CN1039450A - 含亚乙基硫脲、可镀得具耐磨性镀层的无电镀镍-硼溶液组合物 - Google Patents
含亚乙基硫脲、可镀得具耐磨性镀层的无电镀镍-硼溶液组合物 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
Abstract
一种可镀得含硼的镍镀层的无电镀溶液组合物。组合物中包括水溶性镍盐、螯合剂、碱金属氢氧化物、含硼的还原剂和亚乙基硫脲。该组合物尤其适于在燃气轮机部件上覆镀具改良的耐磨性的镀层。
Description
本发明涉及一种无电镀溶液组合物,尤其是涉及镍-硼无电镀溶液组合物。
已知可应用无电镀镍-硼溶液组合物,在各种需耐磨性的基质上覆镀硬质、耐磨的镀层。鉴于对环境污染的重视,无电镀溶液组合物的毒性也日愈受到关注。现在应用的工艺中,应用了例如铊一类物质以稳定无电镀溶液组合物。然而,由于含铊组合物的毒性,造成其排放的难题。另一方面来看,在该无电镀溶液组合物中的铊的应用确实可以使镀层具良好耐磨性。
应用硫脲代替铊的溶液组合物是已知的,这为解决毒性问题提供一种途径。同时应用含硫脲的组合物所得镀层的性质可与应用含铊的组合物所得镀层相媲美。在本技术领域内,人们仍致力研究可镀得具良好性能,如具改良耐磨性镀层的溶液组合物。
本发明公开了一种无电镀镍-硼层的溶液组合物,该组合物中包括碱金属氢氧化物、水溶性镍盐、螯合剂、含硼还原剂和亚乙基硫脲。这种组合物除了不含铊之外,比较其它镀液组合物,可镀得更好镀层,如具改良的光泽性、密度和耐磨性等。
本发明另一方面涉及到应用上述溶液组合物对基质进行无电镀的方法。其中将含镍盐、螯合剂和碱金属氢氧化物的溶液加热至185-215°F。加热之后,在欲镀工件存在的情况下,将亚乙基硫脲和含硼还原剂加入到该起始溶液中。然后将欲镀工件浸于溶液中。在整个无电镀过程中,镍盐、含硼还原剂、亚乙基硫脲和碱金属氢氧化物等的浓度,pH值等都需保持稳定。将工件由镀液中取出后,工件可镀上具改良的耐磨性的镍-硼镀层。
对本发明的上述特点和其它优点,可通过下述说明加以阐明。
本发明镀液组合物中的碱金属氢氧化物一般优选用氢氧化钠或氢氧化钾。其用量应足以使pH值达12-14,较好是13-14,最好是13.7-14。碱金属氢氧化物有助于保持镀液的稳定性,如保持氢硼化物稳定性;和保持整个无电镀过程中基质的活性(有利于无电镀过程和镀层之结合性能)。
水溶性镍盐用于提供镀液中的镍。镍盐优选用氨基磺酸镍。其它可应用的镍化合物是氯化镍、硫酸镍、硫酸镍铵、乙酸镍、甲酸镍和其它水溶性镍盐。含镍组分的浓度最好约0.09摩尔/升,但其浓度也可以是0.01-0.15摩尔/升。
镀液中镍盐含量很大程度上取决于存在于镀液中的螯合剂浓度。螯合剂优选用1,2-乙二胺。其它可用的螯合剂是二亚乙基三胺、三亚乙基四胺、乙二胺四乙酸盐和二亚乙基三胺五乙酸盐。镀液中螯合剂用量取决于镀液中镍含量。一般说来,螯合剂对镍浓度的摩尔比是4/1至12/1,较好是7/1至9/1,而最好是8/1至8.5/1,目标是8.25/1。该摩尔比以及各活性组分的浓度可通过常规的色谱分析和滴定分析来监测。
含硼还原剂可向催化剂表面提供电子以还原镀液中的络合镍阳离子,并且可提供镀层中的硼成分。优选的含硼化合物是氢硼化钠,其它可用的含硼化合物是氢硼化钾、四烷基氢硼化铵、烷基胺硼烷和四苯基氢硼化物等。氢硼化物一般浓度是0.002-0.052摩尔/升,较好是0.002-0.026摩尔/升,而最好是约0.010摩尔/升。
亚乙基硫脲组分对镀液有稳定作用。一般含量为0.1ppm(百万分之一)-10ppm(0.098-9.8×10-5摩尔/升),较好是0.5ppm-4ppm(0.49-3.9×10-5摩尔/升),而最好是0.7ppm-2.5ppm(0.6873-2.455×10-5摩尔/升)。
本发明组合物一般是通过将镍盐、螯合剂和碱金属氢氧化物混溶而制得。然后将溶液加热到185-215°F。随后加入亚乙基硫脲和含硼还原剂。再将欲镀工件浸于溶液中。在无电镀过程中需使各组分浓度、pH值和温度保持稳定。按理温度不应太低,以致使镍无法镀上;但也不应太高,以致使镀液不稳定而产生硼化镍颗粒沉淀。一般适用温度是190-210°F,较好是193-197°F,而最好是195-196°F。
沉积速率在0.0001至0.0005英寸厚度/小时之间变化,它取决于各组分(尤其是含硼还原剂,亚乙基硫脲)浓度的保持情况和温度的保持情况。一般所需的镀层是0.75-1.5密耳厚的硼化镍。可沉积极薄镀层,而高达5密耳厚的镀层也曾镀得。事实上,本发明组合物和方法的另一个优点是所得镀层的低内应力,这样可沉积较厚的镀层而不致超越镀层和基质之结合力所允许限度。因而可沉积更厚镀层(如厚度达50密耳)。对于某些合金(如铜合金),厚度仅为0.1密耳也可接受。而较薄镀层所产生的问题是,当进行热处理时,硼可扩散到基质中,这样降低了生成硼化镍的程度,从而造成耐磨性的降低。
