EP0101936B1 - 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
EP0101936B1
EP0101936B1 EP19830107389 EP83107389A EP0101936B1 EP 0101936 B1 EP0101936 B1 EP 0101936B1 EP 19830107389 EP19830107389 EP 19830107389 EP 83107389 A EP83107389 A EP 83107389A EP 0101936 B1 EP0101936 B1 EP 0101936B1
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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.)
Expired
Application number
EP19830107389
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English (en)
French (fr)
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EP0101936A2 (de
EP0101936A3 (en
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
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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
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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 gold or silver alloy material including at least a boride-dispersed surface portion and a process for manufacturing same.
  • Such alloy is useful as a material for electrical contacts, sliding parts, or the like.
  • a composite material composed of a metal and a boride can be produced by sintering or melting.
  • a 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, however, involves difficulty in the uniform distribution of the boride, and is expensive.
  • a later 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. Moreover, both of these methods fail to have a boride distributed exclusively in the surface portion of a metallic material, and therefore, produced an alloy having low electrical conductivity.
  • the document US-A-2 001 017 discloses a permanently fashioned article (e.g. used for a dish, a crucible or a ring, made of a material consisting of one or more metals of the group consisting of platinum, palladium and gold with small amounts of such metals as copper, nickel, silver, cobalt, tungsten, chromium, tantalum, molybdenum or the like.
  • This material is intended to be used for jewellery, an alloy for dental industry or the like.
  • the surface of the material is hardened by absorbing an element selected from the group consisting of boron, silicon and zirconium.
  • the hardened surface is formed as a continuous layer mainly to improve the deformation resistance and the strength while keeping the color or fine appearance of the surface.
  • This hardened surface has good wear resistance but poor electrical conductivity.
  • the process of this invention comprises: preparing a gold, silver or gold or silver based alloy metallic material having a surface portion containing 0.5 to 40 atom % of at least one boride-forming metal element, the balance being selected from gold, silver, a gold alloy or a silver alloy; and diffusing boron into said surface portion 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 alloy material of this invention comprises a matrix mainly composed of gold or silver.
  • This composition is favorable since gold and silver have high electrical 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 matrix of the alloy material of this invention is composed of one of the following compositions:
  • the matrix material composed of gold and silver has excellent corrosion resistance and oxidation resistance.
  • This material 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 AIB 2 , AIB, o , AsB, AsB s , CdB s , C 02 B, CoB, CrB, CrB 2 , FeB, Fe 2 B, MgB 2 , MgB 4 , MoB 2 , M0 2 B, NbB, NbB 2 , Ni 2 B, PtB, Pt 2 B 3 , TaB, TaB 2 , TiB 2 , VB, VB 2 , W 2 B s , ZrB 2 .
  • the surface layer has a diffusion structure in which fine particles of these borides are uniformly dispersed and thus have high resistance to wear, adhesion and arc. Further, since 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 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, Al, 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 importantto form a boride in the surface layer alone.
  • the matrix of the alloy material may be formed of gold, silver, or a gold or silver based alloy, 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 electrical 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 electrical contact materials.
  • All of these borides have a specific resistance of 14 to 100xlQ-s Q cm, 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 interferes with 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 electrical 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 electrical contact that may be formed from the material according to this invention, while satisfying the requirements for the high electrical 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 electrical 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 alloy 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: AIB 2 , AIB 1o , AsB, AsB 6 , CdB 6 , C 02 B, CoB, CrB, CrB 2 , FeB, Fe 2 B, MgB 2 , MgB 4 , MoB 2 , 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.
  • a boride having an average particle diameter of, 0.1 to 10 ⁇ m The surface layer 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 electrical 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 an alloy material having substantially any matrix composition based on gold or silver 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 um, 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 um 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 pm had been distributed. The boride was identified as Ni 2 B, and found to occupy about 32% by volume in the surface portion.
  • 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.
  • An alloy composed of 93 atom % of Ag and 7 atom % of Ti was prepared by melting 97 parts by weight of silver and 3 parts by weight of titanium.
  • the alloy was boronized by the method employed in Example 1, whereby a boride-dispersed layer having a boride-dispersed layer 1 was produced.
  • 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 p m, and occupied about 8% by volume in the layer 1.
  • the boride was identified 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)

