Europäisches Patentamt

(19) European Patent Office *EP000767252B1*

Office européen des brevets (11) EP 0 767 252 B1
(12) EUROPEAN PATENT SPECIFICATION

(45) Date of publication and mention (51) Int Cl.7: C22F 1/10, C22C 19/05
of the grant of the patent:
22.08.2001 Bulletin 2001/34

(21) Application number: 96307212.9

(22) Date of filing: 02.10.1996

(54) Nickel base superalloy articles with improved resistance to crack propagation
Superlegierung auf Nickelbasis mit verbesserter Rissbeständigkeit
Superalliage à base de nickel résistant aux propagations de fissures

(84) Designated Contracting States: • Jones, Howard B.

DE FR GB Stuart, Florida 34997 (US)
• Rhemer, Chris C.
(30) Priority: 02.10.1995 US 537341 Palm Beach Gardens, Florida 33418 (US)

(43) Date of publication of application: (74) Representative: Leckey, David Herbert

09.04.1997 Bulletin 1997/15 Frank B. Dehn & Co.,
European Patent Attorneys,
(73) Proprietor: UNITED TECHNOLOGIES 179 Queen Victoria Street
CORPORATION London EC4V 4EL (GB)
Hartford, Connecticut 06101 (US)
(56) References cited:
(72) Inventors: EP-A- 0 241 405 EP-A- 0 274 631
• Deluca, Daniel P. GB-A- 2 284 617 US-A- 5 061 324
Tequesta, Florida 33469 (US) US-A- 5 328 659
• Biondo, Charles M.
Jupiter, Florida 33458 (US)
EP 0 767 252 B1

Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give
notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in
a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art.
99(1) European Patent Convention).

Printed by Jouve, 75001 PARIS (FR)

 EP 0 767 252 B1

Description

[0001] This invention relates to high strength nickel base superalloys possessing superior resistance to crack prop-
agation, especially under conditions where hydrogen embrittlement is prone to occur. This invention also relates to
5 heat treatments for such alloys.
[0002] This invention focuses on improvements to the hydrogen embrittlement resistance of high strength nickel
base superalloy materials. High strength nickel base superalloys are defined in the context of this invention as nickel
base alloys having more than about fifty volume percent of the strengthening gamma prime phase in a gamma matrix
and having a yield strength in excess of about 100 ksi (690 MPa) at 1000°F (538°C). The gamma prime phase typically
10 assumes a cuboidal morphology in the gamma matrix with alignment in the <001> direction. Such alloys find their
widest application in the field of gas turbine engines.
[0003] In gas turbine engines, hydrocarbon fuels are burned, and free hydrogen may be present at some points
during the combustion process, but the relatively low concentration of available hydrogen, and the operating conditions
of such engines, have not been found to cause any significant hydrogen embrittlement of the nickel base superalloys.
15 [0004] Hydrogen embrittlement is more frequently encountered in fields other than those relating to the gas turbine
industry. For example, hydrogen embrittlement occurs at times during electroplating, where hydrogen gas is generated
on the surface of a part being plated and is absorbed into the part, greatly reducing the ductility of the part. It is also a
factor in some forms of hot corrosion, especially hot corrosion which is observed in well drilling wherein deep drilled
oil well casings are prone to hydrogen embrittlement as a result of the hydrogen sulfide present in some of the crude
20 petroleum and natural gas which pass through the casings. U.S. Patents 4,099,922, 4,421,571 and 4,245,698 are
typical of the attempts to solve oil well hydrogen embrittlement problems.
[0005] Recently, in the development of the space shuttle main engines, hydrogen embrittlement has been recognized
as a potential problem. The space shuttle main engines are rocket engines which mix and react liquid hydrogen and
liquid oxygen to form the propellant. These reactants are pumped into the main combustion chamber by turbo pumps
25 which are powered by the combustion products of the reaction of hydrogen and oxygen. The hot side of the turbo
pumps, which is exposed to the combustion products of the hydrogen/oxygen reaction, includes a multiplicity of small
turbine blades which are typically investment cast from directionally solidified Mar-M 246 + Hf alloy, an alloy which
meets the previous definition of a high strength nickel base superalloy in that it contains more than fifty volume percent
of the gamma prime phase and has a yield strength of more than 100 ksi (690 MPa) at 1000°F (538°C). The nominal
30 composition of Mar-M 246 + Hf, in weight percent, is 9 Cr, 10 Co, 2.5 Mo, 10 W, 1.5 Ta, 5.5 Al, 1.5 Ti, 1.5 Hf, balance
nickel. Due to this hydrogen exposure, hydrogen embrittlement of these turbine blades, as well as other articles in the
turbo pumps such as vanes, is of great concern.
[0006] Hydrogen embrittlement is encountered in these and other circumstances, and while the exact mechanism
involved is still open to conjecture, the existence of the problem is well documented. Initiation of hydrogen embrittlement
35 cracking in nickel base superalloys has been found to occur at discontinuities in the structure, such as pores, hard
particles and interfaces between precipitated phases and the matrix, such as script type carbides and gamma-gamma
prime eutectic islands. Specifically, during testing fatigue crack initiation has been observed at similar sites in conven-
tionally processed PWA 1489, which is a high strength, equiaxed superalloy having a nominal composition of 8.4 Cr,
10 Co, 0.65 Mo, 5.5 Al, 3.1 Ta, 10 W, 1.4 Hf, 1.1 Ti, 0.015 B, .05 Zr, balance Ni, with all quantities expressed in weight
40 percent. Strong evidence has been observed for the occurrence of interphase cleavage at the interfaces between the
gamma matrix and gamma prime particles, and within gamma-gamma prime eutectic islands. These features have
been identified as fatigue crack initiation sites in this class of alloys in a hydrogen environment. Thus, there is great
concern to minimize the initial occurrence of these crack initiation sites. There is also great concern to minimize crack
propagation or growth should a crack develop.
45 [0007] Accordingly, there exists a need for a high strength nickel base superalloy material which is highly resistant
to hydrogen embrittlement in general and particularly resistant to crack propagation.
[0008] GB-A-2 284 617 discloses a method of manufacturing a cast superalloy in which the alloy is subject to a heat
treatment after cooling from solutionizing to effect Cr diffusion but in which the chromium carbides nuclei are not so-
lutionized
50 [0009] According to the present invention, there is provided a method for making a nickel base alloy having improved
resistance to hydrogen embrittlement, particularly crack propagation, the method comprising the sequential steps of:

