, alternately reducing and oxidizing, ample. In some applications, two or more cast
has been the most successful method for surface iron components are brazed together; in other
preparation and is applicable to all graphitic cast applications, one or more components of a
irons. Ordinary chemical cleaning methods, brazed assembly are made of another metal—
such as degreasing, detergent washing, and acid most often steel but also copper alloys. Local-
pickling, have the distinct disadvantage of not ized heating methods, such as torch and induc-
removing surface carbon, which interferes with tion, have the advantages of restricted heat
bonding. effects and limited metallurgical phase changes
Before any procedure for cleaning is adopted, in base-metal components. Furnace brazing
tests should be made by cleaning samples of the may be desirable for production lots due to cost
iron intended for use in the castings to be savings and/or consistency of results. Brazing
brazed, fluxing the samples, and applying filler with copper and nickel filler metals require
metal (preferably on a smooth, flat surface). The atmosphere controls during heating, usually
samples are then heated to the preestablished accomplished by furnace brazing. The use of
brazing temperature, cooled, and examined dry hydrogen as a protective atmosphere pro-
visually. If the samples show an indication that motes wetting by reducing oxides such as silica.
the filler metal has not uniformly wetted the Electric arc braze welding processes have suc-
testpiece, the surface is not sufficiently clean. cessfully been used with bronze-brass filler
Alkaline-based salts (sodium hydroxide) metals on cast iron and require special preheat-
operating at 400 to 480 °C (750 to 900 °F) are ing techniques to prevent cracking.
extremely effective in removing surface oxides Cast irons that contain pearlite or free carbide
and sand from iron castings. At these tempera- graphitize and decrease in strength at elevated
tures, salt baths exhibit the required high chem- temperatures. Because graphitization is a func-
tion of time and temperature, some experimen- molybdenum steels, and several other types
tation is usually necessary to develop a brazing containing less than 5% total alloy content.
cycle that produces acceptable joints without Leaded steels can be torch brazed using filler
excessive graphitization and decreases in metal and flux combinations normally recom-
strength. Two identical assemblies were heated mended for steel. Tests conducted on low-car-
in different plants for 1 h. In the first plant, the bon free-machining steel containing 0.25 to
assemblies were heated to approximately 705 0.35% Pb show detrimental effects after torch
°C (1300 °F) with no significant decrease in brazing with silver-base filler metals; satisfac-
strength. In the second plant, the assemblies tory joints have been made in these leaded steels
were heated to approximately 790 °C (1450 °F), using copper- and nickel-base filler metals.
again without significant decrease in strength. All the silver-base filler metals can be used
In the latter application, however, heating was for brazing low-carbon and low-alloy steels
done by induction instead of in a furnace, and (Table 4.13). The silver-base filler metals con-
the heating time was much shorter than would taining nickel usually provide better wettability
have been required in a furnace. and are preferred for brazing low-alloy steels
In some plants using furnace brazing, the fur- wherein joint strength is most important.
nace is operated at a considerably higher tem- Copper-base filler metals are used mainly for
perature than is desired for brazing (sometimes preplacement in controlled-atmosphere fur-
as high as 870 °C, or 1600 °F), but the time naces. Copper is also generally preferred
cycles used are so short that the assemblies because of its low cost and the high strength of
never reach furnace temperature. the joints produced. Copper-zinc filler metals
For applications in which little or no decrease often are face fed into the joint but can also be
in strength of the cast iron can be tolerated, it is preplaced for furnace and induction heating.
mandatory to use a filler metal with as low a The high solidus temperatures (1095 to 1150
flow-temperature range as possible, thus per- °C, or 2000 to 2100 °F) necessary when copper-
mitting a low brazing temperature, and to keep base filler metals are used often allow simulta-
the time at brazing temperature to the minimum. neous brazing and heat treating of certain low-
The temperature required for wetting the base alloy steels. Nickel-base filler metals have been
metal and for flow of filler metal having a melt- used for joining low-carbon and low-alloy
ing range of 620 to 645 °C (1150 to 1195 °F) steels when special joint requirements so dic-
may vary from approximately 690 to 845 °C tate. Brazing usually is restricted to controlled-
(1275 to 1555 °F), depending on the complexity atmosphere furnaces.
of the joint design—especially the distance the Low-carbon and low-alloy steels can be
filler metal must flow. Simple joints with short brazed using virtually all known processes.
flow distances can be brazed at lower tempera- Torch, furnace, and induction heating techniques
tures than more complex joints. are the most common. Filler metals in the form of
continuous wire or strip can be automatically
Low-Carbon, Low-Alloy, applied using electromechanical wire feeders;
powder filler metals blended with flux and paste-
and Tool Steels forming ingredients are applied automatically
Brazing of low-carbon and low-alloy steels is with pressurized dispensing equipment. For
a highly developed, low-cost production torch brazing, the equipment would include stan-
process. Filler metals can be either manually or dard oxyacetylene or similar torches. Furnaces
automatically applied or preplaced in the joint. can be of the batch or conveyor type, with or
The heat treatment considerations of low-alloy without atmosphere control; they can be electric,
steels are factors in determining the specific filler gas, or oil fired and should provide accurate tem-
metals and brazing temperatures to be used. perature control.
The steels covered in this section include The principal advantage of furnace brazing
low-carbon (less than 0.30% C) and low-alloy over other brazing processes is that it permits
steels. The low-alloy steels include the Society the use of a variety of prepared protective
of Automotive Engineers/American Iron and atmospheres—notably, the rich exothermic-
Steel Institute (SAE/AISI) 23xx nickel steels, based, endothermic-based, and some prepared
31xx nickel-chromium steels, 41xx chromium- and commercial nitrogen-base atmospheres.
molybdenum steels, 43xx nickel-chromium- These atmospheres are among the least expen-
Table 4.13 Filler metals for torch brazing low-carbon and low-alloy steels
Nominal composition, % Solidus temperature Liquidus temperature Brazing temperature
AWS classification Product form Ag Cu Zn Cd Ni Sn Fe Mn Si P °C °F °C °F °C °F
Silver alloys(a)
BAg-1 Strip, wire, powder 45 15 16 24 ... ... ... ... ... ... 605 1125 620 1145 620–760 1145–1400
BAg-1a Strip, wire, powder 50 15.5 16.5 18 ... ... ... ... ... ... 625 1160 635 1175 635–760 1175–1400
BAg-2 Strip, wire, powder 35 26 21 18 ... ... ... ... ... ... 605 1125 700 1295 700–845 1295–1550

BAg-2a Strip, wire, powder 30 27 23 20 ... ... ... ... ... ... 605 1125 710 1310 710–845 1310–1550
BAg-3 Strip, wire, powder 50 15.5 15.5 16 3.0 ... ... ... ... ... 630 1170 690 1270 690–815 1270–1500
BAg-4 Strip, wire, powder 40 30 28 ... 2.0 ... ... ... ... ... 670 1240 780 1435 780–900 1435–1650
BAg-5 Strip, wire, powder 45 30 25 ... ... ... ... ... ... ... 665 1225 745 1370 745–845 1370–1550
BAg-7 Strip, wire, powder 56 22 17 ... ... 5.0 ... ... ... ... 620 1145 650 1205 650–760 1205–1400
BAg-27 Strip, wire, powder 25 35 26.5 13.5 ... ... ... ... ... ... 605 1125 745 1375 745–860 1375–1575
BAg-28 Strip, wire, powder 40 30 28 ... ... 2 ... ... ... ... 650 1200 710 1310 710–845 1310–1550
Copper-zinc alloys
RBCuZn-A(a) Strip, rod, wire, powder ... 59 40 ... ... 0.6 ... ... ... ... 890 1630 900 1650 910–955 1670–1750
RBCuZn-D(a) Strip, rod, wire, powder ... 48 41 ... 10.0 ... ... ... 0.15 0.025 920 1690 935 1715 940–980 1720–1800
RCuZn -B(b) Rod ... 58 38 ... 0.5 0.95 0.7 0.25 0.08 ... 865 1590 880 1620 ... ...
RCuZn-C(b) Rod ... 58 39 ... ... 0.95 0.7 0.25 0.08 ... 865 1590 890 1630 815–925 1500–1700
Note: AWS, American Welding Society (a) Classified for braze welding and brazing. (b) Classified for braze welding. Source: Abstracted from the mandatory and nonmandatory sections of AWS A5.7, AWS A5.8, and Ref 65
sive; they can be generated in the plant in large ture to avoid damage to joints that are heat
volume, or, in the case of commercial nitrogen- treated after brazing. In some cases, air-harden-
base atmospheres, they can be stored in liquid ing steels can be brazed and then hardened by
form outside the plant. They provide excellent quenching from the brazing temperature.
protection against oxidation, and they can be A filler metal with brazing temperature lower
prepared with any carbon potential in the range than the critical temperature of the steel can be
of approximately 0.2% to more than 1.0% C, used when no change in the metallurgical prop-
depending on the atmosphere. This range of car- erties of the base metal is wanted.
bon potential is sufficient to accommodate all In torch brazing, a neutral or slightly reducing
carbon and low-alloy steels, including those flame usually is preferred, because the filler
carburized before brazing. By selecting an metal is face fed into the prefluxed joint. Flux-
atmosphere with a carbon potential that matches coated filler metal is often beneficial. As in all
the carbon content of the work metal, brazing brazing processes, it is important to avoid over-
can be accomplished without carburizing or heating in brazing to prevent undesirable effects
decarburizing the work metal. on the base metal, the filler metal, or the flux.
Because the protective atmospheres used for Time at temperature is an important considera-
furnace brazing are sufficiently reducing to iron tion, especially when the filler metal contains
oxide, they usually eliminate the need for fluxes volatile elements such as zinc and cadmium.
in brazing carbon steel with copper filler metal. Excessive heat also might affect the integrity of
An oxide-free surface normally promotes wet- the braze and reduce the mechanical properties
ting of the workpiece by the molten filler metal. of the joint.
However, some low-alloy steels that contain a Automated torch and burner-type production
total of more than 2 or 3% Cr, Mn, Al, and Si equipment is available for high-production
form more stable surface oxides, and they applications. These units usually use brazing
require highly reducing atmospheres (such as fluxes and silver-base filler metals.
dry hydrogen or dissociated ammonia), a flux, In production applications, the filler metal
or nickel plating to obtain adequate wetting. (usually copper) is preplaced in, or adjacent to,
Most of the limitations of furnace brazing are the joint before the preassembled parts are
directly related to the high temperatures charged into controlled-atmosphere batch- or
required for brazing of steels with copper filler conveyor-type furnaces for brazing. Induction
metal. These temperatures exceed the average heating for brazing is also advantageous in that
brazing temperature required for brazing with maximum temperature rise is restricted to the
silver-base filler metals by 280 °C (500 °F) or immediate joint area by selective coil design
more. They are high enough to cause grain and the use of an appropriate frequency for the
coarsening in medium-carbon, high-carbon, and induction-heating circuit.
low-alloy steels; however, grain refinement can In joining certain hardenable low-alloy
be obtained by subsequent heat treatment. steels, it usually is desirable to use the lower-
Steels brazed with copper filler metal develop melting silver-base filler metals, which can be
lower tensile and yield strengths and increased applied below the lower transformation temper-
ductility as the brazing time or temperature, or ature of the steel. Some local annealing, how-
both, are increased. ever, may occur. When postheat treatments are
These changes in properties are a result of required, the higher-solidus filler metals are
decarburization in some types of atmospheres necessary to preclude the possibility of joint
and alteration of grain size. Original grain size impairment. Low-alloy steels are sometimes
can be restored by subsequent heat treatment brazed and heat treated simultaneously using
below the remelt temperature of the copper filler metals of the copper-zinc and silver classi-
brazing filler metal. Loss of carbon through fications. The solidus temperature of the filler
decarburization is generally unimportant in metal chosen must be above the austenitizing
low-carbon steels. However, surface hardness temperature recommended for the base metal
of some low-alloy steels may be substantially prior to quenching. In an application of this
lowered. Such loss of surface hardness can be type, the joint is made at normal brazing tem-
very deleterious when thin-gage material is perature, removed from the heat source to per-
involved. mit a drop to the hardening temperature, and
For alloy steels, the filler metal should have a quenched. The procedure is satisfactory only for
solidus well above any heat treating tempera- base metals compatible with rapid cooling.
Dip brazing has also been used to join carbon many components of such vehicles as automo-
and low-alloy steels with silver-base, copper- biles, trucks, bicycles, motorcycles, snowmo-
zinc, and other copper-base filler metals. biles, all-terrain vehicles, and the like. Other
The types of salts used in dip brazing of car- common brazements include window and door
bon and low-alloy steels are neutral chloride frames, ducts, tanks, containers of all types, per-
salts, neutral chloride salts plus a fluxing agent forated and expanded steel panels, steel parti-
such as borax or cryolite, and carburizing and tions, and shelving. A great variety of tubular
cyaniding salts, which are also fluxing-type steel furniture is production brazed, and brazing
salts. Types and compositions of brazing salts is also used in production of cutting tools and
and temperatures used for brazing of carbon and industrial knives, hydraulic oil tanks, reservoirs,
low-alloy steels with various filler metals are electronic chassis and supports, hand tools, hon-
given in Table 4.14. ing appliances, certain instruments, and steel
Neutral salts, so called because normally they assemblies of all types.
do not add or subtract anything from the surface Tool Steels. High-carbon steels contain
of the steel being treated, protect the surface more than 0.45% C. High-carbon tool steels
from attack by oxygen in the air. Oxide on the usually contain 0.60 to 1.40% C. In discussing
workpiece, however, cannot be reduced by the the brazing of tool steels, it is convenient to
salt, and a flux must generally be provided. group them in two broad classifications: carbon
The neutral salts are mildly oxidizing to steel steels and high-speed tool steels.
when they are used at recommended austenitiz- Brazing of high-carbon steels is best accom-
ing temperatures. The oxides produced by heat- plished prior to or during the hardening opera-
ing steel in molten salt are largely soluble; tion. Hardening temperatures for carbon steels
hence, the steel is scale-free after heating. The range from 760 to 820 °C (1400 to 1510 °F).
accumulation of oxide in the molten salt, how- Filler metals having brazing temperatures above
ever, progressively makes the salt more decar- 820 °C should be used. When brazing and hard-
burizing, and for this reason, baths may require ening are done in one operation, the filler metal
periodic rectification (Ref 70). should have a solidus at or below the austenitiz-
Carburizing and cyaniding salts provide their ing temperature.
own fluxing action. In addition, they supply car- Tempering and brazing can be combined for
bon or carbon and nitrogen to the surface of the high-speed tool steels and high-carbon, high-
steel assembly as it is being brazed. Although chromium alloy tool steels that have tempering
silver-base filler metals have been used success- temperatures in the range of 540 to 650 °C (1000
fully, copper-zinc filler metal is generally pre- to 1200 °F). Filler metals with brazing tempera-
ferred. tures in that range are used. The part is removed
Various applications involve the use of filler from the tempering furnace, brazed by localized
metals in brazing low-carbon and low-alloy heating methods, and then returned to the fur-
steels in everyday production. These include nace for completion of the tempering cycle.
Table 4.14 Typical salts used for dip brazing of carbon and low-alloy steels with various brazing
filler metals
Brazing temperature range (a)
Filler metal Type of salt °C °F
BAg-1 through BAg-8, and BAg-18 Neutral 621–871 1150–1600

Cyaniding-fluxing 649–871 1200–1600
RBCuZn-A Neutral 732–871 1350–1600
Neutral 913–940 1675–1725
Fluxing 913–940 1675–1725
Carburizing-fluxing (water soluble) 913–940 1675–1725
RBCuZn-D Carburizing and self-fluxing 816–927 1500–1700
Neutral 1038–1051 1900–1925
Neutral 1093–1149 2000–2100
Neutral 1093–1149 2000–2100
(a) Temperatures shown are those of the salt bath. Source: Ref 65
Localized heating for brazing may decrease stainless steels and the generally more arduous
the hardness of heat treated steels when the service environments in which they are used.
brazing temperature is above the tempering Success in the fabrication of stainless steel com-
temperature of the steel. Except for thin sec- ponents by brazing depends on knowledge of
tions, these steels must be quenched drastically the characteristics of the various types of stain-
during heat treatment to achieve optimal prop- less steels, and rigid adherence to certain items
erties. Alloying elements may be added to car- of process control required by these characteris-
bon steels to impart special properties, such as tics.
reduced distortion on heat treatment, greater All stainless steels are difficult to wet because
wear resistance and toughness, or better high- of their high chromium contents. Brazing of
temperature properties. Such steels are referred these alloys is best accomplished in a purified
to as alloy tool steels; they are known by various (dry) hydrogen atmosphere or in a vacuum.
trade names and grades, and their properties are Dewpoints of –50 °C (–60 °F) or lower must be
adequately covered in manufacturers’ published maintained, because problems with wetting
information and in various handbooks. may arise following the formation of chromium
The alloy steel in question should be studied oxide. In torch brazing of these base metals,
carefully to determine its proper heat treating fluxes are required to reduce any chromium
cycle, the kind of quench necessary (water, oil, oxides present.
or air), the best filler metal, and the proper tech- Austenitic nonhardenable stainless steels
nique for combining the heat treating and braz- contain sufficient nickel or nickel plus man-
ing operations to achieve maximum properties ganese additions to stabilize austenite down to
in service life. room temperature, causing these alloys to be
High-speed steels, although logically falling nonmagnetic and nonhardenable by heat treat-
in the alloy steel group, are classified separately ment. Stainless steels of this class possess the
because their properties depend on relatively highest heat and corrosion resistance. They are
high percentages of such alloying elements as designated as AISI 300- and 200-series alloys.
tungsten, molybdenum, chromium, and vana- One commonly used alloy is type 302, which
dium. Their carbon contents normally are much contains approximately 18% Cr and 8% Ni. In
lower than those of carbon tool steels. High- the 200-series stainless steels, some of the
speed steels are widely used in industry as metal nickel is replaced by manganese. For example,
cutting tools. A common type known as 18-4-1 type 202, the parallel to type 302, contains 18%
contains 18% W, 4% Cr, and 1% V. Cr, 5% Ni, and 9% Mn.
The choice of the filler metal to be used The 300-series stainless steels are used
depends on the properties of the tool steel being widely for both torch- and furnace-brazed
brazed and the heat treatment required to assemblies. These alloys have relatively high
develop its optimal properties. Practically all thermal expansion and low thermal conductiv-
filler metals of the BAg, BCu, and RBCuZn ity. This combination of properties makes ther-
classifications are used at various times. The mal distortion a major concern in furnace braz-
best filler metal to use should be determined for ing of large or complex assemblies or
the specific application. assemblies in which dissimilar materials are
Torch, furnace, and induction heating are the brazed to stainless steel. In design of fixtures,
three most commonly used processes in brazing heat shields, and thermal cycles, the require-
tool steels. Available equipment is frequently ment to provide uniform heating and cooling
the main factor in process selection. must be considered.
In brazed assemblies for which corrosion
resistance is important, precautions must be
Stainless Steels taken to avoid sensitization to intergranular cor-
Stainless steels include a wide variety of iron- rosion. This problem was discussed earlier in
base alloys containing chromium that are used this chapter, but briefly, it occurs when an unsta-
primarily for applications demanding heat or bilized grade of austenitic stainless steel, such
corrosion resistance. Tighter process controls as type 302 or type 304, is held at temperatures
are required than for brazing of carbon steels. in the range from 425 to 815 °C (800 to 1500 °F)
These more rigorous requirements are imposed or slowly cooled through this range. The excess
by the inherent chemical characteristics of carbon combines with chromium and precipi-
tates as chromium carbide along grain bound- filler metal has been developed (63Ag-28.5Cu-
aries of the austenite. The region around the pre- 6Sn-2.5Ni).
cipitate is depleted of chromium and thus The ferritic stainless steels (405, 406, and
becomes susceptible to corrosion. 430) cannot be hardened, and their grain struc-
The 300-series stainless steels have been ture cannot be refined by heat treatment. These
used widely for brazed components; the 200- alloys degrade in properties when brazed at
series alloys, which are only 25 years old, have temperatures above 980 °C (1800 °F), because
not seen as much use. Due to their high man- of excessive grain growth. They lose ductility
ganese content, the 200-series stainless steels after long heating times between 340 and 600
are more difficult to furnace braze in hydrogen °C (645 and 1110 °F). However, some of the
atmospheres than the 300 series. Manganese ductility can be recovered by heating the braze-
forms an oxide that is not reduced easily by dry ment to approximately 790 °C (1455 °F) for a
hydrogen at the furnace brazing temperatures suitable time (Ref 71, 72).
normally used for stainless steels. It is important Martensitic hardenable stainless steels
to start with thoroughly cleaned surfaces and to are Fe-C-Cr alloys of two basic types: the low-
maintain a low dewpoint in the hydrogen atmos- chromium, low-carbon grades (types 403, 410,
phere. and 416) and the high-chromium, high-carbon
All the chromium-nickel steels are subject to grades (types 440A, B, and C). These steels are
SCC in the presence of molten filler metals. closely related to the ferritic nonhardenable
This phenomenon occurs when the base metal is grades, but their alloy compositions are so bal-
under stress—either residual or resulting from anced that they air harden on cooling from braz-
applied loads while the braze is being made. ing; this hardening occurs at a temperature
One form of applied load results from thermal above their austenitizing temperature range.
gradients during brazing. The filler metal pene- Therefore, they must be annealed after brazing
trates the base metal along the grain boundaries or during the brazing operation. These steels are
at the points of stress, producing a greatly weak- also subject to stress cracking with certain filler
ened base metal. Best results, therefore, are metals.
obtained with stress-relieved material. This The primary precaution in brazing compo-
stress relief may be done prior to or during the nents made of these alloys is that the brazing
brazing cycle. If it occurs during the cycle, it thermal cycle must be compatible with the
must be done below the solidus temperature of required heat treatment.
the filler metal (Ref 71, 72). If high-temperature nickel-base filler metals
Ferritic nonhardenable stainless steels are are used, it is possible to reaustenitize the
basically low-carbon alloys of iron and assembly after brazing. Although this procedure
chromium in which sufficient chromium has would increase costs, it may be desirable to
been added to the iron to stabilize ferrite, the develop optimal properties in critical compo-
low-temperature phase in steels, over a wide nents.
temperature range. The more common AISI The thermal expansion properties of marten-
stainless grades in this category are types 405, sitic stainless steels are relatively low—in the
406, 430, and 446. Type 430 is a widely used same range as those of ferritic alloys (Ref 73).
grade that is particularly subject to a form of Precipitation-hardening stainless steels
interface corrosion when brazed with some sil- are basically stainless steels with additions of
ver-base filler metals. This corrosion apparently one or more of the elements copper, molybde-
is caused by electrochemical action whereby the num, aluminum, and titanium. Such alloying
bond between the base metal and the filler metal additions make it possible to strengthen the
is destroyed. In many cases, this action has been alloys by precipitation-hardening heat treat-
found to occur in the presence of tapwater. It has ments.
been found that addition of small percentages of Some of the designations of the precipitation-
nickel to silver-base filler metal prevents inter- hardening stainless steels are 17-7PH, PH14-
face corrosion of brazed joints in most stainless 8Mo, PH13-8Mo, 15-5PH, PH15-7Mo,
steels. The nickel-containing silver-base filler AM350, AM355, 17-4PH, and A-286. As in the
metal is not completely effective, however, with case of the martensitic hardenable stainless
type 430, even though its use greatly reduces the steels, brazing thermal cycles used in joining
rate of attack. For type 430, a special silver-base these alloys must be compatible with their heat
treatments. Because the heat treatments vary Commercial filler metals are available that
rather widely, specific brazing procedures are have copper, silver, nickel, cobalt, platinum,
required for each alloy. palladium, manganese, and gold as the base or
Precipitation-hardening alloys that contain as addition elements; these are grouped conve-
aluminum or titanium are difficult to wet in the niently according to service temperature.
usual furnace brazing atmospheres. Nickel plat- The most widely used filler metals for braz-
ing generally is used as a surface treatment ing stainless steels are the silver-base family
before furnace brazing. (BAg group). Filler metal BAg-3, which con-
Metallurgical Considerations in Brazing tains 3% Ni, is probably the silver-base filler
Stainless Steels. In brazing of stainless steels, metal selected most frequently, although sev-
base-metal inclusions and surface contaminants eral other silver-base filler metals can also be
are even more deleterious than in brazing of car- used successfully. Where improved corrosion
bon steels. Base-metal inclusions, such as resistance is needed, BAg-3 and BAg-4 are rec-
oxides, sulfides, and nitrides, interfere with the ommended.
flow of filler metal. Flow is also impeded by sur- Silver-brazed joints cannot be used for high-
face contaminants, which may include lubri- temperature service; the recommended maxi-
cants such as oil, graphite, molybdenum disul- mum service temperature is 370 °C (700 °F),
fide, and lead that are applied during machining, which is the maximum temperature for BAg-13
forming, and grinding, or by aluminum oxide and BAg-19 filler metals. Of the silver-base
particles produced by grit blasting or by grind- filler metals shown in Table 4.15, all except
ing with aluminum oxide wheels or belts. BAg-19 and possibly BAg-13 are used at braz-
Some filler metals in powder form contain or ing temperatures that fall within the effective
are mixed with an organic binder to form a paste sensitizing range for austenitic stainless steels
that is subsequently applied to stainless steel for (540 to 870 °C, or 1000 to 1600 °F). Chromium
brazing; acrylics and other plastics are often carbide precipitation occurs in the sensitizing
used for this purpose. Although some binders temperature range, resulting in impairment of
form a soot residue, this residue does not usu- the corrosion resistance of the base metal. Car-
ally interfere with filler-metal flow. bide precipitation, however, depends on time as
The brazing characteristics of stainless steels well as temperature, and exposure within the
can also be severely impaired by unsuitable fix- sensitizing temperature range for only a few
turing materials, such as graphite, or by protec- minutes is unlikely to produce a significant
tive atmospheres with nitriding potentials. Car- amount of precipitate. Nevertheless, the lower
bon in graphite fixtures unites with hydrogen to melting temperatures of the silver-base filler
form methane (CH4), which carburizes stainless metals prohibit re-solution treatment of the base
steel and impairs its corrosion resistance. Disso- metal after brazing, and if corrosion resistance
ciated ammonia, unless sufficiently dry and in service is sufficiently critical, an extra-low-
completely (100%) dissociated, nitrides stain- carbon, titanium-stabilized or niobium-tanta-
less steel. lum-stabilized austenitic stainless steel should
Filler Metals for Brazing Stainless be selected instead of a nonstabilized type.
Steels. A wide variety of filler metals, includ- Ferritic and martensitic stainless steels that
ing silver-base, nickel-base, gold-base, and cop- contain little or no nickel are susceptible to
per, are commercially available for brazing interface corrosion in plain water or moist
stainless steel parts (Tables 4.15, 4.16). The fac- atmospheres when brazed with nickel-free sil-
tors to consider in selecting a filler metal for a ver-base filler metals using a flux. Filler metals
particular application include the following: containing nickel (BAg-3) help to prevent inter-
face corrosion. However, for complete protec-
• Service conditions, including operating tem- tion, special filler metals containing nickel and
perature, stresses, and environments tin should be used, and brazing should be done
• Heat treatment requirements if martensitic or in a protective atmosphere without flux.
precipitation-hardening steels are involved The nickel-base filler metals usually rank
• Brazing process to be used second in frequency of use as filler metals for
• Cost brazing of stainless steels. Nickel-base filler
• Special precautions, such as sensitization of metals provide joints that have excellent corro-
unstabilized austenitic stainless steels at cer- sion resistance and high-temperature strength.
tain temperatures These filler metals alloy with stainless steel,
Table 4.15 Typical composition and properties of standard filler metals for brazing stainless steels (silver base)
Composition, %
Solidus Liquidus Brazing temperature
Other temperature temperature range
Filler elements
metal Ag Cu Zn Cd Ni Sn Li Mn (total) °C °F °C °F °C °F
BAg-1 44.0–46.0 14.0–16.0 14.0–18.0 23.0–25.0 ... ... ... ... 0.15 607 1125 618 1145 618–760 1145–1400
BAg-1a 49.0–51.0 14.5–16.5 14.5–18.5 17.0–19.0 ... ... ... ... 0.15 627 1160 635 1175 635–760 1175–1400
BAg-2 34.0–36.0 25.0–27.0 19.0–23.0 17.0–19.0 ... ... ... ... 0.15 607 1125 701 1295 701–843 1295–1550
BAg-2a 29.0–31.0 26.0–28.0 21.0–25.0 19.0–21.0 ... ... ... ... 0.15 607 1125 710 1310 710–843 1310–1550
BAg-3 49.0–51.0 14.5–16.5 13.5–17.5 15.0–17.0 2.5–3.5 ... ... ... 0.15 632 1170 688 1270 688–816 1270–1500
BAg-4 39.0–41.0 29.0–31.0 26.0–30.0 ... 1.5–2.5 ... ... ... 0.15 671 1240 779 1435 779–899 1435–1650

BAg-5 44.0–46.0 29.0–31.0 23.0–27.0 ... ... ... ... ... 0.15 677 1250 743 1370 743–843 1370–1550
BAg-6 49.0–51.0 33.0–35.0 14.0–18.0 ... ... ... ... ... 0.15 688 1270 774 1425 774–871 1425–1600
BAg-7 55.0–57.0 21.0–23.0 15.0–19.0 ... ... 4.5–5.5 ... ... 0.15 618 1145 651 1205 651–760 1205–1400
BAg-8 71.0–73.0 bal ... ... ... ... ... ... 0.15 779 1435 779 1435 779–899 1435–1650
BAg-8a 71.0–73.0 bal ... ... ... ... 0.25–0.50 ... 0.15 766 1410 766 1410 766–871 1410–1600
BAg-9 64.0–66.0 19.0–21.0 13.0–17.0 ... ... ... ... ... 0.15 671 1240 713 1325 713–843 1325–1550
BAg-10 69.0–71.0 19.0–21.0 8.0–12.0 ... ... ... ... ... 0.15 690 1275 738 1360 738–843 1360–1550
BAg-13 53.0–55.0 bal 4.0–6.0 ... 0.5–1.5 ... ... ... 0.15 713 1325 857 1575 857–969 1575–1775
BAg-13a 55.0–57.0 bal ... ... 1.5–2.5 ... ... ... 0.15 771 1420 893 1640 871–982 1600–1800
BAg-18 59.0–61.0 bal ... ... ... 9.5–10.5 ... ... 0.15 601 1115 713 1325 713–843 1325–1550
BAg-19 92.0–93.0 bal ... ... ... ... 0.15–0.30 ... 0.15 760 1400 885 1635 877–982 1610–1800
BAg-20 29.0–31.0 37.0–39.0 30.0–34.0 ... ... ... ... ... 0.15 677 1250 766 1410 766–871 1410–1600
BAg-21 62.0–64.0 27.5–29.5 ... ... 2.0–3.0 5.0–7.0 ... ... 0.15 690 1275 801 1475 801–899 1475–1650
BAg-22 48.0–50.0 15.0–17.0 21.0–25.0 ... 4.0–5.0 ... ... 7.0–8.0 0.15 682 1260 699 1290 699–830 1290–1525
BAg-23 84.0–86.0 ... ... ... ... ... ... bal 0.15 960 1760 971 1780 971–1038 1780–1900
BAg-24 49.0–51.0 19.0–21.0 26.0–30.0 ... 1.5–2.5 ... ... ... 0.15 660 1220 707 1305 707–843 1305–1550
BAg-25 19.0–21.0 39.0–41.0 33.0–37.0 ... ... ... ... 4.5–5.5 0.15 738 1360 790 1455 790–846 1455–1555
BAg-26 24.0–26.0 37.0–39.0 31.0–35.0 ... 1.5–2.5 ... ... 1.5–2.5 0.15 707 1305 801 1475 801–871 1475–1600
BAg-27 24.0–26.0 34.0–36.0 24.5–28.5 12.5–14.5 ... ... ... ... 0.15 607 1125 746 1375 746–857 1375–1575
BAg-28 39.0–41.0 29.0–31.0 26.0–30.0 ... ... 1.5–2.5 ... ... 0.15 649 1200 710 1310 710–843 1310–1550
Table 4.16 Compositions and properties of standard filler metals for brazing steels (copper, gold, cobalt, and nickel base)
Composition, % Solidus temperature Liquidus temperature Brazing temperature range
Filler
metal Cu Zn Sn Fe Mn Ni P Pb Al Si Others (total) °C °F °C °F °C °F
Copper alloys
BCu-1 99.90 min ... ... ... ... ... 0.075 0.02 0.01 ... 0.10 1082 1980 1082 1980 1093–1149 2000–2100
BCu-1a 99.0 min ... ... ... ... ... ... ... ... ... 0.30 1082 1980 1082 1980 1093–1149 2000–2100
BCu-2 86.5 min ... ... ... ... ... ... ... ... ... 0.50 1082 1980 1082 1980 1093–1149 2000–2100
Filler
metal Au Cu Pd Ni Others (total) °C °F °C °F °C °F
Precious-metal alloys
BAu-1 37.0–38.0 bal ... ... 0.15 990 1815 1016 1860 1016–1093 1860–2000
BAu-2 79.5–80.5 bal ... ... 0.15 890 1635 890 1635 890–1010 1635–1850
BAu-3 34.5–35.5 bal ... 2.5–3.5 0.15 974 1785 1030 1885 1030–1090 1885–1995
BAu-4 81.5–82.5 ... ... bal 0.15 949 1740 949 1740 949–1004 1740–1840
BAu-5 29.5–30.5 ... 33.5–34.5 35.5–36.5 0.15 1135 2075 1166 2130 1166–1232 2130–2250
BAu-6 69.5–70.5 ... 7.5–8.5 21.5–22.5 0.15 1007 1845 1046 1915 1046–1121 1915–2050

