The Effect of Final Heat Treatment and Chemical Composition

on Sensitiztation, Strength and Thermal Stability of Alloy 625

M. Kohler, U. Heubner

Krupp VDM GmbH

Plettenberger Str. 2, D-58791 Werdohl / Germany

ABSTRACT

Time-Temperature-Sensitization diagrams have been established for a low-carbon

version of alloy 625 (UNS N06625). Sensitization in terms of a 50 urn (2 mils) intergranular
penetration criterion starts after about 3 h aging time at 750°C (soft annealed condition) or
after less than 1 h aging time at 800°C (solution annealed condition) when tested according to
ASTM-G 28 method A. Grain boundary precipitation of carbides occurs during aging of both
the soft annealed and the solution annealed material, but the soft annealed material exhibits a
more pronounced general precipitation of Ni@b,Mo) phase giving rise to more distinct loss
of ductility. Sensitization of alloy 625 may be retarded by lowering its iron content.

Superalloys 718,625,706 and Various Derivatives

Edited by E.A. Loria
The Minerals, Metals &Materials Society, 1997

795
 INTRODUCTION

Alloy 625 (UNS N06625) is a widely used nickel-chromium-molybdenum alloy in

various industries. Specified according to ASTM-B 443 ’ with a maximum carbon content of
0.1 wt % the alloy is available on the market in two versions: a low carbon version (less than
0.025 wt % carbon) for wet corrosion applications and normally used in the soft annealed
condition (grade l), and a high carbon version (about 0.045 wt % carbon) which is used for high
temperature application in the solution annealed condition (grade 2). Typically soft annealing is
done at 980°C and solution annealing at 1120°C. However, both versions of the alloy exhibit
structural instability if they are exposed to the temperature range of 600 to 900°C. Structural
instability also causes loss of ductility 2 and sensitization ’ , both occurring most rapidly in the
temperature range around 800°C. It has been found that solution annealing causes a noticeable
shift of ductility loss to longer times compared to soft annealing 2 as shown in Fig. 1 whereas the
effect of solution annealing on sensitization is not known so far. Therefore the primary aim of
the work reported in this paper was to study the influence of final annealing on the Time-
Temperature-Sensitization behavior of a low-carbon version of alloy 625

900 ! I I /
100 200 360 400 500 6 10
aging time, h

Figure 1: Minimum aging time required in an intermediate temperature range (around

SOO’C)in order to obtain a reduced Charpy-notch-impact energy of 50 J/cm*
depending on final annealing temperature according to tests at room temperature
on ISO-V-notch samples ’

MATERIALS INVESTIGATED AND EXPERIMENTAL METHOD

The chemical composition of the alloy 625 heat investigated is shown in Table 1. The
material used to study the sensitization behavior was now alloyed with 4.1 wt. % iron in
comparison to the previous investigation ’ where- a lower iron-containing alloy of 2 wt. % iron
was used. Iron in alloy 625 is known to accelerate loss of ductility during aging 4 , so an effect
on sensitization may be expected as well.

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 TABLE 1
CHEMICAL COMPOSITION OF ALLOY 625 INVESTIGATED (WT %)

Ni Cr MoFe 0-W Mn Si Tidal Cb’&:-.C P S.

60.2 22.2 9.2 4.1 0.06 0.06 0.12 0.08 0.17 0.16 3.5 0.04 0.02 0.007 0.002

The alloy of Table 1 was hot rolled to plate of 5 mm thickness and subjected to either a
solution anneal of 15 min at 1120°C or a soft or stabilizing anneal of 15 min at 980°C followed
by a water quench. Subsequently samples of 5 x 20 x 30 mm size were cut from the plates to be
annealed at 600, 700, 800 and 900°C for 1, 10 and 100 h. After annealing the samples were
surface finished using 80 grit abrasive paper, cleaned, degreased, dried and weighed to the
nearest 0 1 mg. After a 120 h immersion in boiling 42 g/l ferric sulfate / 50 % sulmric acid
solution according to ASTM-G 28 A ’ , they were rinsed in water and acetone, dried and
weighed for the corrosion rate calculation. According to the former definition in German
standard SEP 1877/79 method II 6 the samples were determined to be free from intergranular
attack if the depth of intergranular penetration (IP) did not exceed 50 urn (2 mils). The
microstructure was analyzed using optical metallography. Brine11hardness measurements were
also taken

The initial mechanical properties of the material investigated are shown in Table 2. As
would be expected, in the soft annealed condition, mechanical strength and hardness are higher
and ductility is somewhat lower than in the solution annealed condition. These differences are
mainly due to the differences in grain size of ASTM 8 (20 urn mean grain diameter) for the soft
annealed condition and of ASTM 6 (60 urn mean grain diameter) for the solution annealed
condition.

