CN1004010B - 无氰仿金电镀液 - Google Patents
无氰仿金电镀液 Download PDFInfo
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- CN1004010B CN1004010B CN86105831.3A CN86105831A CN1004010B CN 1004010 B CN1004010 B CN 1004010B CN 86105831 A CN86105831 A CN 86105831A CN 1004010 B CN1004010 B CN 1004010B
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- 150000003839 salts Chemical class 0.000 claims abstract description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 9
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims abstract description 9
- 229940095064 tartrate Drugs 0.000 claims abstract description 9
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 7
- 239000003112 inhibitor Substances 0.000 claims abstract description 5
- 238000005187 foaming Methods 0.000 claims abstract description 4
- 239000004094 surface-active agent Substances 0.000 claims abstract description 4
- 150000003751 zinc Chemical class 0.000 claims abstract description 4
- -1 polyoxyethylene Polymers 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 9
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 8
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052737 gold Inorganic materials 0.000 claims description 7
- 239000010931 gold Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 6
- 125000005233 alkylalcohol group Chemical group 0.000 claims description 5
- 238000009713 electroplating Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 235000015320 potassium carbonate Nutrition 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 229940116318 copper carbonate Drugs 0.000 claims description 4
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims description 4
- TVQLLNFANZSCGY-UHFFFAOYSA-N disodium;dioxido(oxo)tin Chemical compound [Na+].[Na+].[O-][Sn]([O-])=O TVQLLNFANZSCGY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 4
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229940079864 sodium stannate Drugs 0.000 claims description 4
- 235000005074 zinc chloride Nutrition 0.000 claims description 4
- 239000011592 zinc chloride Substances 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- IOUCSUBTZWXKTA-UHFFFAOYSA-N dipotassium;dioxido(oxo)tin Chemical compound [K+].[K+].[O-][Sn]([O-])=O IOUCSUBTZWXKTA-UHFFFAOYSA-N 0.000 claims description 3
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 3
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 claims description 3
- 235000013024 sodium fluoride Nutrition 0.000 claims description 3
- 239000011775 sodium fluoride Substances 0.000 claims description 3
- 235000011006 sodium potassium tartrate Nutrition 0.000 claims description 3
- 239000001433 sodium tartrate Substances 0.000 claims description 3
- 229960002167 sodium tartrate Drugs 0.000 claims description 3
