US3591371A - Cobalt base oxidation resistant alloy - Google Patents
Cobalt base oxidation resistant alloy Download PDFInfo
- Publication number
- US3591371A US3591371A US773149A US3591371DA US3591371A US 3591371 A US3591371 A US 3591371A US 773149 A US773149 A US 773149A US 3591371D A US3591371D A US 3591371DA US 3591371 A US3591371 A US 3591371A
- Authority
- US
- United States
- Prior art keywords
- alloy
- cobalt base
- oxidation
- alloys
- oxidation resistant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000956 alloy Substances 0.000 title abstract description 46
- 229910045601 alloy Inorganic materials 0.000 title abstract description 46
- 230000003647 oxidation Effects 0.000 title abstract description 28
- 238000007254 oxidation reaction Methods 0.000 title abstract description 28
- 239000010941 cobalt Substances 0.000 title abstract description 22
- 229910017052 cobalt Inorganic materials 0.000 title abstract description 22
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title abstract description 21
- 239000011572 manganese Substances 0.000 abstract description 11
- 229910052748 manganese Inorganic materials 0.000 abstract description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052746 lanthanum Inorganic materials 0.000 abstract description 8
- 229910052710 silicon Inorganic materials 0.000 abstract description 7
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 abstract description 6
- 239000010703 silicon Substances 0.000 abstract description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 229910052804 chromium Inorganic materials 0.000 description 8
- 239000011651 chromium Substances 0.000 description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 6
- 229910052721 tungsten Inorganic materials 0.000 description 6
- 239000010937 tungsten Substances 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000004584 weight gain Effects 0.000 description 2
- 235000019786 weight gain Nutrition 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- NRUQNUIWEUZVLI-UHFFFAOYSA-O diethanolammonium nitrate Chemical compound [O-][N+]([O-])=O.OCC[NH2+]CCO NRUQNUIWEUZVLI-UHFFFAOYSA-O 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/07—Alloys based on nickel or cobalt based on cobalt
Definitions
- This invention relates to cobalt base alloys suitable for use at elevated temperatures and in oxidizing environments. More particularly, the present invention is directed to chromium-containing cobalt base alloys characterized by excellent oxidation resistance at temperatures of 1200 C. and above.
- Cobalt base alloys have been employed in the past in high temperature applications on account of their advantageous mechanical properties under such conditions but on account of their rather poor resistance to oxidation at high temperature the use of such alloys has been severely restricted.
- the oxidation of cobalt base alloys (and also that of the generally more oxidation resistant nickel base alloys) has been extremely poor at temperatures of 1200 C. and above.
- This situation is unfortunate since at the present time there are many applications, e.g. jet aircraft engine components, in which cobalt base alloys could be used to great advantage if the oxidation resistance of these alloys, at temperatures of 1200 C. and above, could be improved.
- FIGS. 1 and 2 show comparative oxidation data in the form of graphs for various alloys including alloys in accordance with the present invention
- FIG. 3 shows, in the form of a graph, mechanical data for an alloy of the present invention.
- a cobalt base alloy in accordance with the present invention contains at least 35% Co and about:
- the alloy additionally contains manganese in an amount up to about 2% and is characterized by a further improve- 3,591,371 Patented July 6, 1971 ment in oxidation resistance under cyclic conditions, and improved mechanical properties.
- the preferred manganese content is from about 0.4 to 1%.
- cobalt base alloys containing from about 15 to 25% chromium can be remarkably improved in oxidation resistance at high temperatures by the addition of both silicon and lanthanum in controlled amounts when the tungsten content of the alloy is kept below about 3%.
- the tungsten content should be less than 1% and for optimum results the tungsten content should be less than 0.1%, and preferably the alloy is tungsten-free.
- the inclusion of manganese in amounts up to about 2% further enhances the oxidation resistance.
- a particularly preferred alloy compositional range in accordance with the present invention is as follows:
- a specific preferred alloy composition is 20% Cr, 0.3 Si, 0.1% La, 0.5% Mn, Ni, balance Co.
- the alloy of the present invention can contain minor amounts of elements ordinarily present in commercial cobalt base alloys.
- iron can be present up to about 10% and molybdenum up to about 1%, however it is preferred that the alloy be essentially free of molybdenum.
- the isothermal tests involved exposing alloy samples to flowing dry air at a constant temperature and recording the weight gain of the samples as a function of time.
- the samples were in the form of hot rolled sheet 2 mm. thick. Before testing the samples were solution treated for one hour at 1080 C. in argon and quenched in brine.
- compositions of the alloys are shown in Table I below:
- the mechanical properties of the alloy of the present invention shows its suitability as a matrix metal for composite materials.
