CN102732920B - 18开3n金合金的制备方法 - Google Patents
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- 238000000034 method Methods 0.000 title claims abstract description 24
- 229910001020 Au alloy Inorganic materials 0.000 title claims abstract description 16
- 239000003353 gold alloy Substances 0.000 title abstract description 7
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000010949 copper Substances 0.000 claims abstract description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052802 copper Inorganic materials 0.000 claims abstract description 17
- 239000010931 gold Substances 0.000 claims abstract description 15
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 14
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- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
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- 229910052709 silver Inorganic materials 0.000 claims abstract description 11
- 239000004332 silver Substances 0.000 claims abstract description 11
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- 230000008021 deposition Effects 0.000 claims abstract description 7
- 150000002902 organometallic compounds Chemical class 0.000 claims abstract description 4
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- 239000003352 sequestering agent Substances 0.000 claims abstract description 3
- 150000003839 salts Chemical group 0.000 claims description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- -1 dimethyl dodecylamine-N-oxide compound Chemical class 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 229910000906 Bronze Inorganic materials 0.000 claims description 4
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- 239000010974 bronze Substances 0.000 claims description 4
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000004615 ingredient Substances 0.000 claims description 4
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical group I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 claims description 3
- 238000009713 electroplating Methods 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
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- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 claims description 2
- 229940043264 dodecyl sulfate Drugs 0.000 claims description 2
- NYUQKKWCYPVQGE-UHFFFAOYSA-N dodecyl(dimethyl)azanium;propane-1-sulfonate Chemical compound CCCS([O-])(=O)=O.CCCCCCCCCCCC[NH+](C)C NYUQKKWCYPVQGE-UHFFFAOYSA-N 0.000 claims description 2
- 229940050410 gluconate Drugs 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
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- 238000005868 electrolysis reaction Methods 0.000 description 4
