US3395013A - High-temperature ductile alloys - Google Patents
High-temperature ductile alloys Download PDFInfo
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- US3395013A US3395013A US443690A US44369065A US3395013A US 3395013 A US3395013 A US 3395013A US 443690 A US443690 A US 443690A US 44369065 A US44369065 A US 44369065A US 3395013 A US3395013 A US 3395013A
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- tungsten
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
- C22C27/04—Alloys based on tungsten or molybdenum
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/045—Alloys based on refractory metals
Definitions
- This invention relates to tungsten base alloys characterized by high strength at elevated temperatures and low ductile-brittle transition temperatures.
- the tungsten base alloys of the present invention contain rhenium, carbon and a reactive metal selected from Group IV-A of the Periodic Chart.
- rhenium As is well known, the addition of rhenium to tungsten produces alloys having reduced ductile-to-brittle transition temperatures.
- the scarcity and high cost of rhenium has limited the use of these materials for many applications such as sheet, tubing and other wrought forms.
- tungsten base alloys which contain between 1% and 10% rhenium, 0.002% to 0.05% carbon and a reactive metal selected from the group consisting of hafnium, zirconium and titanium.
- the percentage of reactive metal in the alloy depends on the metal used, hafnium being present in an amount between 0.01% and 1.0%, zirconium 0.01% to 0.3% and titanium 0.03% to 0.3%. (All percentages given are by Weight.)
- the ductile-to-brittle transition occurs in the range from less than 50 C. to C. for the new alloys as compared to C. for unalloyed tungsten.
- the recrystallization temperature for unalloyed tungsten is between 1450 C. and 1500 C. whereas the present alloys have recrystallization temperatures in the range 1600 C. to 1850 C.
- the high strengths and high recrystallization temperatures obtained in these tungsten base alloys is believed due to the formation during fabrication of a uniformly dispersed reactive metal carbide having particle size predominantly in the range 50 to 1000 Angstroms.
- Elemental powders of carbon, rhenium and tungsten were blended with hafnium hydride to form a uniform mixture which was then subjected to a pressure of approximately 50,000 pounds per square inch to form a billet.
- the billet was next sintered at a temperature of about 2350 C. for approximately 4 hours to mutually diffuse the different ingredients thereby forming a solid solution of hafnium and rhenium in tungsten, the carbon probably being partitioned between tungsten carbide and a solid solution of carbon in tungsten.
- the billet was then fabricated by forging at a temperature of approximately 1850 C. from 0.05 inch to 0.3 inch thick followed by rolling at a temperature of about 1550 C. to form sheets having a thickness of approximately 0.040 inch. During the fabrication process, carbon precipitates as a finely dispersed reactive metal carbide.
- the alloys may also be consolidated by other suitable processes such as vacuum arc-casting. Fabrication may be accomplished by other techniques such as extruding, forging or drawing .to produce the desired wrought form.
- EXAMPLE III sisting essentially of from 1% to 10% rhenium, 0.002% An alloy consisting of carbon, rhenium, titanium and to 095% f f from 0-01% to 10% hafmum the tungsten was prepared by the method of Example I.
- Table balance Consisting of tungsten- 1v gives the characteristics of various compositions of this A tungsten base alloy characterized y high strength alloy, at elevated temperatures and a low ductile-to-brittle tran- TABLE IV Alloy Percent By Weight Ultimate Duetile-to-Brittle Transition One Hour Tensile Temp. C.) Reerystall. Strength at Temperature Ti Re 0 W 1,050 o. (p.s.i.) Nil Duet. Duetility 0.)
- the alloys also have high to 0.05% carbon, from 0.01% to 0.3% zirconium, the recrystallization temperatures as compared to unalloyed balance consisting of tungsten. tungsten. For applications Where a high melting point is 5.
- conand titanium the balance consisting of tungsten. sisting essentially of from 3% to 10% rhenium, 0.002% 2.
- a tungsten base alloy characterized by high strength to 0.02% carbon, from 0.01% to 0.25% zirconium, the at elevated temperatures and a low ductile-to-brittle tranbalance consisting of tungsten.
- a tungsten base alloy characterized by high strength at elevated temperatures and a low ductile-to-brittle tran sition temperature in the range -50 C. to +125 C. consisting essentially of from 1% to 10% rhenium, 0.002% to 0.05% carbon, 0.01% to 1.0% of a reactive metal selected from the group consisting of hafnium, zirconium and titanium, the balance consisting of tungsten, said alloy containing uniformly dispersed particles of reactive metal carbide having particle sizes predominantly in the range 50 to 1000 Angstroms.
