US2687954A - Alloy - Google Patents
Alloy Download PDFInfo
- Publication number
- US2687954A US2687954A US252198A US25219851A US2687954A US 2687954 A US2687954 A US 2687954A US 252198 A US252198 A US 252198A US 25219851 A US25219851 A US 25219851A US 2687954 A US2687954 A US 2687954A
- Authority
- US
- United States
- Prior art keywords
- percent
- alloys
- nickel
- chromium
- calcium
- 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
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- 229910045601 alloy Inorganic materials 0.000 title description 27
- 239000000956 alloy Substances 0.000 title description 27
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 28
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 22
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 18
- 229910052791 calcium Inorganic materials 0.000 claims description 18
- 239000011575 calcium Substances 0.000 claims description 18
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 16
- 150000002910 rare earth metals Chemical class 0.000 claims description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 15
- 229910052759 nickel Inorganic materials 0.000 claims description 14
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 12
- 229910052804 chromium Inorganic materials 0.000 claims description 12
- 239000011651 chromium Substances 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 11
- 229910001430 chromium ion Inorganic materials 0.000 claims 1
- 238000007792 addition Methods 0.000 description 12
- 229910000640 Fe alloy Inorganic materials 0.000 description 10
- BIJOYKCOMBZXAE-UHFFFAOYSA-N chromium iron nickel Chemical compound [Cr].[Fe].[Ni] BIJOYKCOMBZXAE-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 229910052684 Cerium Inorganic materials 0.000 description 4
- 229910001122 Mischmetal Inorganic materials 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052746 lanthanum Inorganic materials 0.000 description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- -1 cerium Chemical class 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910000599 Cr alloy Inorganic materials 0.000 description 1
- 229910000722 Didymium Inorganic materials 0.000 description 1
- 241000224487 Didymium Species 0.000 description 1
- 241001102334 Janua Species 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 239000000788 chromium alloy Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
Definitions
- This invention relates to alloys and more particularly to alloys for electric resistance units.
- an alloy having the property of resisting oxidation at high temperature is essential.
- the alloys forming the subject matter of this invention are characterized by ability to resist oxidation and by a prolonged life, exceeding that of other known alloys when used under high temperature conditions. Since the introduction of nickel-chromium-iron alloys as electric resistance units, many developments have occurred that have improved their resistance to oxidation. In a number of prior patents I have disclosed and claimed various alloying additions of calcium, zirconium and aluminum which greatly improve the life of heating elements. It has also been proposed to add rare earth metals, such as cerium, to nickel-chromium-iron alloys to improve the life of the heating elements.
- the present invention is, therefore, directed to the addition of small quantities of the rare earths with calcium and aluminum to nickel-chromium-iron alloys. I have found that such combination of addition elements greatly increases the period of life of nickel-chromium-iron alloys when employed under conditions where they are subjected to high temperatures.
- the alloys forming the subject matter of the present invention may also contain small amounts of either silicon or manganese or both of these elements.
- the rare earth metals may be added as misch metal" having an approximate composition of 45 percent cerium, 30 percent lanthanum, 20 percent ytterbium and didymium. Although it is convenient to add the rare earth metals in the form of misch metal," I do not restrict myself to the use of this material as one or more of the rare earth metals may be added singly and its effect is of a similar nature.
- the additions may be used to advantage with the nickel-chromium-iron alloys of which the best known examples are the alloys of 30 to 70 percent nickel, to 25 percent chromium, balance iron.
- the additions were made to the alloys consisting of substantially 35 percent nickel, 20 percent chromium and balance iron.
- Rare earth metals, such as misch metal, with calcium and aluminum may be added to such alloys with or without silicon.
- the proportions of nickel in such alloys may vary from 30 to 50 percent and the chromium from 10 to 25 percent with the balance iron.
- employing nickel-chromium-iron alloys of these proportions, I have added calcium, aluminum and misch metal in the quantities or amounts hereinafter mentioned.
- the quantities of such addition elements are subtracted from the iron content.
- the final alloys will contain 30 to 50 percent nickel, 10 to 25 percent chromium, the addition elements calcium, aluminum and the rare earth metals in the percentages hereinafter stated, and the balance iron. While the proportions of calcium, aluminum and rare earth metals may vary within certain limits, I have found that the best results are obtained when these materials are present in the final alloys within the following limits:
- alloys contain manganese, silicon, or carbon, they may be present within the following limits:
- the alloys so prepared have been tested for resistance to oxidation at high temperature by a modification of the method approved by the American Society for Testing Materials Accelerated Life Test for Metallic Materials, B76-39.
