CN1311830A - 碱性锌镍镀浴 - Google Patents
碱性锌镍镀浴 Download PDFInfo
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- CN1311830A CN1311830A CN99809138A CN99809138A CN1311830A CN 1311830 A CN1311830 A CN 1311830A CN 99809138 A CN99809138 A CN 99809138A CN 99809138 A CN99809138 A CN 99809138A CN 1311830 A CN1311830 A CN 1311830A
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- anode
- nickel
- bath
- plating bath
- zinc
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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
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/02—Tanks; Installations therefor
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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
- C25D3/565—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of zinc
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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
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/12—Process control or regulation
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Automation & Control Theory (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Electrolytic Production Of Metals (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
为了避免不希望的副反应,建议在一个碱性锌-镍电镀浴中使阳极与碱性电解质分开。
Description
本发明涉及一种产生锌-镍镀层的、具有一个阴极、一个阳极和一种碱性电解溶液的电镀浴。
已知,为了改善其耐腐蚀性,可在导电性物质上镀覆上锌-镍合金。为此,通常采用一种酸性电解质电镀液,例如带硫酸盐、氯化物、Fluoropromat或氨基磺酸盐电解质的电镀液。在这样的方法中,在待覆层的材料上获得一层厚度均匀的锌-镍覆层所需的控制技术是花费昂贵的,且在实践中几乎不可能做到。
基于这个原因,在较早的时间采用在德国专利说明书3712511中公开的碱性锌-镍电镀浴液,它具有例如下列组成:
11.3 g/l ZnO
4.1 g/l NiSO4.6H2O
120 g/l NaOH
5.1 g/l 聚乙烯亚胺。
在该电镀溶液中含有的胺用作镍离子的配合物助剂,否则镍离子在碱性介质中就是不溶的。浴液的组成随制造商不同而变。
电镀浴通常用不溶的镍阳极操作、锌浓度通过添加锌、镍浓度则通过加入一种镍溶液,例如一种硫酸镍溶液而维持恒定。
在一些小时的操作之后,这些浴发生不希望的变色,即由蓝紫向棕色变化。在多天或几个星期后,这种着色变强,且可以确认该浴分成两相,其中的上层相是深棕色的。该相对工件的覆层产生显然的干扰,例如不均匀的层厚或产生小气泡。该浴的连续净化,即连续除去这种覆层表面上的浮渣(Absclpfen)是必不可少的。但这既费时又费钱。
此外,在这种操作几周后,在该浴中可发现氰化物。该氰化物的出现要求对该浴进行定期的更新,且引起一种特殊的废水处理,这导致该浴的操作费用显著增加。当废水中具有很高的有机物的浓度时这一情况就明显,且氰化物毒物的CSB-值为约15,000-20,000mg/升时,上述情况就变得严重。要遵守法律中规定的废水标准(镍0.5ppm,锌2ppm),仅只能通过大量添加化学药剂才可实现。
第二相的生成归因于胺的反应,胺在碱性溶液中、在镍阳极上转化成腈(附带也转化为氰化物)。由于胺的分解,必须向该浴中不断地加入新的配合物助剂,这使该工艺的花费高昂。
不可以采用不同于镍阳极的其它阳极,因为它们在碱性电解质中溶解,这也对覆层的质量产生不利的影响。
基于这一背景,本发明的目的是提供一种碱性锌-镍电镀浴,它提供高质量的、费用适合的锌-镍覆层。
为了达到该目的,本发明建议,通过一种离子交换膜将阳极与碱性电解溶液分隔开。
通过该分隔,避免了胺在镍阳极上的反应,其结果是,排除了不希望的副反应,副反应导致后处置问题或导致在浴中沉积下来的反应产物之上的第二相,且不利地影响到锌镍覆层的质量。该覆层所需的耗费的除浮渣过程以及浴液的更新在本发明中将是多余的。另外,覆层的质量显著改进也是另一特点。
特别有利的是,采用一种由全氟代的聚合物制得的阳离子交换膜,因为它具有可忽略的电阻,然而有高的耐化学品和机械作用的能力。
此外,消除了废水中的氰化物毒物,借此显著地简化了所有废水的净化。此外用配合物助剂补充进电解溶液也变得多余,因为配合物助剂不再分解,且它在浴中的浓度几乎保持恒定。因此,该方法的费用适宜。