a. providing a gamma prime strengthened nickel base alloy having a composition, in weight percent, consisting of:

55 (wt. %) range (wt. %)

Carbon 0.006 0.17

2
 EP 0 767 252 B1

(continued)

(wt. %) range (wt. %)

Chromium 6.0 22.0
5
Cobalt ----- 15.0
Molybdenum ----- 9.0
Tungsten ----- 12.5
10 Titanium ----- 4.75
Aluminum ----- 6.0
Tantalum ----- 4.3
Hafnium ----- 1.6
15
Iron ----- 18.5
Rhenium ----- 3.0
Niobium ----- 1.0
20 Boron ----- trace
Zirconium ----- trace

remainder nickel apart from unavoidable impurities

25 b. casting the nickel base alloy;
c. solution heat treating the nickel base alloy at a temperature above its gamma prime solvus temperature as much
as about 50°F (28°C) above so as to dissolve substantially all gamma-gamma prime eutectic islands and script
carbides without causing incipient melting, and slow cooling at between 0.1°F/minute (0.06°C/minute) and 5°F/
minute (2.8°C/minute) from the solution heat treating temperature to a temperature below the gamma prime solvus
30 temperature and then rapid vacuum cooling to below 1000°F (538°C); and then
d. hot isostatic pressing the alloy below the γ' solvus temperature to eliminate porosity;
e. precipitation heat treating the alloy; and
f. aging the alloy,
the steps being such as to produce a nickel base alloy having a microstructure which includes a plurality of
35 regularly occurring large barrier gamma prime precipitates and a continuous field of fine cuboidal gamma prime
precipitates surrounding the large barrier gamma prime precipitates, the microstructure being essentially free of
script carbides, gamma-gamma prime eutectic islands and porosity.

[0010] The resulting high strength nickel base superalloy material is highly resistant to hydrogen embrittlement in
40 general and particularly resistant to crack propagation. The principles taught in this invention are also expected to
provide marked increases in the fatigue resistance and crack propagation when used in more common applications,
such as gas turbine engines.
[0011] Since the existence of such hard particles as carbides, nitrides and borides can be the source of fatigue crack
initiation, the heat treatment process described herein is designed to solution essentially all of these hard particles,
45 while leaving only enough of these particles in the grain boundaries to control grain growth in equiaxed alloys.
[0012] In the presence of hydrogen, eutectic islands provide crack initiation sites by cleaving at the interfaces of the
gamma and gamma prime lamellae. Eliminating eutectic islands thus significantly retards cracking in the presence of
hydrogen. Script carbides also provide fatigue crack initiation sites and, by minimizing their size and frequency of
occurrence, fatigue life is also improved.
50 [0013] The inventive process is applicable to nickel base superalloys in which gamma-gamma prime eutectic islands
and script type carbide can be essentially completely solutioned without incurring incipient melting.
[0014] In a preferred embodiment, the gamma prime strengthened nickel base alloy has a composition, in weight
percent, consisting of:

55 (wt. %) range (wt. %)

Carbon 0.13 0.17
Chromium 8.00 8.80

3
 EP 0 767 252 B1

(continued)

(wt. %) range (wt. %)

Cobalt 9.00 11.00
5 Molybdenum 0.50 0.80
Tungsten 9.50 10.50
Titanium 0.90 1.20
Aluminum 5.30 5.70
10
Tantalum 2.80 3.30
Hafnium 1.20 1.6
Iron ----- 0.25
Niobium ---- 0.10
Boron ------ trace
15 Zirconium ------ trace

remainder nickel apart from unavoidable impurities.

