JP2010506040A - Electroforming method and parts or layers obtained by this method - Google Patents
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- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000005323 electroforming Methods 0.000 title claims abstract description 12
- 239000010931 gold Substances 0.000 claims abstract description 20
- 229910052737 gold Inorganic materials 0.000 claims abstract description 19
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 18
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000010949 copper Substances 0.000 claims abstract description 14
- 229910052802 copper Inorganic materials 0.000 claims abstract description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011701 zinc Substances 0.000 claims abstract description 12
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 11
- 229910001020 Au alloy Inorganic materials 0.000 claims abstract description 10
- 239000003353 gold alloy Substances 0.000 claims abstract description 10
- 239000000758 substrate Substances 0.000 claims abstract description 10
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 9
- 239000000956 alloy Substances 0.000 claims abstract description 9
- 229910052709 silver Inorganic materials 0.000 claims abstract description 8
- 239000004332 silver Substances 0.000 claims abstract description 8
- 239000011787 zinc oxide Substances 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 claims abstract description 5
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 claims abstract description 4
- XTFKWYDMKGAZKK-UHFFFAOYSA-N potassium;gold(1+);dicyanide Chemical compound [K+].[Au+].N#[C-].N#[C-] XTFKWYDMKGAZKK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 150000001879 copper Chemical class 0.000 claims abstract description 3
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 3
- SDKPSXWGRWWLKR-UHFFFAOYSA-M sodium;9,10-dioxoanthracene-1-sulfonate Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)[O-] SDKPSXWGRWWLKR-UHFFFAOYSA-M 0.000 claims abstract description 3
- 150000003751 zinc Chemical class 0.000 claims abstract description 3
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 3
- 229920001522 polyglycol ester Polymers 0.000 claims description 3
- 229910001923 silver oxide Inorganic materials 0.000 claims description 3
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 230000003247 decreasing effect Effects 0.000 claims description 2
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 2
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 2
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 229910001297 Zn alloy Inorganic materials 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 9
- 229910052793 cadmium Inorganic materials 0.000 abstract description 9
- 238000000151 deposition Methods 0.000 abstract description 8
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 abstract description 7
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 abstract description 5
- 239000012190 activator Substances 0.000 abstract 1
- 238000005868 electrolysis reaction Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 7
- 239000013078 crystal Substances 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 3
- GJYCVCVHRSWLNY-UHFFFAOYSA-N ortho-butylphenol Natural products CCCCC1=CC=CC=C1O GJYCVCVHRSWLNY-UHFFFAOYSA-N 0.000 description 3
- VDMJCVUEUHKGOY-JXMROGBWSA-N (1e)-4-fluoro-n-hydroxybenzenecarboximidoyl chloride Chemical compound O\N=C(\Cl)C1=CC=C(F)C=C1 VDMJCVUEUHKGOY-JXMROGBWSA-N 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- -1 ethylenediamino tetra-acetic acid Chemical compound 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920000151 polyglycol Polymers 0.000 description 2
- 239000010695 polyglycol Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 229910001200 Ferrotitanium Inorganic materials 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- SXKZZFLSYPUIAN-UHFFFAOYSA-N [Cu].[Zn].[Au] Chemical compound [Cu].[Zn].[Au] SXKZZFLSYPUIAN-UHFFFAOYSA-N 0.000 description 1
