CN102041527B - 通过电铸在不使用有毒金属的情况下获得黄色金合金沉积物的方法 - Google Patents
通过电铸在不使用有毒金属的情况下获得黄色金合金沉积物的方法 Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 14
- 239000002184 metal Substances 0.000 title claims abstract description 14
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- 239000000956 alloy Substances 0.000 title claims abstract description 9
- 229910001097 yellow gold Inorganic materials 0.000 title claims abstract description 7
- 239000010930 yellow gold Substances 0.000 title claims abstract description 7
- 231100000331 toxic Toxicity 0.000 title abstract description 4
- 230000002588 toxic effect Effects 0.000 title abstract description 4
- 150000002739 metals Chemical class 0.000 title abstract 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 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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- 229910052802 copper Inorganic materials 0.000 claims abstract description 10
- 239000010931 gold Substances 0.000 claims abstract description 10
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- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 8
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- 239000010974 bronze Substances 0.000 claims description 6
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 claims description 6
- -1 dimethyl lauryl amine-N-oxide compound Chemical class 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
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- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-M D-gluconate Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O RGHNJXZEOKUKBD-SQOUGZDYSA-M 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
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- VDNXILQBKLFION-UHFFFAOYSA-N [K].[Cu] Chemical compound [K].[Cu] VDNXILQBKLFION-UHFFFAOYSA-N 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
- 229950005875 laurilsulfate Drugs 0.000 claims description 2
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- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
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- 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
- RMVOECKULIHOQG-UHFFFAOYSA-N ethene;imidazolidine-2-thione;thiourea Chemical compound C=C.NC(N)=S.S=C1NCCN1 RMVOECKULIHOQG-UHFFFAOYSA-N 0.000 description 1
- KDKYADYSIPSCCQ-UHFFFAOYSA-N ethyl acetylene Natural products CCC#C KDKYADYSIPSCCQ-UHFFFAOYSA-N 0.000 description 1
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- 150000002343 gold Chemical class 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
- 238000004519 manufacturing process Methods 0.000 description 1
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 1
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- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
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- 229910052714 tellurium Inorganic materials 0.000 description 1
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- 238000007669 thermal treatment Methods 0.000 description 1
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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- C25D3/00—Electroplating: Baths therefor
