US3857725A - Method for forming an iron-manganese carbide layer on the surface of an iron base alloy article containing carbon - Google Patents
Method for forming an iron-manganese carbide layer on the surface of an iron base alloy article containing carbon Download PDFInfo
- Publication number
- US3857725A US3857725A US00346946A US34694673A US3857725A US 3857725 A US3857725 A US 3857725A US 00346946 A US00346946 A US 00346946A US 34694673 A US34694673 A US 34694673A US 3857725 A US3857725 A US 3857725A
- Authority
- US
- United States
- Prior art keywords
- iron
- article
- treating material
- manganese
- carbon
- Prior art date
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 63
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 42
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 34
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 30
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 24
- 239000000956 alloy Substances 0.000 title claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 52
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 24
- 239000011572 manganese Substances 0.000 claims abstract description 24
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- -1 tetrafluoroborate Chemical compound 0.000 claims abstract description 20
- 238000012856 packing Methods 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910000975 Carbon steel Inorganic materials 0.000 claims description 5
- 239000010962 carbon steel Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 229910000851 Alloy steel Inorganic materials 0.000 claims description 3
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 claims description 3
- 229910052582 BN Inorganic materials 0.000 claims description 2
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 12
- 239000002184 metal Substances 0.000 abstract description 12
- 239000011812 mixed powder Substances 0.000 abstract description 5
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 239000002585 base Substances 0.000 description 14
- 238000009740 moulding (composite fabrication) Methods 0.000 description 11
- 229910001315 Tool steel Inorganic materials 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 229910020261 KBF4 Inorganic materials 0.000 description 5
- 229910000914 Mn alloy Inorganic materials 0.000 description 4
- 229910020808 NaBF Inorganic materials 0.000 description 4
- 229910000640 Fe alloy Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 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 2
- 238000007747 plating Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000221535 Pucciniales Species 0.000 description 1
- 241000221013 Viscum album Species 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
Images
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
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/28—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes
- C23C10/34—Embedding in a powder mixture, i.e. pack cementation
- C23C10/36—Embedding in a powder mixture, i.e. pack cementation only one element being diffused
Definitions
- iron-manganese carbide layer formed on the surface of an iron article is very hard and has a good wear resistance
- the formation of the iron-manganese carbide layers has been applied to the surfaces of metal moulds such as punches and die, tools such as pinchers and screwdrivers, and mechanical parts for the sake of the improvement of their wear resistance.
- vapor plating, metal spraying, spark hardening and pack method has been known.
- these conventional methods have some defects.
- the vapor plating uses halogen compounds as the source of the metal to be plated. Therefore it needs a complex apparatus such as a special atmospheric furnace and the halogen gases erode quickly the apparatus.
- the metal spraying needs a costly treating material and the bonding of the layer formed on the surface of an article is not so good.
- Spark hardening takes a long operation time for the treatment and the surface of the layer formed is not so smooth.
- the conventional pack method is to heat an article to be treated in the nonoxidation atmosphere or to heat a sealed container containing an article to be treated. Therefore the pack method necessitates a special atmospheric furnace or a special sealed container.
- FIG. 1 is a photomicrograph "showing an ironmanganese carbide layer on carbon tool steel, which is formed according to Example 1;
- FIG. 2 is a photomicrograph showing another ironmanganese carbide layer on carbon tool steel, which is formed according to Example 1;
- FIG. 3 is a photomicrograph showing still another iron-manganese carbide layer formed on carbon tool steel according to Example 1;
- FIG. 4 is a graph showing the relation between the contents of carbon and manganese included in the layer formed and the distance from the surface of the layer;
- FIG. 5 is a photomicrograph showing an ironmanganese carbide layer formed on the surface of a structural carbon steel according to Example 2;
- FIG. 6 is a photomicrograph showing an ironmanganese carbide layer formed on the surface of carbon tool steel according to Example 3;
- FIG. 7 is a photomicrograph showing an ironmanganese carbide layer formed on the surface of carbon tool steel according to Example 4.
- the present invention is directed to a new pack method for forming an iron-manganese carbide layer on the surface of an iron base alloy article containing carbon by introducing manganese onto the surface of the article and combining said manganese with the carbon and iron included in the article, also the present invention can be carried out in the air or in an inert gas atmosphere and at a relatively low treating temperature.
