US2736086A - Corrosion-resistant cemented titanium - Google Patents
Corrosion-resistant cemented titanium Download PDFInfo
- Publication number
- US2736086A US2736086A US2736086DA US2736086A US 2736086 A US2736086 A US 2736086A US 2736086D A US2736086D A US 2736086DA US 2736086 A US2736086 A US 2736086A
- Authority
- US
- United States
- Prior art keywords
- titanium carbide
- corrosion
- powder
- chromium
- titanium
- 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
- 238000005260 corrosion Methods 0.000 title claims description 10
- 239000010936 titanium Substances 0.000 title description 4
- 229910052719 titanium Inorganic materials 0.000 title description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title description 4
- TXKRDMUDKYVBLB-UHFFFAOYSA-N methane;titanium Chemical compound C.[Ti] TXKRDMUDKYVBLB-UHFFFAOYSA-N 0.000 claims description 42
- 229910052804 chromium Inorganic materials 0.000 claims description 14
- VYZAMTAEIAYCRO-UHFFFAOYSA-N chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 14
- 239000011651 chromium Substances 0.000 claims description 14
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 12
- 229910052803 cobalt Inorganic materials 0.000 claims description 12
- 239000010941 cobalt Substances 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 6
- 230000001590 oxidative Effects 0.000 claims description 6
- 239000000843 powder Substances 0.000 description 30
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 28
- 239000000463 material Substances 0.000 description 20
- 229910052759 nickel Inorganic materials 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 238000005245 sintering Methods 0.000 description 8
- 241000237858 Gastropoda Species 0.000 description 6
- 229910039444 MoC Inorganic materials 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 150000001247 metal acetylides Chemical class 0.000 description 4
- 239000006104 solid solution Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N TiO Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical class [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000001747 exhibiting Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006011 modification reaction Methods 0.000 description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910001929 titanium oxide Inorganic materials 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium(0) Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/0047—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents
- C22C32/0052—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents only carbides
Definitions
- the present invention relates to corrosion-resistant cemented titanium carbide material for use in applications such as gas turbine rotors or buckets, which require corrosion-resistance and strength at high temperatures within oxidizing temperatures, and the production of such material.
- cemented titanium carbide material of high corrosion-resistance it was essential to combine at least 60% by weight of titanium carbide with a cementing alloy addition of nickel, cobalt and chromium.
- the best prior cemented titanium carbide material of this type exhibited a great degree of brittleness and could not be used in applications which required a material of substantial toughness at elevated temperatures.
- the present invention is based on the discovery that a superior cemented titanium carbide material exhibiting a substantial degree of toughness at elevated temperatures is obtained by combining 40% to 55% and up to 60% of a carbide phase consisting principally of titanium carbide with a cementing addition consisting of at least 10% and up to 30% chromium, at least 4% and up to 25% cobalt and the balance nickel. (Unless otherwise specifically stated, all proportions are given herein by weight).
- the titanium carbide may to advantage be combined wtih a small addition of molybdenum carbide which may form about .5 to 1% of the material.
- the carbide phase may combine titanium carbide with up to about 50% by weight of light carbides of other metals having a high melting point such as carbides of vanadium, zirconium and/ or chromium.
- impure titanium carbide powder obtained by reacting titanium oxide TiOz with carbon, which powder contains approximately 18.2% carbon combined with titanium and approximately 0.6 free carbon.
- the impure titanium carbide is then mixed with 1% molybdenum oxide M003 together with graphite and 10% pure nickel powder.
- the mixture so prepared is then ball milled in dry state for about 20 hours.
- the ball milled mixture is then pressed or compacted into slugs, without any lubricant.
- the compacted slugs are heated at about 225 C. for about 35 minutes in a dry hydrogen atmosphere, whereupon the slugs are crushed and screened into 100 mesh powder.
- the fine powder so obtained is leached with HCl to remove free nickel and iron picked up in ball milling. After leaching, the resulting powder analyzes as consisting of substantially pure titanium carbide containing about /2 molybdenum carbide in solid solution and about 0.4% free carbon.
- cemented titanium carbide body of the invention may be produced by the following procedure. 50% of the pure titanium carbide powder is mixed with a cementing metal either in pure or alloyed form containing 15% chromium, 8% cobalt, 27% nickel. The mixture of the titanium carbide powder and the metal powder is ball milled in acetone for 7 days in a stainless steel mill. The ball milled powder mixture is then dried, screened and mixed with a camphor-ether solution for approximately 1 hour, and the ether is thereafter evaporated.
- the so-treated powder mixture is then powdered into a powder body about mesh particle size.
- the soobtained powder is then pressed or compacted in a die with the pressure raised to about 5 t. s. i. (tons per square inch).
- the compact is presintered at about 900 C. in vacuum.
- the duration of the presintering depends on the size of the compact.