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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)
- Manufacture And Refinement Of Metals (AREA)
Description
United States Patent 3,395,013 HIGH-TEMPERATURE DUCTILE ALLOYS Sam Friedman, Great Neck, N.Y., assignor to General Telephone and Electronics Laboratories, Inc., a corporation of Delaware No Drawing. Filed Mar. 29, 1965, Ser. No. 443,690 9 Claims. (Cl. 75176) ABSTRACT OF THE DISCLOSURE A group of tungsten-base alloys containing between 1% and 10% rhenium, carbon and a reactive metal from the group consisting of hafnium, zirconium and titanium. These low rhenium-content alloys may be used to fabricate wrought forms having high strength at elevated temperatures, high recrystallization temperatures and low duetile-to-brittle transition temperatures.
This invention relates to tungsten base alloys characterized by high strength at elevated temperatures and low ductile-brittle transition temperatures.
The tungsten base alloys of the present invention contain rhenium, carbon and a reactive metal selected from Group IV-A of the Periodic Chart. As is well known, the addition of rhenium to tungsten produces alloys having reduced ductile-to-brittle transition temperatures. However, the scarcity and high cost of rhenium has limited the use of these materials for many applications such as sheet, tubing and other wrought forms.
Accordingly, it is an object of my invention to provide alloys which employ relatively small amounts of rhenium yet have low ductile-to-brittle transition temperatures, high strength at elevated temperatures and high recrystallization temperatures.
In the present invention, tungsten base alloys are provided which contain between 1% and 10% rhenium, 0.002% to 0.05% carbon and a reactive metal selected from the group consisting of hafnium, zirconium and titanium. The percentage of reactive metal in the alloy depends on the metal used, hafnium being present in an amount between 0.01% and 1.0%, zirconium 0.01% to 0.3% and titanium 0.03% to 0.3%. (All percentages given are by Weight.) By varying the constituents within the specified ranges the best combination of mechanical properties and ease of fabricability may be obtained for a given application. In particular, it has been found that a combination of high elevated temperature strength, high recrystallization temperatures and at least partial bend ductility at room temperature are found in the preferred compositions of Table I.
TABLE I Constituents: Weight percent Reactive metal- Hafnium 0.0l0.5 Zirconium 0.01-0.25 Titanium 0.060.25 Rhenium 3-10 Carbon 0.0020.02 Tungsten Balance 3,395,013 Patented July 30, 1968 These alloys compared with unalloyed tungsten made by the same process are generally stronger at 1650 C., have higher recrystallization temperatures and are duetile at lower temperatures. In particular, a number of the alloys in all three systems are completely ductile at room temperature or below. For example, the alloys of Table I exhibit ultimate tensile strength at 1650 C. in the range 35,000 p.s.i. to 67,000 p.s.i., as compared to 13,000 p.s.i. for unalloyed tungsten. The ductile-to-brittle transition occurs in the range from less than 50 C. to C. for the new alloys as compared to C. for unalloyed tungsten. The recrystallization temperature for unalloyed tungsten is between 1450 C. and 1500 C. whereas the present alloys have recrystallization temperatures in the range 1600 C. to 1850 C. The high strengths and high recrystallization temperatures obtained in these tungsten base alloys is believed due to the formation during fabrication of a uniformly dispersed reactive metal carbide having particle size predominantly in the range 50 to 1000 Angstroms.
EXAMPLE I Elemental powders of carbon, rhenium and tungsten were blended with hafnium hydride to form a uniform mixture which was then subjected to a pressure of approximately 50,000 pounds per square inch to form a billet. The billet was next sintered at a temperature of about 2350 C. for approximately 4 hours to mutually diffuse the different ingredients thereby forming a solid solution of hafnium and rhenium in tungsten, the carbon probably being partitioned between tungsten carbide and a solid solution of carbon in tungsten. The billet was then fabricated by forging at a temperature of approximately 1850 C. from 0.05 inch to 0.3 inch thick followed by rolling at a temperature of about 1550 C. to form sheets having a thickness of approximately 0.040 inch. During the fabrication process, carbon precipitates as a finely dispersed reactive metal carbide.
While a powder metallurgy process was used in forming the sheets, it shall be understood that the alloys may also be consolidated by other suitable processes such as vacuum arc-casting. Fabrication may be accomplished by other techniques such as extruding, forging or drawing .to produce the desired wrought form.
