US3770512A - Method for surface hardening steel and cemented carbides - Google Patents

Method for surface hardening steel and cemented carbides Download PDF

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US3770512A
US3770512A US00165948A US3770512DA US3770512A US 3770512 A US3770512 A US 3770512A US 00165948 A US00165948 A US 00165948A US 3770512D A US3770512D A US 3770512DA US 3770512 A US3770512 A US 3770512A
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weight
parts
mixture
liquid carrier
treatment
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A Bopp
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    • 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
    • C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
    • C23C30/005—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process on hard metal substrates
    • 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
    • C23C12/00—Solid state diffusion of at least one non-metal element other than silicon and at least one metal element or silicon into metallic material surfaces
    • C23C12/02—Diffusion in one step
    • 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
    • C23C8/60—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 solids, e.g. powders, pastes
    • C23C8/62—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 solids, e.g. powders, pastes only one element being applied
    • C23C8/68—Boronising
    • C23C8/70—Boronising of ferrous surfaces

Definitions

  • PATENTEDMM a ma 3.770.512
  • the present invention relates to a new and improved method for surface hardening steel and cemented carbides wherein, owing to a thermal treatment in a'mixture, there'is obtained at the material-undergoing treatment a relatively thick, fixedly anchored, infusion layer of high hardness.
  • the inventive method for surface hardening of materials, especially steel and cemented carbides is generally manifested by the features that, the material, at a temperature exceeding approximately 570 C and extensively in the absence of oxygen, is brought into contact with a mixture containing approximately:
  • the method can be used for the most different steels, such as carbon steels, alloyed and highly-alloyed steels, specialty steels, also cemented carbides and pressed cemented carbides and works with prepared powdery materials in accordance with the case-hardening principle.
  • the exceptional action of the previously mentioned mixture is predicated upon the fact that the components are present in a glassy or vitreous condition, so that ionic excitations occur which result, for instance, in reactions of the following occur which result, for instance, in reactions of the following nature:
  • the carbon necessary for this purpose can be either additionally added, especially in the form of carbon black, or it can be removed from the carbon content of the steel. Furthermore, if desired, tetrafluoromethane can be added separately to the mixture in the form of a gas.
  • the mixture used in the practice of the inventive method has added thereto additional materials known to some extent for this purpose.
  • additional materials known to some extent for this purpose.
  • the addition of magnesium in the form of basic magnesium carbonate prevents any desired sintering of the hard metal or cemented carbide composition and permits a lowering of the temperatures, beneath 600 C, for instance.
  • Suitable as the additives are, in particular, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, B, as such, or their oxides, carbides, borides, nitrides or silicides.
  • the components are used in a powdery form, a grain or granulation size of approximately 180 to 320 mesh being preferred.
  • a powdery form a grain or granulation size of approximately 180 to 320 mesh being preferred.
  • the powdery mixture is dispersed in a liquid carrier, such as in particular dibutyl phthalate or an oil, so that it can be conveniently applied to the surface of the object or body.
  • the treatment temperature is dependent upon the type of steel to be treated, generally is in a range above 570 C up to white heat or incandescence.
  • the best steel hardness has been obtained at temperatures between approximately 750 C and 900 C, only conventional high temperature hardners, such as certain stainless steels (SS) and hot forged steels which can core soften between 750 C and 900 C require lower temperatures.
  • SS stainless steels
  • Treatment temperatures in the region of approximately 850 C are quite suitable.
  • the inventive method is carried out extensively in the absence of oxygen, that is, air is excluded, or in the presence of a protective gas, such as nitrogen, inert or rare gases or CO
  • a protective gas such as nitrogen, inert or rare gases or CO
  • the clean steel product to be hardened is embedded in the powder, within a heatand corrosion resistant container or vessel, for instance formed of chromiumnickel-steel, graphite or the like, in such a manner that all sides of such product are tightly or snugly in contact with this powder.
  • the vessel is then hermetically sealed, if desired oxygen is removed, and in a suitable and well known manner electrically heated, or heated in a reverberatory or air furnace up to the required temperature. Even after very short treatment times, for instance between 3 to 5 hours, exceptional hardness results have been obtained.
  • the steel product together with the vessel is advantageously air cooled down to approximately 500 C. At this temperature the strewable powder can be removed through filters or sieves without suffering from contact with air. The steel product, if required, can be easily freed of any adhering powder. The powder then can be reused.
  • FIGS. 1 to 10 there are indicated surface hardness, core hardness and layer thickness of the infusion layer as a function of the employed temperature for different types of steels and cemented carbides.
  • the test samples have been pre-treated by the manufacturer, in the manner indicated in the following table, whereupon such have been treated in accordance with the inventive method as above-described at temperatures between 750 C and 900 C and permitted to cool in the furnace.
  • the chain-dot or phantom line curve in each case indicates the results for a treatment time of 5 hours, the full-line curve for a treatment time of hours.
  • the solid components are dispersed in the liquid carrier and the dispersion is applied by spraying, by immersion, or by wiping such onto the material or product to be treated.
  • the advantages of the inventive method are considerable. At relatively low temperatures and short treatment times it is possible to obtain hardness values which previously could not be attained, values which oftentimes exceed the peak values of extremely hard sintered materials.
  • the mixture of the invention may contain 1 to 10 ppm NaBF and l to 10 ppm sodium fluoride (NaF).
  • the employed powder following treatment, remains completely strewable or pourable, can be used a number of times, sometimes as much as 5 to 10 times.
  • the consumption of material is minimum, since it is limited to 0.02% to 0.8% of the weight of the infusion layer.
  • Carrying out of the inventive method is extremely simple and it has versatile ap plicability.
  • the treated material remains clean, dark in color and previously polished surfaces exhibit a dull gloss.
  • a method of surface hardening materials by a boriding process comprising the steps of placing the material which is at a temperature in a range exceeding approximately 570 C to approximately 900 C and essentially in the absence of oxygen, into contact with a mixture consisting essentially of 5 to parts by weight boron carbide, 1 to 6 parts by weight anhydrous aluminum oxide, trace amounts up to 6 parts by weight N'aBF, and an amount of sodium fluoride up to 10 parts by weight sufficient to effect reaction at the material temperature.
  • composition of matter for use in surface hardening materials, especially steel and cemented carbides consisting essentially of a mixture containing approximately 5 to by weight boron carbide, l to 60% by weight anhydrous aluminum oxide, trace amounts up to 6% by weight NaBF and trace amounts up to 10% by weight sodium fluoride.