- 125000005233 alkylalcohol group Chemical group 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 229910001380 potassium hypophosphite Inorganic materials 0.000 description 1
- CRGPNLUFHHUKCM-UHFFFAOYSA-M potassium phosphinate Chemical compound [K+].[O-]P=O CRGPNLUFHHUKCM-UHFFFAOYSA-M 0.000 description 1
- IIQJBVZYLIIMND-UHFFFAOYSA-J potassium;antimony(3+);2,3-dihydroxybutanedioate Chemical group [K+].[Sb+3].[O-]C(=O)C(O)C(O)C([O-])=O.[O-]C(=O)C(O)C(O)C([O-])=O IIQJBVZYLIIMND-UHFFFAOYSA-J 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C5/00—Alloys based on noble metals
- C22C5/02—Alloys based on gold
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/62—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of gold
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/18—Electroplating using modulated, pulsed or reversing current
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
- C25D5/50—After-treatment of electroplated surfaces by heat-treatment
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/615—Microstructure of the layers, e.g. mixed structure
- C25D5/617—Crystalline layers
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
- Adornments (AREA)
- Laminated Bodies (AREA)
Abstract
【課題】 カドミウムを含有しない金、亜鉛、銅ベースの合金製の数１００μｍの厚さの部品あるいは層を電気鋳造する方法を提供すること。
【解決手段】 本発明は、電気鋳造する方法で製造した、８８〜９４重量％の金と、Ｘ（２と４の間の数）重量％の銅と／または銀と、２Ｘ重量％の亜鉛とを有する金合金の部品である。金合金の層を電気鋳造する本発明の方法は、（Ａ）金属基板をアノードを含むアルカリ電解浴内に浸すステップと、（Ｂ）前記基板の表面上に金属製イオンを堆積するために、アノードとカソードの間に電圧を生成することにより、前記層を電気鋳造するステップと、（Ｃ）８８〜９４重量％の金を含有する層を生成するために、電気メッキされた層が所定の厚さに達した時に、電圧を切るステップとを有する。前記浴は、シアン化金カリウムの形態の金塩と、シアン化銅の形態の銅塩と、酸化亜鉛の形態の亜鉛塩と、シアン化ナトリウムと、水酸化ナトリウムと、エチレンジアミン四酢酸と、表面活性剤と、を含み、前記基板は、カソードを形成する。
PROBLEM TO BE SOLVED: To provide a method for electroforming a part or layer of a thickness of several hundreds μm made of an alloy based on gold, zinc and copper which does not contain cadmium.
The present invention relates to 88-94 wt% gold, X (a number between 2 and 4) wt% copper and / or silver and 2X wt% zinc produced by an electroforming method. And a gold alloy part. The method of the present invention for electroforming a layer of gold alloy comprises: (A) immersing a metal substrate in an alkaline electrolytic bath containing an anode; and (B) depositing metal ions on the surface of the substrate. Electroforming the layer by generating a voltage between the anode and the cathode, and (C) to produce a layer containing 88-94 wt. Turning off the voltage when the thickness is reached. The bath comprises a gold salt in the form of potassium gold cyanide, a copper salt in the form of copper cyanide, a zinc salt in the form of zinc oxide, sodium cyanide, sodium hydroxide, ethylenediaminetetraacetic acid, surface And an activator, wherein the substrate forms a cathode.
Description
本発明は、亜鉛、銅と／または銀を含む金ベースの合金から、部品あるいは層を形成する電気鋳造方法と、この方法により得られた部品または層に関する。特に本発明は、３００μｍのオーダの厚さの合金の層を、基板上に堆積する方法に関する。 The present invention relates to an electroforming method for forming a part or layer from a gold-based alloy containing zinc, copper and / or silver and to the part or layer obtained by this method. In particular, the present invention relates to a method for depositing a layer of an alloy on the order of 300 μm on a substrate.
金と銅に加えてカドミウムを含有するアルカリ性の電気浴(alkaline galvanic bath)内の電気分解により金合金の電気メッキ方法は公知である。カドミウムは、毒性金属であるので、様々な法律がカドミウムの使用を禁じている。 Methods for electroplating gold alloys by electrolysis in an alkaline galvanic bath containing cadmium in addition to gold and copper are known. Since cadmium is a toxic metal, various laws prohibit the use of cadmium.
この種の問題を解決するために、特許文献１は、従来の金合金（Ａｕ、Ｃｕ、Ｃｄ）の電解析出方法（electrolytic deposition method ）において、カドミウムを亜鉛で置換する方法を、既に提案している。 In order to solve this type of problem, Patent Document 1 has already proposed a method of replacing cadmium with zinc in the conventional electrolytic deposition method of gold alloys (Au, Cu, Cd). ing.
