FIELD OF THE INVENTION
[0001] The invention relates to heat treatment processes for nickel-chromium molybdenum-alloys
having a chromium content of from 12 to 23.5 weight percent.
BACKGROUND OF THE INVENTION
[0002] It is well-known that chromium imparts corrosion resistance to nickel base alloys.
Therefore, Ni-Cr-Mo alloys and particularly those with chromium content of 15 to 24%
have been popular for use in corrosive environments such as encountered in the chemical
and petrochemical industries.
[0003] Age-hardening is a process used in the metallurgical industry to give an alloy composition
higher strength, as measured by its yield strength, tensile strength, and by notched
stress rupture tests typically used in the art. Various applications demand a combination
of high tensile strength and low thermal expansion properties. One such application
is in the aerospace industry. Another application is seal rings used in land-based
gas turbines. A combination of high tensile strength and ductility is also very useful
for bolts. Because of the demanding operating conditions and performance parameters
for metal products in these applications, various methods of age-hardening have been
used. One common technique is to heat the alloy to a selected high temperature, hold
the alloy at that temperature for a period of time and then cool the alloy to room
temperature. For some alloy compositions, the alloy may be heated to one temperature,
cooled, heated again to a second temperature and cooled. Examples of these processes
are disclosed in United States Patent No. 3,871,928. The temperatures and time periods
used to age harden an alloy depend upon the composition of the alloy. For all age-hardenable
commercial alloys there are established times and temperatures used that have become
standard in the industry because they are known to produce the desired properties.
For Ni-Cr-Mo alloys having high chromium content, that is chromium greater than 12%
, the general view in the art is that heat treatment beyond the initial annealing
in an effort to improve mechanical properties would be impractical due to the lengthy
required times (hundreds to thousands of hours) and such treatments simply have not
been done.
[0004] Solid-solution strengthened nickel-chromium-molybdenum (Ni-Cr-Mo) alloys and nickel-molybdenum
(Ni-Mo) alloys are widely utilized for commercial applications in the chemical industry,
for example. Generally, considered to be single phase materials, discounting the presence
of minor carbide phases, alloys such as these are not usually considered responsive
to heat treatment, and are therefore used in the annealed condition. There are exceptions,
where some particular alloys do exhibit a commercially exploitable age hardening response.
However, in these instances the age-hardening response observed is attributable to
other elements, such as niobium, aluminum and titanium being present in the alloy
composition. The exception to this is HAYNES® 242™ alloy which will be discussed later.
The fact that Ni-Cr-Mo and Ni-Mo alloys are not commercially age-hardenable does not
mean that they do not exhibit any metallurgical response to thermal exposure at intermediate
temperatures. Actually, alloys of this type can exhibit complex secondary phase reactions
when exposed in the temperature range from about 538°C to 871°C. Unfortunately, the
phases which form can often be deleterious to both alloy ductility and other aspects
of service performance. This is particularly observed with Ni-Mo alloys containing
about 25 to 30 % molybdenum. In such materials, exposure at temperatures from about
538°C to 871°C can result in the rapid formation of embrittling Ni
3Mo or Ni
4Mo phases in the microstructure. This can be a problem for both component manufacturing
and for component performance.
[0005] For lower molybdenum, higher chromium, content Ni-Cr-Mo alloys with about 16 % molybdenum
and 16 % chromium weight percent content, the occurrence of these particular intermetallic
phases is not usually observed after short term thermal exposures. With longer term
exposure at temperatures from about 538°C to 649°C, there is a distinctly different
metallurgical response. After about 500 to 1000 hours the presence of the phase Ni
2(Mo,Cr) is evidenced in the microstructure. A long-range-ordered phase, with structure
similar to that of Pt
2Mo, the Ni
2(Mo,Cr) phase serves to significantly increase the strength of these materials without
a severe loss of ductility. The one major drawback is the prolonged aging time required
to produce this phase.