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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)
  • Powder Metallurgy (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
US00165948A 1970-07-28 1971-07-26 Method for surface hardening steel and cemented carbides Expired - Lifetime US3770512A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CH1148470A CH556394A (de) 1970-07-28 1970-07-28 Verfahren zur oberflaechenhaertung von staehlen und sinterhartmetallen.

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US3770512A true US3770512A (en) 1973-11-06

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US00165948A Expired - Lifetime US3770512A (en) 1970-07-28 1971-07-26 Method for surface hardening steel and cemented carbides

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US (1) US3770512A (de)
CH (1) CH556394A (de)
DE (1) DE2137244A1 (de)
FR (1) FR2099641B1 (de)
GB (1) GB1363764A (de)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3836392A (en) * 1971-07-07 1974-09-17 Sandvik Ab Process for increasing the resistance to wear of the surface of hard metal cemented carbide parts subject to wear
US3874909A (en) * 1971-12-20 1975-04-01 Toyoda Chuo Kenkyusho Kk Method for forming a carbide layer on the surface of an iron or ferrous alloy article
US3935034A (en) * 1972-01-24 1976-01-27 Howmet Corporation Boron diffusion coating process
US3969157A (en) * 1973-08-07 1976-07-13 Vereinigte Edelstahlwerke Ag Method of providing decarbonization protection for metallic surfaces
US4398968A (en) * 1981-08-28 1983-08-16 Koichiro Koyama Method of boronizing transition metal surfaces
WO1983004293A1 (en) * 1982-05-24 1983-12-08 Clark Eugene V Improvements in mechanical seal structures
USRE32110E (en) * 1971-05-26 1986-04-15 General Electric Co. Aluminum oxide coated cemented carbide product
EP1026282A2 (de) * 1999-02-05 2000-08-09 Houghton Durferrit GmbH Pastenförmiges Boriermittel
US6503344B2 (en) 1999-02-05 2003-01-07 Houghton Durferrit Gmbh Boronizing agent in paste form
CN107201495A (zh) * 2017-06-12 2017-09-26 武汉力盾新材料科技有限公司 一种用于硬密封阀门密封面的高耐磨硼化物覆层制备方法