Measurements of ultimate tensile strength, recrystallization temperature and ductile-to-brittle transition temperature were carried out for a number of alloys. The recrystallization temperature was established by determining at what temperature the alloy must be heated for one hour before the fibrous structure completely disappears and recrystallization is essentially complete. The transition from ductile-to-brittle behavior, which occurs over a range of temperatures, was measured by attempting to bend specimens 1 inch long by inch wide by 0.04 inch thick over a radius four times the thickness of the sheet through a 105 angle at several temperatures and determining the minimum temperature at which the samle cracked after a small but perceptible amount of bending '(nil ductility temperature) and the minimum temperature at which the sample bent 105 without cracking (ductility temperature).
Characteristics of the alloys at diiierent compositions sisting essentially of from 3% to 10% rhenium, 0.002% are shown in Table II. A dash in the table indicates that to 0.02% carbon, from 0.01% to 0.5% of a reactive the listed property was not measured for that sample. metal selected from the group consisting of hafnium,
TABLE II Alloy Percent By Weight Ultimate Duetile-to-Brittle Transition One Hour Tensile Temp. C.) Reerystall. Strength at Temperature Hf Re C W 1,050 o. (p.s.i.) Nil Duet. Duetility 0.)
Temp. Temp.
EXAMPLE II zirconium and titanium, the balance consisting of tung- An alloy consisting of carbon, rhenium, zirconium and stem tungsten was prepared by the method described for the 20 A tungsten base alloy charactenzed by hlgh Strength alloy f Example I, bl 111 gives h characteristics f at elevated temperatures and a low ductile-to-brittle tranvarious compositions of this alloy. sition temperature in the range 5 0 C. to +125 C. con- TABLE III Alloy Percent By Weight Ultimate Duetile-to-Brittle Transition One Hour Tensile Temp. C.) Reerystall. Strength at Temperature Zr Re C W 1,650 C. (p.s.i.) Nil Duet. Ductility C.)
Temp. Temp.
0. 010 Bal 65,000 -30 1, 825-1, 850 0. 004 Bal 50 50 1, 800-1, 825 0. 015 Bal 03 000 0 014 Bal 63,000 0 023 Bal ,000 0. 005 Bal 00, 000 0 1, 750-1, 775 0. 01 Bal 59, 000 -10 1, 750-1, 775
EXAMPLE III sisting essentially of from 1% to 10% rhenium, 0.002% An alloy consisting of carbon, rhenium, titanium and to 095% f f from 0-01% to 10% hafmum the tungsten was prepared by the method of Example I. Table balance Consisting of tungsten- 1v gives the characteristics of various compositions of this A tungsten base alloy characterized y high strength alloy, at elevated temperatures and a low ductile-to-brittle tran- TABLE IV Alloy Percent By Weight Ultimate Duetile-to-Brittle Transition One Hour Tensile Temp. C.) Reerystall. Strength at Temperature Ti Re 0 W 1,050 o. (p.s.i.) Nil Duet. Duetility 0.)
Temp. Temp.
From these results it is apparent that the new alloys sition temperature in the range C. to +125 C. conexhibit high strength at elevated temperatures and are sisting essentially of from 1% to 10% rhenium, 0.002%
ductile at low temperatures. The alloys also have high to 0.05% carbon, from 0.01% to 0.3% zirconium, the recrystallization temperatures as compared to unalloyed balance consisting of tungsten. tungsten. For applications Where a high melting point is 5. A tungsten base alloy characterized by high strength desired, the composition containing the minimum alloying at elevated temperatures and a low ductile-to-brittle traningredients consistent with desired mechanical properties sition temperature in the range 50 C. to +125 C. conhave been found most suitable. 0 sisting essentially of from 1% to 10% rhenium, 0.002% As many changes could be made in the above described to 0.05% carbon, from 0.03 to 0.3 titanium, the compositions it is intended that all matter contained balance consisting of tungsten. therein shall be interpreted as illustrative and not in a 6. A tungsten base alloy characterized by high strength limiting sense. at elevated temperatures and a low ductile-to-brittle tran- What is claimed is: 35 sition temperature in the range 50 C. to +125 C. con- 1. A tungsten base alloy characterized by high strength sisting essentially of from 3% to 10% rhenium, 0.002% at elevated temperatures and a low duotile-to-brittle tranto 0.02% carbon, from 0.05 to 0.5 hafnium, the sition temperature in the range -50 C. to +125 C. conbalance consisting of tungsten. sisting essentially of from 1% to 10% rhenium, 0.002% 7. A tungsten base alloy characterized by high strength to 0.05 carbon, from 0.01% to 1.0% of a reactive metal at elevated temperatures and a low ductile-to-brittle transelected from the group consisting of hafnium, zirconium sition temperature in the range 50 C. to +125 C. conand titanium, the balance consisting of tungsten. sisting essentially of from 3% to 10% rhenium, 0.002% 2. A tungsten base alloy characterized by high strength to 0.02% carbon, from 0.01% to 0.25% zirconium, the at elevated temperatures and a low ductile-to-brittle tranbalance consisting of tungsten.