TABLE 2
INITIAL MECHANICAL PROPERTIES OF ALLOY 625 INVESTIGATED

Rp0.z Rp1.0 Rm A5 Brine11

N/mm2 N/mm2 N/mm2 % hardness
soft annealed 451 501 910 45 244
solution annealed 376 415 843 55 208

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 TIME-TEMPERATURE-SENSITIZATION BEHAVIOR

Fig. 2 shows the Time-Temperature-Sensitization diagrams established a) for the soft

annealed condition and b) for the solution annealed condition of alloy 625. In the soft annealed
condition sensitization in terms of the 50 urn (2 mils) intercrystalline penetration criterion,
occurs fastest at about 750°C starting already after about 3 h aging at this temperature. The
whole temperature range of sensitization as shown in Fig. 2a is in good agreement with the
results of previous investigations3 where a distinct increase of corrosion rate in ASTM-G-28 A
solution had been observed after 3 h aging at 700 / 750°C.

temp., “C temp., “F
1000 , , 1832

900 n 0.41 . 0.39

W Oso 1652

500 - -932
starting condition 0.40 mm/a
400 / / I 752
0.1 1 10 100
time, h

a) soft annealed condition (15 rnin at 980°C)

Temp. "C iemp.,

1000

800

starting condifion 0.41 mm/a

I / I,
0.1 1 lb 100
time, h
b) solution annealed condition (15 min at 112OT)

Figure 2: Time-Temperature-Sensitization (TTS) diagram of Alloy 625, composition as

indicated in Table 1, when tested according to ASTM G 28, method A5 over
120 h on a plate of 5 mm thickness. Numbers indicate corrosion loss (mm/year)

798
However, on the previously tested low iron-containing alloy (2 wt. % Fe) 3 start of
intercrystalline corrosion in terms of the 50 urn (2 mils) intercrystalline penetration criterion
only occurred after about 50 h aging at 750°C. This difference might be due to the increased
iron content of the alloy of the present investigation since iron is known to accelerate the
effects of thermal instability of alloy 625 4

Contrarily, as Fig 2b shows, in the solution annealed condition sensitization in terms of

the 50 urn (2 mils) intercrystalline penetration criterion starts within less than 1 h at about
800°C. In addition, the whole range of sensitization is extended to both higher and lower
temperatures than is observed for the soft annealed condition.

So the term “stabilized‘as designated for the soft annealed condition has been proved
to be correct with respect to intercrystalline corrosion of alloy 625. This is not so self-evident
as might be expected from the general observations on stainless steels since according to Fig. 1
ductility loss as another aspect of thermal degradation is delayed not by soft annealing but by
solution annealing of alloy 625 2 which, therefore, is the stabilizing heat treatment with respect
to ductility.

TIME-TEMPERATURE-PRECIPITATION BEHAVIOR

Fig. 3 exhibits selected examples of the microstructure of alloy 625 in the soft annealed
condition after various aging treatments. After 1 h at 600°C optical microscopy reveals no
change of the microstructure with respect to the soft annealed starting condition. Fig. 3a shows
some carbides and carbonitrides in a tine grained austenite matrix only. After 10 h at 600°C a
somewhat more pronounced decoration of grain boundaries by carbide particles is seen as
shown in Fig. 3b. This kind of precipitation is still more pronounced after 100 h at 600°C. In
the same way precipitation occurs at 700°C where after 100 h grain boundaries are covered by
a dense network of carbides, Fig. 3c. After 10 h at 800°C again a preferred precipitation of
carbides on grain boundaries is seen (Fig. 3d) whereas after 100 h at this temperature, as
shown in Fig. 3e, precipitation of a needle-like phase, probably Ni3 (Nb, MO) 2 covers all the
microstructure. Contrarily after 100 h at 900°C much less precipitation occurs as is apparent in
Fig. 3f

The microstructure of alloy 625 in the solution annealed condition after various aging
treatments is shown in Fig. 4. Again Fig. 4a reveals no visible change of the optical
microstructure after 1 h at 600°C compared to the solution annealed starting condition. After
10 h at 600°C some grain boundary precipitation is discernible as shown in Fig. 4b, it is
somewhat more pronounced after 100 h at 600°C. As with the soft annealed condition the
grain boundaries are completely covered by carbide precipitation after 100 h at 700°C as Fig.
4c demonstrates. After 10 h at 800°C (Fig. 4 d) this carbide coverage is less, but becomes
more dense after 100 h at 800°C (Fig. 4e). As Fig. 4f shows there is less precipitation at 900°C
than at 800°C.