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- C25D3/56—Electroplating: Baths therefor from solutions of alloys
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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
- C25D3/58—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of copper
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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
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- Electroplating And Plating Baths Therefor (AREA)
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Abstract
本发明涉及电沉积领域，涉及通过电铸在不使用有毒金属的情况下获得黄色金合金沉积物的方法。具体而言，本发明涉及在浸于电解液中的电极上电铸沉积金合金的方法，所述电解液包含碱性氰亚金酸盐形式的金金属、有机金属化合物、润湿剂、螯合剂和游离氰化物。根据本发明，所述合金金属是铜钾氰化物复盐形式的铜和氰化物形式的银，从而使得镜面光亮的黄色金合金能够沉积在电极上。
Description
技术领域
本发明涉及厚的金合金层形式的电解沉积物及其制备方法。
背景技术
在装饰性镀覆领域中，制造下述黄色的金电解沉积物的方法是已知的：该金电解沉积物的等级等于或大于9克拉，是可延展的，具有10微米的厚度和高的抗失泽等级。这些沉积物是通过在包含0.1至3g·l-1镉以及金和铜的碱性电解液中电解获得的。
但是通过这些已知方法获得的沉积物具有1至10％的镉含量。镉有利于沉积厚层，即1至800微米，并且提供了黄色合金同时降低了合金中铜的量。但镉是剧毒性的，并在许多国家禁用。
不含任何镉、含有铜和锌的18克拉金合金也是公知的。但这些沉积物呈现过分粉红的色调(含铜太高)。最后，这些沉积物的耐蚀性太差，这意味着它们很快失去光泽。
发明内容
本发明的一个目的在于，提供一种能够沉积既不含锌也不含镉作为主成分的厚的黄色金合金层的制备方法，由此克服上述全部或部分缺点。
因此，本发明涉及在浸于电解液中的电极上电铸沉积金合金的方法，所述电解液包含碱性氰亚金酸盐形式的金属金、有机金属化合物、润湿剂、螯合剂和游离氰化物，其特征在于所述合金金属是铜钾氰化物复盐(或double copper and potassium cyanide)形式的铜和氰化物形式的银，使得镜面光亮的黄色金合金能够沉积在电极上。
根据本发明的其它有利特征：
-电解液包含1至10g·l-1的碱性氰亚金酸盐形式的金金属；
-电解液包含30至80g·l-1的碱性氰化物复盐形式的铜金属；
-电解液包含10mg·l-1至1g·l-1的络合形式的银金属；
-电解液包含15至35g·l-1的氰化物；
-所述润湿剂具有0.05至10ml·l-1的浓度；
-所述润湿剂选自聚环氧烷(或polyoxyalkenic)、醚磷酸酯/盐、十二烷基硫酸酯/盐、二甲基十二烷基胺-N-氧化物或二甲基十二烷基氧化胺、丙磺酸二甲基(十二烷基)铵；
-电解液包含0.01至5ml·l-1的胺浓度；
-电解液包含0.1mg·l-1至20mg·l-1的去极化剂浓度；
-电解液包含磷酸盐、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；
-电解液的温度保持在50至80℃之间；
-电解液的pH值保持在8至12之间；
-所述方法是以0.05至1.5A·dm-2的电流密度进行的；
-电解液遵守9.08％金、90.85％铜和0.07％银的比例。
本发明还涉及金合金形式的电解沉积物，它是由前述任一种方法获得的，厚度为1至800微米，包含铜，其特征在于以75％金、21％铜和4％银的比例包含银作为第三主化合物，以获得明亮的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，其出乎意料地以未知的比例包含Au-Cu-Ag合金作为主化合物，以获得3N色，即亮黄色。
在上述实例沉积物中，存在金合金，它不含有毒金属或非金属，且特别不含镉，具有3N黄色，厚度为200微米，具有优异的亮度，并具有非常高等级的耐磨和抗失泽性能。
所述沉积物是通过在下述类型的电解液中电解获得的：
-Au：5.5g·l-1；
-Cu：55g·l-1；
-Ag：40mg·l-1；
-KCN：26g·l-1；
-pH：10.5；
-温度：65℃；
-电流密度：0.3A·dm-2；
-润湿剂：0.05ml·l-1，N，N-二甲基十二烷基胺-N-氧化物；
-亚氨基乙酸：20g·l-1；
-乙二胺：0.5ml·l-1；
-镓、硒或碲：10mg·l-1。
优选地，电解之后在200至450℃进行1至30分钟的热处理，以获得优质沉积物。
在该实施例的情况下，这些条件提供了98mg·A·min-1的阴极产率和大约每小时10μm的沉积速度。
因此，出乎意料的是，根据本发明的电解液以大约75％金、21％铜和4％银的比例提供了沉积物，这相当于3N色，18克拉沉积物，与这种色的常见电解沉积物具有非常不同的比例，常见沉积物通常是约75％金、12.5％铜和12.5％银的沉积物。
所述电解液还可以包含光亮剂。其优选为丁炔二醇衍生物、丙烷磺酸吡啶盐(pyridinio-propanesulfonate)或者二者的混合物、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、亚乙基硫脲(imidazolidinthion)或者硫代苹果酸硫羟苹果酸。
在这些实例中，电解液包含在具有绝热涂层的聚丙烯或PVC电解液容器中。用石英、PTFE、瓷器皿或稳定化的不锈钢热活塞将电解液加热。必须保持良好的阴极棒移动和电解液流动。阳极用镀钛的铂、不锈钢、钌、铱或者后两种的合金制成。
当然，本发明并不局限于所述实施例，而是可以有各种变化和改变，这对于本领域技术人员而言是清楚的。特别地，电解液可以包含下述金属：可忽略量的Zr、Se、Te、Sb、Sn、Ga、As、Sr、Be、Bi。
此外，所述润湿剂可以是能够在碱性氰化物介质中润湿的任何类型。
Claims (12)
1.在浸于电解液中的电极上电铸沉积金合金的方法，所述电解液包含碱性氰亚金酸盐形式的金金属、有机金属化合物、润湿剂、螯合剂和游离氰化物，其中合金金属是铜钾氰化物复盐形式的铜和氰化物形式的银，使得镜面光亮的黄色金合金能够沉积在电极上，该方法的特征在于所述电解液遵守9.08％金、90.85％铜和0.07％银的比例，既不包含镉，也不包含锌。
2.如权利要求1所述的方法，其特征在于所述电解液包含5.5g·l-1的碱性氰亚金酸盐形式的金金属、55g·l-1的碱性氰化物复盐形式的铜金属和40mg·l-1的络合形式的银金属。
3.如权利要求2所述的方法，其特征在于所述电解液包含15至35g·l-1的氰化物。
4.如权利要求1所述的方法，其特征在于所述润湿剂具有0.05至10ml·l-1的浓度。
5.如权利要求1所述的方法，其特征在于所述润湿剂选自聚环氧烷、醚磷酸酯/盐、十二烷基硫酸酯/盐、二甲基十二烷基胺-N-氧化物、丙磺酸二甲基(十二烷基)铵。
