EP0101936A2 - Legierungsmaterial mit dispergierten Boriden und Verfahren zu dessen Herstellung - Google Patents

Legierungsmaterial mit dispergierten Boriden und Verfahren zu dessen Herstellung Download PDF

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Publication number
EP0101936A2
EP0101936A2 EP83107389A EP83107389A EP0101936A2 EP 0101936 A2 EP0101936 A2 EP 0101936A2 EP 83107389 A EP83107389 A EP 83107389A EP 83107389 A EP83107389 A EP 83107389A EP 0101936 A2 EP0101936 A2 EP 0101936A2
Authority
EP
European Patent Office
Prior art keywords
boride
alloy
gold
silver
surface layer
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.)
Granted
Application number
EP83107389A
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English (en)
French (fr)
Other versions
EP0101936A3 (en
EP0101936B1 (de
Inventor
Hironori Fujita
Jiro Mizuno
Tohru Arai
Osami Kasuya
Koichi Ono
Hisahiro Ando
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tokai Rika Co Ltd
Toyota Central R&D Labs Inc
Original Assignee
Tokai Rika Co Ltd
Toyota Central R&D Labs Inc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Tokai Rika Co Ltd, Toyota Central R&D Labs Inc filed Critical Tokai Rika Co Ltd
Publication of EP0101936A2 publication Critical patent/EP0101936A2/de
Publication of EP0101936A3 publication Critical patent/EP0101936A3/en
Application granted granted Critical
Publication of EP0101936B1 publication Critical patent/EP0101936B1/de
Expired legal-status Critical Current

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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
    • 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
    • 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