- the method of the present invention comprises preparing the mixed powders composed of a tetrafluoroborate and metallic manganese or a metal containing manganese, packing the iron base alloy article containing at least 0.1 percent of carbon in said mixed powders and heating the article within said mixed powders so as to form the iron-manganese carbide layer on the surface of said article.
- the method of the invention can form the carbide layer in the air without a special container and at a relatively low temperature 700C. Therefore, this method does not necessiate a special atmospheric furnace or container and is highly suitable for the surface treatment of tools, dies and parts for many kinds of equipments. Further, it is highly productive, and it has been recognized that the carbide layer thus obtained is strongly and tightly integrated to the surface of a mother article and has, in addition, a dense and uniform metallic phase.
- the Vickers hardness of the layer is about Hv 1400.
- a tetrafluoroborate powder and the powder of the metal containing manganese are mixed together.
- the tetrafluoroborate potassium tetrafluoroborate (KBF sodium tetrafluoroborate (NaBF ammonium tetrafluoroborate (NH BF,) and the like can be used.
- KBF sodium tetrafluoroborate NaBF ammonium tetrafluoroborate (NH BF,) and the like
- one or more than one kind of tetrafluoroborate can be used and these alkali tetrafluoroborates work as a promotor of this powdery treating material.
- metallic manganese and manganese alloys can be used and work as the principal ingredient of the treating ma terial.
- Said alloys include the alloys with iron. Especially, the alloys with iron are suitable for the metal of the treating material because the alloys are cheap and easy to obtain. It is preferable that the tetrafluoroborate is selected to be 100 mesh or finer and the metal powder is 40 mesh or finer. The powdery tetrafluoroborate may be included in the treating material in a quantity between 1 and 40 percent. With use of less quantity of tetrafluoroborate than 1 percent, the formation of the carbide layer would not be uniform due to the instability as a result of the introduction of manganese onto the surface of the article. Too much addition of the tetrafluoroborate will make the treating material fused or sintered at a high treating temperature.
- the treating material is solidified after the treating operation and it will be difficult to take the article treated out of the treating material and the treating material will be repeatedly unusable and besides the surface condition of the article will not be good.
- the quantity of the tetrafluoroborate is between 2 and 30 percent.
- the remainder of the treating material is the powdery metal mentioned above. Said powdery metal may be mixed in a quantity between 60 and 99 percent and preferably in a quantity between 70 and 98 percent.
- inactive powdery substance having a high melting point such as alumina (A1 silica (SiO boron nitride (BN), chromic oxide (Cr O- and the like can be added up to 80 percent of the treating material.
- the heating temperature may be selected within the wide range from 650 to 1,200C. At a heating temperature below 650C, the adequate thick carbide layer cannot be formed on the surface of the article treated and in the case that a temperature over 1,200C is selected, the powdery treating material would be sintered and the article treated would be integrated with the treating material. At this time, the property of the iron base alloy article would be worsened.
- the preferable range of the heating temperature is 700 to 1,000C.
- the heating time depends upon the thickness of the carbide to be formed. Heating shorter than 1 hour will, however, provide no practically acceptable formation of said layer, although the final determination of the heating time depends on the heating temperature. With the increase of the heating time, the thickness of the carbide layer will be increased correspondingly. in
- an acceptable thickness of the layer can be realized within 30 hours or shorter time.
- the most preferable range of the heating time will be 2 to hours.
- the iron base alloy article must contain at least 0.1 percent of carbon.
- the carbon in the article becomes to be a composition of the carbide during the treatment. Namely it is supposed that the carbon in the article diffuses to the surface thereof and reacts with the manganese from the treating material to form the carbide on the surface of the article. The higher content of the carbon in the article is more preferable for form ing the carbide layer.
- the iron base alloy article containing less than 0.1 percent of carbon may not be it is not necessary to carry out the method of they present invention in the atmosphere of hydrogen gas or in the atmosphereof non-oxidation gas, but the method can be carried out into effect either under the air atmosphere or in the inert gas atmosphere.
- small rods used as specimens are regarded to be the models of the pins of moulds and of the rod like parts of various apparatuses.
