US3885958A - Method of producing chromium containing alloys - Google Patents
Method of producing chromium containing alloys Download PDFInfo
- Publication number
- US3885958A US3885958A US427094A US42709473A US3885958A US 3885958 A US3885958 A US 3885958A US 427094 A US427094 A US 427094A US 42709473 A US42709473 A US 42709473A US 3885958 A US3885958 A US 3885958A
- Authority
- US
- United States
- Prior art keywords
- nitrogen
- carbon
- melt
- aluminum
- content
- 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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- 239000011651 chromium Substances 0.000 title claims abstract description 44
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 35
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 12
- 239000000956 alloy Substances 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 title claims description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 128
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 65
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 48
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 28
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000007670 refining Methods 0.000 claims abstract description 11
- 229910000838 Al alloy Inorganic materials 0.000 claims abstract description 5
- 239000000155 melt Substances 0.000 claims description 34
- 239000000463 material Substances 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 239000002893 slag Substances 0.000 claims description 6
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 238000005275 alloying Methods 0.000 claims description 3
- 239000010953 base metal Substances 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 229910017083 AlN Inorganic materials 0.000 claims 1
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 claims 1
- 239000004411 aluminium Substances 0.000 claims 1
- 239000000470 constituent Substances 0.000 claims 1
- 229910001148 Al-Li alloy Inorganic materials 0.000 abstract description 5
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 abstract description 5
- 239000001989 lithium alloy Substances 0.000 abstract description 3
- 229940107218 chromium Drugs 0.000 description 30
- 235000012721 chromium Nutrition 0.000 description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 18
- 229910000831 Steel Inorganic materials 0.000 description 10
- 238000007792 addition Methods 0.000 description 10
- 239000010959 steel Substances 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 238000010586 diagram Methods 0.000 description 8
- 239000010936 titanium Substances 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 229910052719 titanium Inorganic materials 0.000 description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 230000001965 increasing effect Effects 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000010955 niobium Substances 0.000 description 4
- 150000004767 nitrides Chemical class 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 3
- 229910001882 dioxygen Inorganic materials 0.000 description 3
- 230000006698 induction Effects 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 238000010313 vacuum arc remelting Methods 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910000599 Cr alloy Inorganic materials 0.000 description 2
- 229910000604 Ferrochrome Inorganic materials 0.000 description 2
- 229910010199 LiAl Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 229910000805 Pig iron Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000788 chromium alloy Substances 0.000 description 2
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000000265 homogenisation Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000161 steel melt Substances 0.000 description 1
- 238000009489 vacuum treatment Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 229910000859 α-Fe Inorganic materials 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
- C22C33/00—Making ferrous alloys
- C22C33/04—Making ferrous alloys by melting
Definitions
- ABSTRACT A chromium-containing alloy, having very low contents of nitrogen and carbon, is produced by refining with a small but effective addition of aluminum, or an aluminum alloy, preferably an aluminum-lithium alloy.
- the present invention relates to a method of producing chromium-containing alloys with low contents of nitrogen and carbon.
- ferritic chromium steels normal contents of carbon or nitrogen cause material problems such as lowered impact strength, a high (ductile-to-brittle) transition temperature, and disposition towards intergranular corrosion. These phenomena are ascribed to chromium-containing nitrideand carbide precipitations which take place as a result of the too low solubility of carbon and nitrogen in ferrite.
- Remelting of chro mium and iron with low contents of carbon and nitrogen in an inert atmosphere in, for example, a HF-(high frequency induction) furnace is impeded because available chromium raw materials such as ferrochromium have too high contents of nitrogen and carbon.
- Chromium pig iron produced in a cupola furnace is decarburized in an LD- converter to about 0.3 C, after which the melt is vacuum-oxidized to the above-mentioned low content of carbon.
- a low nitrogen content of less than 100 ppm is reached thereby that the carbonand silicon-rich chromium pig iron having a relatively low nitrogen content is refined from nitrogen by the very vigorous evolution of gas in the LD-converter during a decrease of the carbon content from 5 to 0.3 percent.
- the method pre-supposes, however, the opportunity of using special equipment.
- the low contents of carbon and nitrogen have been obtained at a Cr content of about 18 percent, thus a rather low content of chromium.
- a low nitrogen content is obtained by using strong nitrideformers to separate the nitrogen from a melt. This nitrogen-impoverished melt is then refined with respect to carbon and finished to steel in, for example. an AOD-converter.
- FIG. 1 is a diagram showing equilibria of Al and N in aluminum nitride formation
- FIG. 2 is a diagram showing influence of lithium in cooperation with aluminum in achieving a low content of nitrogen.