しかし、この方法は、１０μｍオーダの厚さの金亜鉛銅合金の層の堆積を開示するのみである。さらにまた、特許文献１は、堆積された最終合金の組成に関しては、詳細な情報を開示していない。 However, this method only discloses the deposition of a layer of gold-zinc-copper alloy with a thickness on the order of 10 μm. Furthermore, Patent Document 1 does not disclose detailed information regarding the composition of the deposited final alloy.
本発明の目的は、カドミウムを含有しない金、亜鉛、銅ベースの合金の数１００μｍの厚さの部品あるいは層を、電気鋳造する方法を提供することである。 It is an object of the present invention to provide a method for electroforming a few hundred μm thick parts or layers of gold, zinc and copper based alloys that do not contain cadmium.
本発明の他の目的は、良好なレベルの延性を維持しながら、硬度を改善したこの種の層を形成する方法を提供することである。 Another object of the present invention is to provide a method of forming such a layer with improved hardness while maintaining a good level of ductility.
本発明の方法は、８８〜９４重量％の金と、Ｘ（２と４の間の数）重量％の銅と／又は銀と、２Ｘ重量％の亜鉛とを有する金合金の層を電気鋳造する方法であり、この方法は、
（Ａ）金属基板をアノードを含むアルカリ電解浴内に浸すステップと、
前記浴は、シアン化金カリウムの形態の金塩と、シアン化銅の形態の銅塩と／又は酸化銀の形態の銀塩と、酸化亜鉛の形態の亜鉛塩と、シアン化ナトリウムと、水酸化ナトリウムと、酸（例えば、エチレンジアミン四酢酸）と、表面活性剤と、を含み、前記基板が、カソードを形成し、
（Ｂ）前記基板の表面上に金属製イオンを堆積するために、アノードとカソードの間に電圧を生成することにより、前記層を電気鋳造するステップと、
（Ｃ）電気メッキされた層が所定の厚さに達した時に、電圧を切るステップと、
を有する。
The method of the present invention electrocasts a layer of gold alloy having 88-94 wt% gold, X (a number between 2 and 4) wt% copper and / or silver and 2X wt% zinc. And this method is
(A) immersing the metal substrate in an alkaline electrolytic bath containing an anode;
The bath comprises a gold salt in the form of potassium gold cyanide, a copper salt in the form of copper cyanide and / or a silver salt in the form of silver oxide, a zinc salt in the form of zinc oxide, sodium cyanide and water. Sodium oxide, an acid (eg, ethylenediaminetetraacetic acid), and a surfactant, wherein the substrate forms a cathode;
(B) electroforming the layer by generating a voltage between an anode and a cathode to deposit metal ions on the surface of the substrate;
(C) turning off the voltage when the electroplated layer reaches a predetermined thickness;
Have
好ましくは、電圧は、前記（Ｂ)ステップの間変動させる。これにより、堆積時に、層の中に非均質相のαゴールドの結晶を生成する。この均質性の欠如により、結晶の超格子構造により堆積層の表面欠陥を減らす。 Preferably, the voltage is varied during the step (B). This produces non-homogeneous alpha gold crystals in the layer during deposition. This lack of homogeneity reduces surface defects in the deposited layer due to the crystal superlattice structure.
本発明の一実施例によれば、アノードとカソードの間の電圧を、前記（Ｂ)ステップの最終段階で減らし、堆積した層の表面領域内の金の濃度を増加させ、堆積した層の金色を強調する。 According to one embodiment of the present invention, the voltage between the anode and the cathode is decreased in the final stage of the step (B), the concentration of gold in the surface region of the deposited layer is increased, and the gold color of the deposited layer is increased. To emphasize.
本発明の他の態様においては、前記（Ｂ)ステップの後、少なくとも３０分間、３００℃から７００℃の間の熱アニール・プロセスを行い、その後急冷（rapid quenching）する。 In another embodiment of the present invention, after the step (B), a thermal annealing process between 300 ° C. and 700 ° C. is performed for at least 30 minutes, and then rapid quenching is performed.