- EXAMPLE 1 Several kinds of powdery treating materials composed of to 98 percent of iron-manganese alloy (containing 76 percent of manganese) of l00 mesh and the balance of KBF of200 mesh were introduced into each of alumina crucibles of 45 mm inner diameter and 60 mm height, and then specimens of 10 mm diameter and 5 mm height made of carbon tool steel (JlS SK4, containing 1.0 percent of carbon) were packed in each of said treating materials in said crucibles and were heated in an electric furnace under the air atmosphere at a temperature between 700 and 900C for 4 hours, and then they were taken out of the furnace and cooled in the air.
- JlS SK4 carbon tool steel
- the photomicorgraph shown in PK]. 1 was taken from the specimen which was treated at 700C for 4 hours in the powdery treating material composed of 20 percent of KBF4 and 80 percent of iron-manganese alloy. Also the photomicrographs shown in FIGS. 2 and 3 were taken from the specimens which were treated at 800C in the treating material containing 2 percent of KBF4 and at 900C in the treating material containing 30 percent of KBF4, respectively. The photomicrographs indicate that an excellent layer is formed on the surface of each of the specimens. The other specimens treated in this Example were also observed to have an excellent (integral and dense) layer, which is similar to the layers shown in FIGS. 1 to 3.
- the thickness of the layer formed is constant within the range from 2 to 40 percent of KBF4. However, said thickness is greatly effected by the heating temperature and said thickness increases as the heating temperature increases.
- FIG. 4 one of the EPMA test results is shown in FIG. 4 with the relation of the contents of manganese and carbon included in the layer formed and the distance from the surface.
- the test layer was formed on carbon tool steel at 900C in the treating material containing 30 percent of KBF4.
- the ordinate and the abscissa represent the contents (percent) of each manganese and carbon and the distance or depth (micron) from the surface of the specimen, respectively.
- the content of manganese is 4.5 4.7 percent near the surface and becomes to be about 3 percent at the distance of 4 6 microns, and at the distance of 8 microns the content of carbon becomes 1 percent which is the same as the carbon content of the mother steel.
- the layer tested by the EPMA and mentioned above was also tested by the X-ray diffraction method and it was revealed that the layer is composed of ironmanganese carbide. Also the upper portion of the mother material includes manganese in the form of the solid solution of manganese in iron. ln some specimens treated were observed a second layer between the ironmanganese carbide layer and mother material. The second layer was recognized to be the solid solution of iron.
- the manganese of the treating material is introduced into the surface of a carbon tool alloy article and forms iron-manganese carbide with the carbon and iron included in the article by using a powdery treating material including KBF in a wide range.
- EXAMPLE 2 Specimens of l mm diameter and mm height made of structual carbon steel (118 810C, containing 0.1 percent of carbon) with their rust removed were treated under the same conditions of Example 1. All the specimens treated were observed by a micro scope and a few of them were tested by an X-ray diffraction method and/or EPMA. From the micro scopic observation, all the specimens treated were formed with a thin layer. As one example, the layer treated at 800C for 4 hours in the powdery treating material containing 2 percent of KBF, are shown in FIG. 5. From the results of X-ray diffraction and EPMA, the layer is revealed to be iron-manganese carbide, (Fe,Mn) C and the upper portion of the mother material includes an iron solid solution with manganese.
- Fe,Mn iron-manganese carbide
- EXAMPLE 3 NaBF, of 200 mesh or finer was used as the promotor in place of the KBF in the treating materials used in Example 1.
- Specimens of 10 mm diameter and 5 mm height made of carbon tool steel JlS 5K3, C: 1.00 1.10 percent, Si: less than 0.35 percent, Mi: less than 0.50 percent, P: less than 0.030 percent, 5: less than 0.030 percent, balance of iron) were treated with the same conditions of Example 1 except their promotor mentioned above. All the specimens treated were observed by a micro-scope and a few of them were tested by an X-ray diffraction method and/or EPMA. From the micro-scopic observation, all the specimens treated were formed with a layer.
- the photo micrograph taken from the specimen treated at 800C for 4 hours in the treating material containing 10 percent of NaBF are shown in FIG. 6, and the layer was recognized to be iron-manganese carbide (Fe,Mn) C. According to the example, it is apparent that NaBF, works as the promotor of this treating material.
- EXAMPLE 4 NH BF of 200 mesh or finer was used as the promotor of the KBF, in the treating materials used in Example 1.