sition temperature in the range 50 C. to +125 C. eon- 8. A tungsten base alloy characterized by high strength at elevated temperatures and a lOw ductile-to-brittle transition temperature in the range 50 C. to +125 C. consisting essentially of from 3% to 10% rhenium, 0.002% to 0.02% carbon, from 0.06% to 0.25% titanium, the balance consisting of tungsten.
9. A tungsten base alloy characterized by high strength at elevated temperatures and a low ductile-to-brittle tran sition temperature in the range -50 C. to +125 C. consisting essentially of from 1% to 10% rhenium, 0.002% to 0.05% carbon, 0.01% to 1.0% of a reactive metal selected from the group consisting of hafnium, zirconium and titanium, the balance consisting of tungsten, said alloy containing uniformly dispersed particles of reactive metal carbide having particle sizes predominantly in the range 50 to 1000 Angstroms.
6 References Cited UNITED STATES PATENTS 3,116,145 12/1963 Semchyshen 75-476 3,236,699 2/1966 Pugh et a1 75-176 3,243,291 3/ 1966 Dickinson et al 75-176 OTHER REFERENCES "Nb, Ta, Mo and W, Quarrell, Elsevier Publishing Co.,
10 New York, 1961, pp. 321 and 347-361 relied on.
Field, et al., Research and Development of Tantalum and Tungsten Base Alloys, July 6, 1961, pp. 81-84 and 121-124 relied on.
15 CHARLES N. LOVELL, Primary Examiner.
Priority Applications (10)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US443690A US3395013A (en) | 1965-03-29 | 1965-03-29 | High-temperature ductile alloys |
DK155866AA DK116174B (en) | 1965-03-29 | 1966-03-25 | Tungsten alloy with high strength at high temperature. |
CH431466A CH442763A (en) | 1965-03-29 | 1966-03-25 | Tungsten-based alloy |
ES0324652A ES324652A1 (en) | 1965-03-29 | 1966-03-25 | Procedure for preparing ductile ductile alloys based on tungsten. (Machine-translation by Google Translate, not legally binding) |
FR55093A FR1472636A (en) | 1965-03-29 | 1966-03-25 | Tungsten-based ductile refractory alloys |
SE4008/66A SE303382B (en) | 1965-03-29 | 1966-03-25 | |
BE678439D BE678439A (en) | 1965-03-29 | 1966-03-25 | |
DE19661533346 DE1533346B1 (en) | 1965-03-29 | 1966-03-25 | Ductile, high temperature resistant tungsten-rhenium alloys |
NL6603946A NL6603946A (en) | 1965-03-29 | 1966-03-25 | |
AT292066A AT265675B (en) | 1965-03-29 | 1966-03-28 | Tungsten based alloys |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US443690A US3395013A (en) | 1965-03-29 | 1965-03-29 | High-temperature ductile alloys |
Publications (1)
Publication Number | Publication Date |
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US3395013A true US3395013A (en) | 1968-07-30 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US443690A Expired - Lifetime US3395013A (en) | 1965-03-29 | 1965-03-29 | High-temperature ductile alloys |
Country Status (9)
Country | Link |
---|---|
US (1) | US3395013A (en) |
AT (1) | AT265675B (en) |
BE (1) | BE678439A (en) |
CH (1) | CH442763A (en) |
DE (1) | DE1533346B1 (en) |
DK (1) | DK116174B (en) |
ES (1) | ES324652A1 (en) |
NL (1) | NL6603946A (en) |
SE (1) | SE303382B (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3865586A (en) * | 1972-11-17 | 1975-02-11 | Int Nickel Co | Method of producing refractory compound containing metal articles by high energy milling the individual powders together and consolidating them |
US3979209A (en) * | 1975-02-18 | 1976-09-07 | The United States Of America As Represented By The United States Energy Research And Development Administration | Ductile tungsten-nickel alloy and method for making same |