[0006] There are several United States patents that disclose Ni-Cr-Mo alloys. United States
Patent No. 4,818,486 discloses a low thermal expansion nickel based alloy that contains
5% to 12% chromium and 10% to 30% molybdenum. The patent teaches that the aging times
typically required to obtain desired hardness without deleterious phases being formed
is well over 1000 hours at temperatures of 649°C to 816°C for most Ni-Mo-Cr alloys.
However, the aging time to harden the alloy composition disclosed in the '486 patent
is as little as 24 hours at 649°C. The alloy of this patent has been marketed under
the trademarks 242 alloy and HAYNES 242 alloy. HAYNES 242 alloy has been sold for
applications requiring high tensile strength and a low coefficient of thermal expansion.
Other beneficial properties of the 242 alloy include good thermal stability, good
low cycle fatigue resistance, and excellent containment capabilities due to its tensile
strength and ductility. HAYNES 242 alloy consists of about 8 % (weight percent) chromium,
about 20-30 % molybdenum, about 0.35 % to up to about 0.5 % aluminum, up to 0.03 %
carbon, up to about 0.8 % manganese, up to about 0.8 % silicon, up to about 2 % iron,
up to about 1 % cobalt, up to about 0.006 % boron, and the balance weight percent
being nickel.
[0007] There is a need for a shorter commercially exploitable age hardening process for
Ni-Mo-Cr alloys with higher Cr levels (>12% Cr) than found in U.S. Patent No. 4,818,486
that avoids formation of deleterious Ni
3Mo and Ni
4Mo phase, as well as muphase occurrence.
[0008] Another Ni-Cr-Mo alloy is disclosed in United States Patent No. 5,019,184 to Crum
et al. That alloy contains 19% to 23% chromium and 14 to 17% molybdenum. The patent
discloses homogenization heat treatment at temperatures ranging from 1149°C to 1260°C
for periods of from 5 to 50 hours. The purpose of the treatment is to produce a corrosion
resistant alloy having a desired microstructure rather than to strengthen the alloy.
No tensile strength data is given for any of these samples disclosed in the patent.
The alloy of this patent has been commercialized under the designation INCONEL® alloy
686.
[0009] Yet another corrosion resistant Ni-Cr-Mo alloy is disclosed in United States Patent
No. 4,906,437 to Heubner et al. This alloy contains 22% to 24% chromium and 15% to
16.5% molybdenum. There is no disclosure of any heat treatment or age hardening of
this alloy. The alloy disclosed in this patent has been commercialized under the designation
VDM NICROFER 923 h Mo or Alloy 59.
[0010] A high yield strength Ni-Cr-Mo alloy is disclosed in United States Patent No. 4,129,464
to Matthews et al. This alloy contains 13% to 18% chromium and 13% to 18% molybdenum.
The patent says that the alloy could be aged using a single step aging treatment of
at least 50 hours at 482°C to 593°C, but all examples are aged 168 hours or more.
The statement that at least 50 hours is required was an extrapolation of the results
obtained from a 168 hours aging treatment. The patent reports data for three alloys
numbered 1, 2 and 3. Alloy 1 is commercially available under the trademark HASTELLOY
C-276 alloy. Alloy 2 is commercially available as HASTELLOY C-4 alloy. Alloy 3 is
commercially available as HASTELLOY S alloy.
SUMMARY OF THE INVENTION
[0011] We provide an improved two-step age hardening process for certain nickel-chromium-molybdenum
alloys containing from 12% to 23.5% chromium that results in higher yield strength,
high tensile strength and comparable other mechanical properties as those observed
with the current age-hardening process used in the art, such properties being measured
by yield strength, tensile strength, and tensile ductility tests at room temperature.