Definitions

  • This invention relates to a boride-dispersed alloy material, i.e., an alloy material containing a boride distributed in the surface portion of a metallic material and a process for manufacturing same.
  • a boride-dispersed alloy material i.e., an alloy material containing a boride distributed in the surface portion of a metallic material and a process for manufacturing same.
  • Such alloy is useful as a material for eletrical contacts, sliding parts, or the like.
  • a composite material composed of a metal and a boride can be produced by sintering or melting.
  • the former method comprises preparing an appropriate mixture of a fine boride powder and, for example, copper powder, and sintering it at an appropriate temperature in an appropriate gas atmosphere.
  • This method involves difficulty in the uniform distribution of the boride, and is expensive.
  • the latter method comprises preparing a mixture of copper and a boride, heating it to a high temperature to melt it, and cooling the molten mixture to solidify it.
  • This method has the disadvantage of the boride being crystallized when the molten alloy is solidified.
  • the boride forms too coarse particles to be satisfactorily finely divided even by forging.
  • both of these methods fail to have a boride distributed exclusively in the surface portion of a metallic material, and therefore, produces an alloy having low electrical conductivity.
  • the boride-dispersed alloy material of this invention comprises a substrate mainly composed of gold or silver and a surface layer formed in a surface portion of the substrate and having a diffusion structure in which fine particles of a boride are uniformly dispersed.
  • the process of this invention comprises: preparing a metallic matrix containing 0.5 to 40 atom % of at least one boride-forming metal element, the balance being selected from gold, silver, a gold alloy and a silver alloy; and diffusing boron into the matrix to form therein a surface layer in which fine particles of a boride of the boride-forming metal element are uniformly dispersed.
  • the boride-forming metal element is selected from the group consisting of beryllium (Be), magnesium (Mg), aluminum (Al), silicon (Si), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), gallium (Ga), arsenic (As), zirconium (Zr), niobium (Nb), molybdenum (Mo), palladium (Pd), cadmium (Cd), tantalum (Ta), tungsten (W) and platinum (Pt).
  • the boride-dispersed alloy material of this invention comprises a substrate mainly composed of gold or silver.
  • This composition is favorable since gold and silver have high eletrical and thermal conductivity. Further, they have excellent corrosion resistance against every kind of acidic solution such as hydrochloric acid or sulfuric acid and alkaline solution such as sodium hydroxide or calcium hydroxide. Gold and silver also exhibit high resistance against oxidation when, for example, heated in the air.
  • the substrate'of the boride-dispersed alloy material of this inveniton is composed of one of the following compositions:
  • the substrate composed of gold and silver has excellent corrosion resistance and oxidation resistance. Futher, the substrate composed of gold and/or silver alloyed with a boride forming element and/or a boride-non-forming element possesses improved mechanical characteristics, e.g. high mechanical strength.
  • the surface layer has the diffusion structure wherein fine boride particles resulted from boron and at least one boride-forming element are uniformly dispersed in the surface portion of the substrate.
  • the boride-forming element is selected from the group consisting of beryllium, magnesium, aluminum, silicon, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, gallium, arsenic, zirconium, niobium, molybdenum, palladium, cadmium, tantalum, tungsten, platinum, etc. These elements have relatively high hardness, a low specific resistance and a high melting point. All of these elements are capable of forming a solid solution or being dispersed in gold, silver, a gold alloy, a silver alloy or a gold-silver alloy, and combining with boron to form fine and uniformly dispersed particles of a boride.
  • the surface layer of the boride-dispersed alloy material of this invention includes fine and uniformly dispersed particles of at least one boride selected from the group consisting of AlB 2 , AlB 10 , AsB, AsB 6 , CdB 6 , Co 2 B, CoB, CrB, CrB 2 , FeB, Fe 2 B, MgB 2 , MgB 4 , MoB 2 , M 02 B, NbB, NbB 2 , Ni2B , PtB , Pt2B3 , TaB , TaB2 , TiB2 , VB , VB2 , W2B5' ZrB2.
  • boride selected from the group consisting of AlB 2 , AlB 10 , AsB, AsB 6 , CdB 6 , Co 2 B, CoB, CrB, CrB 2 , FeB, Fe 2 B, MgB 2 , MgB 4 , MoB 2 , M 02 B, NbB, NbB 2
  • the surface portion of the substrate includes a surface layer having a diffusion structure in which fine particles of these borides are uniformly dispersed and thus having high resistance to wear, adhesion and arc.
  • the substrate is mainly formed of gold or silver, the surface layer formed thereon also possesses excellent corrosion and oxidation resistance. This composition serves to prevent the formation of oxides on the surface.
  • the surface portion of the metallic material has a surface layer which is 0.01 to 0.25 mm in depth, and which contains 0.5 to 40 atom % of at least one element selected from Be, Mg, A1, Si, Ti, V, Cr, Mn, Fe, Co, Ni, Ga, As, Zr, Nb, Mo, Pd, Cd, Ta, W and Pt, the balance being gold, silver or an alloy of gold or silver, since it is important to form a boride in the surface layer alone.
  • the rest of the metallic material may be added with any metal, depending on the purpose for which the alloy is used.
  • At least one of the metal elements hereinabove listed is used, since they are all capable of forming a solid solution or being dispersed in gold, silver, or an alloy of gold or silver, and combining with the boron diffused in the surface portion of the metallic material to form fine boride particles therein.
  • the boride of any such element has a relatively high degree of hardness, a low specific resistance and a high melting point which are important properties for eletrical contacts or sliding parts for which the material produced by the process of this invention can advantageously be used.
  • TABLE 1 compares the physical properties of various borides with those of conventional eletrical contact materials.
  • All of these borides have a specific resistance of 14 to 100 x 10-6pcm, a melting point of 1,220°C to 3,100°C and a hardness of Hv 1,500 to 3,300, and are superior to the conventional materials in melting point and hardness.
  • the proportion of the boride-forming element is in the range of 0.5 to 40 atom %. If it is less than 0.5 atom %, it is impossible to form the boride in a sufficient quantity to ensure the effect expected from the resulting boride. If it exceeds 40 %, the formation of too much boride disables its proper mixing with gold, silver or a gold or silver alloy in the material produced by this invention, resulting in a reduction in its eletrical conductivity and thermal conductivity, and the formation of a surface layer which is easy to crack or peel.