Filler
metal Cr Ni Si W Fe B C P S Al Ti Zr Co Others (total) °C °F °C °F °C °F
Cobalt alloys
BCo-1 18.0–20.0 16.0–18.0 7.5–8.5 3.5–4.5 1.0 0.7–0.9 0.35–0.45 0.02 0.05 0.05 0.05 0.05 bal 0.50 1121 2050 1149 2100 1149–1232 2100–2250

Filler
metal Cr B Si Fe C P S Al Ti Mn Cu Zr Ni Others (total) °C °F °C °F °C °F
Nickel alloys
BNi-1 13.0–15.0 2.75–3.50 4.0–5.0 4.0–5.0 0.6–0.9 0.02 0.02 0.05 0.05 ... ... 0.05 bal 0.50 977 1790 1038 1900 1066–1204 1950–2200
BNi-1a 13.0–15.0 2.75–3.50 4.0–5.0 4.0–5.0 0.06 0.02 0.02 0.05 0.05 ... ... 0.05 bal 0.50 977 1790 1077 1970 1077–1204 1970–2200
BNi-2 6.0–8.0 2.75–3.50 4.0–5.0 2.5–3.5 0.06 0.02 0.02 0.05 0.05 ... ... 0.05 bal 0.50 971 1780 999 1830 1010–1177 1850–2150
BNi-3 ... 2.75–3.50 4.0–5.0 0.5 0.06 0.02 0.02 0.05 0.05 ... ... 0.05 bal 0.50 982 1800 1038 1900 1010–1177 1850–2150
BNi-4 ... 1.5–2.2 3.0–4.0 1.5 0.06 0.02 0.02 0.05 0.05 ... ... 0.05 bal 0.50 982 1800 1066 1950 1010–1177 1850–2150
BNi-5 18.5–19.5 0.03 9.75–10.50 ... 0.10 0.02 0.02 0.05 0.05 ... ... 0.05 bal 0.50 1080 1975 1135 2075 1149–1204 2100–2200
BNi-6 ... ... ... ... 0.10 10.0–12.0 0.02 0.05 0.05 ... ... 0.05 bal 0.50 877 1610 877 1610 927–1093 1700–2200
BNi-7 13.0–15.0 0.01 0.10 0.2 0.08 9.7–10.5 0.02 0.05 0.04 0.04 ... 0.05 bal 0.50 888 1630 888 1630 927–1093 1700–2000
BNi-8 ... ... 6.0–8.0 ... 0.10 0.02 0.02 0.05 0.05 21.5–24.5 4.0–5.0 0.05 bal 0.05 982 1800 1010 1850 1010–1093 1850–2000
however, and form phases with two undesirable any of the various brazing processes. A large
characteristics: the phases are considerably less volume of controlled-atmosphere brazing is
ductile than either the base metal or the filler being performed on stainless steels, and the suc-
metal even at elevated temperatures and thus are cess of this type of brazing can be attributed to
a potential source of rupture, and the alloys the development of reliable atmosphere and
formed with stainless steel are higher-melting vacuum furnaces.
alloys that are likely to freeze and block further The protective atmospheres most often used
flow into the joint during brazing. in furnace brazing of stainless steels are dry hy-
Because of the relatively high brazing tem- drogen and dissociated ammonia. These atmos-
peratures required for nickel-base filler metals, pheres are effective in reducing oxides, protect-
their use is generally restricted to furnace brazing the base metal, and promoting the flow of
ing in a controlled atmosphere (including vac- filler metal. The low-cost exothermic atmos-
uum), although there are occasional exceptions. pheres that are widely used in furnace brazing of
The nickel-base filler metals normally are low-carbon steels are not suitable for stainless
supplied as powders; however, they can be steels. An inert gas such as argon, or vacuum,
obtained as sintered or cast rods, preforms, plas- may be used to satisfy special requirements and
tic bonded sheet, plastic bonded wire, and tape. provide protection in applications for which
Many of these filler metals now are available as hydrogen or hydrogen-bearing gases are satis-
metallic foils produced by ultrarapid cooling factory.
from the molten state. The BNi filler metals com- A dry hydrogen atmosphere is preferred for
monly are used on stainless steels for oxidation many stainless steel brazing applications.
resistance at temperatures up to 980 to 1095 °C Hydrogen, the most strongly reducing of pro-
(1800 to 2000 °F). Filler metals BNi-1, BNi-2, tective atmospheres, reduces chromium oxide
BNi-3, and BNi-4 (Table 4.16) tend to erode thin and provides for excellent wetting by some filler
sheet metal because of their interaction with metals without the need for flux. The principal
many base metals. Time at brazing temperature disadvantages of hydrogen are high cost, diffi-
and quantity of filler metal should, therefore, be culty in drying sufficiently, need for special fur-
controlled carefully when these filler metals are nace equipment, and danger involved in storing
used. Boron-free filler metals BNi-5, BNi-6, and and handling hydrogen.
BNi-7 are suitable for use in nuclear reactor Dissociated ammonia, when it is free of mois-
components where boron cannot be tolerated ture and 100% dissociated, is a suitable atmos-
because of its absorption of neutrons. Oxidation phere for brazing of stainless steel with some
resistance is good up to 1095 °C (2000 °F). The filler metals without the need for a flux. Dissoci-
BNi-5 material has the highest melting point of ated ammonia is strongly reducing but less so
all the nickel-base filler metals. than pure dry hydrogen. Consequently, although
The gold-base filler metals (BAu group in it promotes wetting by reducing chromium
Table 4.16) are sometimes used for brazing stain- oxide on the surface of the stainless steel, disso-
less steels, although their high cost restricts their ciated ammonia may not be sufficiently reducing
use to specialized applications such as heat to promote the flow of some filler metals, such as
exchangers for manned space-flight vehicles. copper oxide powders. Because of its high
When a gold-base filler metal is used, alloying (75%) hydrogen content, dissociated ammonia
with the stainless steel base metal is minimized, forms explosive mixtures with air and must be
and, as a result, joints exhibit good ductility (Ref handled with the same precautions as those
74). In addition to the gold family of filler metals, required for handling hydrogen.
there are palladium and platinum filler metals, Unless the atmosphere used in brazing of
such as Au-Ni-Pd, Cu-Pt, Ag-Pd-Mn, and Pd-Ni- stainless steel is completely decomposed (100%
Cr, which are useful for brazing heat- and corro- dissociated), even minute amounts of raw
sion-resistant components in the jet- and rocket- ammonia (NH3) in the atmosphere nitride stain-
propulsion and nuclear-energy fields. less steels, especially those containing little or
The cobalt-base filler metal BCo-1 (Table no nickel. Finally, to avoid oxidation of base
4.16) is very rarely used for brazing stainless metal and filler metal, the dissociated ammonia
steels, but it has been included in the table for its atmosphere must be kept dry and pure while it is
availability. inside the furnace.
Furnace Atmospheres for Brazing Stain- Argon is occasionally used as a furnace
less Steels. Stainless steels can be brazed with atmosphere in brazing stainless steels to other
stainless steels or to reactive metals such as tita- those brazed with filler metals such as BAg-1 or
nium. Argon has the advantage of being chemi- BAg-1a, although these filler metals have been
cally inert in relation to all metals; thus, it is a used.
useful protective atmosphere for metals that can Depending on the metallurgical and physical
combine with or absorb reactive atmospheres, properties of particular stainless steels, their
such as hydrogen. An argon atmosphere has the behavior in heating by electrical induction may
disadvantage of being unable to reduce oxides; differ considerably from that of carbon and low-
consequently, the surfaces of stainless steel alloy steels and from that of the more widely
components must be exceptionally clean and used nonferrous metals. In addition, depending
free of oxides when brazed in argon. on whether a stainless steel is magnetic or non-
The principal advantages of furnace brazing magnetic at room temperature, the response of
are high production rates and the means for the steel to induction heating varies consider-
using controlled protective atmospheres at con- ably. Differences in specific heat and electrical
trolled dewpoints, which often make it unneces- conductivity markedly affect response to heat-
sary to use a flux to obtain satisfactory wetting. ing by induction.
In most furnace-brazing applications, both of Ferritic and martensitic (400-series) stainless
these advantages are exploited. Occasionally, steels are ferromagnetic at all temperatures up to
however, furnace brazing is selected solely on the Curie temperature. The Curie temperature is
the basis of production rate, and brazing is per- the temperature of magnetic transformation
formed without a protective atmosphere but below which a metal or alloy is magnetic and
with a suitable flux. The lower-melting filler above which it is paramagnetic (Ref 72). Thus,
metals are generally selected for brazing under given the same power input, these steels gener-
these conditions. ally heat faster than austenitic stainless steels,
Vacuum brazing of many structural configu- which are nonmagnetic in the annealed condi-
rations made of austenitic stainless steels offers tion.
excellent heat and corrosion resistance for high- Stainless steels may be induction brazed in an
temperature-service applications. air atmosphere, using a suitable flux, although
For stainless steels, the fundamentals of torch for critical applications, induction brazing is
brazing, as well as its advantages and limita- sometimes done in a protective atmosphere or in
tions, are basically the same as carbon steels. vacuum, whereas in other applications, an inert
Because of the metallurgical characteristics of gas such as argon may be used as a backing gas
stainless steel and its requirements for corrosion to minimize oxidation.
resistance, however, best results are obtained Brazing of stainless steel by immersion of all
when special consideration is given to the type of or a portion of the assembly in molten salt offers
flame at the torch and to the filler-metal compo- essentially the same advantages that would ap-
sition. ply to brazing similar assemblies of carbon
To aid in reducing the oxide already present, steel. Similarly, the same limitations are appli-
as well as to prevent further oxidation of the cable.
work-metal surfaces, a strongly reducing flame
should be used for torch brazing stainless steel
to itself. A reducing flame is also satisfactory
Maraging Steels
for brazing stainless steel to nickel alloys or car- An investigation (Ref 75) found that thin
bon steels. In brazing stainless steel to copper gold-nickel alloy (BAu-4, 57.5Au-42.5Ni,
alloys, however, some compromise is neces- at.%) interlayer brazes between strong base
sary. Although a slightly oxidizing flame is nor- metals were found to have very high ultimate
mally best for brazing copper, for brazing stain- tensile strengths as a result of the triaxial stress
less steel to copper a slightly reducing flame state within the braze (reducing the effective, or
usually provides a satisfactory compromise in von Mises, stress) and the high strength of the
flame adjustment. filler metal.
The silver-base filler metals that flow at rela- Maraging steel was joined with the previ-
tively low temperatures are used almost exclu- ously mentioned filler metal in this study.
sively for torch brazing of stainless steels. Filler Results of the study found that:
metal BAg-3 is most often used, because it
flows well in the temperature range from 705 to • The transmission electron microscopy
760 °C (1300 to 1400 °F) and provides joints (TEM) of the gold-nickel interlayer brazes
that have greater resistance to corrosion than showed a very fine-grain (0.1 µm) two-phase
microstructure, with both phases coinciden- changers that have been brazed for domestic
tally oriented. water heaters and the stainless steel tube ther-
• The ultimate tensile strength of the gold- mometers for electric cookers and cooker hot
nickel bonds was high, largely due to a high plates.
interlayer yield strength that resulted from Knife handles have been brazed from stain-
the refined microstructure. less steel pressings, as have very much larger
• The yield strength and quasi-steady-state valve bonnets for industrial use.
flow stress of the filler metal were found to be It is very significant that joining stainless
relatively strain-rate insensitive. steel assemblies for food-handling equipment
requires strong ductile joints while preventing
These results explain the absence of time- formation of pits or other imperfections that can
dependent, or delayed, tensile failures that have trap bacteria and contaminate food. When
been observed in other braze interlayers. The developing an assembly process for a dough-
fracture process appears to be one of cavity divider head assembly used in a dough-forming
nucleation by microplasticity, followed by cav- machine, graphite-brazing fixtures were con-
ity coalescence or impingement once the structed for five designs of the divider. When
required nuclei density is achieved. Substantial installed, the ring-and-blade assembly divides
cavity growth does not appear to occur. This dough into portions small enough to make din-
failure process contrasts with that of other inter- ner rolls and large enough to make bread loaves.
layer metals in which the failure mechanism The five designs of divider head range in num-
appears to be unstable cavity growth. ber of parts from 6 to 36. Each design calls for a
ring and band to hold several blades in place; all
materials are of type 304 stainless steel. Nickel-
Other Stainless Steel Applications base BNi-2 filler metal holds the joints.
Another study (Ref 76) found that companies This filler metal has been used in many food-
saved a considerable amount of money by sal- industry applications where clean, smooth sur-
vaging porous stainless steel castings by using faces to deter bacteria formation and resist oxi-
the cleaning potential of the furnace atmos- dation are important. Both the brazing process
phere, vacuum, and the free-flowing character and the nickel-base filler metal used have been
of the filler metal to fill the pores by capillary approved by the United States Department of
action. Agriculture food safety and inspection service
These filler metals can also be used for build- and the privately operated National Sanitation
ing up surfaces, for example, to adjust the throat Foundation.
widths of gas turbine compressor stators made Production begins by placing ring and blades
by precision casting or to replace metal badly in an aluminum fixture. Then, the band is placed
machined from large stainless steel valve com- around the assembly and tack welded to the
ponents used in North Sea oil submersible ends of the outer blades. Operators then use gas
equipment. The nickel-base filler metals have tungsten arc welding to create joints between
corrosion resistance generally comparable with the ring and blades to hold them in place during
Inconel, while some of the filler metals have furnace brazing. Filler metal is applied in paste
oxidation resistances that are satisfactory to form to each butt joint; a 36-part assembly com-
1100 °C (2010 °F). prises 50 such joints. Then, an operator removes
Additional research found and reported on the assembly from the fixture and places it in the
hydrogen detector units comprising a 2.3 mm specially designed graphite fixture for furnace
(0.09 in.) outside diameter by 1.2 mm (0.05 in.) brazing.
wall thickness nickel tube helix brazed into a Brazing the head takes 12 h in an 81.3 by
type 316 stainless steel pressure hub approxi- 106.7 cm (32 by 42 in.) top-loading vacuum fur-
mately 25 mm (1 in.) in diameter and 75 mm (3 nace. Heating, brazing, and slow-cooling cycles
in.) thick; this was an extreme case of difference are strictly controlled to prevent distortion. The
in thermal mass of the components. Brazing procedure holds the bottom of the part flat to
was carried out with BNi-2 filler metal at 1020 within 0.203 mm (0.008 in.), and six assemblies
°C (1870 °F) for 5 min. The joint had to be are brazed per furnace run.
tested using β-dense neutron radiography as Palladium-containing filler metals 30Pd-
well as helium leak testing and airflow checks. 60Cu-10Co, 30Pd-60Cu-10Ni and 30Pd-50Cu-
Finally, the research discussed the many 10Ni-10Co (all in wt%) were studied for use in
thousands of stainless steel/copper heat ex- brazing stainless steel SUS 316 L at high temper-
atures (Ref 77). Palladium-containing filler met- the newly developed palladium-containing fil-
als were selected because of their ductility, oxi- ler metals 40Pd-50Ni-10Co, 30Pd-50Ni-10Cu-
dation resistance, relatively high melting points, 10Co, and 33Pd-64Ag-3Mn.
and lower cost than gold-base filler metals. Wet- The joints brazed with the 30Pd-50Ni-10Cu-
tability, microstructures, and reactions were 10Co and 40Pd-50Ni-10Co filler metals showed
studied with experimental brazed joints between the highest tensile strength of the tested filler
base and filler metal. Joint strengths, tensile metals, and the mean tensile strength of joint
strengths at room and elevated temperatures of clearances ranging from 0.05 to 0.15 mm (0.002
473 to 1073 K, and creep-rupture strengths at 673 to 0.006 in.) was 516 MPa (75 ksi).
to 1073 K were investigated. The joints brazed The 30Pd-50Ni-10Cu-10Co filler metal
with the 30Pd-50Cu-10-Ni-10Co filler metal had showed maximum tensile joint strengths at 873
superior tensile strengths at elevated temperature K or below, and the 33Pd-64Ag-3Mn filler me-
and creep-rupture strengths. The joints with this tal did at 1073 K.
filler metal had tensile strengths of 327 to 429 The brazed joints with the 30Pd-50Ni-10Cu-
MPa (47 to 62 ksi) at temperatures of 293 to 873 10Co and 40Pd-50Ni-10Co filler metals had the
K. The solidus and liquidus of the previously highest creep-rupture strength with the time to
mentioned filler metals are shown in Table 4.17 failure of 1000 h or over at applied stresses of
(Ref 77). 425 MPa (62 ksi) at 673 K and of 125 MPa (18
Joints brazed with the 30Pd-60Cu-10Co filler ksi) at 873 K, respectively. The joints with the
metal had the highest tensile strength of the Ni-Co-Cr-Mo-Fe-B filler metal had good creep-
tested joints, and the mean tensile strength for rupture strength with the time to failure of 1000
joint clearances ranging from 0.07 to 0.15 mm h at applied stress of 50 MPa (7.3 ksi) at 1073 K.
(0.003 to 0.006 in.) was 536 MPa (78 ksi). The 30Pd-50Ni-10Cu-10Co filler metal for
Joints brazed with the 30Pd-60Cu-10Ni filler SUS 316 L was finally found to be the most suit-
metal had the maximum tensile strength at 473 able filler metal for high-temperature brazing,
K, and joints brazed with the 30Pd-50Cu-10Ni- because this filler metal provided superior
10Co filler metal did at 673, 873, and 1073 K. strength properties at room and high tempera-
Joints brazed with the 30Pd-60Cu-10Ni filler tures (Ref 79).
metal had the highest creep-rupture strength at
673 K, and joints brazed with the Ni-Cr-W-Fe- Titanium and Zirconium
B-Si filler metal did at 873 and 1073 K (Ref 77).
It was concluded that 30Pd-50Cu-10Ni-10Co and Their Alloys
filler metal is the most suitable filler metal for Titanium and zirconium combine readily
high-temperature brazing of SUS 316 L. with oxygen and react to form brittle inter-
A parallel research study (Ref 78) examined metallic compounds with many metals and with
two types of palladium-containing filler metals, hydrogen and nitrogen. Parts must be cleaned
40Pd-50Ni-10Co and 30Pd-50Ni-10Cu-10Co before brazing and brazed immediately after
(all in wt%). Commercially available filler met- cleaning.
als, palladium filler-metal braze 33Pd-64Ag- Titanium and Its Alloys. Silver and silver-
3Mn, and nickel-base filler metal Ni-Co-Cr- base filler metals were used in early brazing of
Mo-Fe-B were also used. titanium, but brittle intermetallics were formed,
The microstructures and strength properties and crevice corrosion resulted. Type 3003 alu-
of the brazed joints were studied as well as minum foil as a filler metal joins thin, light-
weight structures, such as complex honeycomb
Table 4.17 Solidus and liquidus temperatures
sandwich panels. Electroplating various ele-
of filler metals studied for brazing of 316L ments on the base-metal faying surfaces lets
stainless steel them react in-situ with the titanium/titanium
alloy base material during brazing to form a tita-
Solidus Liquidus
nium alloy eutectic. That transient liquid phase
Filler metal °C °F °C °F
flows well and forms fillets, then solidifies due
30Pd-60Cu-10Co 1090 1994 1100 2012 to interdiffusion (Ref 69, 80).
30Pd-60Cu-10Ni 1139 2082 1150 2102 Other filler metals with high service capabil-
30Pd-50Cu-10Ni-10Co 1130 2066 1160 2120
Ni-Cr-W-Fe-B-Si 1010 1850 1165 2129
ity and corrosion resistance include Ti-Zr-Ni-
Be, Ti-Zr-Ni-Cu, and Ti-Ni-Cu filler metals.
Source: Ref 77
The best braze processing is obtained in high-
vacuum furnaces using closely controlled tem- must be carefully considered. Nickel or materi-
peratures in the range of 900 to 955 °C (1650 to als containing high amounts of nickel generally
1750 °F). should be avoided; nickel and titanium form a
Selection of filler metals for use in brazing of low-melting eutectic (28.4% Ni) at approxi-
reactive metals is critical to avoid formation of mately 940 °C (1725 °F). Should the titanium
undesirable intermetallic compounds. workpieces contact fixtures or a retort made
Selection of filler metals and brazing cycles from nickel-base alloy, the parts may fuse
that are compatible with the heat treatment together if the brazing temperature is in excess
required for (α-β) and β-titanium base metals of 940 °C. If a fixture material containing a high
may present some difficulty. Ideally, brazing nickel content (such as stainless steel) is used, it
should be conducted at temperatures from 55 to should be oxide coated. In most applications,
83 °C (100 to 150 °F) below the β transus, be- coated graphite or carbon steel fixture materials
cause the ductility of (α-β) base metals may be are used.
impaired if this temperature is exceeded. The β Filler metals initially used for brazing of tita-
transus can be exceeded when β-titanium base nium and its alloys were silver-base filler metals
metals are brazed; however, if the brazing tem- containing lithium, copper, aluminum, or tin
perature is too high, base-metal ductility after (Ref 81–83). Most of these filler metals were
heat treatment may be impaired by considerable used in low-temperature applications (540 to
interaction between the properties of the heat 595 °C, or 1000 to 1100 °F). Later developments
treatable titanium alloys and may be affected produced a number of successful commercial
adversely by brazing, unless the assembly filler metals, including Ag-Pd, Ti-Ni, Ti-Ni-Cu,
can be heat treated afterward. For example, the Ti-Zr-Be (Ref 84), and Ti-Zr-Cu-Ni (Ref 85,
(α-β) titanium alloys must be solution treated, 86). Additionally, these filler metals could be
quenched, and aged to develop optimal proper- used at temperatures from 870 to 925 °C (1600 to
ties. It is not easy to select a filler metal that per- 1700 °F). For joining applications requiring a
mits brazing and solution treating in a single high degree of corrosion resistance, the 48Ti-
operation. Similarly, it is not always possible to 48Zr-4Be and 43Ti-43Zr-12Ni-2Be filler metals
quench a brazed assembly at the desired cooling are outstanding (Ref 84). A Ag-Pd-Ga filler
rate, and certain configurations (e.g., honey- metal (Ag-9Pd-9Ga), which flows at 900 to 915
comb sandwich structures) do not lend them- °C (1650 to 1680 °F), is another excellent filler
selves to rapid quenching without distortion. metal that fills large gaps (Ref 87).
Brazing at the aging temperature is impractical, The following four filler metals are new
because few filler metals melt and flow at these developments now available for use in products
temperatures. (Ref 85):
The possibility of galvanic corrosion must be
• Ti-Cu-Ni-2 (Ti-20Cu-20Ni)
considered when filler metals are selected for
• Ti-Zr-Cu-Ni-1 (Ti-38Zr-12Cu-12Ni)
brazing titanium base metals. Although tita-
• Ti-Zr-Cu-Ni-2 (Ti-38Zr-15Cu-15Ni)
nium is an active metal, its activity tends to
• Ti-Zr-Cu-Ni-Pd (Ti-37Zr-12Cu-12Ni-2Pd)
decrease in an oxidizing environment, because
the surface undergoes anodic polarization in a Initial tensile and corrosion testing of joints
manner similar to that of aluminum. Thus, filler with the latter filler metals shows that the joints
metals must be chosen carefully to avoid prefer- exhibit nearly the same mechanical and chemi-
ential corrosion of the brazed joint. cal characteristics as Ti-6Al-4V.
When titanium is brazed, precautions must be Brazing of titanium honeycomb sandwich
taken to ensure that the brazing retort or cham- structures using aluminum filler metal is an
ber is free of contaminants from previous braz- achievement stemming from supersonic trans-
ing operations. As a precaution against any port materials and process technology (Ref 81).
existing contaminants in the brazing furnace, a Such aircraft structures up to 7 m (23 ft) in
loose cover of pure titanium foil (0.03 to 0.08 length have been successfully fabricated using
mm, or 0.001 to 0.003 in., thick) should be put Al 3003 brazing foils as filler metal, which pro-
over the workpieces. This acts as a getter of any vide satisfactory strength up to approximately
remaining contaminants. Care should be exer- 315 °C (600 °F). High-strength, corrosion-
cised to ensure that the foil does not come into resistant Ti-Zr-Be and Ti-Zr-Ni-Be filler metals
direct contact with the workpieces. are recommended for applications from 540 to
The choice of materials to be used in fixtures 595 °C (1000 to 1100 °F) (Ref 84).
Researchers (Ref 88) examined the effect of time was responsible for much higher require-
joint clearance as a critical parameter for main- ments on brazing joint clearance compared to
taining joint integrity in brazed Ti-6Al-4V and the vacuum brazing process. However, fabrica-
commercially pure titanium (CPTi) materials. tion of titanium joints with mechanical proper-
They determined that the mechanical properties ties comparable to those of the base metal by
of Ti-6Al-4V and CPTi joints brazed with Ti- induction heating were possible, when the max-
(Zr)Cu-Ni-(Pd) filler metals (Table 4.18) are imum brazing joint clearance of the system was
strongly dependent on the microstructure of the not exceeded. This required extremely small
brazing zone, especially with the formation of joint clearances of <30 µm in the case of Ti-
brittle intermetallic phases in the center of the 6Al-4V/Ti-Cu-Ni-Pd joints and <20 µm in the
brazing zone, which reduce the mechanical case of CPTi joints.
strength of the brazed joints. These phases form Using an amorphous 25Ti-25Zr-50Cu filler
due to an exceeding of the maximum joint- metal, researchers (Ref 90) induction brazed Ti-
clearance size of the system. The formation of 6Al-4V alloy using argon as a shielding gas.
these phases can be avoided by minimizing the The brazing cycles were rather short; radio fre-
joint-clearance size of the joint to be brazed and quency inductor power was supplied for only 40
by enhancement of brazing time (Ref 89). to 60 s. The tensile strength and ductility of the
Tensile tests of the brazed Ti-6Al-4V and brazed joint were at the level of that of Ti-6Al-
CPTi joints revealed that especially Ti-6Al-4V 4V base metal.
joints exhibit excellent mechanical properties, It was also found that the postbrazing natural
even comparable to those of the base metal, if cooling rate of 12.5 mm (0.5 in.) diameter rod
the brazing zone is free of brittle intermetallic samples was sufficient to suppress the forma-
phases. Fatigue tests of the Ti-6Al-4V joints tion of undesirable brittle λ-Cu2TiZr Laves
confirm the excellent mechanical properties. phase appearing in vacuum furnace brazing due
The fatigue properties of the Ti-6Al-4V joints to inherently low cooling rates. From the practi-
approach that of the base metal at maximum cal point of view, it was proven that induction
stresses below 700 MPa (102 ksi). brazing of compatible samples located in a sim-
In contrast to the Ti-6Al-4V joints, fabrica- ple closed chamber may be carried out as an
tion of CPTi joints with mechanical properties effective and inexpensive process.
comparable to those of the base metal was not Zirconium and Its Alloys. Zirconium-base
possible. The reason can be seen in the much metals of commercial importance are the pure
lower maximum joint clearance of the system metal and several alloys. The most commonly
CPTi/Ti-Zr-Cu-Ni with regard to the formation used zirconium alloy is Zircalloy, which con-
of intermetallic phases. Therefore, under the tains small percentages of tin, iron, chromium,
given circumstances (50 µm filler-metal foils), and nickel. These structural alloys are used for
formation of intermetallic phases could not be corrosion resistance in nuclear applications,
avoided. especially in pressurized-water nuclear power
This study also revealed that the induction reactors.
brazing process is an interesting alternative to Like titanium and beryllium, zirconium
the vacuum furnace brazing process. Especially reacts readily with oxygen, hydrogen, and nitro-
from the economic point of view, the induction gen and is embrittled. It also reacts with many
brazing process under inert atmosphere had metals and alloys to form intermetallic com-
many advantages due to the short processing pounds. Therefore, as a result of this reactivity,
time. On the other hand, the short processing zirconium must be brazed in a vacuum or in a
Table 4.18 Compositions and critical temperatures of filler metals evaluated for brazing
commercially pure titanium and Ti-6Al-4V
Chemical compositions, wt% Solidus Liquidus Brazing temperature
Filler metal Ti Zr Cu Ni Pd °C °F °C °F °C °F
TiCuNi 60 ... 20 20 ... 923 1695 934 1715 950 1740