- the silky is produced in the form or a wire, drawn to a diameter approximately .025" and tested at a temperature of 1950 F., instead of a temperature of 2050 R, which is the temperature of the standard ASTM method for testing the 60 nickel, 15 chromium alloys.
- the useful life" in hours for wire of substantially 35 percent nickel, fldparcentnchromium containing calcium, zirconium and aluminum as addition elements, balance iron, is of the order of 100 hours.
- the useful life of the alloys of the present invention is of the order '0! 400 hours.
- the useful life is increased around 300 percent over that of the alloys containing the calcium, zirconium, aluminum group when the rare earth metals are added with calcium and aluminum in the proportions herein-stated.
- the alloys are prepared in the usual manner by placing the ingredients in a bath, heating until the alloying elements become molten and then pouring. In adding rare earth metals to a molten bath, it is necessary to add considerably larger quantities than will be found in the cast metal because they vaporize readily and pass out of the bath. In many instances, with additions of the rare earth metals only a spectrographic trace of one or more of the rare earth metals is found in the cast material. The presence of such traces, however, in combination with calcium and aluminum, greatly increases the oxidation resistance of the alloys. added in amounts sufficient to leave a residue in the cast alloys up to .2 percent but in most instances the use of such amounts is not necessary.
- a nickel-chromium-iron alloy consisting substantially of percent nickel, substantially 20 percent chromium, .001 to .20 percent calcium, .01 to 1.0 percent aluminum, a trace to .50 percent of a, rare earth metal, balance essentially iron.
- a nickel-chromium-iron alloy consisting substantially of 35 ,percent nickel, substantially 20 percent chromium, .001 to .07 percent calcium,
- a nickelchromium-iron alloy consisting substantially of 35 percent nickel, substantially 20 percent chromium, .00il to .20 percent calcium, .01 to 1.0 percent aluminum, a trace to .50 percent cerium and lanthanum, balance essentially iron.
- a nickel-chromiumiron alloy consisting substantially of 35 percent nickel, substantially 20 percent chromium, .00 to .07 percent calcium, .01 to .40 percent aluminum, a trace to .20 percent cerium and lanthanum, balance essentially iron.
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- Adornments (AREA)
Description
Patented Aug. 31, 1954 ALLOY James M. Lohr, Morristown, N. J., assignor to Driver-Harris Company, Harrison, N. J a corporation of New Jersey No Drawing. Original a ry 1, 1952. her 19, 1951, Serial No.
1949, Serial No.
2,581,420, dated Janua this application Octo 4 Claims. 1
This invention relates to alloys and more particularly to alloys for electric resistance units.
In the manufacture of electrical resistance units, an alloy having the property of resisting oxidation at high temperature is essential. The alloys forming the subject matter of this invention are characterized by ability to resist oxidation and by a prolonged life, exceeding that of other known alloys when used under high temperature conditions. Since the introduction of nickel-chromium-iron alloys as electric resistance units, many developments have occurred that have improved their resistance to oxidation. In a number of prior patents I have disclosed and claimed various alloying additions of calcium, zirconium and aluminum which greatly improve the life of heating elements. It has also been proposed to add rare earth metals, such as cerium, to nickel-chromium-iron alloys to improve the life of the heating elements.
I have found that when calcium and aluminum as well as rare earth metals are added to nickelchromium-iron alloys, better results are obtained than if the calcium, zirconium, aluminum group or the rare earths are used alone. The present invention is, therefore, directed to the addition of small quantities of the rare earths with calcium and aluminum to nickel-chromium-iron alloys. I have found that such combination of addition elements greatly increases the period of life of nickel-chromium-iron alloys when employed under conditions where they are subjected to high temperatures. The alloys forming the subject matter of the present invention may also contain small amounts of either silicon or manganese or both of these elements. The rare earth metals may be added as misch metal" having an approximate composition of 45 percent cerium, 30 percent lanthanum, 20 percent ytterbium and didymium. Although it is convenient to add the rare earth metals in the form of misch metal," I do not restrict myself to the use of this material as one or more of the rare earth metals may be added singly and its effect is of a similar nature. The additions may be used to advantage with the nickel-chromium-iron alloys of which the best known examples are the alloys of 30 to 70 percent nickel, to 25 percent chromium, balance iron.