- 235000011004 sodium tartrates Nutrition 0.000 claims description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 3
- 229960001763 zinc sulfate Drugs 0.000 claims description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 2
- 239000008151 electrolyte solution Substances 0.000 abstract description 9
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 abstract 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 239000003086 colorant Substances 0.000 abstract 1
- 150000001879 copper Chemical class 0.000 abstract 1
- 229910000027 potassium carbonate Inorganic materials 0.000 abstract 1
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- JJJOZVFVARQUJV-UHFFFAOYSA-N 2-ethylhexylphosphonic acid Chemical compound CCCCC(CC)CP(O)(O)=O JJJOZVFVARQUJV-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical class [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 1
- JEHCHYAKAXDFKV-UHFFFAOYSA-J lead tetraacetate Chemical compound CC(=O)O[Pb](OC(C)=O)(OC(C)=O)OC(C)=O JEHCHYAKAXDFKV-UHFFFAOYSA-J 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910002058 ternary alloy Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Landscapes
- Electroplating And Plating Baths Therefor (AREA)
Abstract
一种无氰仿金电镀用电解液，用铜盐，锡盐，锌盐、碳酸钾、无机调色剂、有机膦酸（或盐）和酒石酸盐、铜粉抑制剂，低泡表面活性剂配制成无氰电解液，镀液具有很高的稳定性和优良的深镀能力和分散能力，对环境无污染，可获得１８～２２Ｋ的各种仿金镀层。
Description
一种无氰仿金电镀用电解液。本发明所涉及的是一种电镀铜锌锡三元合金仿金镀层用的无氰碱性水溶液。
通常仿金电镀工艺用的电解液是氰化物电解液（参见美国专利4，364，804和日本特许昭51-17946）。氰化物是剧毒品，对环境污染严重，必须进行严格的废水处理。近年来，用焦磷酸盐和有机磷酸作电镀液代替氰化物的研究有所进展，但这种电镀液稳定性不好，镀层色泽较差，镀层颜色分布不匀。
本发明的目的是用毒性很小的有机膦酸（或盐）和酒石酸盐配制无氰仿金电镀液。
本发明是通过采用以下组成的电解液实现的：
铜盐 10～40克/升
锌盐 5～30克/升
锡盐 5～15克/升
酒石酸盐 10～60克/升
有机膦酸（或盐） 80～160克/升
碳酸钾 30～80克/升
低泡表面活性剂 0.00001克/升～1克/升
无机调色剂 0.0001克/升～1克/升
铜粉抑制剂 0.01克/升～10克/升
工艺参数：
pH 11～14
阴极电流密度 1～3安/分米2
沉积速度 15～20微米/小时
温度 50℃～60℃
在上述配方中，铜盐是硫酸铜或碳酸铜，锌盐是氯化锌或硫酸锌。锡盐是锡酸钠或锡酸钾。酒石酸盐是酒石酸钾或酒石酸钠或酒石酸钾钠。有机膦酸（或盐）的分子结构式为：
其中M＝H+或Na+或K+或NH <math><msup><mi></mi><msub><mi>+</mi></msup><mi>4</mi></msub></math>
R＝C1～C3脂肪族烷基。
在这类有机膦酸（或盐）中，以R＝CH3的有机膦酸（或盐）用得较多，因为它的价格便宜。
常用的低泡表面活性剂是烷基醇聚氧乙烯醚或烷基醇聚氧乙烯聚氧丙烯醚，其用量在0.00001克/升～1克/升。所用的无机调色剂可以是镍、钴、铟、银、铅等的无机盐，其中铅、铟、镍的无机盐较好，用量在0.0001克/升～1克/升之间。铜粉抑制剂是氟化钾、氟化钠或氟化铵，其用量在0.01克/升～10克/升。铜粉抑制剂主要用于防止阳极和阴极电解时产生一价铜而形成铜粉。
本发明所取得的效果与现有技术相比，具有如下特点：
1.用有机膦酸（或盐）和酒石酸盐代替剧毒氰化物配制的电镀液，使电镀过程不再有剧毒的氰化氢气体析出和氰化物废水排出，明显地改善了工作条件和对环境的污染。
2.镀液十分稳定，在长期生产过程中无沉淀物析出，也无铜粉析出，可保证稳定地获得18～22K的各种仿金镀层，仿金镀层的组成为：铜72～80%;Zn12～20%;Sn6～10%。
3.镀液具有很好的分散能力和深镀能力，适于复杂零件的电镀也适于作为镀真金的中间镀层，以节约黄金的用量。
实例一
碳酸铜 25克/升
氯化锌 15克/升
锡酸钠 10克/升
酒石酸钠 20克/升
1-羟基乙叉-1·1-二膦酸 120克/升
碳酸钾 50克/升
氟化钾 0.01克/升
十二烷基醇聚氧乙烯醚 0.5克/升
硫酸镍 0.2克/升
pH 13.5
温度 50℃～60℃
阴极电流密度 1.5安/分米2
上述组成的电镀液可以稳定地获得18K金色的镀层。
实例二
碳酸铜 20克/升
氯化锌 15克/升
锡酸钠 10克/升
酒石酸钾钠 50克/升
1-羟基丁叉-1·1-二月膦酸 110克/升
碳酸钾 40克/升
氟化钠 0.2克/升