在各组分浓度保持恒定情况下,镀层厚度将取决于基质在镀液中停留时间,并且也取决于保持的温度范围。虽然任何金属基质皆可用本发明方法进行覆镀,但尤其适用于钛、钢质、镍和铜(应指出当列举出金属材料时,也应包括该金属的合金)。其它金属如镁和铝,如果将其预先镀上一薄层或经触击覆镀(如经锌酸盐类浸镀,再经铜触击电镀或任用镍触击电镀),以避免在高pH值下金属受浸蚀,那么它们也可用本发明方法进行覆镀。本发明方法尤其适用于那些易遭磨损的基体。对于各种轻质金属如钛、铝和镁来说,可通过本发明方法使其具有改良的耐磨性,这也是一个优点。本发明方法特别适用于燃气轮机部件的覆镀。应提出的是本发明镀液组合物也可应用于塑料基体(如聚酰胺、聚丙烯酸酯、尼龙、聚乙烯、聚丙烯等)。对于塑料基体需要预先应用敏化溶液进行处理,使塑料质经催化。通过表面催化作用,可使电子由还原剂转移至塑料表面,且再由塑料表面转移而使镍还原。在本技术领域中,常规的敏化处理是先用氯化锡溶液处理塑料基体表面,然后经氯化钯溶液处理。
实施例
36升纯水与2.8升1,2-乙二胺混合。另将1.74公斤氨基磺酸镍四水合物和2.6公斤氢氧化钠加入该溶液中,随后再加足量水使成56升溶液(A溶液)。将0.1022克亚乙基硫脲溶于足量水中使成4升溶液(B溶液)。800克氢氧化钠和160克氢硼化钠溶于足量水中使成4升溶液(C溶液)。320克氨基磺酸镍,300毫升1,2-乙二胺和10克氢氧化钠溶于足量水中使成2升溶液(D溶液)。
在15加仑的聚丙烯和聚四氟乙烯电镀设备中制备A溶液,该设备中还装置循环泵和过滤系统。应用带聚四氟乙烯套的浸入式加热器和温度感应器将溶液温度控制在195°F±2°F。通过磁偶合的变速齿轮泵,由各储槽将B、C和D溶液连续地加入,加入量是根据离子和高效液相色谱分析来控制。通过间断加入浓氢氧化钠溶液(5摩尔),使pH值保持在13.7(或更高)。
将5片AMS 5508试样(Greek ASCOLOY),其总表面积80平方英寸,和3片Inconel 718磨损试样,其总表面积14平方英寸,经过蒸汽喷射。在50%(体积)盐酸溶液中活化,并经过覆镀薄镍层(镀液含盐酸和氯化镍),水洗,并移入镍-硼镀液中。覆镀时,溶液化学组成保持如下:镍阳离子(Ni+2)5600ppm-6400ppm(0.095-0.109摩尔/升之氨基磺酸镍四水合物);1,2-乙二胺47000-53000ppm(0.782-0.883摩尔/升);氢硼化物阴离子(BH-1 4)125-177ppm(8.46-11.90×10-3摩尔/升氢硼化钠);亚乙基硫脲1.1-1.6ppm(1.08-1.57×10-5摩尔/升)。
试样的无电镀过程持续9小时,然后将其经过水洗,干燥和于675°F温度下热处理90分钟。所镀得的镍-硼镀层厚度为0.002英寸,最低硬度1000HV(维氏硬度)。所镀得镀层含无定形镍、硼组成。经随后的热处理生成一种硼化镍细微粒分散于镍基体中的镀层,因此与未经热处理镀层比较,其耐磨性较优。
最好应用自动化的分析/镀液补充系统使镀液进行操作,这种系统可与带高效液相和离子色谱仪的电脑控制镀液补充反馈系统相结合。
按本发明方法,经覆镀工件不仅有良好光泽,而且具较高密度和改良的耐磨性。此外值得提出的是镀液组合物中不含铊。因镀液中不含铊,可大大降低对电镀工作人员的毒性危害。此外因镀液不含铊,因此在有毒物排放和处理方面也较简便。
虽然通过详尽描述优选实施例来说明本发明,但应理解的是,在本发明实质内容和要求保护范围内,本专业领域技术人员可对其进行各种形式和具体的修改。
Claims (14)
1、一种无电镀镍-硼的溶液组合物,主要包括水溶性镍盐,螯合剂,碱金属氢氧化物,含硼的还原剂及浓度是0.098×10-5-9.8×10-5摩尔/升的亚乙基硫脲。
2、按权利要求1的组合物,其中碱金属氢氧化物是氢氧化钠或氢氧化钾,其浓度足以使pH值为12-14。
3、按权利要求1的组合物,其中水溶性镍盐是氨基磺酸镍,其浓度是0.01-0.15摩尔/升。
4、按权利要求1的组合物,其中螯合剂是1,2-乙二胺,并且螯合剂与镍盐的摩尔浓度比是4/l-12/l。
5、按权利要求1的组合物,其中亚乙基硫脲的浓度是0.49×10-5-3.9×10-5摩尔/升。
6、按权利要求1的组合物,其中含硼还原剂是氢硼化钠,其浓度是0.002-0.052摩尔/升。