[0015] One of ordinary skill in the art will recognize that various trace elements, including but not limited to, manga-
nese, silicon, phosphorus, sulfur, boron, zirconium, bismuth, lead, selenium, tellurium, thallium and copper may be
20
present in minor amounts.
[0016] The alloy of the present invention may be formed by providing a nickel base alloy as described above in
molten form, casting the alloy in either an equiaxed or columnar grain form, and subjecting the alloy to a heat treatment.
The alloy is heat treated (preferably, vacuum heat treated) using a stepped ramp cycle and subsequent hold to permit
solutioning at a temperature approximately 50°F (28°C) above the gamma prime solvus temperature (temperature
25
below which gamma prime exists) so that the gamma-gamma prime eutectic islands and the script type carbides are
dissolved. Specifically, the ramp cycle includes the following: heat the superalloy article from room temperature to
about 2000°F (1093°C) at about 10°F/minute (5.5°C/minute); ramp from about 2000°F (1093°C) to about 2240°F
(1227°C) at about 2°F/minute (1.1°C/minute); ramp from about 2275°F (1246°C) to about 2285°F (1252°C) at about
0.1°F/minute (0.06°C/minute); and hold at about 2285°F (1252°C) for between about 3 hours to about 6 hours, pref-
30
erably 4 hours.
[0017] If the alloy material was then rapid vacuum cooled from this point, fine gamma prime precipitates would occur
and the material would exhibit significantly improved resistance to fatigue in hydrogen as well as in air.
[0018] Although the above process is extremely advantageous, it is also desirable to deter crack growth or propa-
gation at any occurring cracks in the material. This would even further increase the useful life of a particle made from
35
the superalloy material. Accordingly, we have determined that the presence of large, barrier gamma prime precipitates
in the microstructure would deter crack propagation by acting as crack arrestors. These large, barrier gamma prime
precipitates may be precipitated out by slow cooling the superalloy material from about 2350°F (1288°C) to about
2000°F (1093°C ) at between about 0.1°F/minute (0.06°C/minute) and about 5°F/minute (2.8°C/minute), and most
preferably from about 2285°F (1252°C) to about 2135°F (1168°C) at about 0.5°F/minute (0.28°C/minute). The material
40
is then rapid vacuum cooled to room temperature and HIPped below the solvus temperature for a period of about four
hours to eliminate all porosity, cavities, and voids. The material is then given conventional lower temperature heat
treatments to produce a superalloy material which is resistant to crack initiation, as well as crack propagation.
[0019] Certain preferred embodiments will now be described, by way of example only, with reference to the accom-
panying drawings in which:
45
[0020] Fig. 1 is a photomicrograph of a prior art PWA 1489 microstructure showing the presence of gamma-gamma
prime eutectic islands, as indicated by the arrows.
[0021] Fig. 2 is a photomicrograph of a prior art PWA 1489 microstructure showing the typical carbide morphology
(presence of script type carbides, as indicated by the arrows).
[0022] Fig. 3 is a photomicrograph of a prior art PWA 1489 microstructure showing the typical gamma prime mor-
50
phology.
[0023] Fig. 4 is a photomicrograph of modified PWA 1489 microstructure embodying the present invention showing
an absence of gamma-gamma prime eutectic islands.
[0024] Fig. 5 is a photomicrograph of modified PWA 1489 microstructure embodying the present invention showing
the typical carbide morphology (absence of script type carbides).
55
[0025] Fig. 6 is a photomicrograph of modified PWA 1489 microstructure embodying the present invention showing
the gamma prime morphology (presence of larger, barrier gamma prime precipitates).
[0026] Fig. 7 and Fig. 8 are graphs (log-log plots) of fatigue crack growth rates (da/dN) at 1200°F (649°C)-Fig. 7;

