US2494267A - Surface hardening of ferrous metals - Google Patents
Surface hardening of ferrous metals Download PDFInfo
- Publication number
- US2494267A US2494267A US712263A US71226346A US2494267A US 2494267 A US2494267 A US 2494267A US 712263 A US712263 A US 712263A US 71226346 A US71226346 A US 71226346A US 2494267 A US2494267 A US 2494267A
- Authority
- US
- United States
- Prior art keywords
- ferrous metals
- metal
- diborane
- surface hardening
- hardened
- 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
- 229910052751 metal Inorganic materials 0.000 title claims description 19
- 239000002184 metal Substances 0.000 title claims description 19
- -1 ferrous metals Chemical class 0.000 title description 7
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- 239000010410 layer Substances 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical class B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005488 sandblasting Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
Definitions
- This invention relates to the art of surface hardening ferrous metals and more particularly the present invention relates to producing boroncontaining deposits on the surface of ferrous metals by the decomposition of gaseous diborane.
- an extremely hard boroncontaining layer is formed on the surface of ferrous metals, such as, for example, iron, steel, cobalt, or nickel, by heating the metal in an atmosphere of gaseous diborane at a temperature above 500 C. but substantially below the melting point of the metal. It has been found that in this range of temperatures ferrous metals react with diborane to give metal borides.
- the boroncontainin layer may be formed either by heating the article to be hardened in a static atmosphere of gaseous diborane or by heating the article while flowing diborane thereover.
- a further feature of the present invention is the control of the pressure of the gaseous diborane which is used in forming the hardened layer on the surface of the ferrous metal. It has been found that it is desirable to perform the hardening operation at subatmospheric pressures preferably below about 50 millimeters. At higher pressures, non-volatile boron hydrides are formed which will accumulate on cool surfaces in the apparatus and thus diminish the yield of hardened metal from a given amount of gaseous diborane. It has also been found that the size of the object to be hardened is also important in determining the optimum pressure at which the process may be carried out.
- the hardening effect is believed to be produced by the reaction between boron formed from the decomposition of diborane and the surface of the ferrous metal, and also, at least partially, to a direct reaction of the metal and diborane.
- This reaction results in the formation of an extremely hard layer of metal boride.
- this surface layer of boride is extremely resistant to acid and alkaline corrosion.
- an iron cylinder may be hardened by treating it with diborane at 700 0.
- the surface to be coated Prior to the coating operation the surface to be coated is thoroughly cleaned, as by machining or sandblasting and is degreased with a suitable solvent such as ethylene dichloride or carbon tetrachloride.
- the cylinder is then placed in a decomposition chamber and is degassed by induction heating to a dull red heat at an absolute pressure of 10- millimeters of mercury.
- the chamber is then filled with purified hydrogen to a. pressure of 20 centimeters, the cylinder is reheated to a dull red heat for about 10 minutes, and gases in the chamber are pumped out while the cylinder is still hot.
- the latter step is repeated until no more water is formed or until the gas removed contains no appreciable content of oxygen.
- the cylinder is then degassed until a pressure of 10- millimeters is attained within the chamber at 500 C., and remains at that pressure without further evacuation of the chamber.
- the temperature is adjusted to 700 C. and diborane is passed through the chamber at a pressure of about 3 millimeters of mercury until a layer of boride about 5 microns thick is formed. This layer is extremely hard and resistant to abrasion. It is unaffected by an ordinary steel file, the teeth of the file being completely worn away.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Description
' boron hydrldes.
Patented Jan. 10, 1950 SURFACE HABDENING F FERROUS METALS Herman I. Schlesinger and George W. Schaelfer,
Chicago, Ill.,
assignors to the United States of America as represented by the United States Atomic Energy Commission No Drawing.
Application November 28, 19, Serial No. 712,263
2 Claims. (Cl- 148-635) This invention relates to the art of surface hardening ferrous metals and more particularly the present invention relates to producing boroncontaining deposits on the surface of ferrous metals by the decomposition of gaseous diborane.