7、在基质上进行无电镀镍-硼镀层的方法,包括以下步骤:混和水溶性镍盐、螯合剂、碱金属氢氧化物、含硼还原剂和浓度为0.098×10-5-9.8×10-5摩尔/升的亚乙基硫脲;加热该溶液至185-215°F;将基质浸于溶液中;由溶液中移出已镀覆的基质,结果可在基质上镀覆具有改良耐磨性的镍硼镀层。
8、按权利要求7的方法,其中包括在整个无电镀过程中,保持溶液各组分浓度和温度恒定。
9、按权利要求7的方法,其中碱金属氢氧化物是氢氧化钠或氢氧化钾,其含量足以使pH值为12-14。
10、按权利要求7的方法,其中水溶性镍盐是氨基磺酸镍,其浓度是0.01-0.15摩尔/升。
11、按权利要求7的方法,其中螯合剂是1,2-乙二胺,并且螯合剂与镍盐的摩尔浓度比是4/l-12/l。
12、按权利要求7的方法,其中亚乙基硫脲的浓度是0.49×10-5-3.9×10-5摩尔/升。
13、按权利要求7的方法,其中基质包括钛、钢质、镍、铜、铝或镁。
14、按权利要求7的方法,其中镀层厚度至少是0.1密耳。
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US07/204,311 US4983428A (en) | 1988-06-09 | 1988-06-09 | Ethylenethiourea wear resistant electroless nickel-boron coating compositions |
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US3782978A (en) * | 1971-07-06 | 1974-01-01 | Shipley Co | Electroless nickel plating |
US3738849A (en) * | 1971-12-22 | 1973-06-12 | Du Pont | Chemical plating solutions |
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US4019910A (en) * | 1974-05-24 | 1977-04-26 | The Richardson Chemical Company | Electroless nickel polyalloy plating baths |
US4309454A (en) * | 1974-10-04 | 1982-01-05 | Nathan Feldstein | Colloidal compositions for electroless deposition stabilized by thiourea |
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US3943168A (en) * | 1974-11-13 | 1976-03-09 | E. I. Du Pont De Nemours And Company | Conductor compositions comprising nickel borides |
US4152164A (en) * | 1976-04-26 | 1979-05-01 | Michael Gulla | Electroless nickel plating |
IT1070268B (it) * | 1976-10-19 | 1985-03-29 | Alfachimici Spa | Composizione per la deposizione anelettrica di leghe a base di nichelio |
US4328266A (en) * | 1977-06-06 | 1982-05-04 | Surface Technology, Inc. | Method for rendering non-platable substrates platable |
US4169171A (en) * | 1977-11-07 | 1979-09-25 | Harold Narcus | Bright electroless plating process and plated articles produced thereby |
US4368223A (en) * | 1981-06-01 | 1983-01-11 | Asahi Glass Company, Ltd. | Process for preparing nickel layer |