在按本发明的方案中,锌-镍浴起阴极电解溶液的作用,而阳极电解溶液可采用例如硫酸或磷酸。在本发明电镀池中,用作阳极材料的有常规阳极,例如镀铂的钛阳极,因为它不再设置在锌-镍浴中。
参照附图中示出的实施方案对本发明进行详细说明。附图中,
图1表示一个按本发明的电镀浴的示意图。
图1表示了一个电镀池,它具有一个阳极2和一个阴极3,它是待覆层的工件。包围着阳极的阴极浴液4是碱性的且由一种已知组成的锌-镍电镀浴液组成,其中用于镍离子配合的助剂是胺。包围着阳极2的阳极浴液5例如可由硫酸或磷酸组成。阳极浴液5和阴极浴液4通过一个全氟代的阳离子交换膜6而相互分开。该膜6使得电流无障碍地通过该浴,但防止了阴极浴液4、尤其是其中含有的胺与阳极2接触,借此避免了在说明书开头所说的反应及其不利的效果。
Claims (4)
1.用于产生锌-镍覆层的碱性电镀浴(1),它具有一个阳极(2)和一个阴极(3),其特征在于,该阳极通过一种离子交换膜(6)与碱性电解溶液分隔开。
2.按照权利要求1的电镀浴,其特征在于,阴极(3)通过一种全氟代的阳离子交换膜(6)与碱性电解溶液(4)分隔开。
3.按照权利要求1或2的电镀浴,其特征在于,硫酸、磷酸、甲烷磺酸、氨基磺酸和/或膦酸用作阳极电解浴液(5)。
4.按照权利要求1-3之一的电镀浴,其特征在于,它使用一种镀铂的钛阳极。
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19834353A DE19834353C2 (de) | 1998-07-30 | 1998-07-30 | Alkalisches Zink-Nickelbad |
DE19834353.1 | 1998-07-30 |
Publications (1)
Publication Number | Publication Date |
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CN1311830A true CN1311830A (zh) | 2001-09-05 |
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Application Number | Title | Priority Date | Filing Date |
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CN99809138A Pending CN1311830A (zh) | 1998-07-30 | 1999-07-29 | 碱性锌镍镀浴 |
Country Status (22)
Country | Link |
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US (4) | US6602394B1 (zh) |
EP (2) | EP1344850B1 (zh) |
JP (2) | JP4716568B2 (zh) |
KR (1) | KR20010071074A (zh) |
CN (1) | CN1311830A (zh) |
AT (2) | ATE346180T1 (zh) |
AU (1) | AU5415299A (zh) |
BG (1) | BG105184A (zh) |
BR (1) | BR9912589A (zh) |
CA (1) | CA2339144A1 (zh) |
CZ (1) | CZ298904B6 (zh) |
DE (3) | DE19834353C2 (zh) |
EE (1) | EE200100059A (zh) |
ES (2) | ES2201759T3 (zh) |
HR (1) | HRP20010044B1 (zh) |
HU (1) | HUP0103951A3 (zh) |
IL (1) | IL141086A0 (zh) |
MX (1) | MXPA01000932A (zh) |
PL (1) | PL198149B1 (zh) |
SK (1) | SK285453B6 (zh) |
TR (1) | TR200100232T2 (zh) |
WO (1) | WO2000006807A2 (zh) |
Cited By (6)
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CN103849915A (zh) * | 2012-12-06 | 2014-06-11 | 北大方正集团有限公司 | 电镀装置和pcb板导通孔镀铜的方法 |
CN103911650A (zh) * | 2014-04-02 | 2014-07-09 | 广东达志环保科技股份有限公司 | 一种应用于碱性锌镍合金电镀的阳极 |
CN104911651A (zh) * | 2005-04-26 | 2015-09-16 | 德国艾托科技公司 | 具有滤过膜的碱性电镀浴 |
CN106987879A (zh) * | 2016-11-23 | 2017-07-28 | 瑞尔太阳能投资有限公司 | 电沉积装置及其电沉积方法 |
CN113383118A (zh) * | 2019-01-24 | 2021-09-10 | 德国艾托特克公司 | 用于电解锌-镍合金沉积的膜阳极*** |
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- 1999-07-29 KR KR1020017001285A patent/KR20010071074A/ko not_active Application Discontinuation
- 1999-07-29 CZ CZ20010189A patent/CZ298904B6/cs not_active IP Right Cessation
- 1999-07-29 ES ES99940077T patent/ES2201759T3/es not_active Expired - Lifetime