Claims (5)

1. Verfahren zur Herstellung eines Gold- oder Silberlegierungsmaterials, das eine hohe elektrische und thermische Leitfähigkeit und wenigstens einen Oberflächenabschnitt mit dispergierten Boriden aufweist, umfassend
Herstellen eines metallischen Materials aus Gold, Silber oder einer auf Gold oder Silber basierenden Legierung mit einem Oberflächenabschnitt, der von 0,5 bis 40 Atom % wenigstens eines ein Borid bildenden Metallelements aufweist, das ausgewählt ist aus der Gruppe enthaltend Beryllium, Magnesium, Aluminium, Silizium, Titan, Vanadium, Chrom, Mangan, Eisen, Kobalt, Nickel, Gallium, Arsen, Zirkonium, Niob, Molybden, Palladium, Cadmium, Tantal, Wolfram und Platin, wobei der Ausgleich ein Element ausgewählt aus der Gruppe enthaltend Gold, Silber, eine Goldlegierung und eine Silberlegierung ist, Diffundieren von Bor in den Oberflächenabschnitt des Materials, um darin eine Oberflächenschicht mit einer Dicke von 0,01 bis 0,25 mm zu bilden, in der kleine Partikel eines Borids des ein Borid bildenden Metallelements über das Gold, das Silber, die Goldlegierung oder die Silberlegierung gleichförmig dispergiert ist, wobei das Borid einen mittleren Partikeldurchmesser von 0,1 bis 10 Ilm aufweist, wodurch ein dispergiertes Borid enthaltendes Legierungsmaterial mit jener Oberflächenschicht geschaffen wird, die von 0,6 bis 50 Volumen % Boridpartikel enthält.
2. Verfahren nach Anspruch 1, bei dem das ein Borid bildende Element nur in der Oberflächenschicht vorhanden ist.
3. Verfahren nach Anspruch 1, bei dem das metallische Material dadurch hergestellt wird, daß das ein Borid bildende Element als Beschichtung auf die Oberfläche eines Matrixmaterials, ausgewählt aus der Gruppe enthaltend Gold, Silber, eine Goldlegierung und eine Silberlegierung, aufgebracht wird und das beschichtete Matrixmaterial zur Verursachung einer Diffusion des Elements in das Matrixmaterial zur Bildung der Oberflächenschicht erhitzt wird.
4. Verfahren nach Anspruch 1, bei dem das metallische Material insgesamt aus einer Legierung aus dem ein Borid bildenden Element und Gold oder Silber besteht.
5. Legierungsmaterial herstellbar nach einem Verfahren eines der vorhergehenden Ansprüche.
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
JP131457/82 1982-07-28
JP13145782A JPS5923835A (ja) 1982-07-28 1982-07-28 硼化物分散合金の製造方法

Publications (3)

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

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EP19830107389 Expired EP0101936B1 (de) 1982-07-28 1983-07-27 Legierungsmaterial mit dispergierten Boriden und Verfahren zu dessen Herstellung

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

Families Citing this family (13)

* 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
JPH02225655A (ja) * 1989-02-28 1990-09-07 Agency Of Ind Science & Technol 光沢のある黒色に着色する金合金とその着色法
JPH03166327A (ja) * 1989-11-22 1991-07-18 Seiko Instr Inc 表面硬化カラー金合金
DE4313272C1 (de) * 1993-04-23 1994-05-05 Degussa Oberflächen gehärtete Gegenstände aus Platin- und Palladiumlegierungen und Verfahren zu deren Herstellung
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)

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Publication number Priority date Publication date Assignee Title
US1990277A (en) * 1930-09-13 1935-02-05 Feussner Otto Metals of the platinum group and certain alloys
US2001017A (en) * 1930-09-13 1935-05-14 Feussner Otto Metal article
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

Also Published As

Publication number Publication date
DE3377990D1 (en) 1988-10-20
JPS5923835A (ja) 1984-02-07
EP0101936A2 (de) 1984-03-07
EP0101936A3 (en) 1985-01-30
JPS6154109B2 (de) 1986-11-20

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