- Specimens made of carbon tool steel which is the same as the steel used in Example I were treated at a temperature between 700 and 900C for 4 hours in the powdery treating material containing 30 percent of NH BF All the specimens treated were observed by a microscope and a few of them were tested by an X-ray diffraction method and/or EPMA. From the microscopic observation, all the specimens treated were formed with a layer. As one example, the photomicrograph taken from the specimen treated 'at 700C are shown in FIG. 7. Also the layer was recognized to be iron-manganese carbide, (Fe,Mn) C.
- a method for forming an iron-manganese carbide layer on the surface of an iron base alloy article containing at least 0.1 percent carbon in a powdery treating material comprising the steps of preparing the powdery treating material consisting essentially of l to 40 percent of at least one member selected from the group consisting of potassium tetrafluoroborate, sodium tetrafluoroborate and ammonium tetrafluoroborate and mixtures thereof and 60 to 99% ofa member selected from the group consisting of metallic manganese and iron-manganese alloys, packing the iron base alloy article in said powdery treating material, heating said article within said powdery treating material at a temperature of between 650C and 1,200C for l to 30 hours, and taking said article out of said powdery treating material, thereby forming an ironmanganese carbide layer on the surface of said article.
- a method according to claim 1, wherein said article is selected from the group consisting of iron containing carbon, carbon steel and alloy steel containing carbon.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Carbon And Carbon Compounds (AREA)
- Powder Metallurgy (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP47035550A JPS5232334B2 (enrdf_load_html_response) | 1972-04-08 | 1972-04-08 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3857725A true US3857725A (en) | 1974-12-31 |
Family
ID=12444821
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US00346946A Expired - Lifetime US3857725A (en) | 1972-04-08 | 1973-03-29 | Method for forming an iron-manganese carbide layer on the surface of an iron base alloy article containing carbon |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US3857725A (enrdf_load_html_response) |
| JP (1) | JPS5232334B2 (enrdf_load_html_response) |
| CA (1) | CA1007524A (enrdf_load_html_response) |
| FR (1) | FR2179819B1 (enrdf_load_html_response) |
| GB (1) | GB1363837A (enrdf_load_html_response) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5514866B2 (enrdf_load_html_response) * | 1974-04-08 | 1980-04-19 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2536774A (en) * | 1946-03-07 | 1951-01-02 | Diffusion Alloys Corp | Process of coating ferrous metal and heat pack mixture therefor |
| US3061463A (en) * | 1959-03-26 | 1962-10-30 | Chromalloy Corp | Metallic diffusion |
| US3257230A (en) * | 1964-03-24 | 1966-06-21 | Chromalloy American Corp | Diffusion coating for metals |
| US3673005A (en) * | 1969-09-18 | 1972-06-27 | Kempten Elektroschmelz Gmbh | Process for borating metals,especially steel |
-
1972
- 1972-04-08 JP JP47035550A patent/JPS5232334B2/ja not_active Expired
-
1973
- 1973-03-29 US US00346946A patent/US3857725A/en not_active Expired - Lifetime
- 1973-04-03 GB GB1582773A patent/GB1363837A/en not_active Expired
- 1973-04-06 CA CA168,155A patent/CA1007524A/en not_active Expired
- 1973-04-06 FR FR7312428A patent/FR2179819B1/fr not_active Expired
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2536774A (en) * | 1946-03-07 | 1951-01-02 | Diffusion Alloys Corp | Process of coating ferrous metal and heat pack mixture therefor |
| US3061463A (en) * | 1959-03-26 | 1962-10-30 | Chromalloy Corp | Metallic diffusion |
| US3257230A (en) * | 1964-03-24 | 1966-06-21 | Chromalloy American Corp | Diffusion coating for metals |
| US3673005A (en) * | 1969-09-18 | 1972-06-27 | Kempten Elektroschmelz Gmbh | Process for borating metals,especially steel |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5232334B2 (enrdf_load_html_response) | 1977-08-20 |
| JPS48102747A (enrdf_load_html_response) | 1973-12-24 |
| FR2179819B1 (enrdf_load_html_response) | 1976-05-21 |
| FR2179819A1 (enrdf_load_html_response) | 1973-11-23 |
| CA1007524A (en) | 1977-03-29 |
| DE2317176A1 (de) | 1973-10-11 |
| GB1363837A (en) | 1974-08-21 |
| DE2317176B2 (de) | 1976-11-25 |
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