- An alloy in accordance with claim 1 containing up to 2% manganese by weight and less than 1% each of tungsten and molybdenum by weight.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Powder Metallurgy (AREA)
- Soft Magnetic Materials (AREA)
- Heat Treatment Of Steel (AREA)
- Manufacture Of Alloys Or Alloy Compounds (AREA)
Abstract
A COBALT BASE, CHROMIUM-CONTAINING ALLOY HAVING MINOR AMOUNTS OF SILICON AND LANTHANUM CHARACTERIZED BY EXCELLENT OXIDATION RESISTANCE AT TEMPERATURES OF 1200*C. AND HIGHER. THE INCLUSION OF SMALL OF MANGANESE IN THE ALLOY FURTHER ENHANCES THE OXIDATION RESISTANCE OF THE ALLOY.
Description
July 6, 1971 Filed Nov. 4, 1968 WEIGHT GAIN mg/cm H. HATWELL ETA!- COBALT BASE OXIDATION RESISTANT ALLOY 5 Sheets-Sheet 1 CoCrNi (A) CoCrNiLa (B) CoCrNiSi (c) Co-Cr-Ni-Si-Mn-La (E) Co-Cr-Ni-Si-La (0) 3 0 4 o s o I 0F EXPQSUREHQURS FIG.|
INVENTORS ATTORNEY July 6, 1971 HATWELL ETAL 3,591,371
COBALT BASE OXIDATION RESISTANT ALLOY I Filed Nov. 4, 1968 3 Sheets-Sheet a a oe 240' TIME HOURS FIG. 2
10 20304050 60 TOBOQOIOO l I. g In OQQFDMQMN- NW9 lHQlHM INVENTORS HENRI HATWELL CHARLES |D.DESFORGES P E L. MOENTACK BY ATTORNEY July 6, 1971 HATWELL ETAL 3,591,371
COBALT BASE OXIDATION RESISTANT ALLOY Filed Nov. 4, 1968 3 Sheets-Sheet 8 "Z I I l I I I ll i- T=a12 c FIG. 3
0.17% Elongation per minute O u R 3 E 2 as C d o L- m 25 1 l 1 l l l l l 1 $0 a e a a o o ww/m SSHHIS rusuzu INVENTORS RI HATW HEN ELL CHARLEES D. DESFORGES PIER L. MOENTACK BY 14% ATTORNEY United States Patent M 3,591,371 COBALT BASE OXIDATION RESISTANT ALLOY Henri Hatwell, Indianapolis, Ind., and Charles D. Desforges, Rhode-St.-Genese, and Pierre L. Moentack, Brabant, Belgium, assignors to Cabot Corporation Filed Nov. 4, 1968, Ser. No. 773,149 Int. Cl. C22c 19/00 US. Cl. 75-171 4 Claims ABSTRACT OF THE DISCLOSURE A cobalt base, chromium-containing alloy having minor amounts of silicon and lanthanum characterized by excellent oxidation resistance at temperatures of 1200 C. and higher. The inclusion of small of manganese in the alloy further enhances the oxidation resistance of the alloy.
This invention relates to cobalt base alloys suitable for use at elevated temperatures and in oxidizing environments. More particularly, the present invention is directed to chromium-containing cobalt base alloys characterized by excellent oxidation resistance at temperatures of 1200 C. and above.
Cobalt base alloys have been employed in the past in high temperature applications on account of their advantageous mechanical properties under such conditions but on account of their rather poor resistance to oxidation at high temperature the use of such alloys has been severely restricted. In particular, the oxidation of cobalt base alloys (and also that of the generally more oxidation resistant nickel base alloys) has been extremely poor at temperatures of 1200 C. and above. This situation is unfortunate since at the present time there are many applications, e.g. jet aircraft engine components, in which cobalt base alloys could be used to great advantage if the oxidation resistance of these alloys, at temperatures of 1200 C. and above, could be improved.
It is therefore an object of the present invention to provide a highly oxidation resistant cobalt base alloy.
It is another object of this invention to provide a cobalt base alloy characterized by excellent resistance to oxidation at temperatures of 1200 C. and above.
Other objects will be apparent from the following description and claims taken in conjunction with the drawing in which FIGS. 1 and 2 show comparative oxidation data in the form of graphs for various alloys including alloys in accordance with the present invention, and
FIG. 3 shows, in the form of a graph, mechanical data for an alloy of the present invention.
A cobalt base alloy in accordance with the present invention contains at least 35% Co and about:
Percent Cr 1-5-25 Ni -35 Si 0.1-1.0
Alloys in the foregoing compositional range have been found to have excellent oxidation resistant properties at high temperatures.