This process works only for those alloys in which the other alloying elements are
present in amounts so that the composition has a P value within the range of 31.2
to 35.9 where P is defined by the equation:

The improved age-hardening process involves an alloy with this P value that has been
given an age hardening treatment at about 704°C for at least 8 hours and preferably
for about 12 to 20 hours, furnace cooling to a temperature from about 538°C to about
718°C and holding the material at that temperature for at least 8 hours and preferably
for about 28 to 36 hours, followed by air cooling to room temperature. A Ni-Cr-Mo
alloy having 12% to 23.5% chromium and treated with this two-step heat treatment or
age-hardening process shows improved or comparable tensile strength to the standard
aging process used in the lower chromium level 242 alloy. Because of the combination
of high yield strength and ductility properties, the alloy and two-step aging process
significantly increase affordability of this alloy for applications requiring such
properties.
[0012] Recently we have observed that a two stage heat treatment performed over a total
time of from 10 to 20 hours can provide acceptable mechanical properties. However,
when a similar two step process was tried for Ni-Cr-Mo alloys with higher chromium
content, some alloys had acceptable properties while other alloys did not. A higher
chromium content is desirable for alloys intended for use as corrosion-resistant alloys
in the chemical process industry. Consequently, we saw a need for determining whether
there existed a definable class of high chromium content alloys which would exhibit
acceptable mechanical properties when subjected to a relatively short two step aging
process.
DESCRIPTION OF THE FIGURE
[0013]
Figure 1 is a graph of the alloys tested based upon the P value and chromium content
of the alloy.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0014] We provide a two-step aging treatment for Ni-Cr-Mo alloys containing from 12% to
23.5% chromium to produce an alloy for applications requiring corrosion resistance,
high tensile strength and excellent tensile ductility. This age hardening process
involves aging the alloy at about 691°C to about 760°C for from 8 to 20 hours, cooling
the alloy to a temperature of at from about 538°C to about 718°C, maintaining the
alloy within that temperature range for at least 8 hours and preferably for from 24
to 36 hours and cooling the alloy to room temperature. We have found, however, that
this process provides acceptable mechanical properties for only those alloys that
contain alloying elements in amounts that provides a P value of from 31.2 to 35.9,
P being defined as:

[0015] We tested 20 nickel base test alloys and 5 Ni-Cr-Mo commercial alloys whose compositions
are set forth in Table 1. The commercial alloys were HASTELLOY S sheet, HASTELLOY
C-276 plate, HASTELLOY C-4 plate, Alloy 59 sheet and INCONEL alloy 686 sheet. The
designation "n.m." in Table 1 indicates that the presence of an element was not measured.
Table 1 also reports the P value for each alloy.
[0016] The chromium content of the test alloys ranged from 11.56% for alloy H to 26.06%
for alloy P. Molybdenum ranged from 9.91% in alloy G to 23.89% in alloy S. All of
the alloys contained similar amounts of aluminum, cobalt, iron, and manganese. Tungsten
was present within a range of 0.11% to 0.34%. The alloys also contained small amounts
of boron, carbon, cerium, copper, magnesium, phosphorus, sulfur, silicon, and vanadium.
The test alloys were annealed after hot rolling to 12.7mm plate at annealing temperatures
in the range of 1038°C to 1093°C for thirty minutes. The commercial alloys were cut
from sheets and plates available from the manufacturer. The sheets were 3.2mm and
the plates were 9.5mm thick. In a first test series all of the alloys were treated
with a two-step aging treatment in which they were first aged at 704°C for 16 hours.
Finally, the samples were air cooled to room temperature.