4
 EP 0 767 252 B1

combination of 400°F (204°C) and 80°F (27°C)-Fig. 8; each at 5000 psig (35 MPa) as a function of stress intensity
(∆K) for conventionally processed PWA 1489 and modified PWA 1489 (processed according to the present invention).
[0027] The fatigue cracking of polycrystalline nickel base superalloys in a hydrogen environment is attributed to the
initiation of fatigue cracks at the interfaces between the gamma and the gamma prime lamellae in the gamma-gamma
5 prime eutectic islands and crack initiation at script-type carbides.
[0028] PWA 1489 is an equiaxed nickel base superalloy used primarily for components requiring high thermal shock
resistance and high strength at cryogenic and elevated temperatures. In prior applications it has been vacuum melted
and cast, HIPped and solution heat treated. Figure 1 shows gamma-gamma prime eutectic islands and Figure 2 shows
script-type carbides present in PWA 1489 processed using prior techniques. Figure 3 shows the corresponding gamma
10 prime morphology. The superalloy of Figures 1-3 was thermally processed using the following parameters: HIP at
2165°F (1185°C) for 4 hours at 25 ksi (172 MPa); solutioned at 2165°F (1185°C) for two hours; rapid vacuum cooled
to below 1000°F (538°C); precipitation heat treated at 1975°F (1079°C) for four hours; air cooled to room temperature;
aged at 1600°F (871°C) for 20 hours; and air cooled to room temperature.
[0029] While the presence of script-type carbides and gamma-gamma prime eutectic islands in alloys such as PWA
15 1489 was acceptable for the high temperature gas turbine applications, cracking of engine test components in a hy-
drogen environment produced inherent design limitations. The elimination of script carbides and eutectic islands by
thermal processing provides significant property improvement and greater design margin for components produced
from these alloys for use in the space shuttle main engine program.
[0030] The essential elimination of these microstructure features requires solutioning the alloy at temperatures sig-
20 nificantly above the gamma prime solvus temperature and can result in incipient melting due to the microstructural
chemical inhomogenities incurred during solidification.
[0031] Thus, a ramp solution cycle is employed to permit heating as much as about 50°F (28°C) above the gamma
prime solvus temperature. This permits sufficient solutioning to virtually eliminate all script type carbides and eutectic
islands. Specifically, the ramp cycle includes the following: heat the superalloy article from room temperature to about
25 2000°F (1093°C) at about 10°F/minute (5.5°C/minute); ramp from about 2000°F (1093°C) to about 2240°F (1227°C)
at about 2°F/minute (1.1°C/minute); ramp from about 2275°F (1246°C) to about 2285°F (1252°C) at about 0.1°F/
minute (0.06°C/minute); and hold at about 2285°F (1252°C) for between about 3 hours to about 6 hours, preferably 4
hours.
[0032] We have developed a post-solution cool down cycle to allow precipitation of large, barrier gamma prime
30 precipitates. We have found that employment of this slow cool down cycle results in large gamma prime precipitates
which act as crack arrestors, significantly deterring crack propagation, should a crack occur. Specifically, the superalloy
article is then cooled from about 2285°F (1252°C) to about 2135°F (1168°C) at about 0.5°F/minute (.28°C/minute)
and rapid vacuum cooled from about 2135°F (1168°C) to below about 1000°F (538°C). This slow cooling enables the
production of a microstructure which is significantly resistant to crack propagation. This improvement will increase the
35 useful life of the superalloy article.
[0033] After employment of the slow cooling step, the superalloy article is then hot isostatic pressed (HIPped) at
about 2165°F (1185°C) +/- about 25°F (14°C) at about 25 ksi (172 MPa) for 4 hours to 8 hours (preferably 4 hours),
precipitation heat treated at about 1975°F (1079°C) +/-about 25°F (14°C) for 4 hours to 8 hours (preferably 4 hours)
and air cooled to room temperature. The article is then aged at between about 1400°F (760°C) and about 1600°F
40 (871°C) (preferably at about 1600°F (871°C) +/- about 25°F (14°C)) for between about 8 hours and about 32 hours
(preferably 20 hours) and air cooled to room temperature.
[0034] It is noted that the temperatures for the heat treatment are selected relative to the gamma prime solvus tem-
perature for the particular alloy, in this case PWA 1489, and are based on a gradient heat treat study for the particular
heat of material. The solution cycle may include several ramps at decreasing rates of temperature rise (with or without
45 intermediate periods of constant temperature rise), or a smoothly increasing curve with a gradually decreasing rate of
temperature increase until the maximum solution temperature is achieved.
[0035] The microstructure of the invention-processed material is shown in Figures 4-6. The superalloy material of
Figures 4-6 was thermally processed using the following parameters: solutioned at 2285°F (1252°C) for 4 hours; slow
cooled to 2135°F (1168°C) at 0.5°F/minute (0.28°C/minute); rapid vacuum cooled from about 2135°F (1168°C) to
50 below 1000°F (538°C); HIP at 2165°F (1185°C) for 4 hours at 25 ksi (172 MPa); precipitation heat treated at 1975°F
(1079°C) for 4 hours; air cooled to room temperature; aged at 1600°F (871°C) for 20 hours; and air cooled to room
temperature.
[0036] The advantages of the present invention can be readily seen from the figures. Specifically, Figure 4 shows
the absence of eutectic islands. Figure 5 shows an absence of script type carbides. Most significantly, large, barrier
55 gamma prime precipitates may be seen on Figure 6. These large, barrier gamma prime precipitates significantly improve
crack propagation resistance.
[0037] The microstructure of the present invention has an average grain size of from about 90 microns (9x10-5 m)
to about 180 microns (1.8x10-4 m). The large gamma prime precipitates are between about 2 microns (2x10-6 m) and