In a preferred embodiment of the present invention, the alloy additionally contains manganese in an amount up to about 2% and is characterized by a further improve- 3,591,371 Patented July 6, 1971 ment in oxidation resistance under cyclic conditions, and improved mechanical properties. The preferred manganese content is from about 0.4 to 1%.
As part of the present invention, it has been discovered that cobalt base alloys containing from about 15 to 25% chromium can be remarkably improved in oxidation resistance at high temperatures by the addition of both silicon and lanthanum in controlled amounts when the tungsten content of the alloy is kept below about 3%. For further improvement in oxidation resistance the tungsten content should be less than 1% and for optimum results the tungsten content should be less than 0.1%, and preferably the alloy is tungsten-free.
Also, as previously mentioned, the inclusion of manganese in amounts up to about 2% further enhances the oxidation resistance.
A particularly preferred alloy compositional range in accordance with the present invention is as follows:
Percent Cr 1 8-24 Si 0.2-0.4 La 0.09-0.15 Mn 0.3-0.6 W 0.05 Ni 18-24 Co Balance A specific preferred alloy composition is 20% Cr, 0.3 Si, 0.1% La, 0.5% Mn, Ni, balance Co.
In addition to the constituents previously mentioned, the alloy of the present invention can contain minor amounts of elements ordinarily present in commercial cobalt base alloys. For example, iron can be present up to about 10% and molybdenum up to about 1%, however it is preferred that the alloy be essentially free of molybdenum.
To demonstrate the advantages of the present invention, extensive testing of various alloys was conducted, including isothermal and cyclical thermal oxidation tests in dry air.
The isothermal tests involved exposing alloy samples to flowing dry air at a constant temperature and recording the weight gain of the samples as a function of time. The samples were in the form of hot rolled sheet 2 mm. thick. Before testing the samples were solution treated for one hour at 1080 C. in argon and quenched in brine.
The compositions of the alloys are shown in Table I below:
TABLE I Alloy composition, percent by weight 1 Balance.
In the isothermal oxidation testing of the above alloys at 1100 C., it was found that alloys D and E, in accordance with the present invention, were superior. The results are shown in the graph of FIG. 1.
Further isothermal oxidation tests were conducted at 1200 C. and these results are shown in the graph of TABLE II.OXIDATION DATATHERMAL CYCLING FOR 100 HOURS Metal con- A M, sumption,
Alloy lug/0111. mg./cm.
F 6.15 (average)-.. 15. 2 E- -0.6 (average) 4.8
Further tests were made at different temperatures to determine mechanical properties for the alloy of the present invention. The results of these tests for alloy E (20% Cr, 0.34% Si, 0.1% La, 0.62% Mn, 20% Ni, balance Co) are shown in the graph of FIG. 3. The samples tested were prepared by being hot rolled to sheet 0.1 mm. thick, solution treated for 30 minutes at 1100 C. and water quenched. The testing was performed in air.
As can be seen from FIG. 3, the mechanical properties of the alloy of the present invention, in conjunction with its oxidation characteristics, shows its suitability as a matrix metal for composite materials.
What is claimed is:
1. A cobalt base alloy having excellent resistance to oxidation at high temperatures, especially at about 1200 C. or higher, containing at least 35% by weight of cobalt and consisting essentially, in proportions by weight, of about:
Percent Chromium 15-25 Nickel 15-35 Silicon 0.1-1.0 Lanthanum 0.020.3 Tungsten 3 with balance basically being cobalt.
2. An alloy in accordance with claim 1 containing up to 2% manganese by weight and less than 1% each of tungsten and molybdenum by weight.