This application is a division of my copending application Serial No. 117,510, filed September 23, 1949, now Patent No. 2,581,420. The claims of this application are directed to alloys containing 30 to 50 percent nickel and 10 to 25 percent chromium, and more specifically to alloys containing pplication September 23, ,510, now Patent No.
Divided and 2 substantially 35 percent nickel and substantially 20 percent chromium.
In the examples hereinafter described, the additions were made to the alloys consisting of substantially 35 percent nickel, 20 percent chromium and balance iron. Rare earth metals, such as misch metal, with calcium and aluminum may be added to such alloys with or without silicon. The proportions of nickel in such alloys may vary from 30 to 50 percent and the chromium from 10 to 25 percent with the balance iron. Employing nickel-chromium-iron alloys of these proportions, I have added calcium, aluminum and misch metal in the quantities or amounts hereinafter mentioned.
In preparing alloys containing the addition elements above mentioned, the quantities of such addition elements are subtracted from the iron content. For example, when additions are made to base alloys containing 30 to 50 percent nickel, 10 to 25 percent chromium, the final alloys will contain 30 to 50 percent nickel, 10 to 25 percent chromium, the addition elements calcium, aluminum and the rare earth metals in the percentages hereinafter stated, and the balance iron. While the proportions of calcium, aluminum and rare earth metals may vary within certain limits, I have found that the best results are obtained when these materials are present in the final alloys within the following limits:
Percent Calcium .001-20 Aluminum .01-1.0 Rare earth metals Trace-0.50
If the alloys contain manganese, silicon, or carbon, they may be present within the following limits:
Percent Manganese .02-4.0 Silicon .20-3.0 Carbon 0.25 max.
While alloys having the properties desired to a very high degree are obtained within the limits before mentioned, the preferred range of addition elements is as follows:
The alloys so prepared have been tested for resistance to oxidation at high temperature by a modification of the method approved by the American Society for Testing Materials Accelerated Life Test for Metallic Materials, B76-39. In conducting such test, :the silky is produced in the form or a wire, drawn to a diameter approximately .025" and tested at a temperature of 1950 F., instead of a temperature of 2050 R, which is the temperature of the standard ASTM method for testing the 60 nickel, 15 chromium alloys, The useful life" in hours for wire of substantially 35 percent nickel, fldparcentnchromium containing calcium, zirconium and aluminum as addition elements, balance iron, is of the order of 100 hours. The useful life" of the alloys of the present invention, according to the above described test, is of the order '0! 400 hours. Thus, the useful life is increased around 300 percent over that of the alloys containing the calcium, zirconium, aluminum group when the rare earth metals are added with calcium and aluminum in the proportions herein-stated.
The alloys are prepared in the usual manner by placing the ingredients in a bath, heating until the alloying elements become molten and then pouring. In adding rare earth metals to a molten bath, it is necessary to add considerably larger quantities than will be found in the cast metal because they vaporize readily and pass out of the bath. In many instances, with additions of the rare earth metals only a spectrographic trace of one or more of the rare earth metals is found in the cast material. The presence of such traces, however, in combination with calcium and aluminum, greatly increases the oxidation resistance of the alloys. added in amounts sufficient to leave a residue in the cast alloys up to .2 percent but in most instances the use of such amounts is not necessary.
In the test referred to above the increase or electrical resistance at temperature with time is The rare earth metals maybe 4 plotted and an increase of 10 percent in resistance is known as the useful life." The life of the tiejsted specimen to burn-out is known as total ilclaim:
l. A nickel-chromium-iron alloy consisting substantially of percent nickel, substantially 20 percent chromium, .001 to .20 percent calcium, .01 to 1.0 percent aluminum, a trace to .50 percent of a, rare earth metal, balance essentially iron.
2. A nickel-chromium-iron alloy consisting substantially of 35 ,percent nickel, substantially 20 percent chromium, .001 to .07 percent calcium,
-01 to .40 percent-aluminum, a trace to .20 percent of a rare'earth metal, balance essentially iron.
3. A nickelchromium-iron alloy consisting substantially of 35 percent nickel, substantially 20 percent chromium, .00il to .20 percent calcium, .01 to 1.0 percent aluminum, a trace to .50 percent cerium and lanthanum, balance essentially iron.