TiCuNiPd 60 ... 19 19 2 923 1695 934 1715 950 1740
TiZrCuNi 35 35 15 15 ... 832 1530 850 1560 870 1600
Source: Ref 88
dry atmosphere of argon or helium. Zirconium As stated earlier, titanium and zirconium are
joint members must be cleaned carefully before both highly reactive metals. The brazing
brazing to remove oxides and other surface con- process, therefore, must not allow the joint sur-
taminants, and brazing should be done immedi- faces to come in contact with air during heating.
ately after cleaning. Induction brazing and furnace brazing in inert-
Compared with the other reactive metals, gas or vacuum atmospheres can be used suc-
very little research has been done to develop cessfully. Torch brazing of these base metals is
filler metals and brazing methods for joining difficult, requiring special precautions and tech-
zirconium and zirconium alloys (Ref 91). To a niques. Induction brazing of small, symmetrical
degree, this lack of research on brazing can be parts is very effective, because the speed mini-
attributed to the availability of other joining mizes reactions between filler metal and base
methods. However, most commercial filler met- metal. For large, precise assemblies, furnace
als do not wet or flow well on zirconium base brazing is favored, because it allows uniformity
metals, nor are they metallurgically compatible of temperature throughout the heating and cool-
with zirconium. In addition, many of these filler ing cycle to be controlled readily. Titanium and
metals do not possess the corrosion resistance zirconium assemblies frequently are brazed in
required in reactor environments. high-vacuum, cold-wall furnaces.
Research was conducted to develop filler met-
als for producing brazed joints in Zircalloy 2 that
possessed good resistance to corrosion in pres- Carbides and Cermets
surized water at 360 °C (680 °F). The data from Carbides of the refractory metals tungsten,
these studies and from metallographic examina- titanium, and tantalum, bonded with cobalt,
tions of the brazed joints indicated that the fol- have been used for years in cutting tools and
lowing filler metals most nearly met the service dies. It is necessary to join these carbides to
requirements: Zr-5Be, Cu-20Pd-3In, Ni-20Pd- metal parts, particularly for cutting tools.
10Si, Ni-30Ge-13Cr, and Ni-6P (Ref 91). Closely related materials called cermets have
Additional studies to develop improved filler been developed and are ceramic particles
metals for brazing Zircalloy base metals for use bonded with various metals. Their high-temper-
in water-cooled reactors were recently com- ature strengths are intermediate between those
pleted (Ref 92). Candidate zirconium-base and of the ceramic materials and the binder metals
non-zirconium-base filler metals were formu- employed. Their greatest disadvantage is their
lated, used in vacuum brazing under pressures brittleness.
of 0.0013 to 0.00013 Pa (10–5 to 10–6 torr), and The term cermets generally describes tita-
screened by wetting tests and corrosion tests in nium-base hardmetals. These cermets bridge the
pressurized, high-temperature water (315 °C, or gap between carbides and ceramics. Cermets are
600 °F). The following filler metals had accept- a unique class of materials that could have excel-
able corrosion resistance and mechanical lent applications in areas such as saws and wear
strength: parts. They are harder and much more wear
resistant than tungsten carbide. They do not have
• Zr-50Ag (brazing temperature, 1520 °C, or
the impact resistance and toughness of tungsten
2770 °F)
carbide, so they are not recommended in high-
• Zr-29Mn (brazing temperature, 1380 °C, or
impact applications such as sawmills or cabinet
2515 °F)
shops where material is hand fed.
• Zr-25Sn (brazing temperature, 1730 °C, or
The cermets are composed entirely of tita-
3145 °F)
nium carbide (TiC) and titanium nitride (TiN).
The Zr-5Be filler metal previously mentioned These are the same materials used to coat ordi-
has been used extensively to braze zirconium nary grades of carbide to make them more wear
base metals to themselves and to other metals resistant. A cermet is not coated; instead, it is
(e.g., stainless steel). For example, zirconium solid coating material.
sheet stock has been brazed with this filler metal It is impractical to use coated carbides in
using the following cycle: 10 min at 1005 °C saws, because the saws are reground and the
(1840 °F), followed by 4 to 6 h at 800 °C (1470 coating would be lost in the first grinding. Typ-
°F). Because of its ability to wet ceramic sur- ical carbide coatings are TiC and TiN. The XT3
faces, Zr-5Be has also been used to braze zirco- grade is solid TiC and TiN, so there is no coat-
nium to uranium oxide and beryllium oxide. ing to wear off.
Cermets have been used successfully in metals. Typically, this is also a chemical bath
clamped or indexable machining operations for and may or may not use electric current. It is
decades. They have not been used in brazed beneficial if non-cyanide nitrogen is intro-
applications because they have not been braze- duced so as to create intermediate metallic
able. compounds. Cyanide compounds may be
There is now a method to successfully braze used, but they are unnecessary and signifi-
cermets to steel holders. Previous brazing cantly add to the cost in several ways.
attempts resulted in the material forming a glob • Postcleaning and passivation: This treatment
in the center of the insert and an extremely weak of the parts may be desirable.
bond. The new braze technology gives excellent
wetting of the insert and excellent braze strength. The parts are then brazed on saws using stan-
A successful braze is one where the strength dard filler metals (such as BAg-24 and those
of the joint is in excess of the rupture strength of similar to it) and are used successfully in sawing
the material. The force to fracture the brazed and other applications (Ref 93) (see Chapter 10,
cermet was approximately equivalent to the “Applications and Future Outlook”).
force required to fracture an unbrazed cermet. Brazing carbides and cermets is generally
Additional research can improve the impact more difficult than brazing metals. Torch,
resistance of brazed cermet joints, as it has for induction, or furnace brazing is used, often with
brazed tungsten carbide joints. a sandwich brazing technique; a layer of weak,
Cermets typically have a life of 3 to 5 times ductile metal (pure nickel or pure copper) (Ref
that of carbide. This is due to superior wear 94) is interposed between the carbide or cermet
resistance. An XT3 grade of cermet has the and a hard metal support. The cooling stresses
approximate toughness of C7 carbide while cause the soft metal to deform instead of crack-
being much harder. There is also a C50 grade of ing the ceramic (Ref 95).
cermet that is much tougher. Silver-base filler metals, copper-zinc filler
Cermets are now brazeable, with tensile metals, and copper are often used on carbide
strengths of up to 685 MPa (100 ksi), and can tools. Although it is possible to use any of the
tolerate temperatures up to 750 °C (1380 °F). BAg-1 through BAg-7 filler metals, those con-
New developments permit cermets to be brazed taining nickel (BAg-3 and BAg-4) are generally
with the same filler metals and for the same cost recommended, because nickel improves wetta-
using the same equipment and techniques used bility. The RBCuZn-D and BCu filler metals
for tungsten carbide. also have been used, particularly where a post-
These newly developed processes use chemi- braze heat treatment is required. The BCu filler
cals that are commonly available, allow for metal retains practically all of its strength up to
brazing using standard filler metals, and also a temperature of 540 °C (1000 °F); however, it
use these at ambient temperatures. requires a hydrogen atmosphere furnace for best
The process involves preparing the cermet brazing results. The 85Ag-15Mn and 85Cu-
body as follows: 15Mn filler metals are used where the brazed
joint is subjected to elevated temperatures in
• Cleaning: A preferred method of cleaning is service and also for wetting the titanium-base or
a cathodic electrocleaning process in an alka- chromium-base carbides. Additionally, the BNi
line solution. filler metals with boron and a 60Pd-40Ni filler
• Surface etching: The part is treated in such a metal have been used successfully for brazing
manner as to prepare the surface to bond with nickel- and cobalt-bonded cermets of tungsten
an intermediate material. Typically, this is a carbide, titanium carbide, and niobium carbide.
chemical bath and may or may not use elec- Tungsten-base carbides generally are readily
tric current. The surface is roughened and wetted by the BAg and BCu filler metals. How-
chemically activated. The part is immersed in ever, titanium-base carbides are somewhat
a solution for an etching effect. This process more difficult to wet. Where it is necessary to
may be accelerated or enhanced by the use of mount TiCs by brazing, either the joint must be
electric current, higher temperature, or differ- made in an inert or vacuum atmosphere or the
ent combinations of chemicals. surfaces must be specially treated by the carbide
• Deposition of cobalt or other metal: The sur- manufacturer, or by nickel plating. In each case,
face is plated with a metal or other material the filler metals just mentioned then wet the TiC
that bonds to the ceramic as well as forms a surface.
layer suitable for brazing with standard filler In specifying a filler metal for a given job,
first consideration should be given to the tem- of a high-silver filler metal with manganese in-
perature range of the anticipated application. creases the bond strength and greatly increases
This and the other considerations of corrosion the impact resistance. It also helps prevent ther-
and mechanical properties dictate the alloy mal stress fractures. Secondly, the development
composition selected, the brazing temperature of a cleaning and surface-treatment process
required, the equipment to be used, and the join- cleans the carbide completely and then selec-
ing atmosphere. Generally speaking, the filler tively removes the cobalt, which leaves the sur-
metals mentioned previously are considered for face rough, because it is all exposed tungsten
the majority of applications that require simple carbide grains. Finally, this surface is extremely
equipment, fluxes, and brazing temperatures wettable and provides an excellent gripping sur-
below 980 °C (1800 °F). face for the filler metal while also promoting the
The carbides, in general, are not wetted as intermetallic joining characteristics for success-
readily by filler metals as are most base metals; ful bonding.
thus, it is preferable, when possible, to preplace
shims in the joint rather than to face feed the Ceramics
filler metal in the form of wire. For larger sur- The increasing use of ceramic-to-ceramic and
faces, shims having a core of copper or nickel ceramic-to-metal joints in industrial and devel-
with a coating of the filler metal on both sur- opmental applications is due to the unique com-
faces are frequently used. The core of the shim bination of properties of ceramic materials (Ref
generally accounts for approximately 50% of 96–100). The large use of ceramic-to-metal
the total thickness, with the filler metal provid- joints in vacuum tubes in the electronics indus-
ing another 25% on each side. try stems from the following properties:
Filler metals can provide a cushioning or a
shock absorber effect that actually helps the car- • Ceramic tubes can be outgassed at higher
bide survive in use. This is generally accom- temperatures than glass tubes.
plished in one of three ways. The first is through • Ceramic tubes can withstand higher tempera-
the use of a soft filler metal, such as 50% Ag tures than glass tubes of similar dimensions.
with cadmium. This is a pure cushioning effect. • Ceramic tubes are mechanically stronger and
The second way is through the use of man- less sensitive to thermal shock than glass
ganese. Manganese is a hard material, but it has tubes.
the property of absorbing impact. This is more • Ceramic components can be ground to the
similar to a shock absorber. The third method is precise tolerances required for vacuum-tube
the use of trimetal sandwiches. These are typi- construction.
cally filler metal/copper/filler metal. During the • Ceramic materials have very low electrical
brazing process, the copper anneals to a dead losses at high frequencies.
soft condition.
The cadmium alloys work well, but the cad- Because of their inertness in many corrosive
mium is a serious health risk; more importantly, environments, ceramics are used as seals in fuel
it is a health risk that the government really tar- cells and other devices that convert chemical,
gets. Cadmium fumes at low temperature nuclear, or thermionic energy to electricity.
escape from the filler metal as it is being heated. Ceramics are also used as friction materials for
It is also fairly soluble and dissolves into the brakes, clutches, and other energy-absorbing
grinding coolants when the saws and tools are devices; coatings for nuclear fuel particles; con-
ground. Finally, cadmium is very readily stituents in high-temperature adhesives; ra-
detectable, so it is easy to find. domes used to enclose antennae; and ablative
Manganese makes a good alloy for filler materials.
metal. However, the manganese makes the Glass-to-metal seals have been made for
alloys a bit brittle, which means it is harder to many years in the vacuum-tube industry, and the
draw into wire or roll into ribbons. experience thus obtained gives a general insight
The trimetal sandwiches are laminated to- into the problem of fabricating ceramic-to-metal
gether, which makes them very expensive. In joints (Ref 98). More recently, the fabrication of
addition, they have to be cut and bent to make refractory-tipped tools, vacuum tubes, and vari-
brazing preforms. The metal sandwiches have ous experimental devices has added to the avail-
to be preplaced into the joint. able knowledge and techniques.
Three practices that can lead to improve- Glass-Ceramic Joining. There are two
ments are recommended (Ref 93). First, the use types of intermediate bonds that can be em-
ployed, and the selection of which to use is assembled together with the major components,
influenced by a number of practical features, as illustrated in Fig. 4.9. The titanium is placed
including the ease of fabrication, the tempera- adjacent to the glass-ceramic, and the copper-
ture-withstand capabilities required, whether or silver eutectic adjacent to the metal, the whole
not the bond must possess insulating properties, being in suitable jigs to provide and maintain
and the cost. alignment. Alternatively, a specially developed
The bonds can be either metallic (e.g., a braze) Cu-Ag-Ti filler metal can be used (Ref 102).
or vitreous (glass or glass-ceramic). In this type The firing is carried out in a vacuum in order to
of bond, the usual design configuration is that of a prevent any oxidation of metallic constituents,
butt seal in which the glass-ceramic components which would inhibit wetting and flow of the
are joined on their end faces to the metallic com- braze at a temperature of approximately 850 °C
ponents, although other types of seal, such as (1560 °F). The titanium serves to react with the
sleeve or concentric seals, are possible. glass-ceramic during this firing, metallizing the
The glass-ceramic body components are ini- surface and permitting reaction with the braze,
tially prepared using glass-forming methods which in turn wets and bonds to the metal sur-
and are then heat treated. The butt type of seal face. This type of bond permits subsequent pro-
usually requires that the end faces of the glass- cessing (e.g., vacuum bakeout) and operation to
ceramic components are machined flat and par- temperatures in the region of 800 °C (1470 °F).
allel, and other surfaces, which are very often Higher temperature-withstand capability can be
inner and outer cylinder surfaces, are machined achieved by using more refractory brazes, such
to tight tolerances to fit the metal parts. The as those containing nickel.
metal parts themselves also require preparation However, it will be appreciated that the limi-
before assembly. In butt seals, the sealing faces tation may become the glass-ceramic compo-
must be flat to ensure good mating with the nent itself, although glass-ceramics are avail-
glass-ceramic seal faces. The preparation given able that withstand temperatures well in excess
to the metal prior to sealing depends on the type of 1000 °C (1830 °F). It should be noted that the
of intermediate bond to be employed—a metal- more-refractory glass-ceramics generally have
lic braze or a vitreous bond. relatively low thermal expansion, and conse-
In the case of a braze metal bond, the metal quently, matched expansion systems are only
seal parts are required to have smooth sealing possible with the lower-expansion metals and
surfaces and to be clean and free from oxidation alloys, for example, molybdenum and tungsten.
and other defects. The type of braze normally It should be borne in mind that work at elevated
employed with a glass-ceramic is an active temperatures may require the presence of an
metal braze. In the butt seal design, thin wash- inert atmosphere to prevent oxidation and dete-
ers of titanium and copper-silver eutectic are rioration of metal parts, including the braze.
In the case of a vitreous bond (glass or glass-
ceramic), the sealing faces of the metallic com-
ponent are roughened by means of grit blasting
or etching, and the components are preoxidized
by heating in a suitable atmosphere. The metal
sealing faces are then coated with the vitreous
bond, which is applied in powder form via a
suitable suspension, usually by spraying. The
coating is allowed to dry and is then fired, often
in a protective atmosphere to protect the metal
from excessive oxidation, to form a continuous
adherent layer on the metal sealing face. It is
usually unnecessary to preglaze the glass-
ceramic sealing faces, although this can be done
in a similar manner, if it is considered desirable.
The various components are assembled, as
shown in Fig. 4.10, for a butt seal and are then
fired to cause the bonding materials to complete
Fig. 4.9 Exploded view of the constituent parts for an
reactions with the glass-ceramic and metal com-
active metal brazed glass-ceramic/metal seal.
Source: Ref 101 ponents and so form the desired bond. If a glass-
ceramic bond is employed, the firing schedule • Glass-ceramic-metal leadthrough seals (e.g.,
also causes the glass to crystallize. A glass bond in thermocouple terminations). In this type of
permits subsequent processing and operation up seal assembly, the glass-ceramic is matched in
to temperatures of approximately 500 °C (930 expansion to the metal(s) of the leadthroughs.
°F), depending on the glass used, and a glass- In a thermocouple termination, these are
ceramic bond enables temperatures in excess of Chromel and Alumel (Hoskins Manufacturing
800 °C (1470 °F) to be withstood, again depend- Company). In other types of light-current
ing on the glass-ceramic used. leadthrough seals, the leadthrough metal is
The use of vitreous bonds is advantageous often a nickel-iron alloy, for example, 48%Ni-
where more than two components are required Fe. In this type of seal, a higher-expansion
to be bonded together in such a manner that metal or alloy, for example, mild steel or a
sequential bonding operations are required. It is stainless steel, is frequently used for the outer
necessary in these circumstances, while main- metal components. A fully hermetic bond is
taining thermal-expansion-matching/setting- developed between the glass-ceramic and the
temperature criteria, that the second and subse- outer metal, and, owing to the differential
quent glasses are used at successively lower expansion, or more precisely contraction, of
temperatures so that the firing conditions do not the two components, the outer joint is in com-
disturb the preceding glass and thereby allow pression, which increases the overall strength
relative movement of the previously bonded of the assembly and its ability to resist thermal
components. Fortunately, glasses are available shock. Clearly, the deliberate introduction of
that permit this sequential operation to be compressive stresses into the outer glass-
achieved, particularly for higher thermal expan- ceramic influences the design of the seal
sion systems. If necessary, a glass-ceramic or assembly.
braze can be used to provide the initial, more
refractory bond. Challenges in Brazing of Ceramics.
Examples of seals produced by direct bond- Ceramic materials are inherently difficult to wet
ing methods, such as in-mold shaping and with conventional filler metals. Most of these
graphite jig shaping, include: filler metals merely ball up at the joint, and little
or no wetting occurs. When bonding does occur,
• Glass-ceramic-molybdenum high-voltage it can be either mechanical or chemical. The
feed through seal, which comprises a glass- strength of a mechanical bond can be attributed
ceramic of the ZnO-Al2O3-SiO2 type that is to interlocking particles or penetration into sur-
matched in expansion and bonded to the face pores and voids, whereas a chemical bond
molybdenum parts to form a concentric derives strength from material transfer between
design (Ref 103) the filler metal and the base material. Discus-
sions of bonding mechanisms can be found in
the literature (Ref 101–109).
Another basic problem in brazing of ceramics
Metal results from the differences in thermal expan-
Pre-glazed layer sion between the base material and the filler
metal and, in the case of ceramic-to-metal
joints, between the two base materials. In addi-
tion, ceramics are poor conductors of heat,
Glass-ceramic
which means that it takes them longer to reach
equilibrium temperature than it does metals.
Both of these factors may lead to cracking in the
joint. Because ceramics generally have lower
tensile and shear strengths, crack propagation
occurs at lower stresses in ceramics than in met-
als. In addition, the low ductilities permit very
little distribution of the stresses set up by stress
raisers. Alumina, zirconia, beryllia, thoria, for-
sterite (Mg2SiO4), and silicon carbide and
Fig. 4.10 Exploded view of the constituent parts for glass- or
nitride are the leading ceramic materials that
glass-ceramic-bonded glass-ceramic/metal seal.
Source: Ref 101 can be joined by brazing.
If the ceramic is premetallized to facilitate and that use temperatures exceeding 750 °C
wetting, copper, silver-copper, and gold-nickel (1380 °F) (Ref 117).
filler metals can be used. Titanium or zirconium Further work (Ref 118) showed the develop-
hydride can also be decomposed at the ceramic- ment of strong, reliable joints containing ce-
metal interface to form an intimate bond. ramic components for applications in advanced
Nonmetallized ceramics have been brazed heat engines. This work was focused on the join-
with silver-copper-clad or nickel-clad titanium ing of Si3N4 by brazing. The technique of vapor
wires and other useful titanium and zirconium coating ceramics to circumvent wetting prob-
filler metals, such as Ti-Zr-Be, Ti-Zr-V, Zr-V- lems that was developed for brazing zirconia at
Nb, Ti-V-Be, and Ti-V-Cr (Ref 65, 96, 101, low temperatures was applied to brazing Si3N4.
110–113). An acceptable porosity-free joint was obtained
Silicon Nitride (Si3N4). One process for with 50Au-25Ni-25Pd filler metal.
brazing Si3N4 with metallic alloys involves The joints made with the 50Au-25Ni-25Pd
vapor coating the ceramic with a 1.0 µm thick (wt%) filler metal were brazed at 1250 °C (2280
layer of titanium before the brazing operation. °F) (approximately 120 °C, or 216 °F, above the
The coating improves wetting of the Si3N4 sur- normal brazing temperature for the Au-Ni-Pd
faces to the extent that strong bonding between filler metal).
the solidified filler metal and the ceramic This work also showed that the 50Au-25Ni-
occurs. Braze joints of Si3N4 are made with Ag- 25Pd (wt%) filler metal is particularly well
Cu, Au-Ni, and Au-Ni-Pd filler metals at tem- suited for brazing titanium-vapor-coated Si3N4.
peratures of 790, 970, and 1130 °C (1455, 1780, Figure 4.11 shows that for this material com-
and 2065 °F) (Ref 114). bination, high joint strength was maintained up
A study also showed that Si3N4 surfaces are to 700 °C (1290 °F) before dramatic loss at 800
not easily wet by common precious-metal-based °C (1470 °F). Investigations continue into the
filler metals, but that vapor coating the surfaces apparent dependence of joint strength on the
with titanium prior to brazing improved their filler-metal thickness, with the tendency for
wetting characteristics and permitted filler met- improvement with reduced braze-layer thick-
als to adhere strongly to the ceramic. The ability ness (from 40 to 50 µm to 10 to 20 µm).
of vapor coatings, particularly of titanium, to Other efforts (Ref 119) to develop filler
improve the wetting characteristics of oxide metals for Si3N4 components for the Advanced
ceramics has been known for some time (Ref Turbine Technology Applications Project
115, 116). Using a metallic vapor coating rather (ATTAP) engine have included the develop-
than incorporating an active element such as tita- ment of filler metals for ceramic-to-metal joints,
nium directly into the filler metal permitted read- including the investigation of the different alloy
ily available commercial filler metals to be used systems Au-Ni-Cr-Mo-Fe-Nb, Au-Ni-Cr-Fe,
for joining. Au-Ni-Cu-Cr-Mo-Fe-Nb, and Au-Ni-Cu-Cr-
The Si3N4 ceramics have recently been joined Fe. The effort was to increase the high-temper-
by an oxynitride brazing method. It was useful
for large-sized parts or ceramics with complex
500
geometries in which the high-temperature (72.5)
mechanical properties of the original ceramic

Joint strength, MPa (ksi)
400
components must be maintained. (58)
Joined parts can withstand temperatures that

300
are 300 to 400 °C (540 to 720 °F) higher than (43.5)
conventionally joined parts can tolerate. Joint
strength is comparable to the 400 MPa (58 ksi) 200
(29)
of the Si3N4 ceramic material. If joint strengths
do not need to exceed 200 MPa (29 ksi), then 100
(14.5)
these joints can be used at temperatures as high
as 1250 °C (2280 °F). 0
0 200 (390) 400 (750) 600 (1110) 800 (1470)
These large or geometrically complex parts Temperature, °C (°F)
are used in gas turbine and adiabatic diesel
engines, magnetohydrodynamic generators,
pumps, and numerous other applications that Fig. 4.11 Variation of joint strength with test temperature
for titanium-vapor-coated SN220 Si3N4 lap joints
require high strength and corrosion resistance brazed with Au-25Ni-25Pd wt% filler metal. Source: Ref 118
ature strength with a minimum loss of other peratures without premetallizing at the Univer-
properties necessary for brazing. sity of Illinois, Chicago. Reactive brazing with
Of those alloys, Au-Ni-Cr-Mo-Fe-Nb alloys, a filler-metal composition of Co-10Ti was used
which melt at 1050 to 1100 °C (1920 to 2010 to join Si3N4 components; the brazing process
°F), seemed to meet the processing require- involved a 15 min hold at 1300 °C (2370 °F)
ments for high-temperature ceramic-metal under a high vacuum.
joints. Preliminary results from mechanical test- Active metal brazing with Ag-Cu-Ti alloys is
ing indicated that these alloys had good ductili- currently used in the automobile industry to fab-
ties and strengths. They wetted well on Si3N4 ricate Si3N4-metal components, and no initial
with various coating materials in the vicinity of metallization of the ceramic surface is required.
1150 °C (2100 °F). Nonetheless, because silver- and copper-base
Researchers (Ref 120) conducted an evalua- filler metals cannot withstand service tempera-
tion of brazed Si3N4 joints, including their tures above 500 °C (930 °F), filler metals with
microstructure and mechanical properties. The higher melting points must be added to really
study involved Cusil ABA (active brazing utilize the high-temperature potential of Si3N4.
alloy) (Wesgo Metals), an Ag-35Cu-1.6Ti filler However, during tests with Co-10Ti filler
metal with a liquidus of 815 °C (1500 °F), metal, the reaction layer that developed was not
which was used to produce Si3N4/Si3N4 (SN/ uniform. While thicker areas were stable, the
SN) joints with room-temperature strengths thinner areas showed some degradation, and
similar to that of the monolithic ceramic. Braz- regardless of thickness, gaps were observed
ing was achieved by holding at 850 °C (1560 between the braze metal and the ceramic sub-
°F) for 30 min under vacuum, using 50 µm thick strate. This was caused by the premature
filler-metal foil. isothermal solidification of the braze as it was
Silicon nitride/AISI 316 steel joints were also depleted of titanium.
produced by brazing with Cusil ABA when Brazing with Ni-13Cr-Hf was also tested but
interlayers were used. Molybdenum was more was only possible with the Si3N4 premetallized.
successful as an interlayer than copper or nio- Hafnium from the braze metal moved toward
bium; its coefficient of thermal expansion the existing reaction layer, while copper dis-
matched that of the ceramic, and it had less solved in the matrix. Silver moved from the
effect on the reacting route for the joint forma- existing reaction layer toward the braze metal
tion. Joint strengths were higher for smaller but did not dissolve; it remained as islands of
workpiece bonded areas. pure silver (Ref 122).
Failure initiated predominantly from sites at In a study (Ref 123) conducted to improve the
the interfaces between the braze and the ceramic joining strength of Si3N4 ceramics, pure nickel
or metal workpieces. and 80wt%Ni-20wt%Cr alloy laminated inter-
An investigation (Ref 121) reported on a join- layers were used for joining.
ing method of ceramics-to-ceramics developed Thin, pure nickel layers in contact with the
with a target goal of retaining high-temperature Si3N4 ceramic were used for the following rea-
flexural strength with more than 80% of that of sons. The gaps between pure nickel and Si3N4
base materials. ceramics closed easily with small joining pres-
To join the Si3N4 material, the system of sure in the early stage of the joining process,
Si3N4/yttrium oxide/alumina was selected for because the flow stress of pure nickel is smaller
the base material. The sintered Si3N4 material than that of the nickel-chromium alloy. Then, the
was joined by using the powder mixture of the nickel and Si3N4 joined. Furthermore, chro-
grain-boundary phase composition. The paste mium diffuses in pure nickel layers toward the
of the powder mixture of the grain-boundary joining interfaces and forms chromium nitrides
phase was screen painted on the joining surfaces there. The decomposition of the nitrides is sup-
of the Si3N4 material. The joining was carried pressed by their interception from the argon join-
out by firing them in a nitrogen atmosphere and ing atmosphere because of the closed gaps.
hot isostatic pressing (HIP). Optimizing the The researchers concluded that the positive
conditions, the strength of joined specimens effects of thin, pure nickel layers placed in con-
resulted in 800 and 640 MPa (116 and 93 ksi) at trast with Si3N4 on the joining strength of
room temperature and 1250 °C (2280 °F). Si3N4ceramics with nickel and nickel-chromium
Silicon nitride braze joints have reportedly alloy laminated interlayers were confirmed
been produced in a single step at elevated tem- experimentally. This joining technique can also
be applied for the fabrication of high-strength were performed at 1220 °C (2230 °F) under a N2
metal-Si3N4 joints. partial pressure of 15 Pa (0.002 psi) for different
A team of researchers (Ref 124) assessed the times between 5 to 15 min. The highest room-
mechanical properties of Si3N4 braze joints after temperature, four-point bend strength of the
fabrication and following exposure to elevated joints was 115 MPa (17 ksi), whereas 220 MPa
temperatures. These tests were conducted at (32 ksi) was achieved when the joints were
room temperature and using four-point bending. tested at 900 °C (1650 °F). The high strength of
The filler metal used in the investigation was pal- the experimental joints was attributed to the
ladium-base 58.2Pd-38.8Ni-3.0Ti. The Si3N4 reduction in residual stresses and the formation
substrate was coated with a Ag-Cu-In-Ti filler of a CrN reaction layer at the ceramic/filler-
metal prior to fabrication of the braze joint. Two metal interface. This study shows that chromium
different sample geometries were used in the is the most reactive element in the Ni-Cr-Si filler
fabrication of the braze joints. Weibull statistics metals used for the brazing experiments.
were applied to the interpretation of the data, but SIALON. Oxynitrides were initially re-
the results contradict what is expected from ferred to by the acronym SIALON, which
monolithic fracture theories. Oxidation was stands for the Si-Al-O-N system. Both terms,
found to be significant when the braze joints oxynitride and SIALON, are used extensively
were exposed to 800 °C (1470 °F) in air, which throughout the literature to refer to specifically
reduced the joint strength. Si-Al-O-N materials as well as compounds
An interlayer consisting of titanium, silver, derived from silicon nitrides or oxynitrides by
and copper (0.1 mm, or 0.004 in., thick titanium simultaneous replacement of silicon and nitro-
foil; 0.1 mm thick silver foil; and 0.5 mm, or gen by aluminum and oxygen. The term has
0.02 in., thick copper plate) was sandwiched become a generic one applied to materials
between two such Si3N4 rods in the symmetrical where the structure involves (Si, Al) (O2, N2) or
arrangement of titanium/silver/copper/silver/ti- (Si, M) (O2, N2) tetrahedral (Ref 109, 127, 128).
tanium, with copper at the center, and then Silicon Carbide (SiC). Joining of SiC to
treated for 60 min at 1273 K and 2 MPa (0.3 ksi) SiC was investigated for advanced heat engine
to form a SN/SN joint. applications (Ref 129). The SiC-SiC joints were
The previously mentioned procedure was produced by cosintering β-SiC green forms
used to investigate the fatigue behavior of brazed with and without the use of pressure (HIP and
SN/SN joint specimens (Ref 125). Three-point vacuum sintering). The joints attained tensile
fatigue testing was conducted under static and strengths equal to or greater than 138 MPa (20
cyclic loading at temperatures ranging from 300 ksi) at 1530 °C (2785 °F), and no glassy phases
to 1038 K in air. were used for the joint.
It was found that the process of strength A program was undertaken to evaluate active
degradation owing to fatigue is controlled by brazing applied to SiC, because there is no suf-
the rate of either the cavity growth or the crack ficient metallizing process available for this
growth, depending on which one is dominant. ceramic (Ref 130).
At low temperatures, the fatigue process is The employment of metallic interlayers is
mainly controlled by crack growth; on the other one way of reducing thermally generated stress.
hand, formation of a small cavity and its growth Ductile metal, such as copper, can be employed
seem to be predominant factors in controlling as an interlayer as well to reduce thermal stress
the fatigue process at high temperatures. There- by plastic deformation of the interlayer.
fore, the triaxial tensile stress component is a Several commercially available active filler
very important factor in evaluating the fatigue metals were evaluated in a program (Table
life of joints at high temperatures. However, a 4.19). Resultant strengths using copper are
fairly good estimation of the fatigue life is reflected in Fig. 4.12.
obtained using nominal bending stress in the Silicon carbide sintered with the addition of
present investigation. It is also found that the both boron carbide and carbon was solid-state
fatigue life can be estimated using the bending diffusion joined by glass-encapsulated HIP. A
strength of joints. strength of 450 MPa (65 ksi) was obtained both
Researchers (Ref 126) brazed Si3N4 with at room temperature and 1400 °C (2550 °F).
nickel-brazed filler metals having the same The joining method for the green body was
nickel-chromium ratio as American Welding adopted to prepare a SiC nozzle ring model for
Society (AWS) BNi-5 (Ni-18Cr-19Si, at.%) but gas turbine bench tests. The model was success-
different silicon content. Joining experiments fully operated at 1400 °C (2550 °F) (Ref 131).
The roles of titanium in active brazing of SiC with the Ag-5Ti (at.%) filler metal at 985 °C
have been studied extensively (Ref 132), while (1805 °F) for 600 s, and fracture initiated at the
studies on the roles of silver and copper, which interface of the reaction product layer and prop-
constitute the major parts of the active filler agated through SiC.
metals, have been overlooked. The effects of the Silicon-carbide-base ceramic materials have
relative contents of silver and copper in the filler been joined by the reaction-forming technique
metal on the interfacial reactions and bond (Ref 133) for high-temperature applications.
strength were investigated in this study (Ref This method is unique in terms of producing
132). The interfacial reactions can be divided joints with tailorable microstructures. The for-
into the decomposition reaction of SiC by the mation of joints by this approach is attractive,
filler-metal melt and the interfacial reaction of because the thermomechanical properties of the
titanium with SiC. Brazing by the Cu-5at.%Ti joint interlayer can be tailored to be very close
filler metal induced SiC to be decomposed, but to those of the SiC-base materials. In addition,
the addition of silver to the filler metal sup- high-temperature fixturing is not needed to hold
pressed the decomposition of SiC. Titanium the parts at the infiltration temperature. A vari-
carbide (TiC) and Ti5Si3 were produced from ety of SiC-base ceramics and fiber-reinforced
the interfacial reactions of titanium independent composites have been joined using this
of the filler metals. However, their morpholo- approach (Ref 133–138).
gies and formation mechanisms differ greatly, A flow diagram of the joining method is
depending on the relative contents of silver and given in Fig. 4.13. The joining steps include the
copper. The bond strength and fracture modes application of a carbonaceous mixture in the
are also dependent on the relative contents of joint area and curing at 110 to 120 °C (230 to
silver and copper. Good bond strength of 159 to 250 °F) for 10 to 20 min. This step fastens the
178 MPa (23 to 26 ksi) was obtained by brazing pieces together. Silicon or a silicon alloy in tape,
Table 4.19 Commercially available active filler metals evaluated for brazing of silicon carbide
Chemical composition, wt% Solidus Liquidus Brazing temperature
Filler metal Cu In Ti Ag °C °F °C °F °C °F
1. Ag-Cu-Ti 27.5 ... 2 70.5 780 1435 795 1465 840 1545
2. Ag-Cu-In-Ti 23.5 14.5 1.25 60.75 605 1120 715 1320 760 1400
3. Ag-Cu-Ti 26.5 ... 3 70.5 803 1477 857 1575 950 1740
4. Ag-Ti ... ... 4 96 960 1760 960 1760 1050 1920
5. Ag-Cu-Ti 6 ... 3 91 875 1610 917 1683 970 1780
6. Ag-Cu-In-Ti 19.5 5 3 72.5 732 1350 811 1492 950 1740
Source: Ref 130
Bending strength SiC – SiC Sample a