この点に関し、熱アニール・プロセスの温度は、ＡｕＺｎの状態図（phase diagram）の「液相線」の温度カーブを、如何なる状況においても、超えてはならない。その理由は、液相から共融凝固（eutectic solidification）の間、α相とβ’相の２つの相での固化を引き起こし、冷却後、機械特性に目立った劣化を起こすことになる。この処理の間、この層の結晶構造は、部分的に均質化し、その後、急速硬化により形成プロセスで固化する。これにより、中間のα１またはα２の結晶相が、目的とする合金に対し、形成されるのを阻止する。 In this regard, the temperature of the thermal annealing process should not exceed the “liquidus” temperature curve of the AuZn phase diagram under any circumstances. The reason is that during the eutectic solidification from the liquid phase, solidification occurs in two phases, the α phase and the β ′ phase, and after cooling, the mechanical properties are noticeably deteriorated. During this treatment, the crystal structure of this layer is partially homogenized and then solidified in the forming process by rapid curing. This prevents the intermediate α1 or α2 crystal phase from forming for the target alloy.
本発明の方法は、電気鋳造された金合金部品に関し、この金合金は、８８〜９４重量％の金と、Ｘ（２と４の間の数）重量％の銅と／または銀と、２Ｘ重量％の亜鉛とを含有する金合金である。 The method of the present invention relates to an electroformed gold alloy part, the gold alloy comprising 88-94 wt% gold, X (number between 2 and 4) wt% copper and / or silver, 2X It is a gold alloy containing zinc by weight.
本発明の一実施例によれば、本発明の合金は、金を８８重量％、亜鉛を８重量％、銅を４重量％含む。 According to one embodiment of the present invention, the alloy of the present invention comprises 88% by weight gold, 8% by weight zinc and 4% by weight copper.
電気鋳造は、４０℃から８０℃の間の温度で行われる。 Electroforming is performed at a temperature between 40 ° C and 80 ° C.
本発明の一実施例によれば、使用される表面活性剤は、ポリグリコール・アルキルアルコール(polyglycol alkyl alcohol)のリン酸エステル(phosphatic ester)である。 According to one embodiment of the present invention, the surfactant used is a phosphatic ester of polyglycol alkyl alcohol.
本発明の方法によれば、電気分解は、ｐＨが８と１０の間のアルカリ性の電気浴内で行われる。具体的には、電気浴は、シアン化金カリウムの形態で金を約７〜１５ｇ／ｌ酸化亜鉛の形態で亜鉛を１．５〜５ｇ／ｌを含み、シアン化銅あるいは酸化銀の形態で銅あるいは銀を１．５〜３ｇ／ｌ含み、シアン化ナトリウム、水酸化ナトリウム、エチレンジアミン四酢酸(ethylenediamino tetra-acetic acid)と、そのカリウム塩と表面活性剤とを含む。 According to the process of the invention, the electrolysis is carried out in an alkaline electric bath with a pH between 8 and 10. Specifically, the electric bath contains about 7-15 g / l zinc oxide in the form of potassium gold cyanide and 1.5-5 g / l zinc in the form of zinc oxide, in the form of copper cyanide or silver oxide. Contains 1.5 to 3 g / l of copper or silver, and contains sodium cyanide, sodium hydroxide, ethylenediamino tetra-acetic acid, its potassium salt and a surfactant.
この電気分解ステップの後に、少なくとも３００℃で少なくとも３０分間熱処理を行う。この熱処理は、酸化亜鉛を還元すために還元性雰囲気中で行うのが好ましい。 After this electrolysis step, a heat treatment is performed at least at 300 ° C. for at least 30 minutes. This heat treatment is preferably performed in a reducing atmosphere in order to reduce zinc oxide.
