CN1127582C - 金属材料表面化学镀镍再套镀硬铬的方法 - Google Patents

金属材料表面化学镀镍再套镀硬铬的方法 Download PDF

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CN1127582C
CN1127582C CN 98118000 CN98118000A CN1127582C CN 1127582 C CN1127582 C CN 1127582C CN 98118000 CN98118000 CN 98118000 CN 98118000 A CN98118000 A CN 98118000A CN 1127582 C CN1127582 C CN 1127582C
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nickel
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王海林
何庆琳
郭庆春
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Central Iron and Steel Research Institute
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    • 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
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    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
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    • 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
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    • 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
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    • 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
    • C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
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    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
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    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/04—Electroplating: Baths therefor from solutions of chromium
    • C25D3/06—Electroplating: Baths therefor from solutions of chromium from solutions of trivalent chromium

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Abstract

本发明属于金属材料表面处理领域。本发明是关于金属材料表面化学镀镍再套镀硬铬的方法，首先将材料表面清洗干净，然后在其表面进行化学镀镍，镀液的成分包括硫酸镍、次亚磷酸钠、有机络合物、缓冲剂、加速剂、添加剂、表面活性剂和稳定剂。镀镍层经清洗后，再在其上电镀硬铬，其镀液的化学成分包括铬酸、硫酸、三价铬、稀土添加剂。之后，在其表面即获得镀镍层和镀铬层。该套镀层具有优异的耐蚀性和较高的抗磨损性能。

Description

金属材料表面化学镀镍再套镀硬铬的方法
本发明属于金属材料表面处理领域。主要适用于金属材料表面防腐蚀和耐磨损的保护镀层。
金属材料表面进行电镀硬铬，获得硬铬镀层，已得到了相当广泛的应用，因为硬铬镀层的表面摩擦系数低，并且存在自愈合作用的氧化物(Cr2O3)表面膜，故抗磨损性能优异。化学镀镍是近十几年发展起来的新兴表面处理技术，其特点是镀层具有优良的耐蚀性和较好抗磨损性能，尤其在某些腐蚀环境中，其耐磨损性能优于硬铬镀层，为此，有人提出化学镀镍层可取代电镀硬铬镀层(《Metal finishing》1989，87(10)，P21-25；《世界机电技术》1990，NO4，P27-29)。然而，在许多非润滑性的干磨损环境中，硬铬镀层的抗磨损性能远优于化学镀镍层。Taber磨损试验表明，化学镀镍层经热处理后的磨损指数为8-12，而硬铬镀层磨损指数只为0.6-2。由此可见，两种镀层各有优点，不能完全取代。同时，也可看出，各自也存在不足之处，如硬铬镀层在一些环境中，抗腐蚀性能不足，而化学镀镍层在非润滑性系统中，抗磨损性能远不如硬铬镀层。在现有技术，未发现金属材料表面化学镀镍再套镀硬铬的报道。
本发明的目的在于镀层既有优异的耐蚀性能，又有优良抗磨损性能的金属材料表面化学镀镍再套镀硬铬的方法。
针对上述目的，本发明先在金属材料表面进行化学镀镍，之后，再在镀镍层上电镀硬铬层，获得双层镀层，该方法的具体工艺步骤如下：
(1)首先对金属材料表面进行清洗和活化
表面清洗采用常规方法进行，首先化学除油，水洗，再阴极除油，经水洗后进行活化，随后水洗、去离子水水洗。
(2)化学镀镍
金属材料表面经清理和活化后进行化学镀镍，
化学镀镍的镀液成分为：硫酸镍20-30g/L，次亚磷酸钠20-35g/L，有机络合剂25-40g/L，缓冲剂10-20g/L，加速剂5-10g/L，添加剂P1-3g/L，表面活性剂10-200ppm，稳定剂2-20ppm；
镀液的溶剂为去离子水或蒸馏水；
镀液的PH值为；4.5-5.5；
化学镀镍温度为：82-95℃；
上述镀液成分中：
有机络合剂为柠檬酸、乳酸、羟基乙酸、氨基酸中任一种或任两种之和。有机络合剂的加入是为了络合镍离子，不使之沉淀析出。
缓冲剂为醋酸或醋酸钠中任一种，它的加入是为了稳定镀液的PH值，防止PH值下降过快，导致镀速大幅度下降。
加速剂为苹果酸、丙酸、琥铂酸、丙二酸中任一种或任两种之和。加入加速剂的目的是促进化学镀的反应速度。
添加剂P为糖精、烯丙基磺酸钠中任一种。它的加入是为了使镍层具有压应力，增强与基体的结合力。
表面活性剂为十二烷基硫酸钠。其加入目的是减小溶液的表面张力，使反应产生的氢气尽快逸出，减少镀层孔隙，提高耐蚀性。
稳定剂为醋酸铅、碘酸钠、钼酸钠、硫脲中任一种或任两种之和。它的加入是为了提高化学镀液的稳定性，防止分解。
化学镀镍层的厚度要求在15μm以上，保证镀层有足够的耐蚀性。
(3)电镀硬铬
化学镀镍完成，在基体表面获取镀镍层之后，经水洗和去离子水清洗，进行电镀硬铬，
电镀硬铬的镀液化学成分为：铬酸130-150g/L，硫酸0.5-0.8g/L，三价铬1-2g/L，稀土添加剂1.5-3.0g/L；
电镀硬铬温度为50-55℃；
电流密度为40-45A/dm2。
上述成分中，稀土添加剂为硝酸铈铵、硫酸镧、硫酸钍中任一种或任两种之和。它的加入目的是为了提高电流效率，减少腐蚀。
电镀硬铬层的厚度可根据实际需要确定。
电镀硬铬层之后，经水洗、干燥，即完成本发明所述方法的全过程，在金属材料表面获得两种镀层，即化学镀镍层和电镀硬铬层。
与现有技术相比，本发明具有如下优点：
(1)与单一化学镀镍镀层相比，不仅具有相同较高的耐蚀性，而且有更强的抗磨损性能。
(2)与单一电镀硬铬层相比，不仅具有相同的抗磨损性能，而且具有更优异的耐蚀性能。
即本发明所述的镀层既有优异的耐蚀性，又有较高的抗磨损性能。
(3)本发明所述镀层，比单一的化学镀镍层和单一的电镀硬铬层有着更为广泛的应用范围，更适用于既要求有优异的耐蚀性，又要求较高抗磨损性能的环境。
实施例
采用本发明所述的金属材料表面化学镀镍套镀硬铬的方法，在三种不同的基体材料表面首先进行了化学镀镍，然后再在其上进行电镀硬铬，化学元素镀镍前，材料表面进行清理和活化，化学镀镍后也进行清洗。
化学镀镍所采用镀液的化学成分及工艺参数如表1所示。电镀硬铬所采用的电镀液化学成分及工艺参数如表2所示。化学镀镍和电镀硬铬完成之后，对这种套镀层分别进行了盐雾试验(按标准ASTM117进行)和磨损试验。磨损试验按Taber试验法进行(CS-10，负载1000g/轮，时间10000转)。试验结果列入表3。
为了对比，在相同的金属材料表面进行单一化学镀镍镀层和单一电镀硬铬镀层的试验，所获单一镀层也在同样条件下，进行相同的盐雾试验和磨损试验。有关参数也列入表1、表2中和表3中。其中，对比例4为单一化学镀镍，对比例5单一电镀硬铬。
另外，单一的化学镀镍镀层还单独进行了400℃保温1小时的热处理。
表1实施例及对比例4化学镀镍的镀液化学成分及工艺参数
表2实施例及对比例5电镀硬铬层的镀液化学成分及工艺参数
Figure C9811800000072
表3实施例和对比例镀层的性能试验结果
批号项目 实施例  对比例
1  2  3  4  5
硬度(Hv100) 1100  1100  1100  850  1100
盐雾试验的耐盐雾性hr ＞1000  ＞1000  ＞1000  ＞1000  ＜24
磨损试验 重量损失mg/10千转 8.64  8.8  8.7  96.2  9.3
Taber指数 0.86  0.91  0.87  9.62  0.93