220 (32) –
200 (29) – Sample b
Bending strength, MPa (ksi)
180 (26) –
Sample c
160 (23) –
140 (20) –
120 (17.5) –
100 (15) –
80 (12) –
60 (9) –
40 (6) –
20 (3) –
0–
1 2 3 4 5 6
Braze filler metal No.
Fig. 4.12 Four-point bending strength of active-brazed SiC-SiC joints. Source: Ref 130
paste, or slurry form is applied in the joint tively. In the joined materials, fracture does ini-
region and heated to 1250 to 1425 °C (2280 to tiate in the joint region. Inhomogeneous silicon
2600 °F)—depending on the type of infiltrant— distribution has been observed in certain areas
for 5 to 10 min. The molten silicon or silicon of these joints.
alloy reacts with carbon to form SiC, with con- This joining method has been used to join a
trollable amounts of silicon and other phases as wide variety of SiC-base materials, including
determined by the alloy composition. Joint fiber-reinforced ceramic-matrix composites in
thickness can be readily controlled in this different sizes and shapes, as shown in Fig.
process by controlling the properties of the car- 4.14. It can also be used to join tubular compo-
bonaceous paste and the applied fixturing force. nents. There is the potential to extend this join-
This process has been applied to two coming approach to the repair of SiC composite
mercially available SiC-base ceramics (Ref components in service (Ref 139).
134). The materials used were Cerastar reac- A pure aluminum foil between two blocks of
tion-bonded SiC (Cerastar RB-SiC) (The Car- SiC was fabricated by diffusion bonding for
borundum Company) and Hexoloy-SA (sin- temperatures ranging from 500 to 600 °C (930
tered alpha-SiC) (Saint-Gobain Advanced to 1110 °F) (Ref 140). An interfacial amorphous
Ceramics Corporation). phase was observed at the aluminum-SiC inter-
The average room-temperature flexural face for diffusion bonds performed at and above
strengths of the as-received and joined speci- 586 °C (1087 °F). The formation of this phase
mens were 157 ± 11 and 147 ± 10 MPa (23 ± 1.6 was essential for producing a strong bond
and 21 ± 1.5 ksi), respectively. These strengths between aluminum and SiC. When the thick-
increase at high temperatures, possibly due to ness of the amorphous phase was greater than
healing of machining flaws. The flexural 9 nm, another amorphous phase was observed
strengths of joined bars are comparable to those to form adjacent to the original amorphous
of as-received materials. The fracture origins phase. The morphology of the two phases indi-
appear to be inhomogeneities inside the parent cated that the two phases are formed by a solid-
material. state reaction.
The 23 and 1350 °C (73 and 2460 °F) flexural The results from indentation and in situ hot-
strength of as-received specimens of Hexoloy- stage TEM experiments demonstrated that the
SA sintered SiC were 401.7 ± 26.2 and 402.1 ± amorphous phase forms by a solid-state reaction
9.3 MPa (58.3 ± 3.8 and 58.3 ± 1.3 ksi), respec- rather than a mechanism involving the forma-
tively. The joined specimens with 45 to 50 µm tion of a low-melting eutectic liquid.
thick joints had strengths of 251 ± 13 and 267 ± Finally, the formation of the interfacial glassy
43.7 MPa (36 ± 1.9 and 39 ± 6.3 ksi), respec- phases was explained using thermodynamic and
kinetic considerations. It was postulated that the
strong attraction between the aluminum, car-
bon, silicon, and oxygen atoms results in the
formation of a glassy phase that has a higher
thermodynamic stability than aluminum and
Apply carbonaceous mixture to joint area
SiC crystals with a thin layer of silica in
Cure at 110–120 °C for 10 to 20 min between. Further, the formation of competing
crystalline phases, such as Al4C3 and Al2O3, is
kinetically suppressed, because the formation of
these phases is composition-specific and hence
Apply silicon or silicon alloy requires longer time.
(paste, tape, or slurry) The major conclusions of a study (Ref 141)
Heat at 1250–1425°C for 5 to 10 min can be summarized as follows:
• Additions of silicon to gold lead to a strong
decrease of the contact angle (from values
much higher than 90° to values much lower
Strong and tough joints
than 90°) without any significant reactivity.
with tailorable properties
Solidified drops adhere well on SiC sub-
strates.
• The good wetting and adhesion are due to the
Fig. 4.13 Flow diagram for reaction forming method for
joining silicon-carbide-base ceramics formation of a strong chemical bond between
the alloy and the ceramic, localized at the were joined with silver-copper eutectic filler
interface and interpreted as a covalent Si-SiC metals that contain titanium or zirconium as
bond. active elements. Although neither the filler-
• The wetting results are sensitive to oxygen, metal compositions nor the processing condi-
even if this element is present in the furnace tions were optimized, four-point bend strengths
at very low levels (PO2 ≈ 10–20 Pa). Dissolved of joined bars were as high as 108 MPa (16 ksi).
oxygen improves the beneficial effect of sili- Joining reactions were studied by conducting
con on wetting, and nearly zero contact separate sessile drop experiments with molten
angles have been reached in some cases. Ti-Ag-Cu and Zr-Ag-Cu filler metals on mullite
Thus, oxygen seems to be tension-active at for times and temperatures that were similar to
metal/covalent ceramic interfaces, as it is at those used for joining. Detailed compositional
metal/ionic ceramic interfaces. and microstructural analyses of those metal-
Mullite and ZrO2-toughened mullite, which ceramic interfaces revealed a complex reaction
were reaction sintered from Al2O3 and ZrSiO2, zone in which the oxide of the active element
Fig. 4.14 Photographs showing components fabricated from joined silicon carbide subelements. Source: Ref 139
was a principal reaction product. Compared with being only 50 to 60% as strong as those with
the titanium-containing filler metals, those with 94% Al2O3. Titanium-containing filler metals
zirconium were more refractory, less reactive were used to join both 94 and 99+% Al2O3 com-
with the mullite, and did not segregate as compositions:
pletely to the interface during heating (Ref 142).
Aluminum Nitride (AlN). Researchers Filler metal composition, %
Brazing temperature
(Ref 143) investigated the brazing of AlN, which Filler metal Cu Ag Ti In range, °C (°F)
is a good ceramic substrate in high-power elec- Cusil ABA 27.5 70.5 2.0 ... 820–860 (1510–1580)
tronic applications, to copper using indium-base Incusil 10 ABA 27.0 62.25 1.25 9.5 770–800 (1420–1470)
active filler metals. Compositions of filler metals
were chosen as In-1wt%Ti (IT1), In-19wt%Ag- Resulting tensile strengths of 76.8 to 109.8
2-wt%Ti (IAT2), In-15wt%Ti (IT15), and In- MPa (11.1 to 15.9 ksi) compared favorably with
52wt%Ag-20wt%Cu-3wt%Ti (ACIT3). Braz- conventional molybdenum-manganese metal-
ing operation was performed in vacuum at lizing of Al2O3 surfaces and subsequent brazing
temperatures of 650 to 900°C (1200 to 1650 °F). (Ref 144). The two different titanium-contain-
The filler metals showed good wetting on AlN ing filler metals that were used were essentially
and led to a strong bond between AlN and the copper-silver eutectic compositions containing
filler metal. From the microstructural analysis, small amounts (1 to 3 wt%) of titanium. The
no evidence of a reaction layer was clearly found basic difference between the two filler metals
at the interface under the experimental brazing was that one contained approximately 10 wt%
conditions. The composition of the filler-metal In, whereas the second filler metal contained no
layer changed into Cu9In4 phase due to the indium. The test results led to two general con-
extensive dissolving of copper from the base clusions concerning the strength data (Ref 144):
metal. Bond strength, measured by the four-
point bend test, was obtained as high as 225 to • For a given ceramic, higher strengths are
295 N (23 to 30 kgf) for the Cu/AlN/Cu joint observed when brazing in a vacuum and
brazed with IT15 and ACIT3 filler metals and when brazing with the indium-containing
was shown to be nearly constant even when the filler metal.
temperature was varied within 700 to 800 °C • All sets of variables examined (filler metal,
(1260 to 1440 °F). Most of the fracture appeared atmosphere, and ceramic composition)
to proceed through the interior of the AlN yielded comparable tensile strength to con-
ceramic. Based on the experimental results, it is ventional metallizing/brazing techniques.
believed that a strong bonding between AlN and
the filler metal can be achieved without the In order to verify the previous conclusions
apparent forming of a titanium-rich reaction concerning the filler metal as an active filler
layer at the interface. metal (ABA), a component was selected (Fig.
Alumina (Al2O3). A major problem with 4.15) to see how well the component (94%
brazing an oxide ceramic is the resistance to Al2O3) performed when brazed with the
wetting caused by the oxides on the surface of indium-containing filler metal. The component
the ceramic. A means of rectifying the problem
is to apply pressure to the filler metal with suffi-
cient force to counteract the repelling force of Copper
contacts
the oxides. A study was undertaken to assess the 94%
alumina
strength of the joints of metals brazed to Al2O3
with a copper filler metal.
Results of tests indicated that the strength of Active
braze alloy
the joint steadily increased as the pressure
increased up to 5 MPa (0.7 ksi) and then leveled
off with any additional pressure. Strength
increased as the brazing temperature rose to
1100 °C (2010 °F) and then dropped with fur- Molybdenum/alumina cermet
ther increases in temperature. Length of holding
time under pressure also affected strength. The
amount of Al2O3 in the ceramic also played a Fig. 4.15 Ceramic header used for testing titanium-contain-
ing filler metals for joining alumina. Source:
role in joint strength, with those of 100% Al2O3 Ref 144, 145
chosen was a 94 wt% Al2O3 ceramic header Al2O3. Compositions with at least 25% Cr read-
with two molybdenum-Al2O3 cermet electrical ily wet and flow on Al2O3; however, less
feedthroughs. Attached to the connector end of chromium results in limited or no flow. The
this header were two copper contacts, which ductility of the filler metals also depends
were subsequently brazed to the molybdenum- on composition. Filler metals with less than
Al2O3 cermet surface. 25% Cr are ductile and can easily be rolled into
The results of the shear tests are contained in sheet. The success of the previously mentioned
Table 4.20. The filler-metal preforms with 10% type of filler metals in wetting ceramics is
In yielded the highest shear strength. As a result, through the employment of active metals, such
it was found that ABAs provide a simplified as titanium and zirconium, as components of the
method of joining Al2O3 ceramics. Second, filler metal.
comparable tensile strengths can be obtained While the joining of ceramics (Al2O3) has
from ABAs as from conventional molybdenum- been successful without coatings prior to braz-
manganese metallizing techniques. Active filler ing, other investigators have examined other
metal sealing results in the migration of tita- metallic coatings in lieu of molybdenum-man-
nium from the bulk braze to the ceramic (Al2O3) ganese processing and the titanium hydride
surface. treatment (Ref 147–149).
Additionally, a filler metal, 25Cr-21V-54Ti, Finally, in a comprehensive study of filler
has been successfully used to join Al2O3 to itself metals and several engineered ceramic materi-
without any metallizing coatings (molybdenum- als for uncooled diesel engines, researchers (Ref
manganese or titanium hydride pretreatment) 149, 150) evaluated two filler-metal systems
(Ref 145, 146). Table 4.21 lists some of the sys- (Cu-Ag-Ti, Table 4.22; and Cu-Au-Ti, Table
tems that have held out promise; however, only 4.23), three types of Al2O3, and two types of
Ti-V-Cr and Ti-Zr-Ta have successfully wet ZrO2 (MgO-stabilized partially stabilized zirco-
Table 4.20 Braze test results in evaluation of titanium-containing filler metals for brazing of
alumina
Temperature Shear strength
Braze material Atmosphere °C °F Time, min N lbf
Incusil-10 ABA (0.05 mm, or 0.002 in.) Vacuum 810 1490 5 525 118
Cusil ABA (0.05 mm, or 0.002 in.) Vacuum 840 1545 5 489 110
Cusil ABA (0.03 mm, or 0.001 in.) Vacuum 840 1545 5 142 32
Cusil ABA (0.03 mm, or 0.001 in.) H2 840 1545 5 187 42
No metallize/nickel/Cusil H2 820 1510 6 534(a) 120(a)
(a) Specification requirement = 289 N (120 lbf). Source: Ref 144
Table 4.21 Ternary systems of filler metals evaluated for brazing of alumina
Approximate brazing temperature Materials
Filler metal system °C °F Refractory metals Graphite Al2O3
Ti-V-Cr 1550–1650 2820–3000 x x x

Ti-Zr-Ta 1650–2100 3000–3810 x x x
Ti-Zr-Ge 1300–1600 2370–2910 x x ...
Ti-Zr-Nb 1600–1700 2910–3090 x x ...
Ti-Zr-Cr 1250–1450 2280–2640 x ... ...
Ti-Zr-B 1400–1600 2550–2910 x ... ...
Ti-V-Nb 1650 3000 x ... ...
Ti-V-Mo 1650 3000 x ... ...
Source: Ref 146
nia, or PSZ, and Y2O3-stabilized tetragonal zir- tact angle, solid-liquid interfacial energy, and
conia polycrystal, or TZP). the work of adhesion values were calculated
From the filler metals based on the silver- based on the experimentally measured spreading
copper eutectic with additions of nickel and tita- radius in the temperature range of 1100 to 1300
nium, the best results were achieved with the °C (2010 to 2370 °F). Using an in situ measure-
Cu-26Ag-29Ti (wt%) composition. This filler ment technique, the spreading radius could be
metal produced wetting angles less than 30° on continuously monitored as a function of time.
all the ceramics and flexural strengths at 400 °C The results were compared to similar work on
(750 °F) of >165 MPa (24 ksi) for Al2O3 and the copper-titanium/Al2O3 system. Similar
>130 MPa (19 ksi) for a PSZ brazement. spreading behavior was observed for both sys-
Of the gold-bearing filler metals, the Cu- tems, and it is proposed that spreading occurs by
20Au-18Ti (wt%) had superior properties. Flex- the same interfacial reaction-product nucleation
ural strengths at 400 °C (750 °F) of brazements and growth mechanism. While the maximum
made with this filler metal range from 106 MPa work of adhesion was lower for copper-man-
(15 ksi) for one Al2O3 to 218 MPa (32 ksi) for ganese filler metals on Al2O3 (1425 mJ/m2) rel-
another Al2O3. The room-temperature flexural ative to that for copper-titanium filler metals on
strength of PSZ brazed with this material was Al2O3 (2800 mJ/m2), the copper-manganese/
258 MPa (37 ksi). Finally, the fracture tough- Al2O3 adhesion values are sufficient for many
ness of composite specimens of PSZ brazed direct-bonding applications.
with a Cu-27Ag-26Ti (wt%) filler metal aver- The formation of a thin reaction layer and the
aged approximately the same as that of the bulk lack of brittle copper-manganese intermetallics
ceramic, 6 MPa·m1/2. provides the potential for better joint mechani-
Researchers (Ref 151) studied the wetting and cal properties and easier processing for direct
spreading of copper-manganese filler metals on brazing of Al2O3, with copper-manganese filler
Al2O3 using a sessile drop technique. The con- metals replacing copper-titanium filler metals.
Sandia National Laboratories sponsored a
series of studies (Ref 152). The researchers
found that titanium and zirconium dissolved in
Table 4.22 Silver-copper filler metals
evaluated for brazing of alumina and
molten silver-copper filler metals wet AlN,
other ceramics Al2O3, and mullite and react with them. Contact
angles were lower for titanium than for zirco-
Brazing range(a)
nium and for higher concentration of either
Composition, wt% °C °F metal in the silver-copper filler metal. Titanium
Cu-27Ag-26Ti 900–950 1650–1740 reacts with AlN to give TiN0.7; zirconium reacts
Cu-26Ag-29Ti 920–1000 1690–1830 to give stoichiometric ZrN. Both reactions are
Ag-38Cu-1Ni-4Ti 950–1050 1740–1920 consistent with thermodynamic predictions and
Ag-37Cu-0.75Ni-7.25Ti 850–950 1560–1740
Ag-35Cu-0.7Ni-10.3Ti 950–1050 1740–1920 with previous studies. Titanium reacts with
(a) Brazing temperature depends to some degree on substrate material and on
Al2O3 to give a reaction layer containing oxy-
the extent of flow desired. Source: Ref 149 gen and titanium in approximately a 0.4 to 0.6
ratio. That is consistent with the reaction 8 Ti +
Al2O3 = 3 TiO0.5 + 2 Ti3Al, which is predicted
Table 4.23 Experimental filler metals with by thermodynamic calculations. Zirconium
copper and gold as major elements evaluated reacts with Al2O3 to give a reaction layer that
for brazing of alumina and other ceramics contains oxygen and zirconium close to the stoi-
Brazing range(a)
chiometric 2-to-1 ratio for ZrO2. That reaction
is not predicted by simple redox thermodynam-
Composition, wt% °C °F
ics. Additional driving force may be provided
Cu-14Au-4Ni-6.5Ti 1090–1190 1995–2175 by formation of aluminum copper and Ag-Al-
Cu-13Au-3.5Ni-14Ti 1050–1150 1920–2100 Cu-Zr phases observed in cooled specimens. In
Cu-22Au-10Ti 1350–1450 2460–2640
Cu-20Au-18Ti 1050–1150 1920–2100
the case of mullite, the reaction product for the
Cu-18Au-26Ti 1050–1150 1920–2100 Ti-Ag-Cu filler metals appears to be a complex
Au-36Ni-11Ti 1050–1200 1920–2190 titanium-copper oxide instead of the simple
Au-30Ni-21Ti 1150–1250 2100–2280
ZrO2 that was found for reaction of Zr-Ag-Cu
(a) Brazing temperature depends to some degree on substrate material and on
the extent of flow desired. Source: Ref 149 filler metals. Although interface reactions have
not been conclusively identified, formation of
titanium and zirconium oxides from metal-mul- braze, as in the case of the explosion bonding
lite redox reactions seems likely. The grains process. Thus, the squeeze cast speed, which is
with the Ti-Cu-O composition in the titanium- determined by the relation between the ram
Cusil specimens require further investigation. speed and the braze-layer thickness, has a cer-
In an investigation (Ref 153), a new joining tain influence on the quality of the SQ-brazed
process for ceramics to ceramics and ceramics interface.
to metals, squeeze (SQ) brazing, was devel- Examples used in the study were limited to
oped. This process uses squeeze casting; a braz- the use of aluminum as a filler metal. However,
ing material is squeezed into the interface chan- other filler metals such as copper alloys, silver-
nel to be brazed and is solidified under a high copper alloys, nickel alloys, and gold alloys
pressure. This new process has several advan- with active metals such as titanium, which have
tages: low cost, mass producibility, high inter- higher melting points than aluminum, could be
face strength, high reliability, no severe reac- used as filler metals under a certain condition
tion, and so on. control. Oxidation of active metals can be pre-
Severe reaction, which sometimes limits vented only by adoption of an inert atmosphere
adoption of the active metal brazing for certain in molten brazing materials. The SQ brazing
kinds of ceramics, for example, not only Al2O3- itself can be performed in an air atmosphere,
silica but also zirconia, diamond, lead-zirco- because the exposure of the active brazing
nium titanate, and so on, is not a serious prob- materials to an oxidative exposure atmosphere
lem in the SQ brazing. Nonactive combinations is limited to a very short period. In addition,
such as Si3N4-aluminum could be tightly brazed glass-ceramics can also be used as brazing
by this process with a simple surface activation materials in the present process, if a sufficiently
treatment (Tables 4.24, 4.25) (Ref 153). low viscosity and high pressure are established.
The simple calculation for the melt infiltra- Thus, it is concluded that SQ brazing has great
tion in the SQ brazing gave a guide to the criti- potential for brazing ceramics for a wide variety
cal pressure required for brazing. In the present of applications.
case, the melt flow was assumed to be laminar. Researchers (Ref 154) evaluated the thermo-
However, if the melt flow is turbulent, it effec- dynamic reaction products and layering in
tively breaks the surface oxidation film and may brazed Al2O3 joints.
cleanse the surface of ceramics by the jet The investigation covered the joints formed
formed preceding the moving melt front of a by brazing Al2O3 to itself or to a titanium alloy
(Ti-6Al-4V) with a Ag-Cu-Ti filler metal. In the
brazing process, titanium in the filler metal
reduces Al2O3 to form a series of reaction prod-
Table 4.24 Summary of bending strength of ucts that have a layered morphology. The for-
alumina joints formed by conventional brazing mation of M6X-type compounds, Ti4Cu2O or
and by squeeze (SQ) brazing Ti3Cu3O, at the interface was characteristic of
Strength these joints. The other reaction products also
Brazing method Atmosphere
Thickness of
braze layer, µm MPa ksi
belong to the Ti-Cu-O system (with the reduced
aluminum in solution), and hence, this subsys-
Conventional Air ... 0 0 tem was chosen to assess the thermodynamic
Argon flow 10 49 7
SQ brazing Air 10 325 47 stability of the joints. The Ti-Cu-O section was
... 300 228 33 established experimentally at 945 °C (1730 °F),
See text for description of the SQ brazing process. Source: Ref 153 and activities of elements in three of the three-
phase regions were estimated based on the
phase boundaries of the ternary section and
available binary thermodynamic data. The esti-
Table 4.25 Summary of bending strength of mated free energies of formation of the two
silicon nitride joints brazed by the squeeze M6X-type compounds, Ti4Cu2O and Ti3Cu3O,
(SQ) method are –120 and –122 kcal/mol, respectively. The
Material Bending strength, MPa (ksi) highly negative values for the free energies of
formation suggest that these compounds are
As-received Si3N4 57 (8)
Preoxidation treated Si3N4 404 (58.5)
thermodynamically stable. The activity data
Source: Ref 153
were also used to generate activity diagrams for
the Ti-Cu-O system. The layer sequences at the
joints satisfied the stability requirements based A method of ceramic-ceramic joining that
on the ternary section and the activity diagrams, exploits a multilayer interlayer designed to form
indicating that even though the interfaces a thin, potentially transient layer of liquid phase
formed in a matter of minutes, they were at local has been used to join Al2O3 to Al2O3. Microde-
thermodynamic equilibrium. signed multilayer copper-niobium interlayers
The suitability of active brazing technology were used to achieve bonding at 1150 °C (2100
for joining TiC-strengthened Al2O3 (ATC) to °F). Flexure strengths of as-bonded samples
itself and to stainless steel was evaluated (Ref ranged from 119 to 255 MPa (17 to 37 ksi), with
155). an average of ≈181 MPa (26 ksi). The ability to
The main emphasis was put on the investiga- form strong ceramic-metal interfaces was also
tion of the microstructural and mechanical indicated by instances of ceramic failure.
properties of the active brazed joints. Further- The impact of postbonding anneals of 10 h
more, the electrical properties were investigated duration at 1000 °C (1832 °F) in gettered argon
by determining the specific electrical resistance on room-temperature joint strength was as-
of active-brazed Al2O3-TiC joints. sessed. High strengths (198 to 238 MPa, or 29 to
For fabrication of the joints, two process tech- 35 ksi) were obtained. The retention of strength
nologies were applied: vacuum furnace brazing following annealing in low-oxygen partial pres-
and induction brazing under shielding gas. sure argon differs from the behavior previously
Four-point bend tests revealed that some of observed in copper-platinum-bonded Al2O3.
the vacuum-brazed ATC joints reach bending The results indicate that, as in the case of plat-
strengths comparable to those of bulk ATC with inum-Al2O3 bonding, high-strength joints be-
the Ag-In-Ti filler metal (Fig. 4.16). tween niobium and Al2O3 can be produced at
Besides joining ATC to itself, active brazing significantly lower temperatures than those pre-
also allows fabrication of ATC-metal joints. viously used for diffusion bonding by intro-
However, mechanical properties are generally ducing a thick intervening layer of copper.
poorer than those of ATC-ATC joints. It was Compared to copper/platinum/copper-inter-
also shown that the induction brazing process is layer-bonded Al2O3, fracture strengths were
an interesting alternative to the vacuum furnace generally higher and less scattered. Sessile drop
brazing technique when ATC has to be joined to experiments comparing the wetting behavior of
steels. When using the very ductile silver-base copper and niobium-saturated copper on Al2O3
filler metals Ag-Ti and Ag-In-Ti, high-quality indicate that niobium acts to decrease the cop-
joints can be fabricated by induction heating. per contact angle, and this is thought to promote
The main advantages of the induction brazing a more favorable strength distribution than
process are short processing time, cheap equip- obtained with copper-platinum-base interlayers.
ment, and low energy input into the parts. More generally, the results suggest that precoat-
A group of researchers (Ref 156–158) exam- ing substrates with a thin layer of a reactive
ined the ceramic joining and bonding of Al2O3 metal may improve the degree of contact
via copper/niobium/copper interlayers. between the transient liquid and the substrate
Four-point bending strength, MPa (ksi)
395
400 (58)
345 352 355 Minimum
350 (51) 320 Average
300 (44) 275
Maximum
238
250 (36)
200 (29) 180
150 153
150 (22)
103
100 (15)
61
50 (7)
0
AgCulnTi CuSiAlTi AuPdTi PdNiTi
900 °C/10ft 1050 °C/10ft 1250 °C/10ft 1250 °C/5ft
(1650 °F/3m) (1920 °F/3m) (2280 °F/3m) (2280 °F/1.5m)
Fig. 4.16 Four-point bend strength of vacuum-brazed TiC-strengthened alumina joints. Source: Ref 155
and thereby increase the average strength, nar- tion of deleterious intermetallic compounds that
row the strength distribution, or both. limit the mechanical properties. Previous
Researchers (Ref 159) compared titanium research indicated that the nickel-titanium sys-
Al2O3 diffusion bonding and titanium active tem would provide the needed reactive, high-
brazing. melting-point alloy, with NiTi providing the
The product layer sequence in the reaction of most acceptable ductility.
solid titanium with Al2O3 and in the reaction of The composition and structure of the coatings
titanium dissolved in liquid silver with Al2O3 and bonded specimen were evaluated by x-ray
were compared. The phase diagram and the dif- diffraction, scanning electron microscopy, and
fusion path in the Ti-Al-O system were used to energy-dispersive microscopy. The highest
describe the interface formation during brazing shear strength values were 54 MPa (8 ksi) for a
of Al2O3 with liquid Ag-4wt%Ti filler metal. NiTi five-layer coating bonded at 12 MPa (2
During brazing, first Ti-Al(O) intermetallics ksi) for 300 min at 900 °C (1650 °F). Shear
were formed. When the filler metal was depleted strengths of the Ti2Ni were generally lower,
from titanium, the formed Ti-Al(O) interme- and, as expected, shear strength diminished
tallics decomposed into oxygen-saturated Ti(O) with the formation of TiNi3.
and Al, which in turn diffused through the Ti(O) Zirconia (ZrO2). Filler-metal systems have
and dissolved in the silver. been developed not only for joining Al2O3 but
Researchers (Ref 160, 161) examined the in- also for joining partially stabilized ZrO2.
terfacial reaction between Al2O3 and copper-tita- The contact angles of molten aluminum-cop-
nium filler metal during reactive metal brazing. per filler metals and their wettability on CaO-
The copper-titanium filler metals reduced stabilized ZrO2 have been measured, and it was
Al2O3 to form TiO at the interface. Thermody- found that a ZrO2 joint brazed with Al-1.7Cu
namically, reduction of Al2O3 is possible (wt%) filler metal has produced the maximum
through the dissolution of the aluminum by the fracture strength of 105 MPa (15 ksi), compared
filler metal. At 1300 K, for example, interfacial to 52 MPa (7.5 ksi) for that brazed with pure
reaction can proceed until the activity of alu- aluminum at room temperature. This improved
minum reaches approximately 0.02 in Cu-20Ti strength of ZrO2 is maintained at elevated tem-
(at.%) filler metal. With time, the TiO layer peratures up to 513 °C (955 °F). The joining
grew toward the center of the filler metal, fol- strength of a ZrO2 joint brazed with an alu-
lowing a parabolic rate law, at the cost of minum-copper filler metal is dominated by the
another complex oxide, presumably Ti3Cu3O, mechanical properties of the aluminum-copper
which formed next to the TiO. The activation in addition to the wettability of the aluminum-
energy of TiO growth was 208 kJ/mol (50 copper filler metal against ZrO2 (Ref 162).
kcal/mol), which corresponds to the activation Researchers (Ref 163) evaluated the effect of
energy of oxygen diffusion in the TiO. There- the interfacial structure on the joining strength
fore, it appears likely that the growth of TiO is of a ZrO2-ZrO2 joint with aluminum foil.
controlled by oxygen diffusion. An oxygen ionic conductivity of ZrO2 was ap-
Coated Al2O3 substrates have been joined plied to strengthen the ZrO2-ZrO2 joint brazed
with a nickel foil interlayer through solid-state with aluminum. The interfacial structure was
diffusion bonding. Here, multilayer nickel and examined by conventional TEM and ultrahigh-
titanium coatings with a 25 µm total thickness voltage electron microscopy, and the joining
were deposited on polycrystalline Al2O3 sub- strength was evaluated by the four-point bend-
strates through direct current (dc) magnetron ing test.
sputtering. Thicknesses and number of layers The results obtained in this work were as fol-
were varied, and each coating was constructed lows:
to produce one of the three intermetallics in the
nickel-titanium system: Ti2Ni, TiNi, or TiNi3. • It can be expected that the ZrO2-ZrO2 joints
The coated substrates were joined by solid-state brazed with aluminum can be strengthened
diffusion bonding at bonding pressures of 4 and by applying a dc voltage across the ZrO2
12 MPa (0.6 and 2 ksi). specimens.
The two major challenges to general brazed • The applied current, the applied quantity, and
ceramic-to-metal components are the lower the initial thickness of the aluminum layer
melting temperature of most filler metals, which strongly affect the joining strength.
limits the service temperature, and the forma- • Interfacial structures differed dramatically,
depending on whether a dc voltage was itself. Titanium and AISI 316 might give prob-
applied or not. lems because of chemical reactions with ZrO2,
• When a dc voltage was not applied, ZrO2 was and molybdenum is not suitable because of the
deoxidized at the aluminum-ZrO2 interface. relatively high residual-stress level in the
(Al2O3)δ was formed at the aluminum side of ZrO2/molybdenum/ZrO2 combination.
the interface; Zr2Al3 was formed between Similar arguments given for the ZrO2/inter-
(Al2O3)δ and ZrO2. layer/ZrO2 combination hold for the case of the
• When a dc voltage was applied, α-Al2O3 or ZrO2/interlayer/Si3N4 combination, as far as the
(Al2O3)δ was formed at the aluminum side of choice of nickel as the most suited interlayer
the interface. Additionally, very fine grains material is concerned. Copper may also be used
were formed between Al2O3 and ZrO2. as an interlayer material, but it is excluded
• The grains of Zr2Al3, α-Al2O3, and (Al2O3)δ because of its low strength and corrosion resis-
were relatively large in size. tance. Titanium and AISI 316 are expected to
• The interfacial structure greatly influenced give severe reactions with Si3N4 and are, there-
the joining strength. fore, not applicable as interlayer material. The
use of molybdenum results in very high
The active brazing of partially stabilized stresses, which make molybdenum also not suit-
ZrO2 to ZrO2 was carried out using 57Ag-38Cu- able as an interlayer material.
5Ti filler metal in a vacuum of 7 × 10–3 Pa (10–6 ZrO2/Interlayer/AISI 316. Joining ZrO2
psi) (Ref 164). The effects of joining conditions, to AISI 316 is expected to be possible using
such as temperature (from 1073 to 1323 K) and copper and nickel as interlayer materials. As
holding time (from 0 to 60 min), on the joint shown previously, nickel has better mechanical
strength and the interfacial reaction were inves- and corrosion properties that make it favorable
tigated. The joint strength was evaluated by in applications under severe circumstances.
shear testing. It was shown that the brazing tem- Although the use of titanium results in relatively
perature and holding time had a strong influence low residual stresses, its chemical behavior in
on the joint strength; the latter was controlled combination with both ZrO2 and stainless steel
mainly by the interfacial morphologies. A lower is expected to be problematic, which hinders its
or higher temperature and a shorter or a longer use as an interlayer material. Application of the
holding time were disadvantageous to joint candidate interlayer materials molybdenum and
strength due to the thinner reaction layer or AISI 316 (direct bonding) results in relatively
cracks present at the interface, the maximum high stress levels. These materials are, there-
joint strength being achieved at 1123 K for 30 fore, assumed to be less suited as an interlayer
min when the interface reaction layer thickness material in diffusion bonding/brazing ZrO2 to
was approximately 4.4 µm. X-ray diffraction stainless steel AISI 316.
analyses revealed that the reaction products at
the interface between ZrO2 and the filler metal Special, Miscellaneous, and
were δ-TiO and γ-AgTi3, and a layer transition
structure of ZrO2/δ-TiO/δ-TiO + γ-AgTi3/γ- Significantly New Materials
AgTi3/Ag-Cu formed at the interface. Diamond. Single-crystal diamond tools are
A definite choice (Ref 165) can now be made well established in many applications involving
of the most suitable interlayer material(s) for the high-precision machining of nonferrous
three diffusion-bonded/brazed material com- materials. While previously this was mainly a
binations (ZrO2-ZrO2, ZrO2-Si3N4, and ZrO2/ preserve of natural diamond, now synthetic
AISI 316). monocrystal diamond products are assuming
ZrO2/Interlayer/ZrO2. In the ZrO2/inter- greater importance as a cutting tool material
layer/ZrO2 combination, copper and nickel (Ref 166).
were the best interlayer materials, in view of For a long time, it was widely, but erro-
their positive behavior during the bonding/braz- neously, considered that diamonds could not be
ing process and the relaxation of residual brazed directly to a support. Normal practice
stresses during cooling. However, copper is rel- has been simply to mount the diamond by sin-
atively weak and has a low corrosion resistance, tering or to fix it in a bed of filler metal, with no
and, therefore, its use as an interlayer material chemical bond forming between the diamond
was limited. This led to the conclusion that and the filler metal. However, by using certain
nickel was the most suited metal to join ZrO2 to metals, such as titanium, zirconium, niobium, or
tantalum, diamond can also be wetted directly and can be adjusted by either the foot pedal or a
by the formation of a carbide. Nevertheless, at hand control. The machine is powered by a stan-
the high temperatures required for this opera- dard 220 V alternating current system.
tion, the components that are to be brazed react The titanium-activated filler metal used in the
extremely sensitively to the presence of even process is of particular importance. It is nor-
the smallest quantities of oxygen. mally 0.4 mm (0.016 in.) in diameter and
Above approximately 450 °C (840 °F), in an becomes eutectic at a temperature of more than
oxidizing atmosphere the carbon near the sur- 900 °C (1650 °F).
face of the diamond reacts with the oxygen in Because clean and oxygen-free surfaces are
the air to form carbon dioxide; the result is that essential for effective brazing, the parts to be
nothing can adhere to the surface of the dia- brazed should first be cleaned by a system rec-
mond. Direct brazing in open atmosphere is, ommended for the cleaning of diamond. Then,
therefore, no longer possible. Consequently, at the active filler metal is placed on the carbide or
these temperatures, brazing must be carried out molybdenum support clamped between the elec-
under a high vacuum or an oxygen-free inert- trodes. On closing the glass door, the inert gas
gas atmosphere. High-vacuum machines/fur- flows into the unit. To ensure that the unit is
naces are relatively expensive, requiring a sub- entirely filled with gas, in other words, that all
stantial investment, and are not economical with the oxygen has been expelled, the operator
small production batches, as would be the case should wait for approximately 20 s before initi-
for most diamond toolmakers. ating resistance heating with either the foot pedal
The development of a diamond brazing unit or the hand control. In order to prevent prema-
(2500 W output), with an inert-gas environ- ture operation, the system works with a time
ment, makes the brazing of monocrystal dia- delay of 18 s before the current starts to flow.
mond blanks (generally between 0.5 and 1.2 The special filler metal is generally used in
mm, or 0.02 and 0.05 in., thick) to WC or the form of a 0.5 mm (0.02 in.) strip per opera-
molybdenum supports substantially less com- tion. This is sufficient for brazing an area of
plicated and more economical. Carbide and approximately 5 mm2 (0.008 in.2), which is ade-
molybdenum are the preferred substrate materi- quate in most cases. The substrate (support) is
als for brazing diamond, because their coeffi- first pretinned with the filler metal, and only
cient of thermal expansion is relatively close to then is the diamond placed on top of the sub-
that of diamond, and therefore, no damage is strate for brazing. The temperature is then care-
likely to be caused as a result of thermally fully raised until the eutectic is reached, at
induced stresses. which time the actual brazing process occurs.
The inert gas, which consists of 95% Ar and
5% H2, is supplied to the braze box through a
reducing valve in order to ensure the flow of gas
required for this operation.
The braze box itself is provided with means
for receiving and discharging the gas and with a
glass door for opening and closing the housing.
The glass door controls the gas supply, in that
by closing the protective door the gas is intro-
duced automatically, and conversely, the supply
is shut off when the door is opened.
The temperature of more than 900 °C (1650
°F) required for brazing is generated by resis-
tance heating, as shown in Fig. 4.17; that is, the
workpiece, which is fixed between two elec-
trodes, is heated by passing an electric current
through the electrodes. With this system, it is
possible to distribute heat uniformly when work-
ing with tool holders up to approximately 10 by
10 mm (0.4 by 0.4 in.) in size (width by height),
(I)
although special designs may be supplied on
Fig. 4.17 The principle of resistance heating. I, electric cur-
request. The current to the electrodes is activated rent. Source: Ref 166
Tests show that with a braze layer 0.02 to pletely melted at approximately 600 °C (1110
0.05 mm (0.0008 to 0.002 in.) thick between the °F). Voids were produced, owing to the solid-
molybdenum and diamond, the shear strength of ification shrinkage of the matrix metal.
the bond is of the order of 340 MPa (50 ksi). • When the melting point of the matrix metal
Composites. Silicon carbide-fiber-rein- was close to the brazing temperature, the re-
forced SiC-matrix composites (SiC-SiC) pro- action between fibers and matrix metal oc-
duced by chemical vapor infiltration have been curred easily. As a result, accurate tempera-
developed for use in structural applications at ture control was needed in the brazing of the
temperatures approaching 1000 °C (1830 °F). MMC using the aluminum alloy matrix (Ref
These composites contain approximately 40- 169).
vol% SiC fibers (Nicalon, Dow Corning Corpo-
ration) and are infiltrated to approximately 85% Researchers (Ref 170) investigated the prop-
of the theoretical density with SiC. In order to erties and microstructure of brazed joints of
fully realize the advantages of these materials, SCS-6 SiC-fiber-reinforced β21S (Ti-15Mo-
practical joining techniques are being devel- 2.7Nb-3Al-0.2Si, wt%) titanium-matrix com-
oped. Successful joining methods will permit the posite (TMC). Brazed joint specimens were fab-
design and fabrication of components with com- ricated from TMC using two different forms of
plex shapes and the integration of component commercially available Ti-15Cu-15Ni filler
parts into larger structures. Joints must possess metal. The brazed joint specimens were tested
acceptable mechanical properties and exhibit in air at room temperature and at 815 °C (1500
thermal and environmental stability comparable °F) using overlap tensile shear tests. Metallurgi-
with the composite that is being joined. cal and fractographic analyses were used to
Studies have focused on joints produced using characterize the microstructure, filler-metal/
TiC+Ni and SiC+Si interlayers. The microstruc- TMC interactions, and joint failure modes. The
tures of joints have been characterized, and the fractographic results indicated that TMC delam-
results appear promising. In one approach, hot ination is a dominant failure mode for this type
pressing elemental titanium, carbon, and nickel of joint. At room temperature, the TMC brazed
powders formed a TiC+Ni joint interlayer, and joint specimens failed by TMC delamination
in a second approach, silicon infiltration of SiC and TMC tensile failure, with the brazed joint
and carbon powders, or carbon cloth, produced remaining intact. Therefore, the performance of
SiC+Si interlayers (Ref 167). the brazed joint specimens at room temperature
Researchers (Ref 168) investigated the was limited by the interlaminar strength of the
effects of brazing temperature on joint proper- TMC and not by the braze strength. At 815 °C
ties of continuous SiC fiber in reinforced-alu- (1500 °F), the TMC brazed joint specimens
minum-alloy-matrix composite and the behav- exhibited a combination of delamination and
ior of the metal-matrix composite (MMC) braze shear failure. Thus, the high-temperature
during the heating process. The following re- performance of the brazed joint specimens may
sults were obtained: be limited by both the TMC interlaminar prop-
erties and the strength of the braze (Ref 171).
• There is a brazing temperature at which max- Concurrently, researchers (Ref 172–174)
imum joint strength is obtained in the brazing were evaluating rapid infrared joining (RIJ) of
process. A brazing temperature lower than SC5-6/β21S TMCs by transient liquid phase
this causes the brazed joint to fail in shear at (TLP).
the brazed interface. A brazing temperature Rapid infrared joining has been shown not to
higher than this makes the brazed joint fail in have many of the problems associated with con-
the MMC. The matrix was Al-10Si-1Mg ventional joining methods. Two models were
filler-metal foil. The maximum joint shear used to predict the joint evolution and fiber reac-
strength in this study was 77.7 MPa (11.3 tion-zone growth. A TMC, 16-ply SCS-6/β21S,
ksi). The brazing condition was 580 °C (1075 has been successfully joined, with total process-
°F) for 1800 s. ing times of approximately 2 min, using the RIJ
• The MMC showed degradation in tensile technique. The process uses a 50 °C/s (90 °F/s)
strength at room temperature after heat treat- ramping rate, a 17 µm Ti-15Cu-15Ni (wt%)
ment higher than 550 °C (1020 °F). filler metal between the faying surfaces, a join-
• The MMC began to melt at a temperature of ing temperature of 1100 °C (2010 °F), and 120
approximately 580 °C (1075 °F) and com- s of time to join the composite material. Joint
shear strength testing of the rapid infrared joints Metallic interlayers have also been used to
at temperatures as high as 800 °C (1470 °F) has bond 8090 (aluminum-lithium) MMC materials
revealed no joint failures. Also, due to the rapid (Ref 177–179).
cooling of the process, no poststabilization of Transient liquid phase diffusion bonding
the matrix material is necessary to prevent the (TLPDB) involves placing a metal foil insert
formation of a brittle omega phase during sub- between the surfaces to be joined, to induce
sequent use of the TMC at intermediate temper- formation of a liquid region. The foils are typi-
atures, 270 to 430 °C (520 to 805 °F), for up to cally copper, zinc, and silver for aluminum
20 h. MMCs (Ref 180, 181). The process of eutectic
Researchers (Ref 175) evaluated the braze- bonding was employed using an interlayer of
ability of several aluminum-matrix composites. copper as a prepared filler metal (Ref 182). This
They found the following: type of bonding is similar to that of liquid phase
diffusion bonding in that the joining is effected
• Wettability and spreading of an Al-12Si filler
by a liquid phase that forms at a temperature
metal on aluminum alloys reinforced with
below the melting point of the base materials.
Al2O3 particles depend on the temperature,
Brazing of 6061-50%B has been carried out
type of matrix, and reinforcement fraction.
using AlSi brazing foils (melting point of 580
An increase in reinforcement fraction de-
°C, or 1075 °F) and a lower-melting-point alloy
creases both wetting and spreading, which
of Al-Cu-Zn with a melting point of 380 °C
hinders the brazeability of the aluminum
(715 °F) (Ref 183). A composite aluminum-
composites.
boron tape has been successfully brazed (and
• Composites with a matrix of 7005 aluminum
diffusion bonded), with use on the space shuttle
alloy present higher wettability and spreading
(Ref 183). Joints apparently of good quality
than those with a matrix of 6061 aluminum
have also been produced in W6A.15A (6061-
alloy because of the decrease in the melting
15%Al2O3p) MMCs using TLPDB (Ref 184).
temperature of the braze metal by zinc diffu-
Foils of silver, copper, and BAlSi-4 were used
sion. Optimal wetting temperatures deter-
as interlayers. The best consistency, in terms of
mined by drop formation test are 570 to 580
joint shear strength (>175 MPa, or 25 ksi), was
°C (1060 to 1075 °F) for the 7005-matrix
achieved using the silver at 575 °C (1070 °F) for
composite and 580 to 590 °C (1075 to 1095
100 min and BAlSi-4 at 585 °C (1085 °F) for 20
°F) for the 6061-matrix composite.
min. However, the copper produced joints of
• Long wetting times aid silicon penetration in
higher shear strength, but results appeared more
the base matrix and the reduction of its melt-
scattered.
ing point and can lead to the penetration of
Liquid phase diffusion bonding has, with
molten braze into the substrate, resulting in
inserts of 2017 aluminum alloy copper and sil-
erosion. This problem is less significant for
ver foils, been used to bond Al2O3-fiber-rein-
the 7005-matrix composite and can be
forced 6061 aluminum alloy. This produced
reduced if shorter wetting times are used.
bonds of higher strengths than bonds made
• The flowability of filler metal into a capillary
using similar procedures but without interlayers
gap in real MMC joints (T or single-overlap
(Ref 180, 185).
joints) is appropriate in the case of 10 vol%
The vacuum brazing of aluminum-boron
reinforced alloys but is limited when
composites involves temperatures of 520 to 620
6061/Al2O3/20p is brazed, because of its low
°C (970 to 1150 °F), and because of this, it is nec-
spread behavior.
essary to protect the boron filaments by covering
• When proper joint filling is obtained, the
them with SiC to prevent aluminum-boron inter-
mechanical strength is controlled by the filler
action and reduction of joint properties (Ref
metal alone. Maximum shear strengths greater
186). Vacuum brazing of aluminum-Borsic
than 90% of the nominal BAlSi4 filler metal
composites (Borsic being boron fibers coated
alone have been reached for the brazed 10%
with SiC for protection) has led to the develop-
particle-reinforced composites, which are
ment of a hybrid titanium-clad aluminum-Borsic
close to 50% of their strengths in the T6 con-
composite. The titanium foil acts as a diffusion
dition.
barrier to prevent fiber-matrix degradation dur-
Using copper and silver as interlayers, pure ing brazing (Ref 187). Using either ER4047 (Al-
Al-20%SiCp and 6061-20%SiCp produced suc- 10–13%Si) filler metal or 250 µm 718 aluminum
cessful bonds (Ref 176). filler-metal foil, titanium-clad aluminum-Borsic
unidirectional composite sheets have displayed paratively high alloy content does not appar-
longitudinal and transverse tensile strengths 0.9 ently compromise the ability of titanium to be
and 2.5 times, respectively, those of the unclad- joined by this process.
aluminum-Borsic MMCs (Ref 187). Joining of titanium aluminide, TiAl, by a
Aluminides. Trial tests have demonstrated rapid infrared processing technique has been
that it is feasible to join the various titanium alu- investigated at 1150 °C (2100 °F) using a tita-
minides, which are ordered intermetallic alloys nium filler metal (Ti-15Ni-15Cu, wt%). The
that are arousing considerable interest in the effects and results of joining and post-annealing
aerospace industry for use in gas turbine on the microstructure and strength of the joint
engines and high-performance military air- show that the joint shear strength is 220 MPa
frames. (32 ksi) when processed at 1150 °C (2100 °F)
Like most materials of this type (ordered in- for 20 s and postannealed at 900 °C (1650 °F)
termetallic alloys), they are very brittle at ambi- for 2 h. Microstructural examinations of the
ent temperature, although they exhibit good hot joint with both optical microscope and scanning
ductility. Intermetallic alloys generally have electron microscope indicate that good wetting
high strength and modulus, which are retained exists between the filler metal and TiAl for most
to very high temperatures, and often have good joints. The braze-affected zone thickness shows
resistance to oxidation at elevated temperatures little increase with joining time and does not
too. show a direct correlation with joint strength.
There has recently been much effort to Meanwhile, the base material exhibits no
improve the low-temperature ductility of these noticeable microstructural or mechanical prop-
materials by suitable alloying as well as to erty changes as a result of infrared processing
develop improved high-temperature mechanical (Ref 188).
properties and oxidation resistance. This work Brazing of NiAl alloys was conducted in a
has reached the point where two types of tita- two-step operation in a vacuum chamber. In the
nium-aluminide-base alloys can be seriously first step, specimens were heated to 1520 °C
considered for use in aerospace applications. (2770 °F) and held for 5 min. Due to local evap-
The two alloy systems of immediate interest oration of aluminum, a thin layer of self-gener-
are based on the intermetallic compounds Ti3Al ated filler metal forms on the faying surfaces,
(α2 aluminides) and TiAl (γ aluminides). producing a glazed appearance. The resultant
The α2 alloys are made more ductile by alloy- nickel-rich alloy had a melting point below
ing with β stabilizers, such as niobium, molyb- 1520 °C (2770 °F), and far below that of the
denum, or vanadium, which improve the num- NiAl base metal (1638 °C, or 2980 °F). In the
ber of slip systems, refine the microstructure, second step, the glazed faying surfaces were
and permit a small amount of β phase to be placed in contact and brazed by heating at 1520
retained at low temperatures. Unfortunately, °C (2770 °F) for 15 min. Sound joints have been
this is at the expense of the density of the alloy. produced with grain growth across the braze
The key to joining lies in controlling the phase interface. Therefore, at the completion of the
transformation from the high-temperature β to brazing process, the joint is not detectable by
the α2 phase.
The TiAl-base γ alloys are less well devel-
oped than the α2 alloys, but their potential is
greater because of their lower density and im-
proved high-temperature performance. Again,
β-stabilizing elements are added to improve the
ductility, and the alloys are usually designed to
give a predominantly γ microstructure, contain-
ing laths of α2.
The Welding Institute has been very active in
developing joining techniques for both α2 and γ
alloys. Figure 4.18 shows a diffusion bond in an
α2 alloy, from which it can be seen that a good- 50µ
quality bond could be obtained at a temperature