[0017] All of the samples were tested to determine their tensile properties. The tests determined
yield strength, ultimate tensile strength, and percent elongation by following the
standard ASTM E-8 test procedures for such alloys. The results of the first test series
are reported in Table 2
TABLE 2
Room Temperature Tensile Properties |
Alloy |
0.2%Yield Strength |
Ultimate Tensile Strength |
percent Elongation |
|
MPa |
ksi |
MPa |
ksi |
|
A |
816 |
118.3 |
1306 |
189.4 |
40.1 |
B |
823 |
119.3 |
1300 |
188.5 |
40.7 |
C |
723 |
104.8 |
1229 |
178.3 |
43.4 |
D |
709 |
102.9 |
1222 |
177.3 |
43.5 |
E |
690 |
100.0 |
1198 |
173.7 |
44.1 |
F |
508 |
73.7 |
962 |
139.5 |
47.6 |
G |
324 |
47.0 |
738 |
107.1 |
61.8 |
H |
359 |
52.0 |
841 |
122.0 |
65.1 |
I |
341 |
49.5 |
806 |
116.9 |
64.3 |
J |
304 |
44.1 |
743 |
107.8 |
64.1 |
K |
822 |
119.2 |
1338 |
194.0 |
41.1 |
L |
659 |
95.6 |
1170 |
169.7 |
47.9 |
M |
663 |
96.1 |
1166 |
169.1 |
45.8 |
N |
644 |
93.4 |
1158 |
168.0 |
47.3 |
O |
629 |
91.2 |
1145 |
166.1 |
47.3 |
P |
343 |
49.8 |
761 |
110.4 |
60.7 |
Q |
747 |
108.4 |
1227 |
177.9 |
34.5 |
R |
809 |
117.4 |
1305 |
189.3 |
32.4 |
S |
962 |
139.5 |
1473 |
213.6 |
28.0 |
T |
409 |
59.3 |
825 |
119.7 |
57.8 |
HASTELLOY S |
465 |
67.5 |
918 |
133.1 |
47.1 |
C-276 |
369 |
53.5 |
803 |
116.4 |
56.7 |
C-4 |
497 |
72.1 |
947 |
137.4 |
47.6 |
Alloy 59 |
594 |
86.2 |
1066 |
154.6 |
47.3 |
INCONEL alloy 686 |
682 |
98.9 |
1169 |
169.6 |
45.0 |
[0018] Only test alloys A through F and K through O and commercial alloys INCONEL alloy
686 and alloy 59 had acceptable tensile properties. Alloys G, H, I, J, P and T, as
well as all the commercial alloys except INCONEL alloy 686 and alloy 59, have unacceptably
low yield strengths. The acceptable alloys had elongation values greater than 40 percent
and yield strengths greater than 500 MPa. Alloys Q, R and S did not posses enough
tensile ductility as measured by the percent elongation. Microstructure analysis confirmed
that this was due to the presence of undesirable precipitation of an unidentified
phase. Since the chromium content and molybdenum content of the commercial alloys
and alloys H, I, J, Q and R are within the range of chromium content and molybdenum
content of the acceptable alloys it is clear that neither chromium content nor molybdenum
content is the sole predictor of acceptable tensile properties in this class of alloys.
We concluded that it is the interaction of nearly all of the alloying elements that
is the predictor of such properties. Indeed, we discovered that when the alloy has
a P value in the range of 31.2 to 35.9 acceptable tensile properties were achieved
with this two-step aging process. An exception to this behavior was found in the HASTELLOY
C-276 alloy which has a P value in the desired range, but did not have sufficient
yield strength. However, the amount of 5.48% Fe in that alloy is sufficient to best
call it a Ni-Cr-Mo-Fe alloy. Therefore, we suggest that a limit of about 3% Fe is
needed for the above relationship to hold.
[0019] Figure 1 is a graph of the tested alloys based upon the P value of the alloy and
the chromium content. Each alloy that had acceptable tensile properties is plotted
with a dot. An X is used to plot those alloys whose tensile properties were not acceptable
after the alloy was subjected to the two-step aging treatment. A box has been drawn
around the acceptable alloys. It is readily apparent from Figure 1 that the acceptable
alloys have a chromium content of 12% to 23.5% and a P value within the range of 31.2
to 35.9.