US4407869A (en) * | 1981-08-24 | 1983-10-04 | Richardson Chemical Company | Controlling boron content of electroless nickel-boron deposits |
US4484988A (en) * | 1981-12-09 | 1984-11-27 | Richmond Metal Finishers, Inc. | Process for providing metallic articles and the like with wear-resistant coatings |
DE3404270A1 (de) * | 1984-02-04 | 1985-08-08 | Schering AG, 1000 Berlin und 4709 Bergkamen | Waessriges alkalisches bad zur chemischen abscheidung von kupfer, nickel, kobalt und deren legierungen |
AU555641B2 (en) * | 1984-03-05 | 1986-10-02 | Omi International Corp. | Aqueous electroless nickel plating bath |
-
1988
- 1988-06-09 US US07/204,311 patent/US4983428A/en not_active Expired - Lifetime
-
1989
- 1989-06-01 EP EP89630101A patent/EP0346265B1/en not_active Expired - Lifetime
- 1989-06-01 DE DE8989630101T patent/DE68902192T2/de not_active Expired - Fee Related
- 1989-06-01 DE DE198989630101T patent/DE346265T1/de active Pending
- 1989-06-06 CN CN89103641A patent/CN1033867C/zh not_active Expired - Fee Related
- 1989-06-09 JP JP1148250A patent/JPH0243371A/ja active Pending
-
1992
- 1992-12-09 SG SG1253/92A patent/SG125392G/en unknown
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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CN100412232C (zh) * | 2006-01-13 | 2008-08-20 | 厦门大学 | 镁合金表面化学镀镍硼合金的方法 |
CN100402699C (zh) * | 2006-03-15 | 2008-07-16 | 厦门大学 | 一种镁合金表面化学镀镍硼合金的方法 |
CN103221579A (zh) * | 2010-10-13 | 2013-07-24 | 温莎大学 | 利用强碱镀浴进行金属无电沉积的方法 |
CN103221579B (zh) * | 2010-10-13 | 2015-04-29 | 温莎大学 | 利用强碱镀浴进行金属无电沉积的方法 |
CN104152876A (zh) * | 2014-08-06 | 2014-11-19 | 宁波华斯特林电机制造有限公司 | 一种气缸套筒内壁形成镍硼镀层的方法以及包括该镍硼镀层的气缸套筒 |
Also Published As
Publication number | Publication date |
---|---|
CN1033867C (zh) | 1997-01-22 |
DE68902192T2 (de) | 1992-12-17 |
EP0346265A1 (en) | 1989-12-13 |
US4983428A (en) | 1991-01-08 |
DE346265T1 (de) | 1990-05-03 |
SG125392G (en) | 1993-02-19 |
DE68902192D1 (de) | 1992-08-27 |
JPH0243371A (ja) | 1990-02-13 |
EP0346265B1 (en) | 1992-07-22 |
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