below the β transus, thus avoiding the compli-
cations of the β-to-α2 transformation. The com- Fig. 4.18 A diffusion bond in Ti-24Al-11Nb alloy
metallography. Some homogenization is pro- nese sulfide, and when wetting large surface
duced during brazing. A separate postbraze heat areas to be joined. It has also been determined
treatment may be required for complete chemi- that high CO2 percentages in the sintering
cal homogenization. atmosphere can oxidize the fluxing agents and
No foreign material (in the form of filler met- reduce the flowability of the filler metal.
als, fluxes, or any other substance) is added to By far, the most common difficulty experi-
the base metal. The mechanical properties of the enced with furnace brazing P/M components is
joint are expected to match the base metal. This the lack of filler metal in the joint. This is gen-
concept may be applicable to other material sys- erally associated with the following conditions:
tems in which one element can be evaporated
from the surface to produce a layer of material • Improper cleaning or oxide reduction
with a lower melting point than the base metal • Excessive joint clearance
(Ref 189). • Low sintering temperature or nonuniform
Powder Metallurgy (P/M) Materials. The part temperature
most often used P/M filler metal is a patented • Insufficient filler metal
Cu-Mn-Ni-Fe powder that can be admixed with • Entrapped lubricant, flux, or gases
flux and a lubricant for preforming into • Movement of the mating parts before solidifi-
slugs/rings or dispensed as a paste (Ref 190). cation
This material is suitable for use with iron, steel,
low-alloy, or stainless P/M components. Typi- Graphite. The joining problems associated
cally, 3 to 4 g (0.1 to 0.14 oz) of filler metal is with brazing of graphite are very similar to those
required for each square inch of surface area to encountered in brazing the ceramic materials
be joined. The quantity is dependent on joint previously discussed (Ref 191, 192). Wetting of
design, joint clearance, and component density. graphite is more difficult than wetting of metals,
Closer joint clearance and higher component and the differences in coefficients of thermal
density favor lower amounts. Some applications expansion between graphite and conventional
requiring specific properties may require the use structural materials are pronounced. It should be
of a silver-or nickel-base filler metal for electri- noted that carbon and graphite can also be brazed
cal, high-temperature, or corrosive environ- both to themselves and to metals. These materi-
ments. als vary widely in degree of crystallinity, in
Uniform heating of the components along degree of orientation of the crystals, and in size,
with sufficient dwell time, to equalize the tem- quantity, and distribution of porosity in the
perature between the parts to be joined, is microstructure. These factors are strongly de-
important for proper flow and joint fill. A com- pendent on the starting materials and on process-
ponent having a lower mass or thinner section ing and, in turn, they govern the physical and
size likely achieves the flow temperature before mechanical properties of this product.
a larger mating part. This results in a greater Carbons and graphites can be manufactured
capillary force toward the area having the high- by several processes that yield materials with a
est temperature or heat energy and may cause wide range of crystalline perfection and proper-
poor joint fill. If this does occur, it is sometimes ties. In the most widely used process, polycrys-
helpful to reposition the components on the fur- talline graphites are made from cokes produced
nace belt to assist in achieving uniform temper- as by-products from the manufacture of petro-
ature between the parts. It may also help to leum or from natural pitch sources (Ref 193).
increase the preheat temperature, so parts can The wetting characteristics of all the carbons
equalize before reaching the liquidus point. For and graphites are strongly influenced by impuri-
Ancorbraze 72, that is approximately 1065.6 °C ties, such as oxygen or water, that are either
(1950.1 °F). absorbed on the surface or absorbed in the bulk
Most of the commonly used sintering atmos- material. Moisture absorption always occurs to
pheres can be used for P/M brazing. To assist in some extent, with levels as high as 0.25 wt%.
oxide reduction, a flux is generally added to the Brazeability also depends on the size and distri-
filler metal. In some circumstances, an addi- bution of pores, which can vary significantly
tional borate or fluoride-type flux may be from one grade to another.
swabbed onto the mating surfaces, particularly A major consideration in brazing of carbon
when brazing sintered parts, stainless steels and graphite is the effect of the coefficient of
grades, materials containing sulfur or manga- thermal expansion of these materials, which can
range from 2 to 8 × 10–6/°C (1 to 4 × 10–6/°F) ments. They include 48Ti-48Zr-4Be, 35Au-