[0020] Those skilled in the art will recognize that while chromium and molybdenum must be
present within the ranges encompassed by the test specimens, other alloying elements
are not so limited. Indeed, those elements could be present in amounts within the
ranges set forth in the UNS descriptions for commercially available Ni-Cr-Mo alloys
which include those tested here and alloys such as C-2000® alloy, C-22® alloy, SM
2060 Mo alloy and MAT-21 alloy. More specifically there could be up to 0.05% aluminum,
0.015% boron, 0.02% carbon, 2.5% cobalt, 2.0% copper, 3.0% iron, 1.5% manganese, 1.25%
niobium, 0.04% phosphorus, 0.03 % sulfur, 0.75% silicon, 2.2% tantalum, 0.7% titanium,
0.35% vanadium and 4.5% tungsten and 0.1% of a rare earth element.
[0021] Having now defined the alloys that can benefit from the two-step age hardening process
we considered what time and temperature range for each step would be acceptable. A
series of aging treatments was given to Alloy M. After the aging treatments were performed
the hardness was measured to determine whether the samples had age hardened. The results
are shown in Table 3. A sample was determined to have age hardened if it had a Rockwell
C (Rc) hardness value of more than 20.0. A sample in the unaged condition confirmed
that the material started out with a hardness of less than 20.0. The test results
for Alloy M indicate that the first step should be at least about 8 hours long at
a temperature ranging from about 691°C to about 760°C while the second step should
be at least about 24 hours long at a temperature ranging from about 538°C to about
691°C. The data also indicates that when a higher temperature is used for the first
step then a lower temperature can be used for the second step. While first step temperatures
of up to 927°C were found to be useful in age hardening the alloy, microstructural
examination revealed that an undesirable grain boundary precipitation occurred when
the first step temperature was 760°C or greater. This precipitation would be expected
to degrade corrosion resistance.
[0022] As is well-known in the art, Ni
2(Mo,Cr) age hardening begins with short range ordering followed by creation of precipitates
that impart the hardening property. Upon continued heating a solvus temperature will
be reached at which the precipitates will go back into solution. The short range ordering
is also related to time and temperature. Both the short range ordering and the solvus
temperature vary from one- alloy composition to another. To provide age hardening
any two-step aging treatment must involve a selection of times and temperatures that
provides either the necessary short range ordering or the initial precipitation of
the hardening phase in the first step and avoids the solvus during the second step.
This can be seen in the data for Alloy M in Table 3. When the first step was 704°C
or 732°C for 16 hours, sufficient short range ordering did not occur to support a
second step of 538°C, while the solvus was reached at 621°C. When the first step was
760°C for 16 hours, sufficient short range ordering did occur to support a second
step of 538°C while the solvus was again reached at 621°C.
[0023] After reviewing the data for Alloy M we treated Alloys N and O using an aging of
704°C for 16 hours as the first step followed by a second aging at 593°C, 621°C or
649°C. We also treated Alloy K using a first aging treatment for 8 or 16 hours at
760°C, for 16 or 32 hours at 732°C or for 16 hours at 704°C and a second step between
593°C and 621°C for 8, 12, 16 or 32 hours. The treatment and results of that test
work are shown in Table 4. For Alloys N and O hardening occurs with a second step
aging treatment at 593°C or 621°C, but not at 649°C. The fact that Alloys N and O
could be successfully hardened at 621°C, while Alloy M did not harden at that temperature,
is attributable to the higher molybdenum and lower chromium in Alloys N and O compared
to Alloy M.
[0024] Alloy K has higher molybdenum and lower chromium than Alloys M, N and O. Alloy K
was tested at 704°C, 732°C and 760°C for 8, 16 and 32 hours as shown in Table 4. The
data shows that the first treatment could be 8 hours at 760°C when the second step
was conducted for 40 hours at 704°C or 718°C but not at 732°C. The second step could
be run for 8 hours at 704°C when the first step was conducted for 32 hours at 732°C.
From this data we conclude that higher temperatures can be used in the second step
for alloys having higher molybdenum and lower chromium. Moreover, either step can
be as short as 8 hours when the other step is 32 to 40 hours.