十二烷基醇聚氧乙烯聚氧丙烯醚 0.5克/升
醋酸铅 0.1克/升
pH 13.5
温度 50℃～60℃
阴极电流密度 1.5安/分米2
上述组成的电解液可以稳定地获得20～22K金色的镀层。
实例三
硫酸铜 15克/升
硫酸锌 10克/升
锡酸钾 10克/升
酒石酸钾 40克/升
1-羟基丙叉-1·1-二膦酸钾（或钠或铵盐） 130克/升
碳酸钾 60克/升
氟化铵 1.0克/升
八烷基醇聚氧乙烯醚 0.5克/升
氯化铟 0.5克/升
pH 13.0
温度 50℃～60℃
阴极电流密度 1.5安/分米2
上述组成的电解液可以稳定地获得20～22K金色的镀层。
Claims (6)
1、一种无氰仿金电镀用水溶液，其特征在于，由铜盐（硫酸铜或碳酸铜）10～40克/升，锡盐（锡酸钠或锡酸钾）5～15克/升，锌盐（硫酸锌或氯化锌）5～30克/升，碳酸钾30～80克/升，无机调色剂（镍、钴、铟、铅或银的无机盐）0.0001～1克/升，酒石酸盐（酒石酸钾或酒石酸钠或酒石酸钾钠）10～60克/升，低泡表面活性剂（烷基醇聚氧乙烯醚或烷基醇聚氧乙烯聚氧丙烯醚）0.00001～1克/升，铜粉抑制剂（氟化钾、氟化钠或氟化铵）0.01～10克/升和有机膦酸（或盐）80～160克/升组成，其中有机膦酸（或盐）的分子结构式为，
2、式中R＝C1-C3脂肪族烷基，
M＝H+或Na+或K+或NH <math><msup><mi></mi><msub><mi>+</mi></msup><mi>4</mi></msub></math> 。
3、权利要求1所述的电镀液，其特征在于，有机膦酸中R＝CH3。
4、权利要求1所述的电镀液，其特征在于，所说的无机调色剂为铅、铟、镍的无机盐。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN86105831.3A CN1004010B (zh) | 1986-07-11 | 1986-07-11 | 无氰仿金电镀液 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN86105831.3A CN1004010B (zh) | 1986-07-11 | 1986-07-11 | 无氰仿金电镀液 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN86105831A CN86105831A (zh) | 1988-02-24 |
| CN1004010B true CN1004010B (zh) | 1989-04-26 |
Family
ID=4802984
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN86105831.3A Expired CN1004010B (zh) | 1986-07-11 | 1986-07-11 | 无氰仿金电镀液 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1004010B (zh) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE502007002479D1 (de) * | 2007-02-14 | 2010-02-11 | Umicore Galvanotechnik Gmbh | Kupfer-Zinn-Elektrolyt und Verfahren zur Abscheidung von Bronzeschichten |
| CN101373651B (zh) * | 2007-08-23 | 2011-12-07 | 北京中科三环高技术股份有限公司 | 湿法喷砂式钕铁硼永磁材料的表面前处理方法 |
| DE102008032398A1 (de) * | 2008-07-10 | 2010-01-14 | Umicore Galvanotechnik Gmbh | Verbesserter Kupfer-Zinn-Elektrolyt und Verfahren zur Abscheidung von Bronzeschichten |
| CN101624714B (zh) * | 2009-08-18 | 2010-12-29 | 杜强 | 含有机添加剂的铜锡锌镀液及利用该镀液进行电镀的工艺 |
| CN103789803B (zh) * | 2014-01-13 | 2016-04-27 | 孙松华 | 一种无氰铜锡合金电镀液及其制备方法 |
| CN103882486A (zh) * | 2014-03-10 | 2014-06-25 | 苏州捷德瑞精密机械有限公司 | 一种仿古青铜电镀液及其制备方法与应用 |
| CN104388988A (zh) * | 2014-11-13 | 2015-03-04 | 无锡伊佩克科技有限公司 | 一种导电导热电镀液及其制备方法 |
| CN104550938A (zh) * | 2015-02-04 | 2015-04-29 | 湖南师范大学 | 一种纳米片状Cu-Sn-P合金及制备方法 |
| CN105256346B (zh) * | 2015-11-25 | 2018-01-02 | 武汉奥邦表面技术有限公司 | 一种无氰四元合金镀液 |
| CN106676594A (zh) * | 2016-06-10 | 2017-05-17 | 太原工业学院 | 一种低成本无氰电镀铜锌锡合金溶液及其电镀铜锌锡合金工艺 |
| CN107383870A (zh) * | 2017-06-23 | 2017-11-24 | 苏州艾酷玛赫设备制造有限公司 | 一种模具的制造方法 |
| CN110592627B (zh) * | 2019-10-31 | 2021-04-06 | 四川轻化工大学 | 一种无氰仿金电镀液及其镁合金电镀工艺 |
-
1986
- 1986-07-11 CN CN86105831.3A patent/CN1004010B/zh not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CN86105831A (zh) | 1988-02-24 |
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