5
 EP 0 767 252 B1

about 20 microns (2x10-5 m) and the fine cuboidal gamma prime precipitates surrounding the large barrier gamma
prime precipitates are between about 0.3 microns (3x10- 7 m) and about 0.7 microns (7x10-7 m). It should be noted
that the grain size is set by the casting process employed.
[0038] The present invention will now be further described by way of example which is meant to be exemplary rather
5 than limiting. Second stage vane ring segments with a nominal composition of 8.4 Cr, 10 Co, 0.65 Mo, 5.5 Al, 3.1 Ta,
10 W, 1.4 Hf, 1.1 Ti, 0.015 B,0.05 Zr, balance Ni, with all quantities expressed in weight percent, were processed
according to the present invention and tested in a hydrogen environment at 1600°F (871°C) and 5000 psi (34 MPa)
for about 5000 seconds of run time. Several standard processed vane segments with the same composition were also
tested for comparison. Following the test, the segments were fluorescent penetrant inspected. The segments processed
10 according to the present invention showed no distress in comparison with the standard processed vane segments
which exhibited trailing edge cracking.
[0039] To further illustrate the advantages of the present invention, Figure 7 and Figure 8 are presented. These
figures illustrate the rate of crack propagation for the prior microstructure of PWA 1489 compared to the new, modified
microstructure of PWA 1489. Specifically, the axes of the graphs show how crack growth rate (da/dN) varies with stress
15 intensity. The arrow in Figure 7 shows how a crack in conventional PWA 1489 (indicated at 1) grows as much as a
hundred times faster than a crack in modified PWA 1489 (indicated at 2) of the present invention. The arrow in Figure
8 shows how a crack in conventional PWA 1489 (indicated at 1) can grow more than ten times faster than a crack in
modified PWA 1489 (indicated at 2). The comparisons are made for tests conducted in high pressure hydrogen gas
representing a rocket environment. Tests were conducted at 45 cycles per minute with zero hold time.
20 [0040] From the above description, it will be seen that in its preferred embodiments, the present invention provides
a gamma prime strengthened nickel base superalloy which is particularly resistant to crack propagation. The micro-
structure of this superalloy is characterized by an absence of intergranular eutectic gamma-gamma prime phase is-
lands, an absence or low incidence of large script type carbides and an absence or low incidence of linear carbides
spanning grains. The microstructure also includes a plurality of regularly occurring large barrier gamma prime precip-
25 itates elongated in the <111> family of crystallographic directions (8<111> vectors in total) and a continuous field of
fine cuboidal gamma prime precipitates surrounding the large barrier gamma prime precipitates. Furthermore, the alloy
has improved resistance to hydrogen embrittlement, particularly fatigue crack initiation and propagation.
[0041] Although this invention has been shown and described with respect to detailed embodiments thereof, it will
be understood by those skilled in the art that various changes, omissions and additions in form and detail thereof may
30 be made without departing from the scope of the claimed invention.

Claims

35 1. A method for making a nickel base alloy having improved resistance to hydrogen embrittlement, particularly crack
propagation, the method comprising the sequential steps of:

a. providing a gamma prime strengthened nickel base alloy having a composition, in weight percent, consisting
of:
40

(wt. %) range (wt. %)

Carbon 0.006 0.17
Chromium 6.0 22.0
45 Cobalt ----- 15.0
Molybdenum ----- 9.0
Tungsten ----- 12.5
Titanium ----- 4.75
Aluminum ----- 6.0
50
Tantalum ----- 4.3
Hafnium ----- 1.6
Iron ----- 18.5
Rhenium ----- 3.0
55 Niobium ----- 1.0
Boron ----- trace
Zirconium ----- trace

6
 EP 0 767 252 B1

remainder nickel apart from unavoidable impurities

b. casting the nickel base alloy;
c. solution heat treating the nickel base alloy at a temperature above its gamma prime solvus temperature as
much as about 50°F (28°C) above so as to dissolve substantially all gamma-gamma prime eutectic islands
5 and script carbides without causing incipient melting, and slow cooling at between 0.1°F/minute (0.06°C/
minute) and 5°F/minute (2.8°C/minute) from the solution heat treating temperature to a temperature below
the gamma prime solvus temperature and then rapid vacuum cooling to below 1000°F (538°C); and then;
d. hot isostatic pressing the alloy below the γ' solvus temperature to eliminate porosity;
e. precipitation heat treating the alloy; and
10 f. aging the alloy,

the steps being such as to produce a nickel base alloy having a microstructure which includes a plurality of
regularly occurring large barrier gamma prime precipitates and a continuous field of fine cuboidal gamma prime
precipitates surrounding the large barrier gamma prime precipitates, the microstructure being essentially free of
15 script carbides, gamma-gamma prime eutectic islands and porosity.