4. A nickel-chromiumiron alloy consisting substantially of 35 percent nickel, substantially 20 percent chromium, .00 to .07 percent calcium, .01 to .40 percent aluminum, a trace to .20 percent cerium and lanthanum, balance essentially iron.
References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 1,941,648 Armstrong Jan. 2, 1934 2,581,420 Lohr Jan. 8, 1952 FOREIGN PATENTS Number Country Date 488,926 Great Britain July 12, 1538
Claims (1)
1. A NICKEL-CHROMIUM-ION ALLOY CONSISTING SUBSTANTIALLY OF 35 PERCENT NICKEL, SUBSTANTIALLY 20 PERCENT CHROMIUM, .001 TO .20 PERCENT CALCIUM, .01 TO 1.0 PERCENT ALUMINUM, A TRACE TO .50 PERCENT OF A RARE EARTH METAL, BALANCE ESSENTIALLY IRON.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US252198A US2687954A (en) | 1949-09-23 | 1951-10-19 | Alloy |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US117510A US2581420A (en) | 1949-09-23 | 1949-09-23 | Alloys |
| US252198A US2687954A (en) | 1949-09-23 | 1951-10-19 | Alloy |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2687954A true US2687954A (en) | 1954-08-31 |
Family
ID=26815367
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US252198A Expired - Lifetime US2687954A (en) | 1949-09-23 | 1951-10-19 | Alloy |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2687954A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2421604A1 (en) * | 1973-05-04 | 1974-11-14 | Nippon Steel Corp | STAINLESS STEEL |
| US3861906A (en) * | 1972-12-29 | 1975-01-21 | Republic Steel Corp | Calcium deoxidized, fine grain steels |
| JPS5093219A (en) * | 1973-12-22 | 1975-07-25 | ||
| US4063935A (en) * | 1973-12-22 | 1977-12-20 | Nisshin Steel Co., Ltd. | Oxidation-resisting austenitic stainless steel |
| US4172716A (en) * | 1973-05-04 | 1979-10-30 | Nippon Steel Corporation | Stainless steel having excellent pitting corrosion resistance and hot workabilities |
| US4494987A (en) * | 1982-04-21 | 1985-01-22 | The United States Of America As Represented By The United States Department Of Energy | Precipitation hardening austenitic superalloys |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1941648A (en) * | 1928-04-18 | 1934-01-02 | Percy A E Armstrong | Ferrous alloy |
| GB488926A (en) * | 1936-04-11 | 1938-07-12 | Heraeus Vacuumschmelze Ag | Improvements in and relating to heat resistant alloys and articles comprising the same |
| US2581420A (en) * | 1949-09-23 | 1952-01-08 | Driver Harris Co | Alloys |
-
1951
- 1951-10-19 US US252198A patent/US2687954A/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1941648A (en) * | 1928-04-18 | 1934-01-02 | Percy A E Armstrong | Ferrous alloy |
| GB488926A (en) * | 1936-04-11 | 1938-07-12 | Heraeus Vacuumschmelze Ag | Improvements in and relating to heat resistant alloys and articles comprising the same |
| US2581420A (en) * | 1949-09-23 | 1952-01-08 | Driver Harris Co | Alloys |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3861906A (en) * | 1972-12-29 | 1975-01-21 | Republic Steel Corp | Calcium deoxidized, fine grain steels |
| DE2421604A1 (en) * | 1973-05-04 | 1974-11-14 | Nippon Steel Corp | STAINLESS STEEL |
| US4172716A (en) * | 1973-05-04 | 1979-10-30 | Nippon Steel Corporation | Stainless steel having excellent pitting corrosion resistance and hot workabilities |
| JPS5093219A (en) * | 1973-12-22 | 1975-07-25 | ||
| US4063935A (en) * | 1973-12-22 | 1977-12-20 | Nisshin Steel Co., Ltd. | Oxidation-resisting austenitic stainless steel |
| US4108641A (en) * | 1973-12-22 | 1978-08-22 | Nisshin Steel Company, Limited | Oxidation-resisting austenitic stainless steel |
| US4494987A (en) * | 1982-04-21 | 1985-01-22 | The United States Of America As Represented By The United States Department Of Energy | Precipitation hardening austenitic superalloys |
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