6.如权利要求1所述的方法，其特征在于所述电解液包含0.01至5ml·l-1的胺浓度。
7.如权利要求1所述的方法，其特征在于所述电解液包含0.1mg·1-1至20mg·l-1的去极化剂浓度。
8.如权利要求1所述的方法，其特征在于所述电解液包含磷酸盐、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。
9.如权利要求1所述的方法，其特征在于所述电解液的温度保持在50至80℃之间。
10.如权利要求1所述的方法，其特征在于所述电解液的pH值保持在8至12之间。
11.如权利要求1所述的方法，其特征在于所述方法在0.05至1.5A·dm-2之间的电流密度进行。
12.金合金形式的电解沉积物，由根据前述权利要求任一项的方法获得，其厚度为1至800微米，其特征在于包含作为第三主化合物的银，且该沉积物由75％金、21％铜以及4％银制成，从而能够获得明亮的3N色。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP09173198.4 | 2009-10-15 | ||
| EP09173198.4A EP2312021B1 (fr) | 2009-10-15 | 2009-10-15 | Procédé d'obtention d'un dépôt d'alliage d'or jaune par galvanoplastie sans utilisation de métaux toxiques |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102041527A CN102041527A (zh) | 2011-05-04 |
| CN102041527B true CN102041527B (zh) | 2014-09-17 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201010552012.7A Active CN102041527B (zh) | 2009-10-15 | 2010-10-15 | 通过电铸在不使用有毒金属的情况下获得黄色金合金沉积物的方法 |
Country Status (6)
| Country | Link |
|---|---|
| US (4) | US20110089040A1 (zh) |
| EP (1) | EP2312021B1 (zh) |
| JP (1) | JP5563421B2 (zh) |
| KR (1) | KR101297476B1 (zh) |
| CN (1) | CN102041527B (zh) |
| HK (1) | HK1157415A1 (zh) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2505691B1 (fr) | 2011-03-31 | 2014-03-12 | The Swatch Group Research and Development Ltd. | Procédé d'obtention d'un dépôt d'alliage d'or 18 carats 3N |
| WO2018066007A1 (en) * | 2016-10-06 | 2018-04-12 | Valmet Plating S.R.L. | A galvanic and thermal process to obtain the coloration of metals, in particular precious metals |
| CN107299364A (zh) * | 2017-06-07 | 2017-10-27 | 常州富思通管道有限公司 | 一种镀锌光亮剂及其制备方法 |
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2009
- 2009-10-15 EP EP09173198.4A patent/EP2312021B1/fr active Active
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2010
- 2010-10-15 CN CN201010552012.7A patent/CN102041527B/zh active Active
- 2010-10-15 US US12/905,788 patent/US20110089040A1/en not_active Abandoned
- 2010-10-15 JP JP2010232903A patent/JP5563421B2/ja active Active
- 2010-10-15 KR KR1020100100585A patent/KR101297476B1/ko active IP Right Grant
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- 2014-08-05 US US14/452,364 patent/US9567684B2/en active Active
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- 2018-02-16 US US15/898,330 patent/US20180171499A1/en not_active Abandoned
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| TW200930844A (en) * | 2007-09-21 | 2009-07-16 | Aliprandini Laboratoires G | Method of obtaining a yellow gold alloy deposition by galvanoplasty without using toxic metals or metalloids |
Also Published As
| Publication number | Publication date |
|---|---|
| EP2312021A1 (fr) | 2011-04-20 |
| EP2312021B1 (fr) | 2020-03-18 |
| US20110089040A1 (en) | 2011-04-21 |
| US20180171499A1 (en) | 2018-06-21 |
| JP2011084815A (ja) | 2011-04-28 |
| US20150027898A1 (en) | 2015-01-29 |
| CN102041527A (zh) | 2011-05-04 |
| US20200240030A1 (en) | 2020-07-30 |
| HK1157415A1 (zh) | 2012-06-29 |
| US9567684B2 (en) | 2017-02-14 |
| KR101297476B1 (ko) | 2013-08-16 |
| JP5563421B2 (ja) | 2014-07-30 |
| KR20110041424A (ko) | 2011-04-21 |
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