2. A method as claimed in claim 1, wherein the large barrier gamma prime precipitates are between 2 to 20 µm.

3. A method as claimed in claim 1 or 2, wherein the fine cuboidal gamma prime precipitates are between 0.3 to 0.7 µm.
20
4. A method as claimed in claim 1, 2 or 3, wherein the hot isostatic pressing step is at 2165°F (1185°C) ± 25°F (14°C)
and 25 ksi (172 MPa) for between four to eight hours.

5. A method as claimed in any preceding claim, wherein the alloy is precipitation heat treated at 1975°F (1079°C) ±
25 25°F (14°C) for between four to eight hours.

6. A method as claimed in claim 5, wherein the alloy is air cooled to room temperature after being precipitation heat
treated.

30 7. A method as claimed in any preceding claim, wherein the alloy is aged at between 1400°F (260°C) and 1600°F
(871°C) for between 8 and 32 hours.

8. A method as claimed in claim 7, wherein the alloy is air cooled to room temperature after aging.

35 9. A method as claimed in any preceding claim, wherein the alloy is solutioned for three or more hours.

10. A method as claimed in any preceding claim, wherein the alloy is solutioned at a temperature of 50°F (28°C) above
the gamma prime solvus temperature.

40 11. A method as claimed in claim 10, wherein the alloy is solutioned at 2285°F (1252°C) for 4 hours.

12. A method as claimed in any preceding claim, wherein a stepped ramp heating cycle is followed when the alloy is
heated to its solutioning temperature.

45 13. A method as claimed in any preceding claim, wherein the alloy is slow cooled from its solutioning temperature to
2135°F (1168°C).

14. A method as claimed in any preceding claim wherein the large gamma prime precipitates grow elongated in the
<111> family of crystallographic directions.
50
15. A method as claimed in any preceding claim, wherein the alloy has a composition, in weight percent, consisting of:

(wt. %) range (wt. %)

55
Carbon 0.13 0.17
Chromium 8.00 8.80
Cobalt 9.00 11.00

7
 EP 0 767 252 B1

(continued)

(wt. %) range (wt. %)

Molybdenum 0.50 0.80
5 Tungsten 9.50 10.50
Titanium 0.90 1.20
Aluminum 5.30 5.70
Tantalum 2.80 3.30
10
Hafnium 1.20 1.6
Iron ------ 0.25
Niobium ------ 0.10
Boron ------ trace
Zirconium ----- trace
15

remainder nickel apart from unavoidable impurities.

16. A method as claimed in any of claims 1 to 15, used in the manufacture of a gas turbine engine component.

20
17. A method as claimed in any of claims 1 to 15 used in the manufacture of a rocket turbo pump component.

Patentansprüche

25
1. Verfahren zur Herstellung einer Legierung auf Nickelbasis mit verbesserter Beständigkeit gegen Wasserstoff-Ver-
sprödung, insbesondere Riß-Fortpflanzung, wobei das Verfahren die folgenden aufeinanderfolgenden Schritte
aufweist:

a. Bereitstellen einer γ'-gefestigten Legierung auf Nickelbasis mit einer Zusammensetzung, in Gewichtspro-
30
zent, bestehend aus:

(Gew. - %) Bereich (Gew. - %)

Kohlenstoff 0,006 0,17
35 Chrom 6,0 22,0
Kobalt --- 15,0
Molybdän --- 9,0
Wolfram --- 12,5
Titan --- 4,75
40
Aluminium --- 6,0
Tantal --- 4,3
Hafnium --- 1,6
Eisen --- 18,5
45 Rhenium --- 3,0
Niob --- 1,0
Bor --- Spuren
Zirkonium --- Spuren

50
Rest Nickel, abgesehen von unvermeidbaren Verunreinigungen
b. Gießen der Legierung auf Nickelbasis,
c. Lösungsglühen der Legierung auf Nickelbasis bei einer Temperatur oberhalb ihrer γ '-Solvus-Temperatur,
die bis zu 50°F (28°C) darüber liegt, um im wesentlichen alle eutektischen γ'- γ'-Inseln und Skript-Carbide zu
lösen ohne beginnendes Schmelzen zu bewirken, und langsam abkühlen mit zwischen 0,1°F/min (0,06° C/
55
min) und 5°F/min (2,8°C/min) von der Lösungsglühtemperatur auf eine Temperatur unterhalb der γ '-Solvus-
Temperatur, und dann schnell abkühlen unter Vakuum auf unter 1000°F (538°C), und dann
d. isostatisch Heißpressen der Legierung unterhalb der γ'-Solvus-Temperatur, um Porosität zu beseitigen,

8
 EP 0 767 252 B1

e. Ausscheidungswärmebehandeln der Legierung, und

f. Altern der Legierung,

wobei die Schritte dergestalt sind, daß eine Legierung auf Nickelbasis hergestellt wird mit einer Mikrostruktur,
5 die eine Mehrzahl regelmäßig auftretender großer Sperr-γ '-Ausscheidungen und ein kontinuierliches Gebiet feiner,
quaderförmiger γ '-Ausscheidungen, welche die großen Sperr-γ '-Ausscheidungen umgeben, aufweist, wobei die
Mikrostruktur im wesentlichen frei ist von Skript-Carbiden, eutektischen γ'-Inseln und Porosität.