好ましくは、電気浴はさらに増白剤を含む。この増白剤は、好ましくは、次亜リン酸カリウム(potassium hypophosphite)又はセレノシアン酸カリウム(potassium selenocyanate)と結合した酒石酸アンチモンカリウム(potassium antimony tartrate)である。 Preferably, the electric bath further comprises a brightener. This brightener is preferably potassium antimony tartrate combined with potassium hypophosphite or potassium selenocyanate.
表面活性剤は、好ましくは、ブチル又はノニル・フェノール・ポリグリコール、フォスファチド・エステル(butyl or nonyl phenol polyglycol phosphatide ester)である。 The surfactant is preferably butyl or nonyl phenol polyglycol phosphatide ester.
電気分解は、ｐＨが８と１０の間の電気浴内で、温度が６０℃と７５℃の間で行うのが、好ましい。 The electrolysis is preferably carried out in an electric bath with a pH between 8 and 10 and at a temperature between 60 ° C and 75 ° C.
電気分解は、１．０Ａ.ｄｍ−２の電流密度で行う。 The electrolysis is performed at a current density of 1.0 A.dm- 2 .
電気分解の後に熱処理を行う。この熱処理は、温度が３００℃以上で３０分から１時間行う。この熱処理は急速空気冷却を含む。これは、例えば、帯状の炉（band furnace）中で行う。この熱処理は還元性雰囲気で行う。 A heat treatment is performed after the electrolysis. This heat treatment is performed at a temperature of 300 ° C. or higher for 30 minutes to 1 hour. This heat treatment includes rapid air cooling. This is done, for example, in a band furnace. This heat treatment is performed in a reducing atmosphere.
以下、本発明の一実施例による電解析出方法とその準備方法を説明する。 Hereinafter, an electrolytic deposition method and a preparation method thereof according to an embodiment of the present invention will be described.
この堆積例は、１８カラットの金合金で、毒性金属または毒性メタロイド、特にカドミウムを含有せず、淡黄色が２Ｎで、硬さが２００と３００ＨＶ０．００５の間で、４０〜３５０μｍの厚さにおいて延性があり、優れた光沢と高いレベルの耐磨耗性と耐変色性がある。 This deposition example is an 18 carat gold alloy that does not contain toxic metals or metalloids, especially cadmium, has a pale yellow color of 2N, a hardness between 200 and 300HV0.005, and a thickness of 40-350 μm. It has ductility, excellent gloss, high level of wear resistance and discoloration resistance.
この堆積は、電解浴(electrolytic bath)内の電気分解により行われ、その後、３００℃で３０分間還元性雰囲気の熱処理を行う。 This deposition is performed by electrolysis in an electrolytic bath, followed by heat treatment in a reducing atmosphere at 300 ° C. for 30 minutes.
電気分解は、以下の組成を含む電解浴内で行われる。
例：
ＫＡｕ（ＣＮ）２の形態のＡｕ：１１ｇ.１−１
ＣｕＣＮの形態のＣｕ：２．５ｇ.１−１
ＺｎＯの形態のＺｎ：２．５ｇ.１−１
ＮａＣＮ：２０ｇ.１−１
ＮａＯＨ：５．５ｇ.１−１
ＫＨＣＯ３：５ｇ.１−１
Ｋ４［ＥＤＴＡ］：５ｇ.１−１
Ｈ４［ＥＤＴＡ］：５ｇ.１−１
ｐＨ：８
温度：７０℃
電流密度：１Ａ.ｄｍ−２
湿潤剤：０．２ｍｇ.１−１ フォスファチド・ブチル・フェノール・ポリグリコール・エステル(phosphatide butyl phenol polyglycol ester)
セレノシアン酸カリウム：１０ｍｇ／ｌ−１
ＥＤＴＡ＝エチレンジアミン四酢酸（ethylenediaminotetraacetic acid)
Electrolysis is performed in an electrolytic bath containing the following composition.