Claims (7)

1、一种金属材料表面化学镀镍再套镀硬铬的方法，其特征在于该方法包括如下具体工艺步骤：
(1)首先采用常规方法对金属材料表面进行清洗和活化；
(2)化学镀镍
金属材料表面经清理和活化后进行化学镀镍，
化学镀镍的镀液成分为：硫酸镍20-30g/L，次亚磷酸钠20-35g/L，有机络合剂25-40g/L，缓冲剂10-20g/L，加速剂5-10g/L，添加剂P1-3g/L，表面活性剂10-200ppm，稳定剂2-20ppm；
镀液的溶剂为去离子水或蒸馏水；
镀液的PH值为：4.5-5.5；
化学镀镍温度为：82-95℃；
(3)电镀硬铬
化学镀镍完成，在基体表面获取镀镍层之后，经水洗和去离子水清洗，进行电镀硬铬；
电镀硬铬的镀液化学成分为：铬酸130-150g/L，硫酸0.5-0.8g/L，三价铬1-2g/L，稀土添加剂1.5-3.0g/L；
电镀温度为50-55℃；
电流密度为40-45A/dm2；
(4)添加剂P为糖精、烯丙基磺酸钠中任一种。
2、根据权利要求1所述的方法，其特征在于有机络合剂为柠檬酸、乳酸、羟基乙酸、氨基酸中任一种或任两种之和。
3、根据权利要求1所述的方法，其特征在于缓冲剂为醋酸或醋酸钠中任一种。
4、根据权利要求1所述的方法，其特征在于加速剂为苹果酸、丙酸、琥珀酸、丙二酸中任一种或任两种之和。
5、根据权利要求1所述的方法，其特征在于表面活性剂为十二烷基硫酸钠。
6、根据权利要求1所述的方法，其特征在于稳定剂为醋酸铅、碘酸钠、钼酸钠、硫脲中任一种或任两种之和。
7、根据权利要求1所述的方法，其特征在于稀土添加剂为硝酸铈铵、硫酸镧、硫酸钍中任一种或任两种之和。
CN 98118000 1998-12-24 1998-12-24 金属材料表面化学镀镍再套镀硬铬的方法 Expired - Fee Related CN1127582C (zh)

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