In accordance with the present invention, it has been found that an extremely hard boroncontaining layer is formed on the surface of ferrous metals, such as, for example, iron, steel, cobalt, or nickel, by heating the metal in an atmosphere of gaseous diborane at a temperature above 500 C. but substantially below the melting point of the metal. It has been found that in this range of temperatures ferrous metals react with diborane to give metal borides. The boroncontainin layer may be formed either by heating the article to be hardened in a static atmosphere of gaseous diborane or by heating the article while flowing diborane thereover.
A further feature of the present invention is the control of the pressure of the gaseous diborane which is used in forming the hardened layer on the surface of the ferrous metal. It has been found that it is desirable to perform the hardening operation at subatmospheric pressures preferably below about 50 millimeters. At higher pressures, non-volatile boron hydrides are formed which will accumulate on cool surfaces in the apparatus and thus diminish the yield of hardened metal from a given amount of gaseous diborane. It has also been found that the size of the object to be hardened is also important in determining the optimum pressure at which the process may be carried out. With larger objects, lower pressures should be used since here the gaseous diborane is in contact with the heated surface for a longer period of time and thus there i more danger of the formation of non-volatile When the hardening is carried out at about 700 C., pressures below 30 millimeters of mercury are found to give the most satisfactory results. It is not desirable to use extremely low pressures, however, since under these conditions the rate of hardening becomes so low as to be impractical.
In the process of the invention, the hardening effect is believed to be produced by the reaction between boron formed from the decomposition of diborane and the surface of the ferrous metal, and also, at least partially, to a direct reaction of the metal and diborane. This reaction results in the formation of an extremely hard layer of metal boride. Furthermore, it has been found that this surface layer of boride is extremely resistant to acid and alkaline corrosion.
In a preferred embodimentof this invention an iron cylinder may be hardened by treating it with diborane at 700 0. Prior to the coating operation the surface to be coated is thoroughly cleaned, as by machining or sandblasting and is degreased with a suitable solvent such as ethylene dichloride or carbon tetrachloride. The cylinder is then placed in a decomposition chamber and is degassed by induction heating to a dull red heat at an absolute pressure of 10- millimeters of mercury. The chamber is then filled with purified hydrogen to a. pressure of 20 centimeters, the cylinder is reheated to a dull red heat for about 10 minutes, and gases in the chamber are pumped out while the cylinder is still hot. The latter step is repeated until no more water is formed or until the gas removed contains no appreciable content of oxygen. The cylinder is then degassed until a pressure of 10- millimeters is attained within the chamber at 500 C., and remains at that pressure without further evacuation of the chamber. After the cylinder has been cleaned and deoxidized by the above-described method, the temperature is adjusted to 700 C. and diborane is passed through the chamber at a pressure of about 3 millimeters of mercury until a layer of boride about 5 microns thick is formed. This layer is extremely hard and resistant to abrasion. It is unaffected by an ordinary steel file, the teeth of the file being completely worn away.
It will be apparent that the above-described embodiment of the invention is illustrative, and many modifications thereof will be apparent to those skilled in the art without departing from the spirit of the invention or the scope of the appended claims.
The deposition of boron in amorphous form is the subject matter of our co-pending application, Serial No. 708,446, filed November '7, '1946.
What is claimed is:
l. The method of producing a hardened surface on ferrous metal which consists in contacting the surface of said ferrous metal and heating face on ferrous metal which consists in contact- (References on following page) 3 REFERENCES CITED The following references are 0! record in the file 0! this UNITED STATES PA'IENTS OTHER REFERENCES- Mellor, A Comprehensive Treatise on Inorganic.
and Theoretical Chemisty. vol. V (1924), pages 5 36 and 37, published by Lonzmans, Green and Co.,
New York.
Schlesinger, Schaefler and Barbaras, Document MDDC-1338, 28 pages; published September 19, 1947, U. S. Atomic Energy Commission, Oak Ridge,