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- 239000011701 zinc Substances 0.000 description 3
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- 239000004743 Polypropylene Substances 0.000 description 1
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
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- 235000019438 castor oil Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- RMGVZKRVHHSUIM-UHFFFAOYSA-N dithionic acid Chemical compound OS(=O)(=O)S(O)(=O)=O RMGVZKRVHHSUIM-UHFFFAOYSA-N 0.000 description 1
- SYELZBGXAIXKHU-UHFFFAOYSA-N dodecyldimethylamine N-oxide Chemical compound CCCCCCCCCCCC[N+](C)(C)[O-] SYELZBGXAIXKHU-UHFFFAOYSA-N 0.000 description 1
- 239000002659 electrodeposit Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
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- LOKAAONKEFJMGO-UHFFFAOYSA-N imidazolidine-2-thione Chemical compound N1C(NCC1)=S.N1C(NCC1)=S LOKAAONKEFJMGO-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
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- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical group [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
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- 229910052712 strontium Inorganic materials 0.000 description 1
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- 238000007669 thermal treatment Methods 0.000 description 1
- NJRXVEJTAYWCQJ-UHFFFAOYSA-N thiomalic acid Chemical compound OC(=O)CC(S)C(O)=O NJRXVEJTAYWCQJ-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
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- 231100000331 toxic Toxicity 0.000 description 1
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- 231100000419 toxicity Toxicity 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
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- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
本发明涉及一种18开3N金合金的制备方法。本发明涉及在浸入浴中的电极上电镀沉积金合金的方法,所述浴含有金金属、有机金属化合物、润湿剂、螯合剂和游离氰化物,所述合金金属为铜金属和银金属,使得在电极上沉积镜般光亮的黄色金合金,其特征在于该浴含有21.53%金、78.31%铜和0.16%银本发明属于电镀沉积领域。
Description
技术领域
本发明涉及厚的金合金层形式的电沉积物以及制备同样产品的方法。
背景技术
在装饰电镀领域中,制备黄色着色的、具有等于或大于9开等级、10微米厚度并且具有高抗蚀性的可延展金电解沉积物的(electrolytic depositions)方法是公知的。这些沉积物可以通过在碱性电镀浴(galvanic
bath)中电解得到,所述电镀浴除金和银外,含有0.1-3g∙L-1的镉。
然而通过这些公知的方法获得的沉积物具有浓度1-10%的镉。镉有利于沉积厚的层,即1-800微米,并且在降低包含在合金中铜含量的同时提供了黄色着色的合金。但是,镉是毒性极大的并且在某些国家是禁止使用的。
公知地,含有铜和锌的18开金合金不含有任何镉。然而,这些沉积物具有过度粉红的色调(过于富含铜)。最终,这些沉积物抗腐蚀性较差,这就意味着会很快地失去光泽(tarnish)。
发明内容
本发明的目的是,通过提供用于沉积厚的、具有3N黄色着色的、18开金合金层的制备方法克服前述的全部或部分缺陷,所述金合金层不含有锌和镉。
因此本发明涉及在浸入电镀浴中的电极上电镀沉积金合金的方法,所述电镀浴含有金金属、有机金属化合物、润湿剂、螯合剂和游离氰化物,合金金属为铜金属和银金属,其能够在电极上沉积镜般光亮的(mirror-bright)黄色金合金,特征在于该电镀浴包含21.53%金、78.31%铜和0.16%银的比例。
因此,令人惊讶地,有利地,按照本发明的电镀浴即使基于高铜含量,其还是能够获得以21.53%金、78.31%铜和0.16%银比例的3N黄色金合金以及5N红色金合金。
按照本发明的其它有益特征:
-所述电镀浴含有1-10g∙L-1的金钾氰化物复盐形式(double