  • the surface layer in which the boride is dispersed has a depth of 0.01 to 0.25.mm. This limitation is important to ensure the wear, adhesion and arc resistance required of the surface of any eletrical contact that may be formed from the material according to this invention, while satisfying the requirements for the high eletrical and thermal conductivity in the inner portion of the alloy matrix.
  • the distribution of a boride throughout the alloy matrix is not always beneficial for imparting high eletrical and thermal conductivity. This purpose can be better attained if gold or silver of higher purity is employed in the matrix, or a reinforcing element is added thereto, depending on the characteristics required, while the boride is dispersed only in the surface layer.
  • the diffusion of boron may, on some occasions, fail to form a uniform layer of fine boride particles, depending on the composition of the material in the surface layer. On such occasions, it is advisable to achieve uniform boride distribution by reducing the quantity of a boride-forming metal element in the matrix alloy, or adding another element that may form a boride more easily.
  • the metallic material may, as a whole, comprise an alloy of a boride-forming element with gold or silver. This alloy may be prepared by melting the metals in question.
  • an alloy is formed only in the surface layer of the metallic material.
  • a metal such as vanadium or nickel
  • a metal is coated on the surface of gold or silver as the matrix, and heated for diffusion into the matrix so that an alloy may be formed only in its surface layer.
  • the metal such as vanadium
  • the diffusion of vanadium, etc. into the matrix may be effected by its thermal diffusion at a high temperature.
  • the metallic material can be of any shape, including that of a plate, bar or wire, depending on the purpose for which the alloy will be used.
  • the metallic material thus prepared is subjected to boronizing by a known method, for example, immersing the metallic material in a molten salt bath containing dissolved boron, burying the metallic material in a mixture of the powder of boron carbide, etc. and the powder of boron fluoride, ammonium chloride, etc. and heating it, or vacuum deposition of boron.
  • the boron diffused in the metallic material combines with vanadium, etc. in the matrix alloy to form a boride or borides.
  • At least one of the following borides is formed: AlB 2 , AIB lO , AsB, AsB 6 , CdB 6 , Co 2 B, CoB, CrB, CrB 2 , FeB, Fe 2 B, MgB 2 , MgB 4 , MoBv, M 02 B, NbB, NbB 2 , Ni 2 B, PtB, Pt 2 B 3 , TaB, TaB 2 , TiB 2 , VB, VB 2 , W 2 B 5 , ZrB 2 , etc.
  • a layer in which boride particles are dispersed is, thus, formed in gold, silver or a gold or silver alloy.
  • the surface layer preferably contains 0.6 to 50 % by volume of boride particles, and has a thickness of 0.01 to 0.25 mm, and preferably 0.01 to 0.1 mm.
  • a thicker layer can, if desired, be formed by a longer boronizing time, or a higher boronizing temperature.
  • the process of this invention facilitates the uniform distribution of fine boride particles exclusively in the surface layer of the metallic material. Moreover, it is less expensive than the conventional sintering method, and produces a boride-dispersed alloy which is superior in properties to the product of the conventional method.
  • the borides are higher than the conventional materials for electrical contacts in hardness, melting point, decomposition temperature and chemical stability. Therefore, the metallic material produced by the dispersion of a boride only in its surface layer in accordance with the process of this invention has a surface layer which is excellent in wear, adhesion and arc resistance, and thus provides a material for eletrical contacts or sliding parts in which the surface layer forms a contact area.
  • the product of this invention is sufficiently high in electrical and thermal conductivity as a material for electrical contacts, since the boride is a relatively good electrical conductor and finely distributed only in the surface layer, while the matrix comprises gold, silver or a gold or silver alloy which is a still better conductor. The material as a whole is low in resistance, since the boride exists only in its surface layer.
  • the process of this invention can produce a boride-dispersed alloy material having substantially any matrix composition so selected as to facilitate its working, such as bending, punching or coining, or improve its thermal conductivity.
  • a cobalt-gold alloy composed of 85.0 atom % of Au and 15.0 atom % of Co and in a shape having a diameter of 10 mm was prepared by melting 95 parts by weight of gold and 5 parts by weight of cobalt. The alloy was swaged into a diameter of 4 mm, and then, rolled into a plate having a thickness of 1 mm. A sample measuring 4 mm by 20 mm was prepared from the plate.
  • the sample was immersed for four hours in a molten salt bath containing 60 parts by weight of borax (Na 2 B 4 0 7 ) and 40 parts by weight of boron carbide (B 4 C) powder having a particle diameter of 79 to 149 pm, and having a temperature of 900°C, whereby boron was diffused into the sample.
  • the sample was removed from the bath, and air cooled.
  • the sample was cut to present a cross section, and it was examined by a microscope.
  • the resulting microphotograph is shown in FIGURE 1, in which a layer in which a boride is distributed is shown at 1, and a cobalt-gold matrix alloy at 2.
  • the results indicate the distribution of boride particles having a diameter of 2 to 10 ⁇ m up to a depth of about 0.08 mm below the surface of the alloy.
  • the boride in the surface layer showed a ratio of about 18 % by volume.
  • the boride was identified by X-ray diffraction and EPMA as CoB.
  • the metal surrounding the boride was gold.
  • a nickel-gold alloy composed of 73 atom % of Au and 27 atom % of Ni was prepared by melting 90 parts by weight of gold and 10 parts by weight of nickel. Boron was diffused in the alloy by the method set forth in EXAMPLE 1. As a result, there was obtained a boride-dispersed alloy having a surface layer which was about 0.1 mm in depth , and in which a boride having a particle diameter of 5 to 20 ⁇ m had been distributed. The boride was identified as Ni 2 B, and found to occupy about 32 % by volume in the surface portion.
  • FIGURE 2 is a microphotograph showing a cross section thereof.
  • the layer 1 had a thickness of about 0.06 mm.
  • the boride had a particle diameter of about 5 to 15 ⁇ m, and was identified as VB 2 .
  • the boride was found to occupy about 36 % by volume in the layer 1.
  • An alloy composed of 95 atom % of Ag and 5 atom % of Co was prepared by melting 97 parts by weight of silver and 3 parts by weight of cobalt.
  • the alloy was boronized by the method employed in EXAMPLE 1 to yield a boride-dispersed alloy.
  • the alloy was found to have a boride-dispersed layer containing very fine CoB particles having a diameter of about 0.5 ⁇ m.
  • the layer had a thickness of 0.09 mm.
  • the boride occupied about 6 % by volume in the layer.
  • FIGURE 3 is a microphotograph showing a cross section thereof.
  • the layer 1 had a thickness of about 0.25 mm.
  • the boride had a particle diameter of about 2 to 15 pm, and occupied about 8 % by volume in the layer 1.
  • the boride was identfied by X-ray diffraction as TiB 2 .