3. An alloy in accordance with claim 1 consisting essentially of about:
Percent Chromium 18-24 Nickel 1 8-24 Silicon 0.20.4 Lanthanum 0.09-0.15 Manganese 0.3-0.6 Tungsten 0.0-5 Cobalt (basically) Balance 4. An alloy in accordance with claim 1 consisting es sentially of about:
Percent Chromium 20 Nickel 20 Silicon 0.3 Lanthanum 0.1 Manganese 0.5 Cobalt Balance References Cited UNITED STATES PATENTS 2,247,643 7/1941 Rohn et al 75-171 3,418,111 12/1968 Herchenroeder 75--171 RICHARD O. DEAN, Primary Examiner
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US77314968A | 1968-11-04 | 1968-11-04 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3591371A true US3591371A (en) | 1971-07-06 |
Family
ID=25097348
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US773149A Expired - Lifetime US3591371A (en) | 1968-11-04 | 1968-11-04 | Cobalt base oxidation resistant alloy |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US3591371A (en) |
| AT (1) | AT296635B (en) |
| BE (1) | BE741042A (en) |
| BR (1) | BR6913788D0 (en) |
| CA (1) | CA918459A (en) |
| DE (2) | DE1953025C3 (en) |
| FR (1) | FR2022561A1 (en) |
| GB (1) | GB1250382A (en) |
| LU (1) | LU59746A1 (en) |
| NL (1) | NL6916456A (en) |
| SE (1) | SE343890B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4169726A (en) * | 1977-12-21 | 1979-10-02 | General Electric Company | Casting alloy and directionally solidified article |
| US4735771A (en) * | 1986-12-03 | 1988-04-05 | Chrysler Motors Corporation | Method of preparing oxidation resistant iron base alloy compositions |
| WO1989009843A1 (en) * | 1988-04-04 | 1989-10-19 | Chrysler Motors Corporation | Oxidation resistant iron base alloy compositions |
| US4891183A (en) * | 1986-12-03 | 1990-01-02 | Chrysler Motors Corporation | Method of preparing alloy compositions |
| US4999158A (en) * | 1986-12-03 | 1991-03-12 | Chrysler Corporation | Oxidation resistant iron base alloy compositions |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2420684A1 (en) * | 1978-03-21 | 1979-10-19 | Pavec Albert | IMPROVEMENTS MADE TO NUT-INSERTS AND RELATED INSTALLATION DEVICE |
| US4764225A (en) * | 1979-05-29 | 1988-08-16 | Howmet Corporation | Alloys for high temperature applications |
| US4339509A (en) | 1979-05-29 | 1982-07-13 | Howmet Turbine Components Corporation | Superalloy coating composition with oxidation and/or sulfidation resistance |
-
1968
- 1968-11-04 US US773149A patent/US3591371A/en not_active Expired - Lifetime
-
1969
- 1969-10-21 CA CA065355A patent/CA918459A/en not_active Expired
- 1969-10-22 DE DE1953025A patent/DE1953025C3/en not_active Expired
- 1969-10-22 DE DE19691966758 patent/DE1966758A1/en active Pending
- 1969-10-29 AT AT1019369A patent/AT296635B/en not_active IP Right Cessation
- 1969-10-30 SE SE14881/69A patent/SE343890B/xx unknown
- 1969-10-30 BE BE741042D patent/BE741042A/xx unknown
- 1969-10-31 BR BR213788/69A patent/BR6913788D0/en unknown
- 1969-10-31 NL NL6916456A patent/NL6916456A/xx unknown
- 1969-11-03 GB GB1250382D patent/GB1250382A/en not_active Expired
- 1969-11-04 FR FR6937943A patent/FR2022561A1/fr not_active Withdrawn
- 1969-11-04 LU LU59746D patent/LU59746A1/xx unknown
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4169726A (en) * | 1977-12-21 | 1979-10-02 | General Electric Company | Casting alloy and directionally solidified article |
| US4735771A (en) * | 1986-12-03 | 1988-04-05 | Chrysler Motors Corporation | Method of preparing oxidation resistant iron base alloy compositions |
| WO1989009841A1 (en) * | 1986-12-03 | 1989-10-19 | Chrysler Motors Corporation | Method of preparing oxidation resistant iron base alloy compositions |
| US4891183A (en) * | 1986-12-03 | 1990-01-02 | Chrysler Motors Corporation | Method of preparing alloy compositions |
| US4999158A (en) * | 1986-12-03 | 1991-03-12 | Chrysler Corporation | Oxidation resistant iron base alloy compositions |
| WO1989009843A1 (en) * | 1988-04-04 | 1989-10-19 | Chrysler Motors Corporation | Oxidation resistant iron base alloy compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| CA918459A (en) | 1973-01-09 |
| DE1953025A1 (en) | 1970-05-27 |
| LU59746A1 (en) | 1970-05-13 |
| DE1953025B2 (en) | 1974-07-04 |
| DE1966758A1 (en) | 1974-03-21 |
| SE343890B (en) | 1972-03-20 |
| AT296635B (en) | 1972-02-25 |
| BE741042A (en) | 1970-04-30 |
| GB1250382A (en) | 1971-10-20 |
| FR2022561A1 (en) | 1970-07-31 |
| BR6913788D0 (en) | 1973-04-05 |
| DE1953025C3 (en) | 1975-02-27 |
| NL6916456A (en) | 1970-05-08 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AS | Assignment |
Owner name: HAYNES INTERNATINAL, INC.,INDIANA Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:CABOT CORPORATION;REEL/FRAME:004770/0271 Effective date: 19870731 Owner name: HAYNES INTERNATINAL, INC., 1020 WEST PARK AVENUE, Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:CABOT CORPORATION;REEL/FRAME:004770/0271 Effective date: 19870731 |