Example:
KAu (CN) 2 in the form Au: 11g.1 -1
CuCN in the form of a Cu: 2.5g.1 -1
In the form of ZnO Zn: 2.5g.1 -1
NaCN: 20g.1 -1
NaOH: 5.5g.1 -1
KHCO 3: 5g.1 -1
K 4 [EDTA]: 5g.1 -1
H 4 [EDTA]: 5g.1 -1
pH: 8
Temperature: 70 ° C
Current density: 1 A.dm -2
Wetting agents: 0.2mg.1 -1 phosphatides-butyl-phenol-polyglycol-ester (phosphatide butyl phenol polyglycol ester)
Potassium selenocyanate: 10 mg / l −1
EDTA = ethylenediaminotetraacetic acid
この実施例においては、電解浴は、断熱性のポリプロピレン製あるいはＰＶＣ製の容器内に入れられるが、ｐＨが８と１０の間で、温度が７０℃である。浴は、水晶、ＰＴＦＥ、磁器、安定化したステンレス製の投入電熱器（immersion heater:直接水中に入れて湯を沸かす電熱器）により加熱する。浴は、２０℃で１６〜３０ｇ.ｃｍ−３の密度を有する。良好なカソードロッドの移動と電解質の流れを維持しなければならない。アノードは、プラチナめっきのチタンあるいはステンレス・スティールである。 In this embodiment, the electrolytic bath is placed in a heat-insulating polypropylene or PVC container with a pH between 8 and 10 and a temperature of 70 ° C. The bath is heated by quartz, PTFE, porcelain, and a stabilized stainless steel heater (immersion heater). The bath has a density of 16-30 g.cm −3 at 20 ° C. Good cathode rod movement and electrolyte flow must be maintained. The anode is platinum-plated titanium or stainless steel.
電気分解は、電流が１〜２Ａ.ｄｍ−２で行われる。この条件により、速度が０．５μｍ.分−１で、１００ｍｇ.Ａ.分−１ｃｍ−２のカソード効率を提供できる。 Electrolysis is performed at a current of 1-2 A.dm −2 . This condition, speed is 0.5 [mu] m. Min -1, can provide a cathode efficiency of 100Mg.A. Min -1 cm -2.
本発明の変形例として、浴は、微量の銀（trace of silver）と以下の金属を含んでもよい。Ｉｎ、Ｃｄ、Ｚｒ、Ｓｅ、Ｔｅ、Ｓｂ、Ｓｎ、Ｇａ、Ａｓ、Ｓｒ、Ｂｅ、Ｂｉ。 As a variant of the invention, the bath may contain traces of silver and the following metals: In, Cd, Zr, Se, Te, Sb, Sn, Ga, As, Sr, Be, Bi.
さらに湿潤剤は、アルカリ・シアン化媒体中で湿式できるいかなる種類の物でよい。 Further, the wetting agent may be any kind of material that can be wetted in an alkaline cyanide medium.
以上の説明は、本発明の一実施例に関するもので、この技術分野の当業者であれば、本発明の種々の変形例を考え得るが、それらはいずれも本発明の技術的範囲に包含される。
The above description relates to one embodiment of the present invention, and those skilled in the art can consider various modifications of the present invention, all of which are included in the technical scope of the present invention. The
Claims (9)
（Ａ）金属基板をアノードを含むアルカリ電解浴内に浸すステップと、
前記浴は、シアン化金カリウムの形態の金塩と、シアン化銅の形態の銅塩と／又は酸化銀の形態の銀塩と、酸化亜鉛の形態の亜鉛塩と、シアン化ナトリウムと、水酸化ナトリウムと、酸と、表面活性剤と、を含み、前記基板は、カソードを形成し、
（Ｂ）前記基板の表面上に金属製イオンを堆積するために、アノードとカソードの間に電圧をかけることにより、前記層を電気鋳造するステップと、
（Ｃ）電気メッキされた層が所定の厚さに達した時に、電圧を切るステップと、
を有する
ことを特徴とする方法。 In a method of electroforming a layer of gold alloy having 88-94 wt% gold, X wt% copper and / or silver and 2X wt% zinc, X is a number between 2 and 4 ,
(A) immersing the metal substrate in an alkaline electrolytic bath containing an anode;
The bath comprises a gold salt in the form of potassium gold cyanide, a copper salt in the form of copper cyanide and / or a silver salt in the form of silver oxide, a zinc salt in the form of zinc oxide, sodium cyanide and water. Sodium oxide, an acid, and a surfactant, wherein the substrate forms a cathode;
(B) electroforming the layer by applying a voltage between an anode and a cathode to deposit metal ions on the surface of the substrate;
(C) turning off the voltage when the electroplated layer reaches a predetermined thickness;
A method characterized by comprising:
ことを特徴とする請求項１記載の方法。 The method according to claim 1, wherein the voltage is varied during the step (B).