gold and potassium cyanide form)的金金属;
-所述电镀浴含有10-60g∙L-1的碘化铜形式的铜金属;
-所述电镀浴含有10mg∙L-1-1g∙L-1的银钾氰化物复盐形式的银金属;
-所述电镀浴含有3-35g∙L-1的氰化物;
-所述润湿剂具有0.05-10ml∙L-1的浓度;
-所述润湿剂选自聚氧化烯、醚磷酸酯、十二烷基硫酸盐、二甲基十二烷基胺-N-氧化物(dimethyldodecylamine-N-oxide)、二甲基(十二烷基)铵丙烷磺酸盐;
-所述电镀浴含有浓度为0.01-5ml∙L-1的胺;
-电镀浴含有浓度为0.1-20mg∙L-1的去极化剂;
-所述电镀浴含有磷酸盐、碳酸盐、柠檬酸盐、硫酸盐、酒石酸盐、葡萄糖酸盐和/或膦酸盐型导电盐;
-所述电镀浴的温度保持在50-90℃之间;
-所述电镀浴的pH值保持在8-12之间;
-所述方法是在0.05-1.5A∙dm-2的电流密度下进行的;
-本发明还涉及由前述任意权利要求的方法得到的金合金形式的电解沉积物,其厚度为1-800微米并且含有铜,其特征在于含有银作为第三主要混配料(compound),以及在于所述沉积物由75%的金、19%的铜和6%的银组成能够获得光亮的3N色。
具体实施方式
本发明涉及具有3N色的金合金的电解沉积物,令人惊讶地,其包括非已知比例的Au-Cu-Ag作为其主要混配料以获得3N色,即亮黄色。
在上述示例的沉积物中,具有金合金,其不含有毒金属或非金属,特别是不含镉和锌,其具有3N黄色,200微米的厚度,优异的光亮度并且具有非常高水平的耐磨损性和抗失泽性。
通过在以下类型的电镀浴进行电解而获得该沉积物:
-Au:5.5g∙L-1;
-Cu:20g∙L-1;
-Ag:40mg∙L-1;
-CN:5g∙L-1;
-pH:10.5;
-温度:80℃;
-电流密度:0.3A∙dm-2;
-润湿剂:0.05ml∙L-1 NN-二甲基十二烷基N-氧化物;
-亚氨基二乙酸(Iminodiacetic):20g∙L-1;
-乙二胺:0.5ml∙L-1;
-镓、硒或碲:10mg∙L-1。
因此,所述电镀浴含有21.53%金、78.31%铜和0.16%银作为主要混配料。
为了获得最佳质量的沉积物,电解后优选进行1-30分钟的200-450摄氏度的热处理。
在该实例的情况中,上述条件提供了具有大约10μm/小时的沉积速度的95mg∙A∙min-1的阴极产率。
因此,令人惊讶地,按照本发明的电镀浴提供了比例为大约75%的金,19%的铜和6%的银的沉积物,其对应于3N色、18开的沉积物,其与针对该颜色的通常电解沉积物的比例非常不同(其倾向于为大约75%的金、12.5%的铜和12.5%的银)。
所述电镀浴还可以含有光亮剂。其优选为丁炔二醇衍生物、吡啶并-丙烷磺酸盐或二者的混合物、锡盐、磺化蓖麻油、甲基咪唑、二硫代羧酸,例如硫脲、硫代巴比妥酸、咪唑啉硫酮(imidazolidinthion)或硫代苹果酸。
在这些实施例中,电镀浴置于具有隔热涂层的聚丙烯或PVC浴容器(bath
holder)中。使用石英、PTFE、瓷料或稳定化不锈钢热插棒(thermo-plunger)来加热该容器。必须保持良好的阴极杆运动和电解质流动。阳极由镀铂钛、不锈钢、钌、铱或后两者的合金制成。
当然,本发明并不局限于示例的实施例,其还可以是本领域技术人员所知晓的各种变化方式和替代方案。特别地,所述电镀浴可以含有可忽略量的下列金属:Zr、Se、Te、Sb、Sn、Ga、As、Sr、Be、Bi。
此外,润湿剂可以是在碱性氰化物介质中能够润湿的任何类型的润湿剂。
Claims (14)
1.在浸入浴中的电极上电镀沉积金合金的方法,所述浴含有金钾氰化物复盐形式的金金属、有机金属化合物、润湿剂、螯合剂和游离氰化物,所述有机金属化合物为碘化铜形式的铜金属和银钾氰化物复盐形式的银金属,使得在电极上沉积镜般光亮的黄色金合金,其特征在于该浴含有21.53重量%金、78.31重量%铜和0.16重量%银,所沉积的金合金由75重量%的金、19重量%的铜和6重量%的银组成。
2.按照权利要求1的方法,其特征在于所述浴含有1-10g∙L-1的金钾氰化物复盐形式的金金属。
3.按照权利要求1的方法,其特征在于所述浴含有10-60g∙L-1的碘化铜形式的铜金属。
4.按照权利要求1的方法,其特征在于所述浴含有10mg∙L-1-1g∙L-1的银钾氰化物复盐形式的银金属。
5.按照权利要求1的方法,其特征在于所述浴含有3-35g∙L-1的游离氰化物。
6.按照权利要求1的方法,其特征在于所述润湿剂具有0.05-10ml∙L-1的浓度。
7.按照权利要求1的方法,其特征在于所述润湿剂选自聚氧化烯、醚磷酸酯、十二烷基硫酸盐、二甲基十二烷基胺-N-氧化物、二甲基(十二烷基)铵丙烷磺酸盐类型的润湿剂。
8.按照权利要求1的方法,其特征在于所述浴含有浓度为0.01-5ml∙L-1的胺。
9.按照权利要求1的方法,其特征在于所述浴含有浓度为0.1-20mg∙L-1的去极化剂。
10.按照权利要求1的方法,其特征在于所述浴含有磷酸盐、碳酸盐、柠檬酸盐、硫酸盐、酒石酸盐、葡萄糖酸盐和/或膦酸盐型导电盐。
11.按照权利要求1的方法,其特征在于所述浴的温度保持在50-90℃。
12.按照权利要求1的方法,其特征在于所述浴的pH值保持在8-12。
13.按照权利要求1的方法,其特征在于所述方法是在0.05-1.5A∙dm-2的电流密度下进行的。
14.由前述任意权利要求之一的方法得到的金合金形式的电解沉积物,其厚度为1-800微米并且含有铜,其特征在于该电解沉积物含有银作为第三主要混配料,和在于所述沉积物由75重量%的金、19重量%的铜和6重量%的银组成,使得获得光亮的3N色。
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EP2505691B1 (fr) | 2014-03-12 |
US10053789B2 (en) | 2018-08-21 |
US10793961B2 (en) | 2020-10-06 |
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US20180320283A1 (en) | 2018-11-08 |
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