When comparing Fig. 4e with Fig. 3e a major difference between the soft annealed and
the solution annealed condition after 100 h at 800°C becomes apparent: there is much less
general precipitation in the solution annealed material. Apparently in addition to grain
boundary precipitation this general precipitation of Nix(Nb,Mo) phase affects very strongly the
ductility of the material 2 Hence, the solution annealed condition is favoured if a delayed loss
of ductility during aging is the prerequisite requirement whereas the soft annealed condition is
preferred if a high resistance to sensitization is the primary requirement.

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 a) 1 h / 600°C

b) 10 h / 6OOT

Figure 3: Microstructure of Alloy 625, soft annealed (15 rnin at 980” C) and aged,
magnification x 500

800
 .) ..
b)lO h /6OOT

20pm
-
c)lOO h /700°C

-' d)10h/800°C

e)lOO h/SOOT

f)lOOh/900“C

Figure 4: Microstructure of Alloy 625, solution annealed (15 rnin at 1120” C) and aged,
magnification x 500

801
 TIME-TEMPERATURE-HARDNESS CJ3ANGE

The results of Brine11hardness testing are demonstrated in Fig. 5. As already shown in

Table 2 the hardness of the soft annealed condition is higher than the hardness of the solution
annealed material mainly due to the smaller grain size. As is obvious from Fig. 5 during a
subsequent aging treatment at 600, 700 and 800°C hardness is increasing. At 900°C hardness
remains constant or slightly decreaseseven in case of the solution annealed condition.

/ .i------- 1

600 700 800 900 time

temperature, “C
ih 235 245 236 239
10h 240 240 239 238
100h 291 268 274 239

a) soft annealed condition ( 15 min at 980°C ) HB = 244

600 700 800 900 time

temperature, “C
lh 215 207 220 208
10h 209 207 215 203
100h 258 245 236 200

b) solution annealed condition ( 15 min at 1120°C ) HB = 208

Figure 5: Brine11hardness numbers of Alloy 625, composition as indicated in Table 1,

after aging at temperatures between 600 and 900” C

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1. Alloy 625 in the soft annealed condition (15 min at 980°C) exhibits sensitization of 50 urn
(2 mils) intergranular penetration after about 3 h aging time at 750°C or, in the solution
annealed condition (15 min at 112O”C), after less than 1 h aging time at 800°C when tested
according to ASTM-G 28, method A.

2 Whereas soft annealing of alloy 625 is a stabilizing heat treatment with respect to
sensitization, solution annealing of alloy 625 is a stabilizing heat treatment with respect to
ductility

3. Grain boundary precipitation occurs during aging of alloy 625 in both its solution annealed
and its soft annealed condition. The more pronounced loss of ductility of the soft annealed
condition is due to more general precipitation of Ni3 (Nb, MO).

4.Sensitization as well as loss of ductility during aging of alloy 625 may be retarded by
lowering the iron content of the alloy.

ACKNOWLEDGMENT

The authors are most grateful to Mr. R. Berndt who performed all experimental work
in an excellent manner.

REFERENCES

1. ASTM-B 443-93 : Standard Specification for Nickel-Chromium-Molybdenum-Columbium

Alloy (UNS N06625), Annual Book of ASTM Standards, Vol. 2.04 Philadelphia, PA., 1995

2. M. Kohler: Effect of the Elevated Temperature-Precipitation in Alloy 625 on Properties and

Microstructure, Superalloys 7 18, 625 and Various Derivatives, Edited by E. A. Loria, TMS,
1991, pp. 363 - 374

3. U Heubner, M. Kohler: Time-temperature-precipitation and time-temperature-sensitization

behavior of highly corrosion resistant nickel-chromium-molybdenum alloys (in German),
Werkstoffe und Korrosion 43 (1992) pp. 1X1 - 190

4. U. Heubner, M. Kohler: Effect of Carbon Content and Other Variables on Yield Strength,
Ductility and Creep Properties of Alloy 625, Superalloys 718, 625, 706 and Various
Derivatives, Edited by E. A. Loria, TMS, 1994, pp. 479 - 488

5. ASTM-G 28 A-94: Standard Test Methods of Detecting Susceptibility to Intergranular

Corrosion in Wrought Nickel-Rich, Chromium-Bearing Alloys, Annual Book of ASTM
Standards, Vol. 3.02 Philadelphia, PA., 1995

6. SEP 1877 / 79, Method II: Standard Test Method of Detecting Susceptibility to
Intergranular Corrosion in Corrosion Resistant Materials (boiling ferric sulfate - 40 %
sulfuric acid test), Verlag Stahleisen, Dusseldorf, 1994

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