これにより、堆積した層の表面領域の金の濃度を増加させる
ことを特徴とする請求項２記載の方法。 The voltage is decreased in the final stage of the step (B),
3. A method according to claim 2, characterized in that this increases the gold concentration in the surface area of the deposited layer.
（Ｘ）４２０℃と７００℃の間で、少なくとも３０分熱アニールと、
（Ｙ）急速硬化と
を行う
ことを特徴とする請求項１−３のいずれかに記載の方法。 After step B,
(X) a thermal anneal between 420 ° C. and 700 ° C. for at least 30 minutes;
(Y) Rapid hardening is performed, The method in any one of Claims 1-3 characterized by the above-mentioned.
ことを特徴とする請求項１−４のいずれかに記載の方法。 The method according to any one of claims 1 to 4, wherein the surfactant is butyl phosphatide or nonyl phenol polyglycol ester.
ことを特徴とする請求項１−５のいずれかに記載の方法。 The method according to claim 1, wherein the step (B) is performed at a temperature between 40 ° C. and 80 ° C. 6.
ことを特徴とする金合金製の電子部品。 Gold produced by an electroforming method and having 88 to 94% by weight of gold, X (number between 2 and 4)% by weight of copper and / or silver and 2X by weight of zinc Alloy electronic parts.
ことを特徴とする請求項７記載の電子部品。 The electronic component according to claim 7, wherein the alloy is formed of 88 wt% gold, 8 wt% zinc, and 4 wt% copper.
ことを特徴とする請求項７又は８記載の電子部品。
The electronic component according to claim 7 or 8, wherein the gold in the alloy is formed of α-phase gold.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH01583/06A CH714243B1 (en) | 2006-10-03 | 2006-10-03 | Electroforming process and part or layer obtained by this method. |
| PCT/EP2007/060506 WO2008040761A2 (en) | 2006-10-03 | 2007-10-03 | Electroforming method and part or layer obtained using said method |
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| US (1) | US20100024930A1 (en) |
| EP (1) | EP2079859A2 (en) |
| JP (1) | JP2010506040A (en) |
| KR (1) | KR101326883B1 (en) |
| CN (1) | CN101611176A (en) |
| CH (1) | CH714243B1 (en) |
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| EP2505691B1 (en) * | 2011-03-31 | 2014-03-12 | The Swatch Group Research and Development Ltd. | Process for obtaining a gold alloy deposit of 18 carat 3N |
| CN102539217A (en) * | 2011-12-26 | 2012-07-04 | 昆山全亚冠环保科技有限公司 | Silver-gold alloy metallographic corrosive agent and metallographic display method |
| CN112725653A (en) * | 2020-12-21 | 2021-04-30 | 有研亿金新材料有限公司 | Novel high-plasticity gold-based electric brush material and preparation method thereof |
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| Publication number | Publication date |
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| US20100024930A1 (en) | 2010-02-04 |
| WO2008040761A3 (en) | 2008-11-06 |
| KR101326883B1 (en) | 2013-11-11 |
| EP2079859A2 (en) | 2009-07-22 |
| WO2008040761A2 (en) | 2008-04-10 |
| CN101611176A (en) | 2009-12-23 |
| KR20090069324A (en) | 2009-06-30 |
| CH714243B1 (en) | 2019-04-15 |
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