between 25 and 1000 °C (75 and 1830 °F). 35Ni-30Mo, 70Au-20Ni-10Ta, nickel-clad tita-
Before carbon or graphite is brazed, the type nium, 54Ti-21V-25Cr, 43Ti-42Zr-15Ge, and
and grade of the material must be established so 47Ti-48Zr-5Nb (Ref 192). Additionally, the
as to ascertain its expansion characteristics. filler metal 49Ti-49Cu-2Be has been recom-
This information is also important for brazing of mended for brazing of graphite as well as oxide
carbon or graphite to itself. Joint failure, partic- ceramics. The filler metals mentioned previ-
ularly during thermal cycling, may occur if too ously wet graphite and most metals well in either
great a difference exists between the coeffi- a vacuum or inert atmosphere (pure argon or
cients of thermal expansion of the graphite and helium) and span a fairly wide range in brazing
the filler metal. temperatures, from 1000 °C (1830 °F) for 49Ti-
If the joint gap increases significantly on 49Cu-2Be to 1350 °C (2460 °F) for 35Au-35Ni-
heating because of a large mismatch in coeffi- 30Mo (Ref 193, 194).
cient, the filler metal may not be drawn into the At least two commercially available filler
joint by capillary flow. On the other hand, if the metals wet carbon and graphite as well as a num-
materials and joint design cause the gap to ber of metals. The first has a composition of
become too small, the filler metal may not be 68.8Ag-26.7Cu-4.5Ti, a solidus of 830 °C (1525
able to penetrate the joint. In conventional braz- °F), and a liquidus of 850 °C (1560 °F). This
ing of dissimilar materials, the material having filler metal is suitable for low-to-medium-tem-
the greater coefficient of expansion is made the perature applications but appears to have only
outer member of the joint. Joint tolerances are moderate oxidation resistance. The second com-
used that do not allow the gap between the sur- mercially available filler metal for graphite braz-
faces to become too great for capillary flow. ing has a composition of 70Ti-15Cu-15Ni. With
Additional problems occur in brazing of dis- a somewhat higher melting range (solidus, 910
similar materials when one part of the joint is a °C, or 1670 °F; liquidus, 960 °C, or 1760 °F), and
carbon or graphite. Carbons and graphites have by virtue of its greater titanium content, it has
little or no ductility and are relatively weak better oxidation resistance than the silver-base
under tensile loading. These adverse conditions filler metal. Some workers in Europe and the for-
are usually compensated for in graphite-to- mer countries of the Soviet Union have reported
metal joints by brazing the graphite to a transi- successful joining of graphite to steel using a
tion piece of a metal, such as molybdenum, tan- filler metal with a composition of 80Cu-10Ti-
talum, or zirconium, with a coefficient of 10Sn at 1150 °C (2100 °F) (Ref 195). In other
expansion near that of the graphite. This transi- work, using a technique called diffusion brazing,
tion piece can be subsequently brazed to a struc- a metallic interlayer was placed between the
tural metal if required. This minimizes shear graphite components; the components were
cracking in the graphite by transposing the pressed together at a specific pressure and heated
stresses resulting from the large difference in to the temperature of formation of a carbon-bear-
thermal expansion to the metallic components. ing melt or eutectic. On heating to higher tem-
Thin sections of metals that deform easily when peratures, the melt dissociated with the precipi-
stressed, such as copper or nickel, have also tation of finely divided crystalline deposits of
been successfully used for brazing dissimilar carbon that interacted with graphite base mate-
metals. rial to form a strong joint (Ref 196, 197).
Metals that have strong tendencies to form Researchers (Ref 198) have developed a pro-
carbides (titanium, zirconium, silicon, chromi- cedure for brazing a special grade of graphite to
um) have been found to wet graphite when they a ferritic stainless steel for a seal in a rotary heat
are molten. A commercial filler metal frequently exchanger. It seems apparent that the selection
used for brazing of graphite is silver-copper-clad of type 430 stainless steel was based at least
titanium wire. Graphite is also readily wetted by partly on its lower coefficient of thermal expan-
molybdenum disilicide, titanium, and zirco- sion compared with that of a typical austenitic
nium. In recent years, the requirements of the stainless steel. In addition, a joint geometry was
aerospace and nuclear industries have resulted in developed that minimized the area of the brazed
the development of several additional filler met- joint, thereby reducing thermally induced
als. In general, these filler metals incorporate stresses to acceptable levels. Specimens of
substantial quantities of carbide-forming ele- graphite brazed in a vacuum furnace to thin type
430 stainless steel sheet with either Ni-20Cr- forms an intimate bond. In some cases, the tita-
10Si or Ni-18Cr-8Si-9Ti filler metal at 1125 to nium or zirconium is merely painted on the
1175 °C (2060 to 2150 °F) performed well in ceramic surface and placed in contact with a
tests at 650 °C (1200 °F). suitable filler metal and the base metal to which
the ceramic is to be joined. This process has an
Special Ceramic Joining advantage over some others in that only one fir-
Methods (Coatings) ing operation is required.
The affinity of reactive and refractory metals
Ceramic and Ceramic-Metal Joining for ceramics is also the basis for the direct braz-
Methods. It is difficult to form joints by brazing approach. In this case, active metals are
ing ceramics and/or ceramics-to-metals, partic- incorporated as one or more of the constituents
ularly oxide ceramics, because few commer- in the filler metal, which is placed at the joint as
cially available filler metals can wet their in conventional brazing. An interesting means
surfaces. This problem is usually overcome by of promoting flow of the filler metal involves
treating the ceramic surfaces to give them vapor-deposited coatings of titanium, zirco-
metallic-wettable characteristics. For example, nium, or other metals on the ceramic substrate.
metal coatings can be applied by vapor deposi- Electron beam heating has provided a unique
tion or sputter ion plating. However, the most means for producing the metal vapor (Ref 96,
widely used metallization process for oxide 199–201).
ceramics is that in which mixtures of a glassy Active metal brazing (ABA) has been prac-
phase and a refractory metal are applied as paint ticed since the 1940s, when titanium hydroxide
by brushing or screen printing, as exemplified in an organic solvent was coated onto ceramic
by the moly-manganese process. The prime pur- seals that were then sandwiched around a silver
pose of the glassy phase is to bond the refractory (or gold or copper) filler metal and brazed
metal to the ceramic oxide, while that of the together in vacuum. The trouble was that under
refractory metal is to render the surface high vacuum, the excess titanium in the filler
amenable to electroplating and ultimately, braz- metal formed a brittle joint, while under low
ing to make a joint. vacuum, most of the titanium formed brittle
Metallization of oxide ceramics followed by oxides and nitrides, and little was left for the
plating and brazing has been established for actual active brazing.
several decades. Therefore, the problems One way around the problem was to clad tita-
involved in its application are those of practice nium wire or foil with a filler metal. While that
rather than principle. protects the titanium from the furnace atmos-
Several other techniques for joining ceramics phere until the filler metal starts to melt so that
have been reported in the literature (Ref 97, more titanium is available for brazing, the filler
113). The sintered metal powder technique is a metal itself is not ductile enough to yield to
widely used brazing method. This process stresses caused by the different rates of thermal
requires several steps to produce a joint: expansion for the ceramic and metal.
Filler-metal manufacturers attacked the prob-
• The firing of metal powder held in suspension lem by developing a series of filler metals con-
on the ceramic sisting of Cu-Ag-Ti and Cu-Ag-In-Ti. Similar
• Plating or deposition of a thin copper or to cladding, alloying protects the active ele-
nickel film ments (titanium) until the filler metal starts to
• Brazing by conventional methods to make melt. Because the titanium is protected, less is
the ceramic-to-metal joint needed (1.25 to 2.0 wt%), and the resulting
braze is less hard and ductile enough to form
The affinity of titanium and zirconium for strong, reliable ceramic-to-ceramic and cera-
ceramics is the principle behind the active-alloy mic-to-metal hermetic bonds without prior met-
process. Highly active titanium or zirconium allization (Table 4.20, Fig. 4.15) (Ref 98, 101,
can be made available at the ceramic-metal 102, 147, 150, 202–205).
interface by hydride decomposition of a powder The system works best when the ceramic sur-
slurry on the ceramic surface. The reaction of face is free of surface fractures. Researchers
the titanium or zirconium with the ceramic, or found it took more than twice as much energy to
with additional metals placed at the interface, peel apart an Fe-Ni-Co (Kovar) strip brazed to a
lapped ceramic surface as from a ground strength of between 40 and 100 MPa (6 and 15
ceramic surface. Joint strength for Al2O3 ksi). In cases where high-temperature-resistant
ceramic has been shown to be equal whether metals, such as tungsten or niobium, are
prepared and joined by the molybdenum-man- involved, their thermal resistance depends on
ganese braze system or the ABA system (Fig. the behavior of the filler metal used.
4.18) (Ref 101, 203–206). The steps seen in Fig. 4.19 initially start as a
A unique ceramic-to-metal seal system was primary metallizing layer, which is the mixture
developed (Ref 200) based on a composite of refractory metal and glass that is coated onto
Al2O3 insulator and a 49%Ti-49%Cu-2%Be the surface of the ceramic. The most commonly
filler metal. Pulsed laser beam, furnace, and used material is a “paint” containing molybde-
induction joining techniques were all successful num and manganese. An alternative choice of
in brazing the sensor electrodes, ceramic insula- refractory metal is tungsten, which is used when
tor, and end seals in a number of brazing gold is to be plated onto the surface without an
sequences and operations. intermediate layer of nickel.
Pure metal coatings have also been evaluated. The paint is an intimate blend of a refractory
A niobium coating film has been electrolytically metal (tungsten or molybdenum), manganese
precipitated at a temperature of approximately oxide when the metal is molybdenum, a glass
740 °C (1365 °F) out of a fluoride melt onto sin- frit, a carrying vehicle, and a solvent. Typical
tered Al2O3. A thin film of niobium produced by formulations are given in Ref 204, 207, and 208.
gas phase precipitation provided the electrical In achieving the best possible metallizing, many
conductivity of the surface that is essential for parameters need to be considered, of which the
electrolysis. Metallizing coatings can also be most important are the application method and
created completely by means of gas phase pre- the process parameters, particularly the temper-
cipitation, for example, by the thermal dissocia- ature, time, atmospheric conditions, and the
tion of halides or organic metal compounds thickness of the paint.
(chemical vapor deposition). Tungsten coatings, There are several ways of applying the paint
for example, can be produced from WCl6 in a to the ceramic, ranging from simple manual dip-
helium atmosphere at a temperature of approxi- ping to fully automated machines. Among the
mately 1000 to 1300 °C (1830 to 2370 °F). more popular methods are spraying, screen
Brazed joints on this type of metal coating printing, syringe or nozzle brushing, and trans-
have created high-vacuum seals; at ambient fer using a wheel or tape. The application
temperature, they have a transverse tensile method chosen is largely determined by the
Fig. 4.19 Comparison of two methods (metallizing/brazing and active brazing) for joining Kovar to Al2O3. Source: Ref 9
shape of the article, the complexity of the met- quire SiO2 from the ceramic in order to create a
allizing pattern, and the quantity or quality bonding phase, the former method permits
desired. No matter which method is chosen, it is strongly bonded metallization of very pure
essential to ensure that the paint layer is of the Al2O3 ceramics (99.8% Al2O3) and other
correct thickness, usually at least 5 times the ceramic oxide materials such as ZrO2 (Ref 148).
molybdenum or tungsten particle size, which is Considerable success is being achieved at
commonly approximately 5 µm. The thickness present in the application of reactive metal braz-
achieved in practice depends on both the paint ing (Ref 210). The next few years, however,
and the method of application. One of the most could see a considerable expansion in the mar-
important paint characteristics is its viscosity. ket for reactive metal brazes if their perfor-
Paint thicknesses of less than 5 µm can result mance and associated fabrication procedures
in braze penetration during subsequent assem- are optimized. Current filler metals for ceramics
bly operations, while thicknesses greater than employ titanium as their reactive component,
5 µm may cause cracks or blisters during drying but it should be possible and perhaps technically
that may result in leaks or peeling of the metal- preferable to use other reagents for some appli-
lizing. cations. Thus, the capability of titanium to form
During the firing cycle, the metallizing paint intermetallic compounds with many workpiece
undergoes many changes. At an early stage, metals can be detrimental, and replacement by
there is decomposition and elimination of or- other multivalent metals, such as chromium,
ganic materials in the paint. Later, and even that can form ceramic reaction products with
more importantly, there is sintering of the refrac- wide ranges of stoichiometry could be advanta-
tory metal particles and diffusion of the glassy geous—although substantial development work
phase from the paint onto and into the ceramic, will be required to optimize and produce the
or vice versa. new filler metals in commercially usable forms.
The bonding between the ceramic and the Improving the usability of existing filler metals
metallizing layer is produced by diffusion of a is also of importance, and developments could
glassy phase from the paint, in the case of high- come from the application of the rapid solidifi-
purity ceramics, or by diffusion of glassy binder cation technique to brittle alloys to produce the
phase from the ceramic into glass-free paint on thin sheets needed for stamping out preforms.
the surface of a debased ceramic. Of equal importance with the development of
The most commonly used filler metals do not materials are the production of joint design
wet the surface of the primary metallizing lay- codes and the acquisition of engineering per-
ers. To achieve wetting, a secondary metallizing formance data. These, combined with the tailor-
layer of a metal, such as nickel, copper, gold, ing of filler metals for use with specific materi-
tin, or lead, is deposited by plating (electrolytic als, should enhance the acceptability of brazing
or electroless). The plating operation con- as a joining process for ceramics and make it
tributes as much to the success or failure of the possible to exploit it more efficiently in ad-
metallizing structure as the primary layer. The vanced engineering projects (Ref 211).
process must be controlled throughout. Finally, aluminum nitride (AlN) is currently
The roles of the plated layer are to aid wetting under investigation as a potential candidate for
of the refractory metal by the filler metal and to replacing Al2O3 as a substrate material for elec-
resist braze penetration into the primary layer. tronic circuit packaging. The requirements for
One key parameter that affects both these roles such a material are that it can be metallized and
is the thickness of the plated layer. If it is too joined to produce hermetic enclosures for semi-
thin, the filler metal may dissolve it, but if it is conductor devices as well as its coupling with
too thick, blisters can form during the braze its expansion matching that of silicon. A tech-
process that lead to very poor adherence and nique for brazing AlN using a nonactive filler
leaks. In general, a plating thickness of 2 to 4 metal has been developed.
µm is sufficient to avoid such problems. The study found that active filler metals,
This molybdenum-manganese-silicate coat- namely titanium, wet the AlN, whereas nonac-
ing (Ref 148) is a particular coating that enables tive ones are nonwetting. This method has been
joints having a transverse tensile strength of used to successfully join AlN to a low-expan-
between 70 and 120 MPa (10 and 17 ksi) to be sion lead-frame alloy.
effective. In contrast to the conventional molyb- The interfacial reactions led to the formation
denum-manganese processes (Ref 209) that re- of titanium and zirconium nitrides, and these
interfacial reactions enable the ceramic surface temperature. For example, when brazing a
to be wet by the molten filler metal in the devel- molybdenum plug in a copper block, the parts
opment of AlN packages for microcircuit appli- must press fit at room temperature; if a copper
cations (Ref 211). plug is to be brazed in a molybdenum block, a
The characteristics of the molybdenum- properly centered loose fit at room temperature
manganese, active metal, and active hydride is required.
processes are summarized in the following: In brazing tube-and-socket-type joints
between dissimilar base metals, the tube should
• The molybdenum-managanese process is a be the low-expansion metal and the socket the
multistep sealing process in which the high-expansion metal. At brazing temperature,
ceramic surface is metallized and plated with the clearance is maximum, and the capillary fills
one or two metals before brazing can take with filler metal. When the joint cools to room
place. The operations are conducted at a high temperature, the brazed joint and the tube are in
temperature in a controlled atmosphere of H2; compression.
H2 firing may discolor some ceramics and For a tongue-in-groove joint, one should
produce conductive surfaces. Despite the place the groove in the low-expansion material.
number of steps required to produce a seal, The fit at room temperature should be designed
the moly-manganese process can be auto- to give capillary joint clearances on both sides
mated quite readily, and minor deviations in of the tongue at brazing temperature.
the process variables can be tolerated (Ref 96, As noted previously, the joining of dissimilar
101, 212). metals has become increasingly important dur-
• The active hydride process is essentially a ing the past two decades because of the service
single-step process in which hydride reduc- requirements for structures used in missiles and
tion and brazing proceed simultaneously. rockets, supersonic aircraft, nuclear equipment,
Joining in a vacuum or in a controlled atmos- marine systems, electronics, and chemical-pro-
phere of H2 or an inert gas is accomplished at cessing equipment. Although certain dissimilar
relatively low temperatures, permitting a fast metals have been routinely joined for many
brazing cycle. This process is more difficult years, the advent of space and nuclear require-
to automate than the moly-manganese ments has produced a need for sophisticated
process, particularly if the joints are produced methods of joining the new structural materials
in a vacuum. Careful control must be exer- that have been developed for these demanding
cised in coating the ceramic with the hydride. applications. These new alloys possess excep-
Even though the process is considered a one- tional mechanical properties and resistance to
step process, the hydride process has been corrosive media under extreme operating condi-
supplanted by the active metal process. tions. However, such alloys are frequently used
• The active metal process may be a one-step only for sections of a structure where their spe-
operation similar to the active hydride cific properties are required; conventional
process. Joining proceeds at high tempera- alloys are used for the remainder of the structure
tures in a vacuum or in a controlled atmos- for reasons of economy, weight, ease of fabrica-
phere; vacuum joining is not readily auto- tion, and so on. Thus, there is a need for proce-
mated. dures for producing reliable joints between dis-
similar metals. The ability to design and
fabricate such joints is essential to many seg-
Dissimilar-Material Combinations ments of our industrial economy.
Many dissimilar-metal combinations may be The selection and use of dissimilar metals in
brazed, even those with metallurgical incompat- structural applications is governed by the ser-
ibility that precludes welding. vice requirements of the structure and by mate-
Important criteria to be considered start with rial and fabrication costs. For example, a rela-
differences in thermal expansion. If a metal with tively inexpensive grade of steel may be used in
high thermal expansion surrounds a low-expan- fabricating the shell of a vessel for the chemical
sion metal, clearances at room temperature, industry for reasons of economy, whereas the
which are satisfactory for capillary flow, are too corrosion requirements are satisfied by lining
great at brazing temperature. Conversely, if a the vessel with thin-gage tantalum or titanium.
low-expansion metal surrounds a high-expan- Corrosion of a dissimilar-metal joint is
sion metal, no clearance may exist at brazing inevitable if there is an electrolyte present. The
degree of corrosion that takes place is depen- special properties—such as oxidation resis-
dent on the type of electrolyte and the difference tance, corrosion resistance, and so on—pro-
in electromotive potential between the dissimi- vided by nonferrous metals. Joining of ferrous
lar metals and/or materials. to nonferrous metals is far more complicated
The problem of galvanic corrosion between than joining of dissimilar ferrous metals
dissimilar metals has been discussed (Ref 213). because of the wider variation in the physical,
The magnitudes of the solution potentials of mechanical, and metallurgical properties of the
metals and intermediate compounds depend on metals being joined. The extent of these prop-
the nature of the electrolyte and the difference in erty differences is an excellent indication of the
potential between the alloys being joined. difficulty to be anticipated in joining such met-
Applications requiring the joining of dissimi- als (Ref 215–218).
lar metals are discussed briefly: In brazing steel to copper, the steel heats
much more rapidly than the copper, unless pro-
• The lunar module contains 26 pressure ves- vision is made to equalize the heating rates. In
sels in its descent and ascent stages (Ref 214). the practice of induction brazing, the inductor is
Depending on their functions, these vessels coupled more closely to the copper than to the
are fabricated from various alloys plus tita- steel or has additional turns to that portion of the
nium. Coextruded titanium/stainless steel inductor heating the copper. Similar provision
transition joints are used to connect the tita- must be made in brazing carbon steel to brass or
nium pressure vessels to the stainless steel austenitic (nonmagnetic) stainless steel. Carbon
feed system. steel heats faster than either of these materials,
• Joints between beryllium and such metals as although the differential in heating rates is less
aluminum, stainless steel, and titanium are than that between carbon steel and copper.
encountered in space-vehicle design, where The problems inherent in joining dissimilar
beryllium is an attractive structural metal nonferrous metals are similar to those encoun-
because of its low density, its stiffness under tered when ferrous and nonferrous metals are
load, its resistance to damage by impact with joined, because of the differences in the physi-
meteors, and its high heat capacity. cal and metallurgical properties of the base met-
• Procedures are required for joining dissimilar als. Some dissimilar nonferrous metals have
metals in nuclear reactor construction. These been joined routinely for many years; others,
applications range from the cladding of fuel such as aluminum to titanium, titanium to
elements with zirconium alloys to fabrication nickel, titanium to Al2O3, and aluminum to ura-
of dissimilar-metal piping joints. nium, are new combinations that owe their exis-
• Dissimilar-metal joints are encountered in tence to their applications in aerospace, elec-
aircraft hydraulic and ducting systems as well tronic, and nuclear hardware (Ref 9, 15).
as in engine and airframe construction. Be- Brazing and metallizing of ceramics to form
cause significant quantities of titanium alloys joints with metals find many uses, especially in
are used in new aircraft, there are occasions small-scale and electronic applications, for
to join titanium to other structural alloys to example, Al2O3 to Fe-Ni-Co alloy for vacuum-
meet specific design requirements (Ref 212). tube production. The molybdenum or molybde-
num-manganese metallization layer is painted
In general, dissimilar metals are used in struc- onto a ceramic, allowing a subsequent braze
tures to provide: layer to wet. Brazing temperatures are high,
with 1580 °C (2875 °F) being typical. At this
• High-temperature or low-temperature temperature, the glassy phase in Al2O3 begins to
strength mix with the metallizing mixture of semisin-
• Resistance to oxidation, corrosion, or wear tered molybdenum or molybdenum-manganese.
• Resistance to radiation damage The literature discloses several theories relating
• Other required properties to this mechanism, including capillary action
(Ref 101, 219–221).
Also, the use of dissimilar metals is often Metal-to-Metal Joining with Coatings. A
attractive from the standpoint of cost. study was conducted (Ref 222) of the brazeabil-
Joints between ferrous and nonferrous metals ity of nickel-base filler-metal foil for joining
are of interest to industry because they combine nickel base metal to mild steel base metal. Alloy
the strength and toughness of steels with the 600 was selected, which was clad to a mild steel
base metal, SM41B. Four different nickel filler At 1050 °C, the shear strength of the specimen
metals in foil form were tested. was not influenced by brazing time. In this case,
These foils were BNi-3, Ni-Si-B, BNi-1, and the break of the specimen during the shear test
BNi-2. The brazeability of these filler metals occurred in the brazed layer. At 1250 °C (2280
was determined by the shear strength, the obser- °F), the value of 450 MPa (65 ksi) was obtained
vation of the cross-sectional microstructure, the as the maximum shear strength in this study; the
hardness distribution, and the elemental distri- break of the specimen occurred in the base
bution. The following results were obtained: metal.
The shear strength of the specimen increased
• The shear strength of the specimens made with increasing brazing temperature and with
with BNi-1 and BNi-2 filler-metal foils con- increasing chromium content in the filler-metal
taining chromium and iron was higher than foil to 7 mass%.
clad specimens made with BNi-3 and Ni-Si- Researchers (Ref 224) developed a new
B filler-metal foils. Under all brazing condi- method of brazing aluminum to austenitic stain-
tions, the location of the failure during the less steel, involving squeeze casting, that has
shear test occurred in the brazed joint. If the been named cast brazing. Without melt flow
eutectic structure remained in the brazed control, strengths exceeding 40 MPa (5.8 ksi)
joint, the break occurred in the eutectic struc- were achieved for the aluminum/stainless steel
ture. The shear strength was increased by joint. The presence of a porous sintered layer on
decreasing the amount of cross-sectional area the bond face of the stainless steel increased the
of the eutectic structure at the brazed joint. strength of the joint to ~70 MPa (10 ksi). By
The shear strength was increased to maxi- controlling the flow of aluminum filler metal
mum by increasing the diffusion brazing during casting, the formation of an intermetallic
time, which eliminated the eutectic structure reaction layer at the interface was effectively
in the brazed joint. suppressed, and the strength of the brazed inter-
• Brazing temperatures were 1050, 1100, and face was increased to a value exceeding the
1150 °C (1920, 2010, and 2100 °F). Brazing strength of the aluminum. On brazing aluminum
times were 10, 20, 30, and 60 min for each to aluminum with a preliminary nickel coating
type of foil. on the surfaces to be joined, interfacial strengths
• The maximum shear strength observed on exceeding 50 MPa (7.3 ksi) were attained.
this type of specimen was approximately 310 Before fracture, this type of joint exhibited an
MPa (45 ksi) for each of the four filler metals elongation of up to 10%.
tested. The elemental distributions of nickel, Researchers (Ref 225) furnace brazed
chromium, and boron were concentrated in X2CrNi18/9 stainless steel/aluminum joints at
the eutectic structure. It appears that the 600 °C (1110 °F) using an aluminum-silicon
migration of boron influenced the reduction eutectic filler metal and found that the interfa-
of the eutectic structure. cial zone between the aluminum-rich braze joint
• With the BNi-3 filler metal, the eutectic struc- and the stainless steel substrate features two
ture was formed in the first minutes of braz- intermetallic layers. The first is formed in the
ing. As time at the brazing temperature was first instants of the process and has an overall
increased, boron diffused into the base metal, composition roughly similar to that of the com-
resulting in the elimination of the eutectic pound FeSiAl5. The second appears after a 10
structure. Chromium and/or iron diffuses min hold at the brazing temperature and features
from the base metal into the brazed joint, thus an overall composition that parallels the FeAl3
assisting in increasing the joint strength with intermetallic. Both layers are more complex in
added time at brazing temperature. structure than is suggested by these stochiomet-
ric relations, featuring several phases and
In a similar study (Ref 223), the same microstructural gradients. Both layers grow
researchers evaluated Inconel 600 and SUS 304 after the first 10 min of the brazing cycle, in
stainless steel with the same filler-metal foils. accordance with the parabolic rate law. By com-
The brazed joint was obtained for all of the parison with published data gathered on 1100
brazing conditions in this study. The shear aluminum/304 stainless steel solid-state diffu-
strength of the specimen increased with increas- sion couples, it would appear that formation of
ing brazing time, except at 1050 °C (1920 °F). the second (iron-aluminum) layer is delayed by
the presence of silicon in the braze, and that the characterization of these compounds should
rate of layer growth is controlled by diffusion extend into the immediate base metal next to
through this second (iron-aluminum) layer once the filler metal.
it has formed. • Not all intermetallics are necessarily hard and
The shear strength of the bonds peaks at 21 detrimental to the properties of the joint. For
MPa (3 ksi) after a 10 min hold time at the braz- example, Ti2Cu was present in the filler metal
ing temperature. This peak is associated with but did not deteriorate the mechanical proper-
growth of the second intermetallic layer into a ties of the brazed joints.
continuous layer, which is thus shown to make • To design an optimal filler metal, the extent
the joint significantly fragile. of diffusion of alloying elements in the base
A practical implication of this work is that metal and in the filler metal, the kinetics of
strong joints between stainless steel and alu- intermetallic compounds formation, and the
minum via furnace brazing can be produced mechanical and physical properties of the
using a eutectic aluminum-silicon filler metal, intermetallic compounds must be considered.
provided brazing times are kept sufficiently
short to avoid formation of the second, more Researchers (Ref 227, 228) have conducted a
fragile (iron-aluminum) intermetallic layer. At a variety of investigations joining Inconel 625,
brazing temperature of 600 °C (1110 °F), braz- AISI 316L, and AISI 4130 low-alloy steel to
ing times should remain less than approxi- commercially pure titanium and titanium 6242
mately 10 min. Care and process control are alloy (Ti-6Al-2Mo-4Cr-2Mn) by diffusion
thus required for success in the process; how- bonding.
ever, it should be noted that 10 min represent a Encouraging results were obtained by joining
sufficient time window for viable industrial Nb-1Zn/Inconel 718 where joints that were
application of the furnace brazing process to pressure brazed using nickel-base metallic-
join aluminum with stainless steel. glass foil had shown the most promise (Ref
Several titanium and/or titanium alloys 229). Direct-diffusion-welded joints and joints
brazed or diffusion bonded to various stainless diffusion welded with nickel and iron interlay-
steels in studies (Ref 226, 227) and develop- ers were judged to be unsuitable because of
ment programs have proven successful. cracking and porosity problems.
In one study (Ref 226), the following conclu- More brazing development studies will be
sions were made: required when the need is defined for a Nb-
1Zr/Inconel 718 joint of a specific size and
• Brazed joints are complex in nature and geometry. Items to be addressed would include
require detailed characterization to determine the composition of the metallic-glass filler
the distribution of alloying elements along metal, the effect of pressure on braze joint com-
the brazed joint and the intermetallics forma- position changes resulting from filler-metal
tion. expulsion, the effect of pressure on joint sound-
• Titanium/304 stainless steel brazed joints ness and diffusion kinetics, joint design, post-
using filler metal No. 1 (Ag-28wt%Cu) brazing heat treatment, and mechanical prop-
showed invariably better shear strength than erty determination.
the ones made using filler metal No. 2 (Ag- Graphite-, Composites-, Diamond-, Alu-
46wt%Cu). minides-to-Metals. Direct brazing of graphite
• To maximize shear strength of titanium/304 to metal has been successfully carried out by a
stainless steel brazed joints, the brazing time one-step brazing process using a copper-base
must be limited to a maximum of 15 min. active filler metal. Researchers (Ref 230) car-
• Increase in copper concentration resulted in ried out double-brazed shear tests to assess the
an increase in titanium content in the tita- shear strengths of the brazed joints. High shear
nium/304 stainless steel filler metal and strengths were obtained in all cases examined.
enhanced the formation of intermetallic com- The shear strength of the graphite-to-copper
pounds between titanium and 304 stainless joint was high (29 MPa, or 4.2 ksi). This high
steel. shear strength can be attributed to the fact that
• Intermetallic compounds are not limited to copper plastically deformed to accommodate
the filler metal. They can also form in the the residual stress caused by a large thermal
base metal next to the interface. As such, the expansion mismatch between the graphite and
copper. In the case of graphite-to-molybdenum, Researchers (Ref 231, 232) conducted an

where the thermal expansion mismatch is small, investigation into the transient liquid phase dif-
the shear stress was 8 MPa (1.2 ksi), which is fusion bonding (TLPDB) of continuous SiC-
lower than that for the graphite-to-copper joint. fiber-reinforced Ti-6Al-4V composite to Ti-
The accommodation by plastic deformation in 6Al-4V alloy. They concluded:
molybdenum is limited, due to its high yield
stress, resulting in high residual stress (Table • A Ti-Cu-Zr amorphous filler metal was used
4.26). in the bonding of Ti-6Al-4V/SiC composite
Heat radiators of a proposed type feature to Ti-6Al-4V alloy plate via the TLPDB
thermally conductive fibers protruding from process. A joint strength of 850 MPa (123
metallic surfaces to provide increased heat-dis- ksi) was obtained, and this value corre-
sipation surface areas. Originally intended for sponded to 90% of the tensile strength of Ti-
use in the vacuum of outer space, these radiators 6Al-4V.
may prove useful on earth in special industrial • Isothermal solidification was almost com-
and scientific applications that involve dissipa- pleted after 1.8 ks at the bonding temperature
tion of heat in vacuum or in relatively still air. of 1153 K. The bonding layer had a typical
Because these radiators do not rely on internally acicular microstructure composed of Ti2Cu
contained liquid or gaseous heat-exchange and α titanium with dissolved zirconium.
media, they are free of leaks and more reliable • Liquid phase diffusion bonding can reduce
than are radiators that incorporate heat pipes. bonding pressure in comparison with solid-
They are also lightweight and relatively inex- state diffusion bonding. The deformation
pensive. Figure 4.20 illustrates a radiator of the ratio of Ti-6Al-4V alloy necessary to obtain
proposed type, consisting of a spherical metal sufficient joint strength of 850 MPa (123 ksi)
shell covered with a sparse, brushlike array of for TLPDB was ~2%; contrarily, the defor-
graphite fibers extending perpendicularly from mation ratio necessary for solid-state diffu-
the surface. The shell surrounds the source of sion bonding was greater than 5%.
heat. The inner ends of the fibers are attached to • Brittle products such as (Ti,Zr)5Si3 or
the shell by solder joints. The fibers increase the (Ti,Zr)5Si4 were formed at the interface
effective radiative surface area to approxi- between fibers and the filler metal at 1153 K
mately 100 times that of a flat-plate radiator of for a bonding time of 3.6 ks. These products,
comparable size. Each fiber is paced approxi- however, did not affect joint strength,
mately 10 fiber diameters from its nearest because they were formed only at the end of
neighbors, so that shadowing of fibers by other fibers in very small amounts.
fibers is small, and there is ample solid angle for
each fiber to radiate directly to space. Researchers (Ref 233) performed brazing
Each fiber is metallized at one end so that it experiments at 750 °C (1380 °F) for 2 h between
may be soldered or brazed to the shell. The first Ag-Cu-In-Ti filler metal and SiCw/Al2O3. They
layer to be deposited in the metallization process found that the first clearly nonbraze layer con-
is one of silicon, which bonds to the graphite sisted of an oxide layer of metallic composition
fiber by forming SiC on its surface. Next, a layer 33Ti-31Al-22Cu-14Si. Areas adjacent to the
of copper containing a small amount of titanium SiC whiskers were of different composition. A
or zirconium is deposited to provide a solderable thin, continuous layer on the Al2O3 portion of
or brazeable surface. the composite appeared to be γ-TiO. The SiC
Table 4.26 Shear strengths of graphite brazed joints

Filler-metal Number Average shear Standard deviation,
Material thickness, µm of tests strength, MPa (ksi) MPa (ksi) Comment
Graphite-to-graphite 50 4 40.0 (5.8) 1.8 (0.26) ...

Graphite-to-molybdenum 50 4 6.1 (0.9) 1.4 (0.20) ...
100 4 8.0 (1.2) 1.4 (0.20) ...
Graphite-to-copper 50 4 28.6 (4.15) 1.5 (0.22) ...
100 2 28.6 (4.15) 1.0 (0.15) ...
Copper-to-copper 50 1 >40 (5.8) ... Specimen bent
Molybdenum-to-molybdenum 50 1 >138 (20) ... Testing machine capacity limit
whiskers were preferentially consumed and grits or peeling of the filler-metal layer took
underwent reductions in diameter of approxi- place.
mately 40%. Observed were knobby whisker Researchers (Ref 235) evaluated the diffu-
morphologies that may be related to SiC stack- sion brazing of NiAl, which is a promising can-
ing faults. The η-type phases detected near the didate material for high-temperature applica-
silver-copper eutectic portion of the joint tions. However, NiAl suffers from poor
appeared to consist of Ti-Cu-Al-Si-O and low-temperature ductility and toughness. Thus,
Ti3Cu3O. If accurate, this suggests that joint in many potential applications, NiAl has to be
strength may be partially controlled by the used locally, in combination with nickel-base
quantity and orientation of these faults. alloys, rather than to form entire components.
Researchers (Ref 234) fabricated a surface Hence, suitable technologies are required for
set of diamond tools by an active metal brazing NiAl-to-nickel-base-alloy joining. In view of
process, using bronze (Cu-8.9Sn) powder and the poor low-temperature ductility and strong
AISI 316L stainless steel powder mixed to var- Al2O3-forming tendency of NiAl, diffusion
ious ratios as the filler metals. The diamond brazing seems to be the most suitable technol-
grits were brazed onto a steel substrate at 1050 ogy for joining NiAl to itself and to nickel-base
°C (1920 °F) for 30 min in a dry hydrogen alloys.
atmosphere. After brazing practice, an interme- The authors examined the diffusion brazing
diate layer rich in chromium formed between of NiAl to nickel using Ni-Si-B interlayers and
the filler metal and diamond. A filler metal com- determined:
posed of 70 wt% bronze powder and 30 wt%
stainless steel powder was found to be optimal
• The progression of the diffusion brazing at
in that the diamond grits were strongly impreg-
the NiAl substrate side of the joints was not
nated in the filler metal by both mechanical and
incompatible with that predicted by standard
chemical types of holding. The diamond tools
diffusion brazing models. No qualitative
thus fabricated performed better than conven-
changes were found with respect to the two
tional nickel-plated diamond tools. In service,
brazing temperatures studied (1065 °C, or
the filler metal wore at almost the same rate as
1950 °F, and 1150 °C, or 2100 °F).
the diamond grits, and no pullout of diamond
• Marked deviations from conventional models
of the diffusion brazing process were
observed at the nickel side of the joints. A
prominent layer of borides was formed in the
substrate adjacent to the original solid-liquid
Radiated heat interface when the brazing temperature was
below the nickel-boron binary eutectic tem-
perature. When the brazing temperature was
taken above the nickel-boron binary eutectic
temperature, substantial liquation of the
nickel substrate took place. This type of
Spherical shell
boride precipitation was consistent with pre-
vious observations of substrate boride forma-
Source tion at the brazing temperature after complete
of heat melting of the interlayer in nickel/Ni-Si-
Core
B/nickel joints.
Another series of investigations (Ref 236)