2. Verfahren nach Anspruch 1, bei dem die großen Sperr-γ '-Ausscheidungen zwischen 2 und 20 µm sind.
10
3. Verfahren nach Anspruch 1 oder 2, bei dem die feinen quaderförmigen γ'-Ausscheidungen zwischen 0,3 und 0,7
µm sind.

4. Verfahren nach Anspruch 1, 2 oder 3, bei dem der Schritt des isostatischen Heißpressens zwischen 4 und 8
15 Stunden lang bei 2165°F (1185°C) ± 25°F (14°C) und 25 ksi (172 MPa) stattfindet.

5. Verfahren nach irgendeinem vorhergehenden Anspruch, bei dem die Legierung zwischen 4 und 8 Stunden lang
bei 1975°F (1079°C) ± 25°F (14°C) ausscheidungswärmebehandelt wird.

20 6. Verfahren nach Anspruch 5, bei dem die Legierung nach der Ausscheidungswärmebehandlung auf Raumtempe-
ratur luftgekühlt wird.

7. Verfahren nach irgendeinem vorhergehenden Anspruch, bei dem die Legierung zwischen 8 und 32 Stunden lang
bei zwischen 1400°F (260°C) und 1600°F (871°C) gealtert wird.
25
8. Verfahren nach Anspruch 7, bei dem die Legierung nach dem Altern auf Raumtemperatur luftgekühlt wird.

9. Verfahren nach irgendeinem vorhergehenden Anspruch, bei dem die Legierung drei oder mehr Stunden lang lö-
sungsgeglüht wird.
30
10. Verfahren nach irgendeinem vorhergehenden Anspruch, bei dem die Legierung bei einer Temperatur von 50°F
(28°C) oberhalb der γ '-Solvus-Temperatur lösungsgeglüht wird.

11. Verfahren nach Anspruch 10, bei dem die Legierung vier Stunden lang bei 2285°F (1252°C) lösungsgeglüht wird.
35
12. Verfahren nach irgendeinem vorhergehenden Anspruch, bei dem ein stufenförmig ansteigender Heizzyklus befolgt
wird, wenn die Legierung auf ihre Lösungsglüh-Temperatur erwärmt wird.

13. Verfahren nach irgendeinem vorhergehenden Anspruch, bei dem die Legierung langsam von ihrer Lösungsglüh-
40 Temperatur auf 2135°F (1168°C) abgekühlt wird.

14. Verfahren nach irgendeinem vorhergehenden Anspruch, bei dem die großen γ '-Ausscheidungen länglich in der
<111>-Familie kristallographischer Richtungen wachsen.

45 15. Verfahren nach irgendeinem vorhergehenden Anspruch, bei dem die Legierung eine Zusammensetzung hat, in
Gewichtsprozent, bestehend aus:

(Gew. - %) Bereich (Gew. - %)

50
Kohlenstoff 0,13 0,17
Chrom 8,0 8,80
Kobalt 9,00 11,00
Molybdän 0,50 0,80
Wolfram 9,50 10,50
55 Titan 0,90 1,20
Aluminium 5,30 5,70
Tantal 2,80 3,30

9
 EP 0 767 252 B1

(fortgesetzt)

(Gew. - %) Bereich (Gew. - %)

Hafnium 1,20 1,6
5 Eisen --- .0,25
Niob --- 0,10
Bor --- Spuren
Zirkonium --- Spuren
10
Rest Nickel, abgesehen von unvermeidbaren Verunreinigungen.

16. Verfahren nach einem der Ansprüche 1 bis 15, das bei der Herstellung eines Gasturbinenmaschinen-Bauteils
verwendet wird.
15
17. Verfahren nach einem der Ansprüche 1 bis 15, das bei der Herstellung eines Raketen-Turbopumpen-Bauteils
verwendet wird.

20 Revendications

1. Procédé de fabrication d'un alliage à base de nickel, ayant une résistance accrue à une fragilisation par l'hydrogène,
en particulier à la propagation des fissures, le procédé comprenant les étapes successives de :

25 a. fourniture d'un alliage à base de nickel, renforcé gamma prime, ayant une composition, en pour cent en
poids, consistant en :

(% en poids) plage (% en poids)