US4432794A (en) * | 1980-07-19 | 1984-02-21 | Kernforschungszentrum Karlsruhe Gmbh | Hard alloy comprising one or more hard phases and a binary or multicomponent binder metal alloy |
US20140301891A1 (en) * | 2011-12-20 | 2014-10-09 | Kabushiki Kaisha Toshiba | Tungsten alloy, tungsten alloy part, discharge lamp, transmitting tube, and magnetron |
CN112410634A (en) * | 2020-11-25 | 2021-02-26 | 广东省科学院中乌焊接研究所 | Alloying powder, tungsten-based alloy, preparation method thereof and stirring tool |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3116145A (en) * | 1962-04-30 | 1963-12-31 | American Metal Climax Inc | Tungsten-hafnium alloy casting |
US3236699A (en) * | 1963-05-09 | 1966-02-22 | Gen Electric | Tungsten-rhenium alloys |
US3243291A (en) * | 1963-10-29 | 1966-03-29 | Gen Telephone & Elect | High-temperature alloy |
-
1965
- 1965-03-29 US US443690A patent/US3395013A/en not_active Expired - Lifetime
-
1966
- 1966-03-25 NL NL6603946A patent/NL6603946A/xx unknown
- 1966-03-25 DE DE19661533346 patent/DE1533346B1/en active Pending
- 1966-03-25 SE SE4008/66A patent/SE303382B/xx unknown
- 1966-03-25 BE BE678439D patent/BE678439A/xx unknown
- 1966-03-25 DK DK155866AA patent/DK116174B/en unknown
- 1966-03-25 CH CH431466A patent/CH442763A/en unknown
- 1966-03-25 ES ES0324652A patent/ES324652A1/en not_active Expired
- 1966-03-28 AT AT292066A patent/AT265675B/en active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3116145A (en) * | 1962-04-30 | 1963-12-31 | American Metal Climax Inc | Tungsten-hafnium alloy casting |
US3236699A (en) * | 1963-05-09 | 1966-02-22 | Gen Electric | Tungsten-rhenium alloys |
US3243291A (en) * | 1963-10-29 | 1966-03-29 | Gen Telephone & Elect | High-temperature alloy |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3865586A (en) * | 1972-11-17 | 1975-02-11 | Int Nickel Co | Method of producing refractory compound containing metal articles by high energy milling the individual powders together and consolidating them |
US3979209A (en) * | 1975-02-18 | 1976-09-07 | The United States Of America As Represented By The United States Energy Research And Development Administration | Ductile tungsten-nickel alloy and method for making same |
US4432794A (en) * | 1980-07-19 | 1984-02-21 | Kernforschungszentrum Karlsruhe Gmbh | Hard alloy comprising one or more hard phases and a binary or multicomponent binder metal alloy |
US20140301891A1 (en) * | 2011-12-20 | 2014-10-09 | Kabushiki Kaisha Toshiba | Tungsten alloy, tungsten alloy part, discharge lamp, transmitting tube, and magnetron |
US9834830B2 (en) * | 2011-12-20 | 2017-12-05 | Kabushiki Kaisha Toshiba | Tungsten alloy, tungsten alloy part, discharge lamp, transmitting tube, and magnetron |
US10167536B2 (en) | 2011-12-20 | 2019-01-01 | Kabushiki Kaisha Toshiba | Tungsten alloy, tungsten alloy part, discharge lamp, transmitting tube, and magnetron |
CN112410634A (en) * | 2020-11-25 | 2021-02-26 | 广东省科学院中乌焊接研究所 | Alloying powder, tungsten-based alloy, preparation method thereof and stirring tool |
CN112410634B (en) * | 2020-11-25 | 2021-09-07 | 广东省科学院中乌焊接研究所 | Alloying powder, tungsten-based alloy, preparation method thereof and stirring tool |
Also Published As
Publication number | Publication date |
---|---|
AT265675B (en) | 1968-10-25 |
NL6603946A (en) | 1966-09-30 |
ES324652A1 (en) | 1967-05-01 |
BE678439A (en) | 1966-09-01 |
SE303382B (en) | 1968-08-26 |
CH442763A (en) | 1967-08-31 |
DK116174B (en) | 1969-12-15 |
DE1533346B1 (en) | 1970-04-02 |
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