examined transient liquid phase (TLP) bonding
Graphite fibers for NiAl, which offers the advantages of toler-
ance of the strong Al2O3-forming tendency of
NiAl and compatibility with the poor low-tem-
perature ductility of NiAl.
Fig. 4.20 Advanced radiator featuring radial graphite fibers
Techniques have been developed for the TLP
to carry heat away from a spherical shell and radi-
ate the heat into space bonding of NiAl-NiAl (Ref 237, 238). How-
ever, relatively high bonding temperatures are Another unique metallizing process has been
required for these procedures, ranging from developed and applied at temperatures as low as
approximately 1200 °C (2190 °F) (Ref 237) to 850 °C (1560 °F). This makes it especially suit-
above 1460 °C (2665 °F) (Ref 238). These high able for materials (such as magnesium/partially
bonding temperatures impede application to the stabilized zirconia, or PSZ) that cannot with-
joining of NiAl-nickel-base superalloys (which stand temperatures above 1000 °C (1830 °F).
typically have melting temperatures of approxi- The filler metal consists of 95% Sn, with the
mately 1300 °C, or 2370 °F). Thus, alternative balance containing carbide or carbonyl formers
interlayer materials are required if TLP bonding and other alloying elements. The process con-
is to be applied successfully to the joining of sists of the formation of a chemical bond with
NiAl to nickel-base superalloys. the surface of the ceramic that continues to wet
Ceramic-to-Metal Joining (Ref 239–243). the surface even when it becomes molten. While
Some excellent work was performed in the the basic filler metal melts at relatively low tem-
active alloy sealing of an Al2O3 ceramic to a cop- peratures, it is capable of alloying with brazing
per stud via a titanium-nickel eutectic metalliza- metals during joining to form ternary alloys
tion for use as a high-reliability transistor pack- with high melting points.
age. The titanium-nickel metallization was Coatings and Metallizing. Of course, sig-
chosen in lieu of the more widely used molybde- nificant improvements in the techniques of met-
num-manganese metallization because of batch- allizing have been made, and several new pro-
to-batch variations with the latter technique. The cedures have been developed and evaluated.
process used 0.5 µm of titanium evaporated onto Also, extensive research on the reactions that
the ceramic, followed by 7 µm of nickel. This occur when a ceramic surface is metallized has
was followed by heating to 1000 °C (1830 °F) contributed to the effectiveness of metallizing.
for 2 min in dry H2. This heating step bonded the Metallizing procedures were originally
titanium to the ceramic by forming a liquid phase developed to improve the wettability of ceramic
of titanium-nickel eutectic between the bulk of surfaces by conventional low-temperature filler
the nickel layer and the ceramic. The bulk of the metals. Later, investigators found that some
nickel layer remained solid, because the propor- active metals and their alloys or compounds
tion of nickel was far higher than required for the (e.g., titanium and zirconium) wet unmetallized
71.5Ti-28.5Ni eutectic composition with its ceramic surfaces under certain conditions.
melting point of 955 °C (1750 °F). Close control Although variations of the so-called active
of this postevaporation heating was found neces- metal process have been used commercially to
sary. With too short a time or temperatures produce ceramic-to-metal seals, they have not
below 955 °C (1750 °F), the reaction to form the been accepted to the extent characterized by the
eutectic was complete; a weak joint between the metallizing-brazing concept of joining these
metallization and the ceramic resulted. An materials.
excessively long heating time resulted in tita- To ensure the production of reliable ceramic-
nium diffusing through to the nickel surface, to-metal seals, most metallized surfaces are
reacting with impurities in the H2 and rendering coated with nickel, copper, or other metals. The
the surface difficult to braze. After this postevap- metals are usually deposited by electroplating;
oration heating, the joining was completed by in some cases, however, the coatings are pro-
brazing with a 72Ag-28Cu filler metal at >780 duced by reducing oxides of the desired metal.
°C (1435 °F). These coatings perform several functions,
Other studies of brazing (Ref 244) include an depending on the method used to produce the
investigation into the use of an amorphous filler ceramic-to-metal seal. If the joints are to be
metal between Al2O3 and Fe-Ni-Co alloy and brazed with conventional silver- or copper-base
the effect of brazing conditions on the resulting filler metals, the coatings serve the following
shear strength. This complements other work purposes:
(Ref 245) in the use of amorphous filler metals
between two ceramic components. These • A metallizing layer is composed of metals
results showed that, when using a copper-tita- and residual oxides not completely reduced
nium filler metal, the joint strength was depen- during sintering. Such a surface is not con-
dent on the amount of joining between Al2O3 ducive to good wetting by the filler metal.
and the intermediary TiO2. Plating with nickel or copper eliminates the
adverse effects of the surface on the wetting these silver-base filler metals (Cusil and Incusil)
and flow characteristics of the filler metal. are ductile and adaptable to brazing metals to
• When the metals used for metallizing are not such materials as Si3N4, PSZ, transformation-
wet readily by low-temperature filler metals, toughened Al2O3, and SiC as well as many other
plating provides the surface with a metal eas- refractory materials (Tables 4.27, 4.28). These
ily wet by such filler metals. brazing processes are shown in Table 4.29.
• To a degree, the plated metal acts as a barrier Researchers (Ref 266) recently concluded in
to the penetration of the metallizing layer by an investigation that the hermetic seal of
the filler metal. Some filler metals react with Kovar/iron/aluminum/Al2O3 joints by the alu-
the metals used for metallizing. If the reaction minum-silicon interlayer method depends not
is allowed to proceed too long, the filler metal only on the composition and properties of the
may penetrate the metallized coating and lift compound layer but also on the thermal stress
it away from the ceramic. Metallized coatings induced by thermal expansion mismatch, espe-
are usually plated with nickel to retard pene- cially on the circumferential stress parallel to
tration and with copper to provide good wet- the joint interface and on the radial stress.
ting. In trying to determine the influence of copper,
Kovar, molybdenum, and tungsten interlayers
There are numerous methods to coat the on the magnitude and distribution of thermal
metal-ceramic surface: stresses and on the tensile strength of brazed
Si3N4-steel joints, researchers (Ref 267) found
• Sintered metal powder (Ref 246–254) that joints made using low-yield-strength/high-
• Reactive or refractory metal salt (Ref ductility interlayers, such as copper, have lower
254–256) thermal stresses and higher strengths than those
• Metal-glass powder (Ref 257–261) made using low-thermal-expansion/high-yield-
• Vapor deposition (Ref 250) strength interlayers, such as molybdenum or
tungsten. A composite interlayer comprising
However, with the previously mentioned copper and tungsten produces the lowest ther-
techniques and the early investigations, joining mal stresses during brazing. Increasing the
ceramics to metals by the active metal or active thickness of the interlayer decreases the thermal
hydride process has advanced significantly. The stresses produced during brazing, because the
strengths of joints made by this process are as rigid restraint effect due to the high-yield-
great as those obtained with joints made by the strength/high-elastic-modulus steel substrate is
moly-manganese process. Some difficulty has reduced (Ref 267–271).
been experienced in making seals by the active Other studies (Ref 272) found that the silver-
metal or active hydride process in dry H2. The copper eutectic with 5% Ti filler metal for
dew-point of H2 must be extremely low to pre- ceramic-metal joints has inherently poor oxida-
vent oxidation of titanium. Producing ceramic- tion resistance. It is necessary to improve this
to-metal seals in a vacuum is advantageous in filler metal by adding other elements. Current
that the parts are outgassed during brazing. work has demonstrated that aluminum is a very
The concept of fabricating ceramic-to-metal effective element in enhancing the oxidation
joints and seals by the active metal or active resistance of Ag-Cu-Ti-base filler metals by
hydride process was first applied in the elec- forming a layer of protective copper-Al2O3 film.
tronics industry. In recent years, however, these Other efforts (Ref 273) found that the oxidation
joining processes have found other uses to meet behavior of titanium-containing filler metals on
the need of high-temperature vacuumtight seals PSZ and Al2O3 can be improved. The filler met-
in the nuclear and aerospace industries (Ref als included Cu-41.1Ag-3.6Sn-7.2Ti, Ag-
262–264). 44.4Cu-8.4Sn-0.9Ti, Ag-41.6Cu-9.7Sn-5.0Ti,
Other New Ceramic-Metal and Filler- and Ag-37.4Cu-10.8In-1.4Ti.
Metal Combinations. New active filler metals In investigations and evaluation of palla-
are constantly undergoing changes and modifi- dium-base filler metals, selected because of
cations in composition to meet the ever- their oxidation resistance, ductility, and rela-
demanding requirements to permit metals (Ref tively high melting points in brazing ceramics to
265) to be joined to ceramics without the metals for heat engine applications, researchers
ceramic materials being metallized. Some of (Ref 274) studied the brazed joints between
Si3N4 and nickel. They found that the joints produced joints with shear strengths up to 135
brazed with the low-palladium filler metals, MPa (20 ksi).
70Au-8Pd-22Ni, 93Au-5Pd-2Ni, and 82Au- • Many low-stress failures resulted from exces-
18Ni, had shear strengths of 75 to 105 MPa (11 sive oxidation of titanium arising from too
to 15 ksi) from 20 to 500 °C (70 to 930 °F), high an oxygen partial pressure in the vac-
while the joints brazed with the high-palladium uum furnace. The work emphasized the
filler metals, 60Pd-40Ni, 30Au-34Pd-36Ni, and importance of furnace atmosphere when
50Au-25Pd-25Ni, all had shear strengths near 0. brazes containing titanium were used.
Using copper filler metals Cu-5Cr, Cu-1Nb, • Diffusion bonding PSTZ to SG iron at 850 °C
Cu-3V, Cu-5Ti, and Cu-10Zr, researchers (Ref (1560 °F) with titanium and copper foil inter-
275) studied the reactions of Si3N4 and refrac- layers has produced an apparently crack-free
tory metals (tungsten, molybdenum, niobium, joint, but others made at different tempera-
tantalum). tures or with titanium and silver foils con-
Combinations of brazed SiC (Ref 276) and tained internal cracks.
others (Ref 277, 278) and various metals for • Vacuum-brazed joints made with silver-cop-
automotive and aerospace applications include per + 5% Ti between RB-SiC and a 0.4% C
two combinations of interest to, for example, steel failed by lack of wetting of the carbide
the automotive industry, namely, partially stabi- surface, which was attributed to an undesir-
lized tetragonal zirconia (PSTZ) to a spheroidal able reaction between titanium and free sili-
graphite (SG) cast iron, and reaction-bonded con in the RB-SiC.
SiC (RB-SiC) to a 0.4% C steel: • Surface treatments can improve the pro-
cesses.
• Vacuum-brazed joints between PSTZ and SG
cast iron were made with shear strengths of As a result, it was found (Ref 279) that filler
approximately 200 MPa (29 ksi). metals containing titanium can make strong
• As an alternative to a complex alloy filler joints between PSTZ and SG iron, provided that
metal, a simple silver-copper eutectic together excessive oxidation of titanium is prevented.
with a sputtered titanium coating on the PSTZ Using titanium demands standards of vacuum
Table 4.27 Filler metals for brazing ceramics

Name Composition, % Liquidus, °C (°F) Solidus, °C (°F)
Copper, BCu-1(a) 100 Cu 3598 (1981) 3598 (1981)

Nicoro, BAu-3(a) 62Cu, 35Au, 3Ni 3427 (1886) 3330 (1832)
Cu-Au(1) 65 Cu, 35 Au 3362 (1850) 3297 (1814)
Cu-Au(2), BAu-1(a) 62.5 Cu, 37.5 Au 3346 (1841) 3281 (1805)
Cu-Au(3) 60 Cu, 40 Au 3330 (1832) 3265 (1796)
Cocuman 58.5 Cu, 31.5 Mn, 10 Co 3326 (1830) 2993 (1645)
Cu-Au(4) 50 Cu, 50 Au 3232 (1778) 3184 (1751)
Silver 100 Ag 3200 (1760) 3200 (1760)
Ticuni 70Ti, 15 Cu, 15 Ni 3200 (1760) 3038 (1670)
Nicuman 23 67.5 Cu, 23.5 Mn, 9 Ni 3184 (1751) 3087 (1697)
Nicoro 80 81.5 Au, 16.5 Cu, 2 Ni 3087 (1697) 3038 (1670)
Nicuman 37 52.5 Cu, 38 Mn, 9.5 Ni 3087 (1697) 2941 (1616)
Palcusil 15 65 Ag, 20.3 Cu, 14.7 Pd 3006 (1652) 2844 (1562)
Silcoro 75 75 Au, 20 Cu, 5 Ag 2989 (1643) 2957 (1625)
Gapasil 9 82 Ag, 9 Ga, 9 Pd 2941 (1616) 2827 (1553)
Palcusil 10 58.5 Ag, 31.8 Cu, 9.7 Pd 2851 (1566) 2760 (1515)
Ticusil 68.8 Ag, 26.7 Cu, 4.5 Ti 2844 (1562) 2779 (1526)
Silicoro 60 60 Au, 20 Cu, 20 Ag 2827 (1553) 2795 (1535)
Palcusil 5 68.5 Ag, 26.8 Cu, 4.7 Pd 2714 (1490) 2705 (1485)
Nicusiltin 6(b) 62.5 Ag, 29 Cu, 2.5 Ni, 6 Sn 2689 (1476) 2327 (1275)
Nicusil 3 71.15 Ag, 28.1 Cu, 0.75 Ni 2665 (1463) 2617 (1436)
Cusil, BAg-8(a) 72 Ag, 28 Cu 2617 (1436) 2617 (1436)
Incusil 10 63 Ag, 27 Cu, 10 ln 2455 (1346) 2309 (1265)
Incusil 15 61.5 Ag, 24 Cu, 14.5 ln 2374 (1301) 2131 (1166)
Georo 88 Au, 12 Ge 1243 (673) 1243 (673)
Au-Sn 80 Au, 20 Sn 997 (536) 997 (536)
(a) American Welding Society specification. (b) Aerospace Material Specification (AMS) 4774A. Source: Ref 263, 264
Table 4.28 Selection guide to filler metals for brazing metal-ceramic joints
Nickel, Titanium,
Carbon and Stainless Tool cobalt zirconium Refractory Ceramic, Tungsten
low-alloy steel steel steel alloys(a) Copper(b) Nickel(b) alloys metals metallized Carbon(c) carbine
Ceramic metallized
Copper Copper ... ... Copper-gold Copper ... ... Copper-gold ... ...
Copper-gold Copper-gold Cusil Copper-gold Cusil
Cusil Palcusil Georo Cusil Incusil
Nicusil Silcoro Gold-tin Nicoro Silver
Palcusil Incusil Nicusil
Silver Nicoro Palcusil
Nicusil Silcoro
Palcusil
Silver
Carbon (b)
Ticusil Ticuni Ticuni Ticuni Ticuni Ticuni Ticuni Ticusil ... Ticuni Ticusil
Ticusil Ticusil Ticusil Ticusil Ticusil Ticusil Ticusil
Tungsten carbide
Cocuman Cocuman Cocuman Cocuman Copper-gold Cocuman Gapasil Cocuman ... Ticusil Cocuman
Copper Copper Nicoro Nicoro Nicuman Copper Ticuni Gapasil Copper
Nicuman Nicoro Nicuman Nicuman Nicusiltin Copper-gold Ticusil Nicuman Nicuman
Nicusiltin Nicuman Nicusiltin Nicusiltin Nicoro Ticusil Silver
Nicusiltin Palcusil Palcusil Nicuman
Nicusiltin
(a) Corrosion- and heat-resistant alloys. (b) Includes alloys. (c) Graphite and diamond. Source: Ref 9, 264
Table 4.29 Summary of methods for metallizing ceramics

Metallizing Metallizing Additional Suitable
Metallized Suitable materials in temperature, layers solders
No. layer type ceramics finely divided form °C (°F), atmosphere required or brazes
1. Silver, silver- Hard glasses, Mixtures of PtCl4, 500–900 None Sn, Pb, or
platinum most ceramics Ag2O, Ag, and Pt (930–1650) in air Pb solders(a)
2. Silver, Hard glasses, Mixtures of PtCl4, 500–900 Ag, Ag-Pt Sn, Pb, or
silver-platinum most ceramics Ag2O, Ag, and (930–1650) in air Pb solders(a)
+ fluxing glass Pt + <20% soft glass
or flux, e.g., lead borate
3. Silver + copper oxide Most ceramics Ag2O + <10% CuO, >940 (1725) in air Ag, At-Pt Sn, Pb,
Cu2O or Pb solders(a)
4. Molybdenum + silver Most ceramics Mo + ~10% Ag2O 1300 (2370) Ni(b) Cu, Cu-Ag, Ag
in dry H2
5. Molybdenum + glass Most ceramics Mo + 10–20% glass 1200–1300 Ni(b) Cu, Cu-Ag, Ag
(2190–2370)
in dry H2
6. Nickel + glass Most ceramics NiO + ~10% glass 1300 (2370) Metallized layer Solders, Cu-Ag
in dry H2 needs buffing
7. Copper, copper alloys Most ceramics CuO (+ alloying oxides) 1100 (2010) in air + None Solders
900 (1650) in H2
8. Tungsten or molybde- Oxide ceramics, W or Mo (+Mn or 1450–1650 Ni(b) Cu-Ag, Au-Cu
num (+ manganese BeO, Al2O3 Fe compounds, (2640–3000)
or iron) (debased type) e.g., 80% Mo, 20% Mn) in wet H2
9. Titanium or Oxide and some Ti and Zr or, more >1000 (1830) in None Zr, Ti eutectic
zirconium(c) (active nonoxide commonly, TiH4, ZrH4, inert atm. brazes
metal joints) ceramics or other compounds
10. Molybdenum Pure alumina Mo + TiN or TiC 1450–1900 Ni(b) Cu-Ag, etc.
+ titanium (2640–3450)
in wet H2
(a) Excessive reaction between solder and metallized layer can be prevented by an additional electroplated layer of copper on the metallizing or by using a solder with
a high silver content, e.g., Cu-Ag. (b) Nickel coating can be achieved by electroplating or by a second coating, as in No. 6, but without glass. (c) This process can be
done by direct brazing in vacuum with an active metal braze, using optionally TiH4 or ZrH4 as fluxes to wet the ceramic, i.e., a one-stage process.
practice well above those for conventional vac- good solution to the problem of making Al2O3-
uum brazing. steel joints with large dimensions. Using this
The use of sputtered coatings of titanium on type of interlayer allowed for the relaxation of
oxide-ceramic surfaces prior to vacuum brazing stresses generated during the bonding cycle. It
could be commercially viable. Also, the was concluded that a copper-material interlayer
improvement of the wettability of RB-SiC by was suitable for this purpose. Direct bonding
modifying the surface or the filler metal should using active products of the reduction reaction
be studied further. Finally, the treatment of cast of CuO (Cu2O, O2) can also be adequately used
iron surfaces to avoid excessive diffusion of in the process of bonding joints with a copper
carbon into the joint and to give better bonding interlayer. Using this method, they were able to
with the filler metal should be explored (Ref fix the relationship between the quality of the
279). bond (homogeneous microstructure at the
Finally, a research program (Ref 277) on the whole bonding surface) and a protective atmos-
mechanism of joining graphite to a high-Al2O3- phere.
content ceramic (up to 95%) found that the Ti- They showed that their method can be used in
Ag-Cu filler metal was very successful in braz- joining Al2O3 to copper and copper to steel in
ing the combination. For the existence of one thermal cycle. Such bonded joints have
carbon, the Ti-Ag-Cu was used to produce high mechanical strength and a homogenous
AlAg3 and Ti3Al in the physical phase of the microstructure. Compared to other joining
sealed region, which was an essential factor in methods, this process does not need to imple-
the possible forming of a gastight seal between ment any special joining conditions using the
graphite and the 95% Al2O3 ceramic. following features: low bonding temperatures
For the existence of AlAg3 and TiAl3, the use of ~1340 K, a protective atmosphere of nitrogen
of Ti-Ag-Cu could be a significant advance to containing below 40 ppm oxygen, and a bond-
future research of sealing between 95% Al2O3 ing time of ~90 min.
ceramics and oxygen-free copper (Ref 280), Particular attention must be paid to two
Kovar, beryllium, beryllium oxide (Ref 281), effects when joining Si3N4 to metallic materials:
tungsten, molybdenum, and stainless steel (Ref interfacial bonding and residual stress. A wide
282). variety of joining methods that depend on the
A number of studies have investigated the fact that Si3N4 reacts with many metallic ele-
active brazing of Al2O3 to superalloys (Ref ments to form well-bonded interfaces have been
283), to steel with copper interlayers (Ref 284), developed for bonding to Si3N4 metals. Several
and to titanium (Ref 285). categories can be involved, and each process
In one study (Ref 283), the brazing of Al2O3 has its own advantages. However, much
to nickel-base superalloy (Inconel 600) and remains to be learned. Thus, further experimen-
cobalt-base superalloy (UMCo-50) was per- tal evidence could allow a more detailed under-
formed. The Ag-Cu-Ti active filler metals with standing of the stress-corrosion effects pro-
titanium contents of 2 and 8 wt% were em- duced not only by water but by other corrosive
ployed in this study. However, experiments and oxidizing environments as well. Small com-
showed that the Ag-Cu-2wt%Ti resulted in poor ponents (up to 15 mm, or 0.6 in., in diameter)
bonding, which was not suitable for the brazing can be joined using soft metal or laminated lay-
investigation. With an increase of the titanium ers. How to join a large-sized Si3N4 component
content to 8 wt%, the specimens could be to a metal, however, is still a major problem,
bonded. However, the bonding strengths were due to the severe residual stresses. Because
still too low. The four-point bending strengths most Si3N4 components are used at elevated
in this case were only 43 to 54 MPa (6.2 to 7.8 temperatures, evaluation of high-temperature
ksi). An improvement of the bending strength properties, such as strength, oxidation, and ther-
was achieved by inserting a Kovar interlayer. In mal stress, is required.
this case, the bending strength was dramatically It can be concluded (Ref 286) that strong and
increased to 240 and 226 MPa (34.8 and 32.8 reliable joints can be obtained between Si3N4
ksi) for the Al2O3/UMCo-50 joint and the and austenitic stainless steel by diffusion bond-
Al2O3/Inconel 600 joint, respectively. ing when using thin, metallic interlayers. Best
Researchers (Ref 284) carried out experi- results (average shear strength of 95 MPa, or
ments to show that multilayer bonding by using 13.8 ksi, with a Weibull modulus of 6.8) were
thin and very plastic material interlayers was a obtained when using an Invar (Carpenter Tech-
nology Corporation) interlayer at a bonding rials with low CTE. Joining strength surpassing
pressure between 7 and 20 MPa (1 and 3 ksi), a 500 MPa (73 ksi) at 400 °C (750 °F) has been
bonding temperature between 1000 and 1100 realized through these improvements. The joint
°C (1830 and 2010 °F), and a bonding time is extremely tough, and the strength does not
between 90 and 1440 min: deteriorate, even under an unprecedented exact-
ing thermal cycle test with 1000 cycles between
• During the diffusion bonding process, a reac- room temperature and 400 °C (750 °F).
tion layer was formed at the interface Other studies and investigations combining
between the ceramic and the interlayer. This Si3N4, steels (Ref 288), superalloys, and molyb-
reaction layer consisted of a porous zone denum evaluated the role of titanium in the
anchored into the Si3N4 and a diffusion zone development of the reaction layer in braze join-
extending into the interlayer. The formation ing Si3N4 to stainless steel using titanium-active
of the reaction layer was due to the diffusion copper-silver filler metals. This reaction layer
of free nitrogen and free silicon generated by formed as a result of titanium diffusing to the
decomposition of the Si3N4 in contact with filler-metal/Si3N4 interface and reacting with
the interlayer material. the Si3N4 to form the intermetallics titanium
• The mechanical strength of the joint nitride (TiN) and titanium silicide (Ti5Si3). This
depended strongly on the thermal stress reaction layer allows wetting of the ceramic
developed in the vicinity of the interface due substrate by the molten filler metal (Ref 289).
to the difference in shrinkage between the Two filler metals were used in this study,
ceramic and the metal and was directly Ticusil (Wesgo Metals) (68.8Ag-26.7Cu-4.5Ti,
related to the thickness of the reaction layer. wt%) and CB4 (70.5Ag-26.5Cu-3.0Ti, wt%).
The joints were processed in vacuum at temper-
A researcher has been developing joining atures of 840 to 900 °C (1545 to 1650 °F) at var-
technology for ceramics and, in addition to the ious times. Bonding strength was affected by
development of materials, for the expansion of reaction-layer thickness in the absence of tita-
the use of ceramic applications in the fields led nium-copper intermetallics in the filler-metal
by the ceramic turbine. The aim of the research matrix.
is the application of these joining techniques to The reaction-layer thickness increased with
the joining of a Si3N4 turbine with a metal shaft temperature and time. Its growth rate obeys the
designed to resist high temperatures (Ref 287). parabolic relationship. Activation energies of
The research was aimed at the improvement 220.1 and 210.9 kJ/mol (53 and 51 kJ/cal) were
of joining strength and of thermal-cycle charac- calculated for growth of the reaction layer for
teristics at high temperatures. It was found that the two filler metals used. These values were
the formation of a high-strength interface and close to the activation energy of nitrogen in TiN
the reduction of thermal stress were necessary (217.6 kJ/mol, or 52.3 kJ/cal).
for a successful joining between ceramics and Researchers (Ref 290) examined the effect of
metals. The realization of high-strength joining pressure in brazing Si3N4 to AISI 5140 steel.
of Si3N4 with metal was extremely difficult in Pressures (0 to 40 MPa, or 0 to 5.8 ksi) were
the past, owing to the poor wettability of this applied to the joints of Si3N4 ceramic to 5140
ceramic with metal, in addition to its low coef-
ficient of thermal expansion (CTE) (approxi-
mately 3 × 10–8K–1), with a large difference
from the CTE of metal materials.
The formation of an interface was based on
the ion-plating method shown in Fig. 4.21. The
researcher has established a new method of
combining brazing with the multilayer metal-
lization, with titanium, an active metal, as the
innermost layer. The outer layers serve in pre-
venting the oxidation of titanium and improving
the wettability of the filler metal, thereby
achieving a durable interface. The reduction of
thermal stress has become possible with the
application of a WC-base alloy and other mate- Fig. 4.21 Tapered Si3N4 joined to stainless steel shaft.
steel during vacuum brazing with Ag-Cu-Ti both systems. A cylindrical lap geometry with
active filler metal. Pressurization started at var- an interlayer was selected for these joints.
ious temperatures (873, 973, and 1073 K) and Room-temperature and 500 °C (930 °F) tor-
ended at room temperature during cooling. sion strengths of the 650 °C (1200 °F) system
Results showed that there is an optimal starting were measured in the range of 30 to 100 N · m
temperature to pressurize, at which the maxi- (22 to 74 lbf · ft) with a 2 cm2 (0.3 in.2) brazed
mum room-temperature shear strength of the area, while the strength at 650 °C was signifi-
joint is obtained. cantly lower (1.6 to 7.0 N · m, or 1.2 to 5.2 lbf ·
Researchers (Ref 291) successfully fabri- ft). This was attributed to a reduction in the
cated joints of Si3N4 and molybdenum with a shrink fit at 650 °C. The Si3N4/nickel/Incoloy
vanadium interlayer using a vacuum hot press- 909 joints showed excellent room-temperature
ing facility. The optimal joining conditions for fatigue behavior. A similar trend was seen in the
producing a joint with the highest shear strength high-temperature strength of the Si3N4/molyb-
were found to be as follows: a temperature of denum/Inconel 718 joints, which had lower
1328 K, a mechanical pressure of 20 MPa (3 strength than the Si3N4/nickel/Incoloy 900
ksi), and a bonding time of 5.4 ks. The strength joints due to the high CTE of Inconel 718.
level was initially 118 MPa (17 ksi) at room Transient liquid phase bonding is a method
temperature, and this level gradually decreased for joining high-temperature metal alloys at rel-
as the test temperature rose. At 973 K, the atively low temperatures. The method uses a
strength level was still 70 MPa (10 ksi). Obser- bonding interlayer of a composition similar to
vations of the interface by scanning electron that of the articles to be bonded, which contains
microscopy and electron probe x-ray micro- a small amount of a melting-point-lowering
analysis revealed that a layer of reaction product material. To form the bond, the metal/inter-
V3Si formed at the Si3N4-vanadium interface. layer/metal assembly is heated to, and held at, a
Researchers (Ref 292) carried out detailed temperature above the melting point of the
observations on the metallurgical behavior of interlayer to obtain the TLP. During this
joint brazing of nickel-base alloy Inconel 600 to process, the melting-point-lowering material
Si3N4 with Ag71Cu27Ti2 filler metal, with diffuses into the surrounding materials, raising
emphasis on the interface between the filler the melting point of the interlayer and leaving a
metal and the Inconel 600 and the effects of solid bond.
nickel, which was the predominant element in The TLP bonding principle has been
the base metal. Based on the experimental extended to the joining of ceramics to metals
results, the mechanism of bonding Inconel 600 and ceramics to ceramics. To form these bonds,
to the filler metal is attributed to the diffusion of multilayer interlayer structures are employed
silver and copper along the grain boundaries of between the articles to be bonded.
the Inconel 600, which results in mechanical In the simplest case, the multilayer structure
anchoring. The effects of nickel on the metal- is a refractory metal sandwiched between two
lurgical behavior of filler metal are summed up layers of a metal with a melting point lower than
as enhancing the separation of silver- and cop- that of the refractory metal. Such a structure
per-rich liquid phases from the molten filler may be gold/niobium/gold.
metal, combining titanium and decreasing its Heating of this structure results in gold diffu-
activity in the reaction with Si3N4 at the inter- sion into the refractory metal layer and the for-
face with ceramics, promoting the diffusion of mation of the required solid bond.
silver and copper into Inconel 600, and facilitat- A more complicated system consists of two
ing the flow of filler metal over the surface of ceramic layers and, for instance, Si3N4 bonded
Inconel 600. together using an assembly that comprises lay-
Material systems designed for 650 and 950 ers of a refractory metal, gold, titanium, and
°C (1200 and 1740 °F) applications were evalu- gold. Here, an additional function of gold is to
ated in terms of torsion, torsion fatigue, and protect the other metals against oxidation.
thermal fatigue (Ref 293). Researchers selected Researchers evaluated TLP-insert metal
Si3N4/nickel/Incoloy 909 as the 650 °C (1200 brazing of Al2O3 and AISI 304 stainless steel
°F) system, while Si3N4/molybdenum/Inconel (Ref 294). This joining technique allows the
718 was selected as the 950 °C (1740 °F) sys- continuous replenishment of the active solute
tem. The Au-5Pd-2Ni filler metal was used in that is consumed by the chemical reaction that
occurs at the ceramic/filler-metal interface. son, the particle-segregation tendency is

Replenishment is facilitated by employing a markedly increased when these dissimilar
sandwich of filler metals comprising tin-base substrates are TLP bonded.
filler metal and amorphous Cu50Ti50 or NiCrB • During TLP bonding at 853 K, the highest
interlayers. During Al2O3/AISI 304 stainless joint shear-strength properties are produced
steel bonding, the highest shear-strength prop- using 5 µm thick copper foil. When the width
erties were produced using a bonding tempera- of the particle-segregated layer at the joint
ture of 500 °C (930 °F). Thick reaction layers interface exceeds 10 µm, this region acts as a
containing defects formed at the ceramic/filler- site for preferential failure during mechanical
metal interface when higher bonding tempera- testing. However, when a thin (<10 µm thick)
tures were applied. Bonding at temperatures particle-segregated layer is formed at the
above 500 °C (930 °F) also increased the tensile bond line joint, failure occurs in Al2O3 mate-
residual stress generated at the periphery of rial immediately adjacent to the bond line.
Al2O3/AISI 304 stainless steel joints. The shear
A joining pair of SiC and molybdenum was
strength of joints produced using NiCrB inter-
fabricated using vanadium foil as an insert
layers markedly increased following heat treat-
material (Ref 296). The optimal fabricating con-
ment at 200 °C (390 °F) for 1.5 h. Heat treat-
ditions were a bonding temperature of 1198 K,
ment had little influence on the shear strength of
a bonding pressure of 30 MPa (4 ksi), and a
the joint produced using Cu50Ti50 interlayers.
bonding time of 10.8 ks. The joint had high
Researchers (Ref 295) also investigated TLP
shear-strength levels of 150 MPa (22 ksi) at
bonding of metal-matrix composite (MMC) and
room temperature and 52 MPa (7.5 ksi) at 973
Al2O3 ceramic substrates and reached the fol-
K. At the interface of SiC and vanadium, a layer
lowing conclusions:
of vanadium silicide, V3Si, was formed.
• The completion time is much longer and the Table 4.30 summarizes the use of interlayers
rate of movement of the solid-liquid interface in joining a variety of ceramics and metals.
is much slower in dissimilar MMC-Al2O3 An investigation was conducted (Ref 298) to
joints, because copper can only diffuse into gain information about the capabilities of some
the aluminum-base composite. For this rea- filler metals for direct brazing of cubic boron
Table 4.30 Summary of interlayers for reducing thermal expansion mismatch in ceramic-metal joints
Group(a) Ceramic/metal Interlayer Joining conditions Strength, MPa (ksi)
I Al2O3/type 321 steel Al 873 K, 50 MPa (7.3 ksi), 30 min. 70 (10.2)