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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)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)
  • Contacts (AREA)
EP19830107389 1982-07-28 1983-07-27 Legierungsmaterial mit dispergierten Boriden und Verfahren zu dessen Herstellung Expired EP0101936B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP13145782A JPS5923835A (ja) 1982-07-28 1982-07-28 硼化物分散合金の製造方法
JP131457/82 1982-07-28

Publications (3)

Publication Number Publication Date
EP0101936A2 true EP0101936A2 (de) 1984-03-07
EP0101936A3 EP0101936A3 (en) 1985-01-30
EP0101936B1 EP0101936B1 (de) 1988-09-14

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Application Number Title Priority Date Filing Date
EP19830107389 Expired EP0101936B1 (de) 1982-07-28 1983-07-27 Legierungsmaterial mit dispergierten Boriden und Verfahren zu dessen Herstellung

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EP (1) EP0101936B1 (de)
JP (1) JPS5923835A (de)
DE (1) DE3377990D1 (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2245590A (en) * 1989-02-28 1992-01-08 Agency Ind Science Techn Gold alloy for black coloring, processed article of black colored gold alloy and method for production of the processed article
US5518556A (en) * 1993-04-23 1996-05-21 Degussa Aktiengesellschaft Surface-hardened objects of alloys of platinum and palladium and method for their production

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59104467A (ja) * 1982-12-06 1984-06-16 Mitsubishi Metal Corp 装飾用表面硬化Ａｕ合金部材
JPS59143032A (ja) * 1983-02-04 1984-08-16 Mitsubishi Metal Corp 装飾用表面硬化Ｐｔ合金部材
JPS6021347A (ja) * 1983-07-12 1985-02-02 Mitsubishi Metal Corp ほう化処理表面硬化層を有する高強度Ａｕ合金部材
JPS6052540A (ja) * 1983-09-01 1985-03-25 Mitsubishi Metal Corp 基体部材に接合されて使用される硬質Ａｕ合金チツプ材
JPS60110867A (ja) * 1983-11-18 1985-06-17 Mitsubishi Metal Corp 耐摩耗性および耐食性のすぐれた表面硬化Ａｇ合金部材
JPH0415177Y2 (de) * 1984-10-24 1992-04-06
JPH01223992A (ja) * 1988-03-03 1989-09-07 Brother Ind Ltd サイクルミシンの制御装置
JPH03166327A (ja) * 1989-11-22 1991-07-18 Seiko Instr Inc 表面硬化カラー金合金
US6274254B1 (en) * 1999-08-23 2001-08-14 Lucent Technologies Inc. Electrodeposited precious metal finishes having wear resistant particles therein
CN102277524B (zh) * 2010-06-13 2013-04-24 厦门鑫柏龙仪器仪表有限公司 金铁镍铬合金
CN114107725B (zh) * 2021-12-07 2022-05-20 扬州亚光电缆有限公司 一种耐热抗氧化银合金材料及其制备方法和应用

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2001017A (en) * 1930-09-13 1935-05-14 Feussner Otto Metal article
US1990277A (en) * 1930-09-13 1935-02-05 Feussner Otto Metals of the platinum group and certain alloys
FR1231094A (fr) * 1959-03-27 1960-09-26 Soc Metallurgique Imphy Procédé de réalisation de pièces métalliques borurées et pièces obtenues par ce procédé
NL265282A (de) * 1960-06-22
DE3307182A1 (de) * 1982-05-26 1983-12-01 Technical Materials, Inc., Lincoln, R.I. Legierung fuer elektrische kontakte und verwendung fuer eine solche legierung

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2245590A (en) * 1989-02-28 1992-01-08 Agency Ind Science Techn Gold alloy for black coloring, processed article of black colored gold alloy and method for production of the processed article
US5518556A (en) * 1993-04-23 1996-05-21 Degussa Aktiengesellschaft Surface-hardened objects of alloys of platinum and palladium and method for their production

Also Published As

Publication number Publication date
EP0101936A3 (en) 1985-01-30
JPS5923835A (ja) 1984-02-07
DE3377990D1 (en) 1988-10-20
EP0101936B1 (de) 1988-09-14
JPS6154109B2 (de) 1986-11-20

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