[0025] For other nickel-chromium-molybdenum alloys we can expect to see similar results
although the temperature combinations may be different. Furthermore, the combinations
that work are related to the chromium and molybdenum levels in the alloy. Yet, for
alloys containing chromium content of 12% to 23.5% and a P value within the range
of 31.2 to 35.9, an acceptable age hardening response can be obtained when the first
step is at least about 8 hours long at a temperature ranging from about 691°C to about
760°C and the second step is at least about 8 hours long at a temperature of from
about 538°C to about 718°C.
Table 3
The Effect of Different Aging Treatments on the Hardness of Alloy M |
1st Step Temp |
1st Step Time (h) |
2nd Step Temp |
2nd Step Time (h) |
Hardness (Rc) |
Unaged |
--- |
--- |
--- |
<20.0 |
649°C/1200°F |
16 |
538°C/1000°F |
32 |
<20.0 |
649°C/1200°F |
16 |
566°C/1050°F |
32 |
<20.0 |
649°C/1200°F |
16 |
593°C/1100°F |
32 |
<20.0 |
649°C/1200°F |
16 |
621°C/1150°F |
32 |
<20.0 |
649°C/1200°F |
16 |
649°C/1200°F |
32 |
<20.0 |
677°C/1250°F |
16 |
538°C/1000°F |
32 |
<20.0 |
677°C/1250°F |
16 |
566°C/1050°F |
32 |
<20.0 |
677°C/1250°F |
16 |
593°C/1100°F |
32 |
<20.0 |
677°C/1250°F |
16 |
621°C/1150°F |
32 |
<20.0 |
677°C/1250°F |
16 |
649°C/1200°F |
32 |
<20.0 |
704°C/1300°F |
16 |
538°C/1000°F |
32 |
<20.0 |
704°C/1300°F |
16 |
566°C/1050°F |
32 |
20.7 |
704°C/1300°F |
16 |
593°C/1100°F |
32 |
28.6 |
704°C/1300°F |
16 |
621°C/1150°F |
32 |
<20.0 |
704°C/1300°F |
16 |
649°C/1200°F |
32 |
<20.0 |
732°C/1350°F |
16 |
538°C/1000°F |
32 |
<20.0 |
732°C/1350°F |
16 |
566°C/1050°F |
32 |
27.4 |
732°C/1350°F |
16 |
593°C/1100°F |
32 |
31.2 |
732°C/1350°F |
16 |
621°C/1150°F |
32 |
<20.0 |
732°C/1350°F |
16 |
649°C/1200°F |
32 |
<20.0 |
760°C/1400°F |
16 |
538°C/1000°F |
32 |
24.9 |
760°C/1400°F |
16 |
566°C/1050°F |
32 |
26.6 |
760°C/1400°F |
16 |
593°C/1100°F |
32 |
28.4 |
760°C/1400°F |
16 |
621°C/1150°F |
32 |
<20.0 |
760°C/1400°F |
16 |
649°C/1200°F |
32 |
<20.0 |
816°C/1500°F |
16 |
593°C/1100°F |
32 |
31.0 |
871°C/1600°F |
16 |
593°C/1100°F |
32 |
30.4 |
927°C/1700°F |
16 |
593°C/1100°F |
32 |
27.8 |
704°C/1300°F |
4 |
593°C/1100°F |
4 |
<20.0 |
704°C/1300°F |
4 |
593°C/1100°F |
8 |
<20.0 |
704°C/1300°F |
4 |
593°C/1100°F |
16 |
<20.0 |
704°C/1300°F |
4 |
593°C/1100°F |
44 |
<20.0 |
704°C/1300°F |
8 |
593°C/1100°F |
4 |
<20.0 |
704°C/1300°F |
8 |
593°C/1100°F |
8 |
<20.0 |
704°C/1300°F |
8 |
593°C/1100°F |
16 |
<20.0 |
704°C/1300°F |
8 |
593°C/1100°F |
32 |
20.1 |
704°C/1300°F |
8 |
593°C/1100°F |
40 |
29.4 |
704°C/1300°F |
16 |
593°C/1100°F |
4 |
<20.0 |
704°C/1300°F |
16 |
593°C/1100°F |
8 |
<20.0 |
704°C/1300°F |
16 |
593°C/1100°F |
16 |
<20.0 |
704°C/1300°F |
16 |
593°C/1100°F |
24 |
20.4 |
Table 4
The Effect of Different Aging Treatments on the Hardness of Alloys N and O |
Alloy |
1st Step Temp. |
1st Step Time (h) |
2nd Step Temp. |
Step 2nd Time (h) |
Hardness (Rc) |
K |
Unaged |
--- |
--- |
--- |
< 20 |
K |
740°C/1300°F |