1 Tennessee.
Claims (1)
1. THE METHOD OF PRODUCING A HARDENED SURFACE ON FEROUS METAL WHICH CONSISTS IN CONTACTING THE SURFACE OF SAID FERROUS METAL AND HEATING IT TO ABOUT 700*C. WITH GASEOUS DIBORANE AT SUBATMOSPHERIC PRESSURE OF BELOW 30 MILLIMETERS OF MERCURY WHEREBY METAL BORIDE IS FORMED.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US712263A US2494267A (en) | 1946-11-26 | 1946-11-26 | Surface hardening of ferrous metals |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US712263A US2494267A (en) | 1946-11-26 | 1946-11-26 | Surface hardening of ferrous metals |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2494267A true US2494267A (en) | 1950-01-10 |
Family
ID=24861397
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US712263A Expired - Lifetime US2494267A (en) | 1946-11-26 | 1946-11-26 | Surface hardening of ferrous metals |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2494267A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2827403A (en) * | 1956-08-06 | 1958-03-18 | Pacific Semiconductors Inc | Method for diffusing active impurities into semiconductor materials |
| US3151001A (en) * | 1962-12-04 | 1964-09-29 | United States Steel Corp | Method of treating boron coated steel to eliminate luders' bands |
| US3276903A (en) * | 1953-02-04 | 1966-10-04 | Onera (Off Nat Aerospatiale) | Heat treatment of metals |
| US3355318A (en) * | 1963-09-26 | 1967-11-28 | Union Carbide Corp | Gas plating metal deposits comprising boron |
| US4019926A (en) * | 1974-07-01 | 1977-04-26 | The Secretary Of State For Industry In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland | Prevention of corrosion of metals |
| DE3305426A1 (en) * | 1982-03-05 | 1983-09-08 | N.V. Philips' Gloeilampenfabrieken, 5621 Eindhoven | METHOD FOR BORING A SUPPLY CATHODE |
| US5064691A (en) * | 1990-03-02 | 1991-11-12 | Air Products And Chemicals, Inc. | Gas phase borosiliconization of ferrous surfaces |
| US5242741A (en) * | 1989-09-08 | 1993-09-07 | Taiho Kogyo Co., Ltd. | Boronized sliding material and method for producing the same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB245753A (en) * | 1925-01-09 | 1927-01-27 | Siemens Ag | Method of increasing the ohmic resistance of pure iron, especially electrolytic iron |
| US1855562A (en) * | 1928-02-11 | 1932-04-26 | Siemens Ag | Method of insulating bodies |
| GB427623A (en) * | 1932-07-19 | 1935-04-23 | Deutsche Edelstahlwerke Ag | A method of treating metallic articles or the metallic surface layers or coatings of articles |
-
1946
- 1946-11-26 US US712263A patent/US2494267A/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB245753A (en) * | 1925-01-09 | 1927-01-27 | Siemens Ag | Method of increasing the ohmic resistance of pure iron, especially electrolytic iron |
| US1855562A (en) * | 1928-02-11 | 1932-04-26 | Siemens Ag | Method of insulating bodies |
| GB427623A (en) * | 1932-07-19 | 1935-04-23 | Deutsche Edelstahlwerke Ag | A method of treating metallic articles or the metallic surface layers or coatings of articles |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3276903A (en) * | 1953-02-04 | 1966-10-04 | Onera (Off Nat Aerospatiale) | Heat treatment of metals |
| US2827403A (en) * | 1956-08-06 | 1958-03-18 | Pacific Semiconductors Inc | Method for diffusing active impurities into semiconductor materials |
| US3151001A (en) * | 1962-12-04 | 1964-09-29 | United States Steel Corp | Method of treating boron coated steel to eliminate luders' bands |
| US3355318A (en) * | 1963-09-26 | 1967-11-28 | Union Carbide Corp | Gas plating metal deposits comprising boron |
| US4019926A (en) * | 1974-07-01 | 1977-04-26 | The Secretary Of State For Industry In Her Britannic Majesty's Government Of The United Kingdom Of Great Britain And Northern Ireland | Prevention of corrosion of metals |
| DE3305426A1 (en) * | 1982-03-05 | 1983-09-08 | N.V. Philips' Gloeilampenfabrieken, 5621 Eindhoven | METHOD FOR BORING A SUPPLY CATHODE |
| US4530669A (en) * | 1982-03-05 | 1985-07-23 | U.S. Philips Corporation | Method of making a borided dispenser cathode |
| US5242741A (en) * | 1989-09-08 | 1993-09-07 | Taiho Kogyo Co., Ltd. | Boronized sliding material and method for producing the same |
| US5064691A (en) * | 1990-03-02 | 1991-11-12 | Air Products And Chemicals, Inc. | Gas phase borosiliconization of ferrous surfaces |
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