- the sintering temperature is reached within about 4 hours and the compact is thereafter maintained at the sintering temperature of about 900 C. for about 20 minutes. Thereafter, the compact is cooled in a hydrogen atmosphere.
- the presintered compact so obtained is then machined to give it the desired final shape allowing approximately 50% for shrinkage during the final sintering.
- the shaped sintered compact is heated in a vacuum within a furnace to a temperature between about 1000 to 1200 C. and below about 1300 C. and maintained at such elevated temperature for approximately 2 hours to permit removal of oxides from the body. Thereafter, the temperature of the furnace is raised to bring the body to about l400 to 1450 C. followed by cooling in vacuum.
- the body so obtained has a modulus of rupture between about 150,000 to 200,000 p. s. i. (pounds per square inch) and about 81 to 88 Rockwell A hardness. It has a stress-to-rupture life at 14,000 p. s. i. of 100 hours at 950 C. and good oxidation resistance at temperatures up to about 950 C.
- Similar desirable materials may be produced with other proportions of the ingredients of the ranges given above such as 40% titanium carbide, 12% chromium, 12% cobalt and 36% nickel.
- a shaped body of high hot strength and resistance to corrosion in oxidizing gases at high temperatures 40% to 60% of said body consisting principally of titanium carbide, the balance of said body consisting of at least 10% and up to 30% chromium, 4% to 5% cobalt and as balance nickel, said body having been shaped after presintering at a temperature below about 1300 C. and further sintered at an elevated temperature above about 1300 C.
Description
CIDE MATE Thomas Raine, Braall, Cheshire, England, assignor to American Electric Metal Corporation, Yonkers, N. Y a corporation of Maryland No Drawing. Application May 22, 1953, Serial No. 356,873
l 2 Claims. (Cl. 29-1825) The present invention relates to corrosion-resistant cemented titanium carbide material for use in applications such as gas turbine rotors or buckets, which require corrosion-resistance and strength at high temperatures within oxidizing temperatures, and the production of such material.
In the past, it was believed that in producing cemented titanium carbide material of high corrosion-resistance it was essential to combine at least 60% by weight of titanium carbide with a cementing alloy addition of nickel, cobalt and chromium. However, the best prior cemented titanium carbide material of this type exhibited a great degree of brittleness and could not be used in applications which required a material of substantial toughness at elevated temperatures.
The present invention is based on the discovery that a superior cemented titanium carbide material exhibiting a substantial degree of toughness at elevated temperatures is obtained by combining 40% to 55% and up to 60% of a carbide phase consisting principally of titanium carbide with a cementing addition consisting of at least 10% and up to 30% chromium, at least 4% and up to 25% cobalt and the balance nickel. (Unless otherwise specifically stated, all proportions are given herein by weight).
In the tough corrosion-resistant material of the invention, the titanium carbide may to advantage be combined wtih a small addition of molybdenum carbide which may form about .5 to 1% of the material. In some cases, the carbide phase may combine titanium carbide with up to about 50% by weight of light carbides of other metals having a high melting point such as carbides of vanadium, zirconium and/ or chromium.
There will now be described, by way of example, one method for producing tough cemented titanium carbide material of the invention which has proven satisfactory in commercial use.
In producing pure titanium carbide powder for cemented bodies of the invention, one may start with impure titanium carbide powder obtained by reacting titanium oxide TiOz with carbon, which powder contains approximately 18.2% carbon combined with titanium and approximately 0.6 free carbon. The impure titanium carbide is then mixed with 1% molybdenum oxide M003 together with graphite and 10% pure nickel powder. The mixture so prepared is then ball milled in dry state for about 20 hours. The ball milled mixture is then pressed or compacted into slugs, without any lubricant. The compacted slugs are heated at about 225 C. for about 35 minutes in a dry hydrogen atmosphere, whereupon the slugs are crushed and screened into 100 mesh powder. The fine powder so obtained is leached with HCl to remove free nickel and iron picked up in ball milling. After leaching, the resulting powder analyzes as consisting of substantially pure titanium carbide containing about /2 molybdenum carbide in solid solution and about 0.4% free carbon.
With the pure titanium carbide powder so obtained,- a
2,736,086 Patented Feb. 28, 1956 desired cemented titanium carbide body of the invention may be produced by the following procedure. 50% of the pure titanium carbide powder is mixed with a cementing metal either in pure or alloyed form containing 15% chromium, 8% cobalt, 27% nickel. The mixture of the titanium carbide powder and the metal powder is ball milled in acetone for 7 days in a stainless steel mill. The ball milled powder mixture is then dried, screened and mixed with a camphor-ether solution for approximately 1 hour, and the ether is thereafter evaporated.