- FIG. 1 A 0 I535 B 0 25 I500 C 2 25 I300 D 2 25 I500
- the diagram in FIG. 1 is thus specifically constructed for the purpose of explaining the invented method, and it shows that a low content of nitrogen in the presence of a high content of chromium ought to be obtained by an addition aluminum to a melt containing carbon at a low temperature, i.e., a temperature near the melting temperature.
- a low content of nitrogen in the presence of a high content of chromium ought to be obtained by an addition aluminum to a melt containing carbon at a low temperature, i.e., a temperature near the melting temperature.
- the equilibrium 5 A] at 1,300 C. corresponds to 2 ppm nitrogen in a steel melt with 2 C and Cr.
- the importance of chromium is shown in the curves A and B. It may be mentioned that in case of titanium, the dissolved N- content first decreases with increasing Ti-content, but already at a Ti-level of about 1 with the equilibrium content of N in the
- Al-metal corresponding to 5.0 percent was added at 1.350" C. After mixing. a sample taken from the furnace showed 57 ppm nitrogen.
- Al-metal corresponding to 9 percent was added at 1.350 C.
- the nitrogen content was 40 ppm in samples taken from the furnace. From the examples [-3 it is obvious that the nitrogen is reduced with increased additions of Al. See also the diagram in FIG. 2.
- EXAMPLE 5 The influence of the chromium content was examined. A charge was produced in a 50 kilogram open HF furnace. Starting analysis:
- EXAMPLE 7 Pure lithium was added in two charges to control the effect in the foregoing example. The amounts were 0.05 and 0.20 Li, respectively. The content of nitrogen before the addition was 285 ppm. After addition of Li the content was 250 ppm nitrogen. No important effect was thus obtained by an addition of Li as such.
- EXAMPLE 8 The influence of changing from an iron-base to a nickel-base alloy was examined. A charge was produced in a 50 kg HF furnace. Starting analysis:
- Example 8 shows the result when using a nickel base alloy.
- the example 9 relates to a Cr-Ni steel.
- the example l0 shows the final removal of C and Al which should be done in a larger charge and not in a small 50 kg furnace. (Examples 2, 3 and 4 have iron as remainder.)
- the given examples all relates to chromium steel.
- nickel has an increasing effect upon the activity of the nitrogen, it is self-evident that the invention is applicable also to chromium steels.
- other Al-alloys than pure Al and LiA] can be used, for example CaAl and MgA].
- the raw materials may for example be melted in a normal arc furnace so that a carbon content of 1-2 percent is obtained.
- a charge may be based upon cheap raw materials and also contain a high content of circulating internal scrap. The latter material has great economical importance.
- the melt is then taken for example to an ADD-converter, vacuum furnace or the like, in which aluminum or aluminum-lithium is added to the melt. After that, the normal process of removing carbon is carried out.
- An intermediate slag separation preferably is made, because aluminum gives rise to great amounts to slag during the oxidation.
- A] is oxidized by oxygen gas, a great amount of heat is evolved.
- the metal bath may then be cooled by substituting chromium ore for the oxygen gas or by adding suitable scrap.
- the nitrogen refining addition of Al or LiAl may also be performed in a ladle.
- the metal must, however, be protected from nitrogen pick up from the air when the content of the ladle is taken to the unit for oxidation of carbon. If the ladle has a high freeboard, meaning that the level of the melt is far below the upper edge of the ladle, vacuum oxidation can be done directly in the la die.
- the carbon content should be relatively high in the melt bath when the addition of Al is effected. Carbon has a favorable inlluence, as it in itself decreases the solubility of nitrogen as well as lowering the melting point of the melt bath. A suitable content of carbon has shown to be at least 1 at C.
- the invented method is particularly applicable to melts containing between and 7: Cr. At actual contents of Cr and C the melt should have a temperature between l 300-l ,500 C.