16 |
593°C/1100°F |
32 |
36.7 |
K |
740°C/1300°F |
16 |
649°C/1200°F |
32 |
40.3 |
K |
732°C/1350°F |
16 |
677°C/1250°F |
16 |
37.0 |
K |
732°C/1350°F |
32 |
704°C/1300°F |
8 |
37.0 |
K |
732°C/1350°F |
16 |
704°C/1300°F |
12 |
36.9 |
K |
760°C/1400°F |
16 |
704°C/1300°F |
32 |
37.9 |
K |
760°C/1400°F |
8 |
704°C/1300°F |
40 |
36.9 |
K |
760°C/1400°F |
16 |
718°C/1325°F |
32 |
<20 |
K |
760°C/1400°F |
8 |
718°C/1325°F |
40 |
30.7 |
K |
760°C/1400°F |
16 |
732°C/1350°F |
32 |
<20 |
K |
760°C/1400°F |
8 |
732°C/1350°F |
40 |
<20 |
N |
Unaged |
--- |
--- |
--- |
<20 |
N |
704°C/1300°F |
16 |
593°C/1100°F |
32 |
30.7 |
N |
704°C/1300°F |
16 |
621°C/1150°F |
32 |
32.7 |
N |
704°C/1300°F |
16 |
649°C/1200°F |
32 |
<20 |
O |
Unaged |
--- |
--- |
--- |
<20 |
O |
704°C/1300°F |
16 |
593°C/1100°F |
32 |
30.2 |
O |
704°C/1300°F |
16 |
621°C/1150°F |
32 |
23.9 |
O |
704°C/1300°F |
16 |
649°C/1200°F |
32 |
<20 |
[0026] This process represents a significant advancement. Prior to the present invention
Ni-Cr-Mo alloys having greater that 12% chromium were not produced in the age hardened
condition since the required aging times were considered to be too great. Because
of the energy costs associated with such long treatments the estimated cost of a higher
chromium, age-hardened alloy was considered too high and no such alloys are in commercial
existence. The two-step age-hardening treatment here disclosed can be done in a total
time of less than 100 hours and preferably less than 50 hours. Indeed, we prefer to
complete the process in from 40 to 48 hours. By using heat treatments totaling less
than 100 hours, and preferably not greater than 50 hours, one can produce lower cost,
high chromium, Ni-Cr-Mo alloys that have desirable tensile properties. While the process
here disclosed may also work when total aging times exceed 100 hours, the energy costs
associated with such treatments make the process less desirable and commercially impractical.
[0027] Although we have described certain present preferred embodiments of our alloy and
method of producing that alloy, it should be distinctly understood that our invention
is not limited thereto but may be variously embodied within the scope of the following
claims.
1. A nickel-chromium-molybdenum alloy comprised of:
from 12% to 23.5% chromium;
from 13% to 23% molybdenum;
up to about 3% iron;
at least one alloying element selected from the group consisting of aluminum, boron,
carbon, cobalt, copper, hafnium, iron, manganese, niobium, silicon, tantalum, tungsten,
vanadium and zirconium; and
a balance of nickel plus impurities;
wherein the alloy has a P value of from 31.2 to 35.9, P being defined as:

and the alloy is processed with a two step heat treatment comprised of:
aging the alloy at about 691°C to about 760°C for at least 8 hours;
cooling the alloy to a temperature of from about 538°C to about 718°C;
maintaining the alloy within that temperature range for at least 8 hours; and
cooling the alloy to room temperature.