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2450286A1 (fr) * 1979-02-27 1980-09-26 Armines Procede et dispositif de boruration de pieces en metal
FR2466512A1 (fr) * 1979-09-28 1981-04-10 Zaets Inna Composition pour le revetement de metaux ferreux par diffusion
JPS58500329A (ja) * 1981-03-05 1983-03-03 タ−バイン・メタル・テクノロジ−・インコ−ポレ−テッド 耐摩耗性および耐壊食性部材およびそのための方法
US4555326A (en) * 1984-05-17 1985-11-26 Betz Laboratories, Inc. Methods and compositions for boronizing metallic surfaces
JPH07188898A (ja) * 1993-12-27 1995-07-25 Parker Netsushiyori Kogyo Kk 固形ボロナイジング方法及びそれに用いる容器
GB2363391B (en) * 1998-07-09 2002-06-12 Sachs Race Eng Gmbh Friction clutch with nickel-chromium alloy spring means and processes associated with making such spring means
US6478887B1 (en) * 1998-12-16 2002-11-12 Smith International, Inc. Boronized wear-resistant materials and methods thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3029162A (en) * 1959-05-21 1962-04-10 Chromalloy Corp Process for the production of metallic borides on the surface of metals
US3286684A (en) * 1962-12-24 1966-11-22 Ling Temco Vought Inc Cementation coating pack
US3622374A (en) * 1969-01-14 1971-11-23 Ritter Praulder Corp Diffusion coating of ferrous articles
US3673005A (en) * 1969-09-18 1972-06-27 Kempten Elektroschmelz Gmbh Process for borating metals,especially steel

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3029162A (en) * 1959-05-21 1962-04-10 Chromalloy Corp Process for the production of metallic borides on the surface of metals
US3286684A (en) * 1962-12-24 1966-11-22 Ling Temco Vought Inc Cementation coating pack
US3622374A (en) * 1969-01-14 1971-11-23 Ritter Praulder Corp Diffusion coating of ferrous articles
US3673005A (en) * 1969-09-18 1972-06-27 Kempten Elektroschmelz Gmbh Process for borating metals,especially steel

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USRE32110E (en) * 1971-05-26 1986-04-15 General Electric Co. Aluminum oxide coated cemented carbide product
US3836392A (en) * 1971-07-07 1974-09-17 Sandvik Ab Process for increasing the resistance to wear of the surface of hard metal cemented carbide parts subject to wear
US3874909A (en) * 1971-12-20 1975-04-01 Toyoda Chuo Kenkyusho Kk Method for forming a carbide layer on the surface of an iron or ferrous alloy article
US3935034A (en) * 1972-01-24 1976-01-27 Howmet Corporation Boron diffusion coating process
US3969157A (en) * 1973-08-07 1976-07-13 Vereinigte Edelstahlwerke Ag Method of providing decarbonization protection for metallic surfaces
US4398968A (en) * 1981-08-28 1983-08-16 Koichiro Koyama Method of boronizing transition metal surfaces
WO1983004293A1 (en) * 1982-05-24 1983-12-08 Clark Eugene V Improvements in mechanical seal structures
EP1026282A2 (de) * 1999-02-05 2000-08-09 Houghton Durferrit GmbH Pastenförmiges Boriermittel
EP1026282A3 (de) * 1999-02-05 2000-10-18 Houghton Durferrit GmbH Pastenförmiges Boriermittel
US6503344B2 (en) 1999-02-05 2003-01-07 Houghton Durferrit Gmbh Boronizing agent in paste form
CN107201495A (zh) * 2017-06-12 2017-09-26 武汉力盾新材料科技有限公司 一种用于硬密封阀门密封面的高耐磨硼化物覆层制备方法
CN107201495B (zh) * 2017-06-12 2019-11-22 武汉力盾新材料科技有限公司 一种用于硬密封阀门密封面的高耐磨硼化物覆层制备方法

Also Published As

Publication number Publication date
FR2099641A1 (de) 1972-03-17
DE2137244A1 (de) 1972-02-03
GB1363764A (en) 1974-08-14
FR2099641B1 (de) 1973-06-29
CH556394A (de) 1974-11-29

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