- Method of producing a chromium-containing alloy having very low contents of nitrogen and carbon not amounting, in toto, to more than 0.01 percent by 8 weight. which comprises melting a charge containing at least 1 percent by weight of carbon and consisting essentially of a chromium-containing initial material together with a base metal and desired alloying elements;
- a nitridable member of the group consisting of aluminum and aluminum alloys. in an amount corresponding to at least 3 percent by weight of said melt. thereby converting nitrogen to aluminum nitride in the form of a constitutent of the resulting slag;
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Treatment Of Steel In Its Molten State (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Refinement Of Pig-Iron, Manufacture Of Cast Iron, And Steel Manufacture Other Than In Revolving Furnaces (AREA)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
SE17146/72A SE368420B (enrdf_load_stackoverflow) | 1972-12-29 | 1972-12-29 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3885958A true US3885958A (en) | 1975-05-27 |
Family
ID=20303297
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US427094A Expired - Lifetime US3885958A (en) | 1972-12-29 | 1973-12-21 | Method of producing chromium containing alloys |
Country Status (7)
Country | Link |
---|---|
US (1) | US3885958A (enrdf_load_stackoverflow) |
JP (1) | JPS5222889B2 (enrdf_load_stackoverflow) |
DE (1) | DE2365054C3 (enrdf_load_stackoverflow) |
FR (1) | FR2212437B1 (enrdf_load_stackoverflow) |
GB (1) | GB1395873A (enrdf_load_stackoverflow) |
IT (1) | IT1002432B (enrdf_load_stackoverflow) |
SE (1) | SE368420B (enrdf_load_stackoverflow) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3985550A (en) * | 1975-01-23 | 1976-10-12 | United States Steel Corporation | Method of producing low sulfur steel |
US4589916A (en) * | 1984-02-23 | 1986-05-20 | Daido Tokushuko Kabushiki Kaisha | Ultra clean stainless steel for extremely fine wire |
US5578265A (en) * | 1992-09-08 | 1996-11-26 | Sandvik Ab | Ferritic stainless steel alloy for use as catalytic converter material |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS53143992U (enrdf_load_stackoverflow) * | 1977-04-19 | 1978-11-13 | ||
JPS6023182B2 (ja) * | 1979-12-01 | 1985-06-06 | 新日本製鐵株式会社 | 中炭素高クロム溶湯の溶製方法 |
RU2184170C2 (ru) * | 2000-09-04 | 2002-06-27 | Мошкина Ирина Станиславовна | Способ получения азотированных ферросплавов |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3314782A (en) * | 1963-12-12 | 1967-04-18 | Fur Tech Entwicklung Und Verwe | Refining agent for steel-works |
US3333954A (en) * | 1963-08-10 | 1967-08-01 | British Cast Iron Res Ass | Manufacture of inoculants for cast iron |
US3467167A (en) * | 1966-09-19 | 1969-09-16 | Kaiser Ind Corp | Process for continuously casting oxidizable metals |
-
1972
- 1972-12-29 SE SE17146/72A patent/SE368420B/xx unknown
-
1973
- 1973-12-20 GB GB5916473A patent/GB1395873A/en not_active Expired
- 1973-12-21 US US427094A patent/US3885958A/en not_active Expired - Lifetime
- 1973-12-28 IT IT32400/73A patent/IT1002432B/it active
- 1973-12-28 FR FR7346852A patent/FR2212437B1/fr not_active Expired
- 1973-12-28 JP JP744610A patent/JPS5222889B2/ja not_active Expired
- 1973-12-28 DE DE2365054A patent/DE2365054C3/de not_active Expired
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3333954A (en) * | 1963-08-10 | 1967-08-01 | British Cast Iron Res Ass | Manufacture of inoculants for cast iron |
US3314782A (en) * | 1963-12-12 | 1967-04-18 | Fur Tech Entwicklung Und Verwe | Refining agent for steel-works |
US3467167A (en) * | 1966-09-19 | 1969-09-16 | Kaiser Ind Corp | Process for continuously casting oxidizable metals |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3985550A (en) * | 1975-01-23 | 1976-10-12 | United States Steel Corporation | Method of producing low sulfur steel |
US4589916A (en) * | 1984-02-23 | 1986-05-20 | Daido Tokushuko Kabushiki Kaisha | Ultra clean stainless steel for extremely fine wire |
US5578265A (en) * | 1992-09-08 | 1996-11-26 | Sandvik Ab | Ferritic stainless steel alloy for use as catalytic converter material |
Also Published As
Publication number | Publication date |
---|---|
IT1002432B (it) | 1976-05-20 |
FR2212437B1 (enrdf_load_stackoverflow) | 1976-10-08 |
GB1395873A (en) | 1975-05-29 |
DE2365054C3 (de) | 1980-03-06 |
DE2365054B2 (de) | 1979-07-05 |
JPS5222889B2 (enrdf_load_stackoverflow) | 1977-06-21 |
DE2365054A1 (de) | 1974-07-11 |
FR2212437A1 (enrdf_load_stackoverflow) | 1974-07-26 |
JPS4998318A (enrdf_load_stackoverflow) | 1974-09-18 |
SE368420B (enrdf_load_stackoverflow) | 1974-07-01 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: SANTRADE LTD., ALPENQUAI 12, CH-6002, LUCERNE, SWI Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:SANDVIK AKTIEBOLAG, A CORP. OF SWEDEN;REEL/FRAME:004085/0132 Effective date: 19820908 |