- 1999-07-29 EP EP03003890A patent/EP1344850B1/de not_active Expired - Lifetime
- 1999-07-29 EP EP99940077A patent/EP1102875B1/de not_active Revoked
- 1999-07-29 AU AU54152/99A patent/AU5415299A/en not_active Abandoned
- 1999-07-29 AT AT03003890T patent/ATE346180T1/de active
- 1999-07-29 AT AT99940077T patent/ATE242821T1/de active
- 1999-07-29 WO PCT/EP1999/005443 patent/WO2000006807A2/de active IP Right Grant
- 1999-07-29 ES ES03003890T patent/ES2277624T3/es not_active Expired - Lifetime
- 1999-07-29 TR TR2001/00232T patent/TR200100232T2/xx unknown
- 1999-07-29 BR BR9912589-7A patent/BR9912589A/pt not_active Application Discontinuation
- 1999-07-29 CA CA002339144A patent/CA2339144A1/en not_active Abandoned
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- 1999-07-29 JP JP2000562585A patent/JP4716568B2/ja not_active Expired - Lifetime
- 1999-07-29 SK SK89-2001A patent/SK285453B6/sk not_active IP Right Cessation
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- 1999-07-29 DE DE59914011T patent/DE59914011D1/de not_active Expired - Lifetime
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- 1999-07-29 HU HU0103951A patent/HUP0103951A3/hu unknown
- 1999-07-29 CN CN99809138A patent/CN1311830A/zh active Pending
- 1999-07-29 DE DE59905937T patent/DE59905937D1/de not_active Expired - Lifetime
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2001
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- 2001-01-25 BG BG105184A patent/BG105184A/xx unknown
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2003
- 2003-07-11 US US10/618,352 patent/US20040104123A1/en not_active Abandoned
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CN104911651A (zh) * | 2005-04-26 | 2015-09-16 | 德国艾托科技公司 | 具有滤过膜的碱性电镀浴 |
CN104911676A (zh) * | 2005-04-26 | 2015-09-16 | 德国艾托科技公司 | 具有滤过膜的碱性电镀浴 |
CN104911676B (zh) * | 2005-04-26 | 2017-11-17 | 德国艾托科技公司 | 具有滤过膜的碱性电镀浴 |
TWI384094B (zh) * | 2008-02-01 | 2013-02-01 | Zhen Ding Technology Co Ltd | 電鍍用陽極裝置及包括該陽極裝置之電鍍裝置 |
CN103849915A (zh) * | 2012-12-06 | 2014-06-11 | 北大方正集团有限公司 | 电镀装置和pcb板导通孔镀铜的方法 |
CN103849915B (zh) * | 2012-12-06 | 2016-08-31 | 北大方正集团有限公司 | 电镀装置和pcb板导通孔镀铜的方法 |
CN103911650A (zh) * | 2014-04-02 | 2014-07-09 | 广东达志环保科技股份有限公司 | 一种应用于碱性锌镍合金电镀的阳极 |
CN103911650B (zh) * | 2014-04-02 | 2016-07-06 | 广东达志环保科技股份有限公司 | 一种应用于碱性锌镍合金电镀的阳极 |
CN106987879A (zh) * | 2016-11-23 | 2017-07-28 | 瑞尔太阳能投资有限公司 | 电沉积装置及其电沉积方法 |
CN113383118A (zh) * | 2019-01-24 | 2021-09-10 | 德国艾托特克公司 | 用于电解锌-镍合金沉积的膜阳极*** |
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