TZP/type 316 steel Cu 1273 K, 1 MPa (0.15 ksi), 4 h 52 (7.5)
MgO/steel Cu/metal foam 1273–1473 K (b) 33 (4.8)
Al2O3/steel BA03 883 K, 10 MPa (1.5 ksi), 30 min 30 (4.4)
II SiC/Al(c) Cu-C fiber 1043 K (Al was joined at 823 K) (b) ...
Al2O3/W (d) Al2O3-W 2125 K, 8 h ...
Al2O3/Fe (d) Al2O3-Fe 1473 K, 3 GPa (435 ksi), 30 min ...
TiN/Mo(d) TiN/Mo 1573 K, 3 GPa (435 ksi), 30 min 80 (11.6)
Al2O3/Fe (d) FeO-Fe 1473 K, 29 MPa (4.2 ksi), 1 h ...
TZP/W(d) TZP-W 1673 K, 1 h in H2 200–400 (29–58)
III Al2O3/type 405 steel Nb/Mo 1673 K, 100 MPa (14.5 ksi), 30 min 500 (72.5)
Al2O3/type 316 Ti/Mo 1373 K, 9 MPa (1.3 ksi), 3 h 70 (10.2)
Si3N4/steel ... ... 200 (29)
SiC/steel BA03/WC 883 K, 2 MPa (0.3 ksi), 1 h 150 (21.8)
Sialon/steel ... ... 300 (43.5)
Sialon/steel Type 304/WC steel 1373 K, 5 MPa (0.7 ksi), 1 h 150 (29)
Si3N4/type 405 steel Fe/W 1473 K, 10 MPa (1.5 ksi), 30 min 60 (8.7)
SiC/super alloy Ni/Kovar/Cu 1323 K, 54 MPa (7.8 ksi), 2 h 100 (14.5)
Si2N3/super alloy Ni/Kovar/Cu 1323 K, 54 MPa (7.8 ksi), 2 h ...
SiC/type 316 steel Ti/Mo 1083 K, 0 min(b) 50 (7.3)
IV Si3N4/type 405 Al/Invar (cracking in 1073 K, 0.15 MPa (0.015 ksi), 60 (8.7)
intermetallic 7 min(b)
compound)
(a) I, soft metal; II, composite; III, laminate (soft metal/low expansion and hard metal); IV, crack layer. (b) Brazing; the others are diffusion or eutectic joining. (c) Soft
metal with carbon fiber. (d) Grading (cermet). TZP, tetragonal zirconia polycrystal. Source: Ref 297
nitride (CBN) grits to a steel substrate. It has imately 57 MPa (8.3 ksi), whereas the Weibull
been found that a nickel-chromium filler metal, modulus is approximately 1.6. Failure occurs
known for effective diamond brazing, failed to almost always at the Si3N4-nickel interface,
show satisfactory wetting and bonding charac- which therefore turns out to be the weakest link
teristics toward CBN under the same brazing of the ZrO2-nickel-Si3N4 combination.
conditions as that of diamond. The situation The optimal bonding conditions obtained for
could not be improved either by increasing the this material combination were used to make a
weight percent of chromium or the brazing tem- diffusion bond in a practical application. A
perature. Also, prolongation of the brazing time Si3N4 ring was diffusion bonded to a cylindrical
did not show any significant change. It was fur- part of a gear pump consisting of ZrO2. It turns
ther revealed that a Ag-Cu-Ti filler metal, which out that bonding was possible but that due to
is well established for the brazing of diamond residual stresses in this large geometry, cracks
and ceramics, exhibited good wetting and bond- occurred in the ZrO2. The situation could be
ing toward CBN at moderate temperature. improved by using interlayers with modified
Based on the thermodynamic properties of var- geometry.
ious materials, the characteristic properties of The same combination, except AISI 316
the elements, and the physical observations stainless steel (Ref 299), was substituted for
made during the investigation, it was suggested Si3N4 and was successfully joined under the fol-
that transition elements such as titanium or zir- lowing conditions: temperature, 1000 to 1250
conium are preferred to transition elements such °C (1830 to 2280 °F); time, 90 to 360 min;
as chromium as an activator to promote the wet- bonding pressure, 2 to 20 MPa (0.3 to 3 ksi); and
ting characteristics of the filler metal toward interlayer thickness, 0 to 1.2 mm (0 to 0.05 in.).
CBN, which is far more chemically stable than It was found that direct bonding without an
diamond. interlayer leads to unreliable bonds with low
The ability of titanium to react with CBN was strength. Finite-element modeling calculations
achieved, thus changing its surface chemistry show that the level of residual stresses is rather
and the wettability of the silver-copper system. high in the vicinity of the interface between
The combination of ZrO2-nickel-Si3N4 (Ref ZrO2 and AISI 316. These stresses are consid-
299) was successfully joined under the follow- ered to be the most important cause of the poor
ing conditions: temperature, 850 to 1300 °C bond strength.
(1560 to 2370 °F); time, 90 min; bonding pres- A number of ZrO2/nickel/AISI 316 diffusion
sure, 14 to 37 MPa (2.0 to 5.4 ksi); and interlayer bonds were made with different interlayer thick-
thickness, 0.1 to 0.8 mm (0.004 to 0.03 in.). It nesses between 0.2 and 1.2 mm (0.008 and 0.05
appears that the shear strength of the ZrO2- in.). The bonds were found to have a relatively
nickel-Si3N4 combination is maximal for bond- low strength with a large scatter (σ0 = 30.4 MPa,
ing temperatures in the range of 1000 to 1100 °C or 209.6 ksi), independent of the interlayer thick-
(1830 to 2010 °F). It was found that two effects ness. Calculations of the residual stresses in
play a role in the bonding process. At low tem- ZrO2/nickel/AISI 316 diffusion bonds showed
peratures, diffusion-controlled interface forma- that high residual stresses were present in the
tion dominates, yielding an exponential depend- vicinity of the ZrO2-nickel interface. These
ence of the shear strength on temperature, with stresses, in particular, the tensile stresses in the
an activation energy of approximately 110 ZrO2, limit the strength of the bonds.
kJ/mol (26 kJ/cal). At high temperatures, Si3N4 A new brazing technique was developed (Ref
decomposes, forming free silicon and nitrogen at 300) for joining graphite to itself or to metals
the Si3N4-nickel interface. The silicon diffuses such as molybdenum, tungsten, or copper with
into the nickel, whereas the nitrogen atoms conventional filler metals.
recombine to form molecular nitrogen, which Essentially, it is impossible to braze graphite
escapes to the surrounding and/or forms pores with copper filler metal (AWS BCu-1), because
along the interface. Due to the solid solution of no wetting occurs. However, when a graphite
silicon in nickel, partial melting of the nickel can base material is combined with an iron base
occur during the bonding process, which is detri- metal in copper brazing, the iron base metal dis-
mental for the bond strength. The bonding pres- solves in molten copper. Simultaneously, the
sure and the interlayer thickness do not affect the dissolved iron grows as part of a columnar Fe-
bond strength. The characteristic strength of 6–9 Cu-1.6C alloy phase at the graphite inter-
bonds made under optimal conditions is approx- face at a constant brazing temperature; that is,
the dissolution and deposit of base metal takes are generated in the border zone of the hard
place. metal. As a result, the tensile strength of the joint
By placing an iron foil insert between both is greatly reduced, with fracture occurring pref-
graphite base materials, therefore, the columnar erentially in the border area of the hard metal.
phase is formed at both graphite faces and The calculation of the molar Gibbs energies of
grows toward the iron foil during heating. As a the different phases and of some of the element
result, both graphite base materials are united by chemical potentials, as well as the experimental
the columnar phase through the iron foil. In the determination of some potential gradients, were
same way, a graphite-molybdenum or -tungsten used to explain the different processes (phase
joint can be produced. Moreover, when using formation and multiphase diffusion) taking
BAu-1, which has a lower melting point than place during brazing.
that of BCu-1, it is also possible to braze
graphite to copper.
The shear strength of a graphite-graphite Case Histories and Problem-Solving
joint with a 0.12 mm (0.005 in.) thick iron foil Examples
at room temperature was approximately 32 MPa
(4.6 ksi). Further, the bending strength of the Example 1: Brazing Cast Irons to Dissim-
graphite-graphite and -copper joints at 600 °C ilar Metals. Joining dissimilar metals is not an
(1110 °F), as measured using the four-point easy problem to solve. Many firms have
bending test, was 35 and 11 MPa (5.0 and 1.6 encountered problems in joining cast iron in a
ksi), respectively. furnace exothermic atmosphere. The several
In addition, the technique can be applied to kinds of cast irons include white, gray, mal-
the brazing of AISI 304 stainless steel to high- leable, and ductile. There are many applications
carbon steel with BCu-1 where, normally, in which it is desirable to braze gray, malleable,
Cr23C6 and Cr7C3 layers are formed at the high- and ductile irons either to themselves or to dis-
carbon steel/braze interface; these carbide lay- similar metals; however, white cast irons are
ers result in the loss of mechanical properties of seldom brazed.
the joint. When inserting a 0.3 mm (0.01 in.) Brazing of ductile and malleable irons must
thick iron foil between AISI 304 and 1.04 car- not be performed above 760 °C (1400 °F),
bon steel in order to prevent the formation of because the metallurgical structure may be
chromium carbides, the dissolution and deposit damaged. In an exothermic atmosphere, type
of base metal takes place on either side of the BAg-18 filler metal could be used.
foil. On the 1.04 carbon steel side, the 1.04 car- Gray cast iron presents the most problems in
bon steel and the iron foil are united with a brazing. Wetting the surface is difficult, because
columnar Fe-7–9 Cu-0.8C alloy phase that there can be interference from graphite, sand,
comes from the 1.04 carbon steel, and, on the oxides, and so on. The primary method of clean-
AISI 304 side, the AISI 304 and the iron foil are ing is a proprietary molten salt bath employing
also united with a columnar Fe-12–13 Cr-6–9 a reversing direct current. Other methods of
Cu-4–5 Ni-0.2C alloy phase coming from the cleaning include searing with an oxidizing
iron foil. Consequently, both base metals are flame, grit blasting, and chemical cleaning.
united by each columnar phase through the foil, When heating in an oxidizing atmosphere, the
so the Charpy U-notch impact toughness of the silicon, if high, could oxidize, thus interfering
joint increased markedly from 1.0 to 9.0 J (0.7 with surface wetting of the filler metal.
to 6.6 ft · lbf) at room temperature. Further, this It has been suggested that there is a specially
uniting with each columnar phase exhibited a formulated copper filler metal that has improved
remarkable effect on the impact toughness of the wetting of copper on gray cast iron.
the joint in the range between room temperature With the many formulations and mixtures of
and 700 °C (1290 °F). cast iron that are available, there appears to be
Researchers (Ref 301) reported on their work no easy one-step method of copper furnace
regarding the thermochemical aspects of multi- brazing gray cast iron.
phase diffusion during brazing of hard metal. Example 2: Brazing Aluminum Bronze to
During brazing of WC-cemented carbide parts Naval Brass. In another application, a firm
(hard metal) on steel using pure copper as a filler wished to braze aluminum bronze to naval brass
metal, an intermetallic compound is formed at in pure dry hydrogen with a BAg-8 silver-cop-
the hard-metal/braze interface, whereas pores per eutectic filler metal. The results initially pro-
duced very poor braze joints, and the filler metal per or nickel. Dezincification is noted as a
did not wet and flow well. change from the brass color to a white surface,
The aluminum-bronze base metal had an alu- or, depending on the furnace, by brown fumes
minum content of 7 to 10%. Because aluminum coming out of the furnace. Some firms have
oxidizes very readily, even in the driest of been very successful in brazing cartridge brass,
hydrogen, this was undoubtedly the major prob- which has only 30% Zn, with the BAg-18 at 760
lem being encountered. Likewise, if the atmos- °C in a pure dry hydrogen atmosphere.
phere is quite dry, some aluminum gases off Example 3: Brazing Stainless Steel to
from the surface and aluminizes the filler metal Titanium. How would one braze AISI type
(either in wire or powder form). This also 304L stainless steel to titanium with nickel 200?
causes the filler metal not to melt properly and Titanium picks up oxygen quite readily, thus
to leave more of a residue. the parts are normally brazed in a high vacuum
One of the simplest methods for solving this of 0.13 Pa (2 × 10–5 psi) or better. In brazing
problem is to use a grade of flux specifically for- titanium, it is essential that the furnace be leak-
mulated to handle aluminum-bronze base met- free and have a clean interior prior to brazing. It
als, that is, AWS brazing flux type No. 4. When is good to run a test cycle with titanium foil to
running the part in hydrogen, only a very small assure that the furnace is clean and leak-free
amount of this flux is required, because the dry prior to brazing. If the titanium foil, when bent,
atmosphere protects it from oxidation, so it may exhibits brittleness, the furnace is not ade-
be thinned down and used as a thinner liquid quately clean. When the foil comes out essen-
rather than a heavy paste. tially the same color as it went in, and when it
If it is desired not to have any flux in the joint can be bent over on itself, ironed flat, and
area, then it is possible to plate the aluminum opened back up again without cracking, the fur-
bronze with either nickel or copper. The thick- nace is adequately clean, and brazing can then
ness of the plating must be thick enough so that be accomplished. Before brazing, the 304L,
the aluminum does not diffuse up to the surface nickel 200, all of the fixtures, and any materials
before the filler metal melts and flows. This, of that will be in the furnace during the brazing
course, is dependent on time and temperature; operation (except the titanium and filler metal)
thus, the plating thickness can be varied, should be put into the furnace and adequately
depending on these two variables. However, the outgassed. Many materials have included
higher the temperature and the longer the time oxides and other elements that gas off and are
to come up to heat, the thicker the plating that is picked up by the titanium. Precleaning ensures
required. It is suggested that 0.01 mm (0.0004 a better braze assembly. After the 304L is pre-
in.) thickness is a good starting place. If, on cleaned, plate it with approximately 0.01 mm
brazing, the surface of the plating discolors to a (0.0004 in.) of electrolytic nickel. This plating
gray color and flow is not adequate, a thicker provides a better surface for the filler metal and
plating is required. improves wetting and flow. If there is a question
In brazing naval brass in a hydrogen atmos- about the bond of the nickel plate, it is desirable
phere, the vapor pressure of zinc is increased to to test the bond by putting the part into the vac-
the point that dezincification occurs. This is true uum furnace, taking it up to 982 °C (1800 °F)
whether the atmosphere is exothermic, pure for 1 to 5 min, cooling it down, and then remov-
nitrogen, pure hydrogen, nitrogen-hydrogen, or ing it from the furnace. If the nickel plate is blis-
any of the gas atmospheres. Because the BAg-8 tered, the part should not be brazed but should
silver-copper eutectic filler metal is used, braz- be returned to the plater for stripping and replat-
ing is approximately 788 to 816 °C (1450 to ing. The blisters indicate that the cleaning was
1500 °F). To reduce the amount of dezincifica- not sufficient for plating, whereas, if no blister-
tion, it is better to use the BAg-18 filler metal, ing occurs, the nickel plating is now diffusion
which has a lower melting point and thus lowers welded to the 304L and is ready for brazing.
the amount of zinc vaporization that occurs. After all the parts, fixtures, and other materials
Brazing range on this filler metal starts at 718 to be put in the furnace are outgassed and
°C (1324 °F), and it is suggested that 760 °C cleaned, brazing may be accomplished.
(1400 °F) is a suitable brazing temperature. If it There are several different filler metals that
is necessary to reduce the amount of dezincifi- may be used, but one that works well is a 68Ag-
cation further, the parts may be plated with cop- 27Cu-5Pd filler metal. This filler metal has a
solidus of 807 °C (1485 °F) and a liquidus of polishing media was used or some polishing
810 °C (1490 °F). The brazing temperature is media had previously been used for deburring
816 to 843 °C (1501 to 1549 °F). parts of aluminum, magnesium, or other parts
When vacuum brazing with filler metal at a that contained elements that were not cleaned
temperature of 816 to 843 °C, a partial pressure up by the atmosphere or that produced an oxide
of argon is used to prevent evaporation of the in the standard brazing atmosphere. The parts
silver. A partial pressure of 50 µm prevents the that are not wet by the copper obviously have a
silver from vaporizing. Good, clean argon is contaminated surface. The fact that some parts
used, because the titanium picks up any con- braze satisfactorily and the copper wets the 400-
taminants. For this reason, nitrogen atmosphere series stainless steel indicates there is not an ele-
is not used to provide the partial pressure, ment, such as aluminum or possibly selenium,
because the titanium picks up the nitrogen, with in the stainless steel that also causes problems
deleterious effects. with wetting of the surface. The best method is
As a note of caution, it is wise to remember to contact the supplier of the 400-series stainless
that titanium does alloy with most other metals steel and to check the previous operations. If a
and, if taken up in temperature too far, alloys deburring media was used, some contaminant
with and melts down the stainless steel fixturing may be the culprit.
and other metal parts in the furnace. Thus, it The problem with the copper flowing all over
should not be placed directly on metal parts if the surface of the 305 stainless steel is caused by
the temperature is to be taken to the 927 °C (170 the very thin 305 stainless steel heating up first
°F) range and above. Because the braze in ques- and the 400 series heating up later. The filler
tion is titanium directly to stainless steel and to metal flows toward the hottest surface. The top
nickel, in this case, it is essential that the braz- of the assembly, which gets up to heat first,
ing temperature is below the eutectic melting tends to be wet with the copper.
point of the titanium-nickel and titanium/stain- There are several ways to control the flow of
less steel. Thus, the filler metal suggested previ- copper. The first approach is to bring the part up
ously accomplishes this. to heat more uniformly. Heat shielding of the
Example 4: Copper Brazing of Stainless top of the parts assists in slowing down the rapid
Steel Inserts. A manufacturing firm recently heating of the top end of the assembly. Heat
attempted to copper braze 305- to 400-series shields are very effective ways of controlling
stainless steel inserts. Sometimes, the copper the surface heating of parts where one section
wet the 400-series inserts, and sometimes, it heats up much faster than another.
flowed away from them and did not wet, cover- A second approach is to lighten the fixture so
ing the surface of the 300-series stainless steel. the part heats up more uniformly.
The problem was why the copper did not wet The third approach is to change the dewpoint
the 400-series stainless steel, even though once of the atmosphere in the furnace. The copper
in a while it brazed satisfactorily. Why did the then has less tendency to flow out on the surface
copper flow all over the 305 steel, but the 400- and thus stays closer to the joint. This approach
series stainless steel did not wet? is rather difficult and takes special equipment.
In dissecting the problem, there are several A fourth approach is to change the ratio of
points. hydrogen to nitrogen, keeping the dewpoint
First, the most serious problem is discussed: constant.
the wetting of the 400-series stainless steel. In Example 5: Brazing of a Ceramic-Matrix
looking at the part, it is obvious that it was Composite. Joining ceramic-matrix composite
stamped from a sheet and thus normally has (CMC) materials has attracted considerable
burrs at the edges. These burrs were removed, interest in recent years as a class of materials
apparently by tumbling or vibratory polishing. that can combine the strength and high-temper-
This part has a dull, gray finish, which is quite ature properties of ceramics with improved
common for parts that have been tumbled or damage tolerance. In many applications, it is
vibratory polished. This color, and the fact that necessary to join ceramics to metals, and braz-
the copper does not wet the 400-series stainless ing is a common means of achieving this.
steel, indicates there has been some material A Si3N4-fiber-reinforced cordierite glass
smeared on the surface of the part during the CMC was brazed to titanium and stainless steel
deburring operation. It is possible that a stone- using silver-copper filler metal in argon and
four different interlayers: copper, nickel, tung- the vertical orientation, with the flanges at the
sten, and MMC (SiC continuous fiber rein- lower ends.
forced with aluminum). The CMC needs to be Example 6: Brazing Nickel Alloy Strip to
coated with titanium to induce wetting and Copper-Aluminum Bar. Is it possible to braze
bonding. Joints brazed normal to the CMC lay- a 15 by 19 by 50.8 mm (0.6 by 0.75 by 2 in.)
up plane are generally much stronger than those Hastelloy X strip onto a 12.7 by 19 by 50.8 mm
brazed parallel to the lay-up plane. (0.5 by 0.75 by 2 in.) long copper (0.6 to 0.9%)-
The highest joint strength measured for a aluminum bar? Since it is not possible to silver
CMC-titanium joint was 91.6 MPa (13.3 ksi) in braze Hastelloy X, and it must be brazed with a
shear using a 1.0 mm (0.04 in.) copper inter- nickel filler metal at 1121.1 °C (2050 °F), what
layer. The highest CMC/stainless steel joint does one do?
strength was 106.1 MPa (15.4 ksi) using a 1.5 First, it should be pointed out that a copper-
mm (0.06 in.) MMC interlayer. Defect-free aluminum bar cannot be brazed at 1121.1 °C
joints are produced with all combinations because the melting point of this material is
except when tungsten interlayers are used, but ~1085 °C (1985 °F); therefore, at 1121.1 °C, it
some debonding is evident at the edges of other is molten. Because the bar contains 0.6 to 0.9%
specimens where residual shear stresses are Al and is to be furnace brazed with a nickel filler
highest. In shear testing, all joints except the metal, it must be plated with either electrolytic
strongest failed within the ceramic composite. nickel or copper. This will protect the aluminum
Brazing has been found to be an effective from the atmosphere and will not allow it to oxi-
technique for joining ordinary structural metals dize and prevent brazing. The assembly may be
to brittle, low-thermal-expansion refractory brazed with a BNi-2 filler metal at 1037.8 °C
metals. Specifically, a brazing process has been (1900 °F), and BNi-7 or BNi-6, brazed at 1010
established for joining copper or nickel flanges °C (1850 °F).
to the ends of vacuum-plasma-sprayed tungsten To torch silver braze a copper-aluminum bar,
tubes and for joining stainless steel flanges to it is first required to have the FB4-A flux to
the ends of tubes made of an alloy of molybde- inhibit the formation of aluminum oxides that
num with 40% Rh. prevent wetting the copper. The FB4-A flux has
In the original application, the tubes were fur- been specifically designed for brazing alu-
nace cartridge tubes 59.7 cm (23.5 in.) long and minum-bronze base metals. The next considera-
25.4 mm (1 in.) in diameter, with a wall thick- tion is the heating of the copper, preferably from
ness of 0.76 mm (0.03 in.). The tubes were of the bottom with a ribbon burner, and uniformly
test-tube configuration, and the flanges were applying the extra heat needed to the Hastelloy
joined to the open ends. X, which is on the top of the bar.
In preparation for brazing, the tubes were Example 7: Vacuum Brazing of Nickel
cleaned of surface contaminants by placing Alloy Tubes to Titanium Alloy Fittings. A
them in a hydrogen furnace in the temperature warm-gas fuel pump manifold consisting of 30
range of ~1100 to 1150 °C (2010 to 2100 °F) for vacuum-brazed joints between Inconel 600
15 min. That area on each tube that was to be tubes and Ti-6Al-4V fittings was successfully
joined to a flange was then pretinned by wrap- joined. The components were part of a piston-
ping the area with a thin filler-metal foil and pumped rocket propulsion system, and the braze
heating it to the melting temperature. joints had to withstand high-temperature and
After pretinning, each flange was machined short-term exposure to hydrazine propellant.
to provide a braze-joint gap of 0.076 to 0.10 mm The filler metal used was Ag-9Pd-9Ga.
(0.003 to 0.004 in.). Each tube was then put A second assembly was a warm-gas pressur-
together with its flange, and a small amount of ization regulator. It required the brazing of a 1.5
filler metal was placed at the opening of the mm (0.06 in.) diameter Inconel 600 U-tube into
braze joint to provide sufficient material to fill a Ti-6Al-4V body.
the gap. A braze stopoff solution was applied to Because of the different configurations of the
the surfaces surrounding the joint to prevent the components joined, two types of vacuum fur-
filler metal from flowing onto these surfaces, naces were used. Both brazing systems incorpo-
thereby making it unnecessary to perform a rated liquid-nitrogen-trapped diffusion pumps
postbraze cleanup. The tubes were then brazed, backed by rotary mechanical pumps. The base
variously, in an inert or vacuum environment in pressure of both systems was on the order of
10–5 Pa (10–9 psi) with the brazes typically per- Example 8: Brazing of Copper-Graphite
formed at approximately 10–3 Pa (10–7 psi). Assemblies. Copper-graphite assemblies are
The system used to braze the manifold was a used as targets for pulsed proton beams. The
10 kW, 450 kHz radio frequency (RF) induction graphite used is paralytic grade and is engi-
furnace. Induction heating took place in an elec- neered to have a lamellar structure, perpendicu-
trically conducting object, not necessarily mag- lar to the proton beam, such that the heat gener-
netic, when the object was placed in a varying ated within the target during operation flows
magnetic field. The joint was placed within (but vertically through the graphite to the copper
not in contact with) a water-cooled copper coil base. Copper is used because it has a high ther-
in the vacuum enclosure, and heating was per- mal conductivity and is subsequently water
formed locally—only the joint got hot. During cooled to maintain efficient heat removal.
the braze operation, the joint could be moved When the brazing of these materials was first
vertically inside the furnace to selectively apply attempted, the graphite sections all failed as a
heat to different parts of the assembly. The result of cracking at the sharp-edged corners.
advantage to RF heating was that, depending on Initially, it was felt that procedures/equipment
its size, the entire assembly is not necessarily could be at fault.
raised to the braze temperature each time a joint Examination of the failed bonds produced at
was brazed. This resulted in a reasonably quick this stage showed classical residual-stress
turnaround time and avoided remelting previous cracks emanating from each corner of the
joints each time a new joint was brazed. graphite. This was due to both the large differ-
Where the RF induction furnace was inappro- ence in CTE between graphite (0.1 × 10–6/°C, or
priate, because of the part configuration, a radi- 0.06 × 10–6/°F) and copper (18 × 10–6/°C, or 10
ant heating furnace was used. This furnace used × 10–6/°F) and also the presence of sharp cor-
the radiant energy from a series of tungsten fila- ners, which act as stress concentrators. The
ments to heat the part. Molybdenum shielding potential ways of resolving this problem are:
contained the heat in the brazing zone, which
was located inside a double-wall, water-cooled • A change in filler metal to reduce the brazing
stainless steel vacuum chamber. The tempera- temperature and hence reduce the thermal
ture was monitored and controlled by using stresses induced during the heat treatment
thermocouples located within the hot zone. • Modification to the copper heat sink, either
Radiant heating was very uniform, because the by changing the composition to reduce the
entire hot zone was elevated to the braze tem- CTE (by alloying with a low-CTE metal such
perature. The furnace was allowed to cool as tungsten) or by a change of dimensions to
overnight under vacuum before venting to reduce the cross-sectional thickness
argon and removing the brazed assembly. • Modification to the design of the graphite to
The filler metal selected was specifically remove the sharp edges, which act as local
developed to braze titanium alloys to them- stress concentrators
selves and was composed of 82% Ag, 9% Pd,
and 9% Ga. A 0.508 mm (0.020 in.) diameter An active filler metal was selected containing
wire was used in brazing. This filler metal is titanium, which is capable of wetting onto both
very ductile and has a brazing range between graphite and copper and is Ag-Cu-Ti. This filler
895 and 950 °C (1645 and 1740 °F), which is metal brazes at 850 °C (1560 °F) and forms a
below the beta transus of the titanium alloy. TiC with the graphite. The combination of
Work performed on brazed samples revealed reduced brazing temperature and the formation
the presence of a layer of palladium-gallium of a slightly more elastic carbide phase may
at the filler-metal/titanium interface, which alleviate some of the cracking problems en-
appears to act as a diffusion barrier to silver, countered. Experimentally, this one change in
preventing the formation of titanium-silver brazing procedure (and no change to either the
intermetallics. Because of the high vapor pres- graphite or copper) reduced the cracking in each
sure of silver and gallium, it is recommended component by 50%. Therefore, this method
using this filler metal in a system backfilled with may be used in conjunction with the other
dry helium or argon. However, brazing can be design modifications.
performed in a hard vacuum by minimizing the A further alteration made to the use of the
time at braze temperature. filler metal was the use of stopoff compound
(based on titanium oxide) near the joint area. 4. K. Suganuma, Y. Miyamoto, and M.
Previous joints appeared to have failed at a point Koizumi, Joining of Ceramics and Met-
of initiation close to areas of excess braze mate- als, Annual Review of Materials Science,
rial. These areas of excess braze wetting form Vol 18, R.A. Huggins, Ed., 1988, p 47–73
due to flow of the filler metal as it wets onto the 5. M. Naka, M. Kubo, and L. Okamoto,
two substrates. To inhibit this excessive braze Joining of Silicon Nitride with Al-Cu
wetting, stopoff solution was painted around the Alloys, J. Mater. Sci., Vol 22 (No. 12),
joint area, so that the filler metal could only wet 1987, p 4417–4421
onto the bond area itself. 6. H.D. Steffens, B. Wielage, and K. Bier-
The hermeticity of the bond was further mann, Modified High Temperature Braz-
improved by fine polishing of the graphite joint ing Techniques for Nickel Based Materi-
area prior to bonding. In this way, all sharp als, Ind. Heat., 17–18 May 1989
edges were removed from the joint area, and a 7. M. Ueki, M. Naka, and L. Okamoto, Join-
surface finish of 0.15 µm was achieved on the ing and Wetting of CaO-Stabilized ZrO2
graphite. The roughness and surface finish can with Al-Cu Alloys, J. Mater. Sci., Vol 23
influence the strength of bonding, because a (No. 8), 1988, p 2983–2988
rough surface can prevent complete contact at 8. M. Ueki, M. Naka, and I. Okamoto, Wet-
an interface and can damage the ceramic (in this tability of Some Metals Against Zirconia
case, graphite) because of severe residual Ceramics, J. Mater. Sci. Lett., Vol 5 (No.
stresses caused by deep scratches or poor sur- 12), 1986, p 1261
face finish. Conversely, there is an effect of 9. Y.R. Mahajan and S. Kirchhoff, Rapidly
anchoring on a rough interface due to mechani- Solidified Structures of an Al-Zr-Gd
cal keying. In reality, it appears to be a combi- Alloy, Scr. Metall., Vol 21 (No. 8), 1987,
nation of these two properties that influences the p 1125–1130
mechanical properties of the joint. Wherever 10. E. Lugscheider and K.-D. Partz, High
possible, a fault-free surface is preferred in Temperature Brazing of Stainless Steel
order to inhibit cracks manifesting from resid- with Nickel Base Filler Metals BNi-2,
ual flaws or surface imperfections. BNi-5 and BNi-7, Weld. J., Vol 62 (No.
A combination of the previously mentioned 6), 1983, p 160s–164s
modifications allowed the production of sound 11. E. Lugscheider, K.-D. Partz, and J. Kru-
graphite-copper bonds for proton targets. In ger, Rechnerunterstutzte Gefugebeurtei-
summary, these were: lung an Hochtemperaturlotverbindungen-
Prozessoptimerung zur Qualitatssiche-
• Use of a lower-temperature filler metal rung and Bauteilsicherheit (Prerequisite
• Reduction of the copper thickness at the bond Variables for High Temperature Joining—
areas, and slotting to produce mechanical Process Optimization Resulting in Good
keying as well as chemical bonding Quality Techniques and Control), DVS-
• Polishing of the graphite to remove surface Berichte 75, Dusseldorf: Deutscher Verlag
irregularities, and removal of sharp corners fur Schweisstechnik, 1989
from the joint area 12. E. Lugscheider, O. Knotek, and K. Klohn,
Development of Nickel-Chromium-Sili-
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Base Metals and Base-Metal Family Groups: Metallurgical Reactions

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CHAPTER 4

Base Metals and Base-Metal

Fig. 4.1 (continued)

mm D (in.) Nomograph for equation

Shear strength, ksi

Microstructural changes were analyzed that

Table 4.1 Compositions and densities of some important aluminum-lithium alloys

Production route Alloy Li Cu Mg Si Fe Zr Density, 103 kg/m3

alloy interlayer and a pressure of 10 MPa (1.5 Cu - Al

sure for 30 min at 510 °C, shear strength of 54 Al - Cu - Ag

anism for bonding that reflects diffusion behav-

oped for brazing aluminum, copper, and brass Al - Cu - Ag Al - Cu - Ag

In these applications, at least one of the alu- Ag2Al Al

Table 4.2 Composition limits for selected aluminum alloys

Aluminum alloy Si Fe Cu Mn Mg Zn Cr Ti Others

Table 4.3 Compositions of filler metals investigated for brazing of dispersion-strengthened

Coppers BCuP-2, BCuP-5 None None Do not braze oxygen-containing

tion is performed in a flux bath. Furnace brazing

AZ10A 632 1170 643 1190 582–616 1080–1140 X X

AZ92A(a) 443 830 599 1110 604–616 1120–1140 ... ...

Table 4.6 Commercially available nickel-base filler metals

Table 4.6 (continued)

Other Solidus Liquidus Brazing range

Nickel-base alloy filler metals(a)

Other Solidus Liquidus Brazing range

Other Solidus Liquidus Brazing range

Cobalt-base alloy filler metals

Base metal Brazing filler metal °C °F Nominal composition

TD-Ni TD-20 1302 2375 Ni-16Cr-25Mo-4Si-5W

Table 4.9 Composition of materials used in brazing a nickel-base single-crystal superalloy

The filler metals used for brazing of refrac-

• Recrystallization of molybdenum systems, and the best filler-metal base on over-

43 43 2 12 ... ... 799 1470 816 1500

AWS classification Product form Ag Cu Zn Cd Ni Sn Fe Mn Si P °C °F °C °F °C °F

Chapter 4: Base Metals and Base-Metal Family Groups / 103

Filler metal Type of salt °C °F

BAg-1 through BAg-8, and BAg-18 Neutral 621–871 1150–1600

Chapter 4: Base Metals and Base-Metal Family Groups / 109

Composition, % Solidus temperature Liquidus temperature Brazing temperature range

Composition, % Solidus temperature Liquidus temperature Brazing temperature range

TiCuNi 60 ... 20 20 ... 923 1695 934 1715 950 1740

mechanical properties of the original ceramic

Joined parts can withstand temperatures that

Bending strength SiC – SiC Sample a

Braze material Atmosphere °C °F Time, min N lbf

Filler metal system °C °F Refractory metals Graphite Al2O3

Ti-V-Cr 1550–1650 2820–3000 x x x

quality bond could be obtained at a temperature

range from 2 to 8 × 10–6/°C (1 to 4 × 10–6/°F) ments. They include 48Ti-48Zr-4Be, 35Au-

copper. In the case of graphite-to-molybdenum, Researchers (Ref 231, 232) conducted an

Table 4.26 Shear strengths of graphite brazed joints

Graphite-to-graphite 50 4 40.0 (5.8) 1.8 (0.26) ...

Another series of investigations (Ref 236)

Table 4.27 Filler metals for brazing ceramics

Copper, BCu-1(a) 100 Cu 3598 (1981) 3598 (1981)

Table 4.29 Summary of methods for metallizing ceramics

occurs at the ceramic/filler-metal interface. son, the particle-segregation tendency is

I Al2O3/type 321 steel Al 873 K, 50 MPa (7.3 ksi), 30 min. 70 (10.2)