2. The alloy of claim 1 wherein the two step heat treatment is comprised of:
aging the alloy at about 704°C to 760°C for 16 hours;
cooling the alloy to a temperature of about 593°C to about 621°C; maintaining the
alloy at that temperature for 32 hours; and
cooling the alloy to room temperature.
3. The alloy of claim 1 also comprising:
up to about 0.1% of a rare earth element;
up to about 2.0% copper
up to about 1.25% niobium;
up to about 0.04% phosphorus;
up to about 0.75 silicon;
up to about 0.03% sulfur;
up to about 2.2% tantalum;
up to about 0.7% titanium; and
up to about 0.35% vanadium.
4. The alloy of claim 1 which contains hafnium or tantalum.
5. The alloy of claim 1 wherein the alloy is comprised of:
from 12% to 23.5% chromium;
from 13% to 23% molybdenum;
from 0.12% to 0.2% aluminum;
from 0.002% to 0.006% carbon;
from 0.30% to 0.34% manganese;
from 1.0% to 1.7% iron;
from 0.05% to 0.8% cobalt;
from 0.10% to 0.34% tungsten; and
from 0.002% to 0.005% boron.
6. The alloy of claim 5 also comprising:
from 0.005% to 0.009% cerium;
from 0.01% to 0.06% copper;
from 0.001% to 0.004% magnesium;
from 0.002 to 0.005% phosphorus;
from 0.001% to 0.004% sulfur; and
from 0.01% to 0.02% vanadium.
7. The alloy of claim 1 wherein the alloying elements consist of:
up to about 0.5% aluminum;
up to 0.02% carbon;
up to about 1.5% manganese;
up to about 3% iron;
up to about 2.5% cobalt;
up to about 4.5% tungsten; and
up to about 0.015% boron.
8. The alloy of claim 1 also comprising up to about 1.25% niobium and up to about 0.015%
boron.
9. The alloy of any preceding claim wherein cooling the alloy to a temperature of from
about 538°C to about 718°C is accomplished by cooling the alloy to room temperature
and then heating the alloy to the temperature from about 538°C to about 718°C.
10. The alloy of claim 1 wherein the two step heat treatment is completed in not more
than 50 hours.
11. A method for treating an alloy having a composition comprised of from 12% to 23.5%
chromium, from 13% to 23% molybdenum, up to about 0.5% aluminum, up to 0.02% carbon,
up to about 1.5% manganese, up to about 3% iron, up to about 2.5% cobalt, up to about
4.5% tungsten, up to about 0.015% boron, up to about 1.25% niobium; up to about 0.75%
silicon; up to about 2.2% tantalum; up to about 0.7% titanium and the balance nickel
plus impurities, wherein the alloy has a P value of from 31.2 to 35.9, P being defined
as:

the method comprised of:
aging the alloy at about 691°C to about 760°C for at least 8 hours;
cooling the alloy to a temperature of from about 538°C to about 718°C;
maintaining the alloy within that temperature range for at least 8 hours; and
cooling the alloy to room temperature.
12. The method of claim 11 wherein the two step heat treatment is completed in not more
than 50 hours.
13. The method of claim 11 wherein the alloy is aged at about 704°C to 760°C for 16 hours,
cooled to a temperature of about 593°C to about 621°C, maintained at that temperature
for 32 hours, and cooled to room temperature.
14. The method of claim 11 wherein the alloy is furnace cooled to a temperature of from
about 538°C to about 718°C.
15. The method of claim 11 wherein cooling the alloy to a temperature of at least 538°C
is accomplished by cooling the alloy·to room temperature and then heating the alloy
to the temperature of from about 538°C to about 718°C.
16. The method of claim 11 wherein the alloy further comprises up to about 1.25% niobium
and up to about 0.015% boron.