Carbone 0,006 0,17
30
Chrome 6,0 22,0
Cobalt -- 15,0
Molybdène -- 9,0
Tungstène -- 12,5
35 Titane -- 4,75
Aluminium -- 6,0
Tantale -- 4,3
Hafnium -- 1,6
Fer -- 18,5
40
Rhénium -- 3,0
Niobium -- 1,0
Bore -- traces
Zirconium -- traces
45
le reste étant constitué de nickel, à part les impuretés inévitables,
b. coulée de l'alliage à base de nickel ;
c. traitement thermique en solution de l'alliage à base de nickel à une température au-dessus de sa température
de solvus gamma prime de jusqu'à environ 50°F (28°C), de façon à dissoudre la presque totalité des îlots
50 eutectiques gamma-gamma prime et des carbures aciculaires sans provoquer de fusion naissante, et refroi-
dissement lent à une vitesse de refroidissement d'entre 0,1°F/minute (0,06°C/minute) et 5°F/minute (2,8°C/
minute), de la température de traitement thermique en solution à une température au-dessous de la tempé-
rature du solvus gamma prime, puis refroidissement rapide sous vide jusqu'à au-dessous de 1000°F (538°C) ;
puis
55 d. pression isostatique à chaud de l'alliage au-dessous de la température du solvus gamma prime pour éliminer
la porosité ;
e. traitement thermique de l'alliage par précipitation ; et
f. vieillissement de l'alliage,

10
 EP 0 767 252 B1

les étapes étant telles qu'elles produisent un alliage à base de nickel ayant une microstructure qui comprend
une pluralité de gros précipités gamma prime à effet barrière régulièrement répartis, et un champ continu de pré-
cipités gamma prime cuboïdaux fins entourant les gros précipités gamma prime à effet barrière, la microstructure
étant essentiellement exempte de carbures aciculaires, d'îlots eutectiques gamma-gamma prime et de porosité.
5
2. Procédé selon la revendication 1, dans lequel les gros précipités gamma prime à effet barrière sont de 2 à 20 µm.

3. Procédé selon la revendication 1 ou 2, dans lequel les précipités gamma prime cuboïdaux fins sont de 0,3 à 0,7 µm

10 4. Procédé selon la revendication 1, 2 ou 3, dans lequel l'étape de compression isostatique à chaud s'effectue à
2165°F (1185°C) ± 25°F (14°C) et 25 ksi (172 Mpa) pendant quatre à huit heures.

5. Procédé selon l'une quelconque des revendications précédentes, dans lequel l'alliage est soumis à un traitement
thermique par précipitation à 1975°F (1079°C) ± 25°F (14°C) pendant quatre à huit heures.
15
6. Procédé selon la revendication 5, dans lequel l'alliage est refroidi à l'air jusqu'à la température ambiante après
avoir subi le traitement thermique par précipitation.

7. Procédé selon l'une quelconque des revendications précédentes, dans lequel l'alliage est vieilli à entre 1400°F
20 (260°C) et 1600°F (871°C) pendant entre 8 et 32 heures.

8. Procédé selon la revendication 7, dans lequel l'alliage est refroidi à l'air jusqu'à la température ambiante après
vieillissement.

25 9. Procédé selon l'une quelconque des revendications précédentes, dans lequel l'alliage est mis en solution pendant
trois heures ou plus.

10. Procédé selon l'une quelconque des revendications précédentes, dans lequel l'alliage est mis en solution à une
température de 50°F (28°C) au-dessus de la température du solvus gamma prime .
30
11. Procédé selon la revendication 10, dans lequel l'alliage est mis en solution pendant quatre heures à 2285°F
(1252°C).

12. Procédé selon l'une quelconque des revendications précédentes, dans lequel on suit un cycle de chauffage à
35 rampe étagée quand l'alliage est chauffé jusqu'à sa température de mise en solution.

13. Procédé selon l'une quelconque des revendications précédentes, dans lequel l'alliage est lentement refroidi à
partir de sa température de mise en solution à 2135°F (1168°C).

40 14. Procédé selon l'une quelconque des revendications précédentes, dans lequel les gros précipités gamma prime
subissent une croissance allongée dans la famille <111> des directions cristallographiques.

15. Procédé selon l'une quelconque des revendications précédentes, dans lequel l'alliage a une composition, en pour
cent en poids, comprenant :
45

(% en poids) plage (% en poids)

Carbone 0,13 0,17
Chrome 8,00 8,80
50 Cobalt 9,00 11,00
Molybdène 0,50 0,80
Tungstène 9,50 10,50
Titane 0,90 1,20
Aluminium 5,30 5,70
55
Tantale 2,80 3,30
Hafnium 1,20 1,6
Fer -- 0,25

11
 EP 0 767 252 B1

(suite)

(% en poids) plage (% en poids)

Niobium -- 0,10
5 Bore -- traces
Zirconium -- traces

le reste étant constitué de nickel, à part les impuretés inévitables.

10
16. Procédé selon l'une quelconque des revendications 1 à 15, utilisé dans la fabrication d'un composant de turbo-
moteur.

17. Procédé selon l'une quelconque des revendications 1 à 15, utilisé dans la fabrication d'un composant d'une tur-
15 bopompe de fusée.

20

25

30

35

40

45

50

55

12
EP 0 767 252 B1

13
EP 0 767 252 B1

14
EP 0 767 252 B1

15
EP 0 767 252 B1

16