The so-treated powder mixture is then powdered into a powder body about mesh particle size. The soobtained powder is then pressed or compacted in a die with the pressure raised to about 5 t. s. i. (tons per square inch). After removing from the die, the compact is presintered at about 900 C. in vacuum. The duration of the presintering depends on the size of the compact. Thus, in the case of a large compact such as 6 inches diameter and 4 inches height, the sintering temperature is reached Within about 4 hours and the compact is thereafter maintained at the sintering temperature of about 900 C. for about 20 minutes. Thereafter, the compact is cooled in a hydrogen atmosphere.
The presintered compact so obtained is then machined to give it the desired final shape allowing approximately 50% for shrinkage during the final sintering. In the final sintering, the shaped sintered compact is heated in a vacuum within a furnace to a temperature between about 1000 to 1200 C. and below about 1300 C. and maintained at such elevated temperature for approximately 2 hours to permit removal of oxides from the body. Thereafter, the temperature of the furnace is raised to bring the body to about l400 to 1450 C. followed by cooling in vacuum. The body so obtained has a modulus of rupture between about 150,000 to 200,000 p. s. i. (pounds per square inch) and about 81 to 88 Rockwell A hardness. It has a stress-to-rupture life at 14,000 p. s. i. of 100 hours at 950 C. and good oxidation resistance at temperatures up to about 950 C.
Similar desirable materials may be produced with other proportions of the ingredients of the ranges given above such as 40% titanium carbide, 12% chromium, 12% cobalt and 36% nickel.
The features and principles underlying the invention described above in connection with specific exemplifications will suggest to those skilled in the art many other modifications thereof. It is accordingly desired that the appended claims shall not be limited to any specific features or details shown and described in connection with the exemplifications thereof.
I claim:
1. A shaped body of high hot strength and resistance to corrosion in oxidizing gases at high temperatures, 40% to 60% of said body consisting principally of titanium carbide, the balance of said body consisting of at least 10% and up to 30% chromium, 4% to 5% cobalt and as balance nickel, said body having been shaped after presintering at a temperature below about 1300 C. and further sintered at an elevated temperature above about 1300 C.
2. A shaped body as claimed in claim 1, wherein the titanium carbide contains up to about 1% of molybdenum carbide in solid solution.
References Cited in the file of this patent UNITED STATES PATENTS 1,728,909 Schroter Sept. 17, 1929 1,992,372 Holzberger Feb. 26, 1935 2,162,574 Dawihl June 13, 1939 2,170,432 Schwarzkopf Aug. 22, 1939
Claims (1)
1. A SHAPED BODY OF HIGH HOT STRENGTH AND RESISTANCE TO CORROSION IN OXIDIZING GASES AT HIGH TEMPERATURES, 40% TO 60% OF SAID BODY CONSISTING PRINCIPALLY OF TITANIUM CARBIDE, THE BALANCE OF SAID BODY CONSISTING OF AT LEAST 10% AND UP TO 30% CHROMIUM, 4% TO 5% COBALT AND AS BALANCE NICKEL, SAID BODY HAVING BEEN SHAPED AFTER PRESINTERING AT A TEMPERATURE BELOW ABOUT 1300* C. AND FURTHER SINTERED AT AN ELEVATED TEMPERATURE ABOVE ABOUT 1300* C.
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2736086A true US2736086A (en) | 1956-02-28 |
Family
ID=3445429
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US2736086D Expired - Lifetime US2736086A (en) | Corrosion-resistant cemented titanium |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2736086A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4704336A (en) * | 1984-03-12 | 1987-11-03 | General Electric Company | Solid particle erosion resistant coating utilizing titanium carbide |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1728909A (en) * | 1925-12-12 | 1929-09-17 | Gen Electric | Method of making tools from hard-metal alloys produced by sintering |
| US1992372A (en) * | 1930-05-07 | 1935-02-26 | Boehler & Co Ag Geb | Hard metal alloy |
| US2162574A (en) * | 1937-05-15 | 1939-06-13 | Gen Electric | Hard metal alloy |
| US2170432A (en) * | 1929-05-16 | 1939-08-22 | American Cutting Alloys Inc | Hard metal tool alloy |
-
0
- US US2736086D patent/US2736086A/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1728909A (en) * | 1925-12-12 | 1929-09-17 | Gen Electric | Method of making tools from hard-metal alloys produced by sintering |
| US2170432A (en) * | 1929-05-16 | 1939-08-22 | American Cutting Alloys Inc | Hard metal tool alloy |
| US1992372A (en) * | 1930-05-07 | 1935-02-26 | Boehler & Co Ag Geb | Hard metal alloy |
| US2162574A (en) * | 1937-05-15 | 1939-06-13 | Gen Electric | Hard metal alloy |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4704336A (en) * | 1984-03-12 | 1987-11-03 | General Electric Company | Solid particle erosion resistant coating utilizing titanium carbide |
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