CN103492610A - 化学镀液组合物和镀覆颗粒物的方法 - Google Patents

化学镀液组合物和镀覆颗粒物的方法 Download PDF

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CN103492610A
CN103492610A CN201280005227.4A CN201280005227A CN103492610A CN 103492610 A CN103492610 A CN 103492610A CN 201280005227 A CN201280005227 A CN 201280005227A CN 103492610 A CN103492610 A CN 103492610A
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S·E·小佩尼克
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Abstract

提供用于镀覆颗粒物的化学镀液组合物。所述镀液组合物包含含金属组分和还原组分。所述颗粒物通过化学金属沉积镀覆至少一层包含至少两种金属的金属层，以提供具有改善的耐磨性能的切削和打磨工具。

Description

化学镀液组合物和镀覆颗粒物的方法
相关申请的交叉引用
该专利申请要求申请日为2011年1月11日的美国临时专利申请61/431,675号的权益，其公开内容通过引用明确并入本文。
技术领域
本发明涉及化学镀液组合物。更特别地，本发明涉及化学镀镍的镀液组合物，以及使用所述组合物在颗粒物上镀覆包含至少两种金属的金属层。
背景技术
物体的化学涂层的是公知的。本领域还所公知的是，金属层的镀覆能提高切削工具和研磨工具的基质中的金刚石颗粒的留存(retention)，切削工具例如用于锯石头和水泥的工具，研磨工具例如金属结合砂轮。金属镀覆的颗粒材料(包括天然的或者人造的金刚石)是市售的，具有一般通过化学沉积法施涂的镍涂层。由于这种镀覆的颗粒材料具有良好的性能，因此需要加以改进以降低粒子的过早损失和降低切削工具的磨损。
已知通过化学沉积施涂的镀覆金属层化学结合到颗粒物的表面，能更强力地粘附到颗粒物表面并在其上形成金属层的其它金属包括钼、钛和铬。这些金属能够形成碳化物且通常经化学气相沉积或者溅射至颗粒表面。
这些能形成碳化物的金属层已经用作金刚石颗粒上的多层涂层的一部分，以有助于提高其在工具基质中的留存。该合金层可以被另一层覆盖，例如通过化学沉积或电解沉积的镍。该合金包含至多30wt％的所述碳化物形成金属，以形成碳化物，在通过真空蒸发或溅射沉积后，在高温下加热该涂层。这些施涂多层涂层的工序复杂性在于，或者是金属合金作为其中一层施涂，或者是采用三个独立涂层。而且，这些工序通过金属涂层的渗碳提供了增强的金刚石颗粒与工具基质之间的粘结强度，在渗碳过程中金刚石颗粒被暴露于高温。高温会导致金刚石晶体劣化(degradation)，这对于切削工具的性能是有害的。
尽管本领域现有的状态如本文所述，仍然需要化学镀液组合物来通过简单的方法在颗粒物上镀覆至少一层金属层，其有助于颗粒物在切削和研磨工具基质内的留存和提高工具耐磨性能。
发明内容
总体而言，本发明一方面提供了用于镀覆颗粒物表面的化学镍镀液组合物。所述镀液包含含金属组分，其中所述含金属组分包含镍盐，选自钙盐、镁盐、锶盐和钡盐的至少一种金属盐，螯合剂和水。所述镀液还包含还原组分，其中该还原组分包含还原剂和水。
本发明另一方面提供了对颗粒物进行化学镀覆的方法。所述方法包括如下步骤：向容器中装载颗粒物，然后向含有颗粒物的容器中装载包含化学镀液组合物和活化组分的溶液。该镀液组合物包含含金属组分和还原组分，其中所述含金属组分包含镍盐，选自钙盐、镁盐、锶盐和钡盐的至少一种金属盐，螯合剂和水，且所述还原组分包含还原剂和水。该方法还包括在约60℃至约100℃的温度和约4至约13的pH值下混合镀液组合物、活化组分和颗粒物，以及在颗粒物上镀覆至少一层金属层，其中该金属层包含至少两种金属。
本发明再一方面提供了通过颗粒物的化学镀覆形成的镀覆物品。该镀覆物品包含具有确定的外表面面积的颗粒物，其中所述颗粒物选自具有至少一层金属层的天然金刚石和人造金刚石，其中所述至少一层金属层镀覆在所述颗粒物的外表面且包含镍和选自钙、镁、锶和钡的至少一种另外的金属。
本发明又一方面提供了用于切屑和研磨工具的具有改善的耐磨性能的金属镀覆的颗粒物，其包括由镍和选自钙、镁、锶和钡的至少一种另外的金属构成的金属层。
本发明另一方面提供了具有改善的耐磨性能的切屑和研磨工具，其包括金属镀覆的颗粒物，该颗粒物具有至少一层由镍和选自钙、镁、锶和钡的至少一种另外的金属构成的金属层。
附图说明
图1为依据本发明一实施方式的镀覆后的颗粒物的扫描电子显微镜图像；且
图2为依据本发明另一实施方式的镀覆后的颗粒物的扫描电子显微镜图像。
具体实施方式
在本发明的一一实施方式中，颗粒物镀覆有至少一层通过化学金属沉积法沉积的金属层，其包含镍和选自钙、镁、锶和钡的至少一种另外的金属，从而赋予切削和研磨工具改善的耐磨性能。优选地，可在颗粒物上镀覆包括多达20层或者更多层的复数层。
所述镀覆到颗粒物上的至少一层金属层通过化学镀液组合物提供，并形成了镀覆的物品。所述镀液包含含金属组分和还原组分。
所述含金属组分包含镍盐、至少一种另外的金属盐、螯合剂和水，其中所述金属盐的金属选自钙、镁、锶和钡。按含金属组分的重量计，水的量大致占约60.0％-80.0％，或者可选地占约50.0％-70.0％。在一实施方式中，镍盐选自硫酸镍、氯化镍和醋酸镍。按含金属组分的重量计，所述镍盐大致占约6.0％-12.0％重量，或者可选地占约8.0-10.0％。在另一实施方式中，所述至少一种另外的金属盐选自硫酸钙、氯化钙、醋酸钙、硫酸镁、氯化镁、醋酸镁、硫酸锶、氯化锶、醋酸锶、硫酸钡、氯化钡和醋酸钡。优选地，所述至少一种金属盐包括氯化钙、氯化镁及它们的组合。按含金属组分的重量计，该至少一种另外的金属盐大致占约3.0-18.0％重量，或者可选地占约10.0-14.O％。在另一实施方式中，所述螯合剂为醋酸，且按含金属组分的重量计，大致占约5.0％-11.0％重量，或者可选地占约7.0-9.0％。所述含金属组分还可包含苛性含金属碱，包括苛性钠，其中所述碱能够平衡该组合物的pH值，而该组合物在化学镀覆过程中存在变酸的趋势。按含金属组分的重量计，所述苛性含金属碱大致占约2.0％-8.0％重量，或者可选地占约4.0-6.0％。
所述还原组分包含还原剂和水。按还原组分的重量计，水的量大致占约50.0-70.0％重量，或者可选地占约55.0-60.0％。在一实施方式中，所述还原剂选自次磷酸钠、硼氢化钠和氢气。按还原组分的重量计，所述还原剂大致占约30.0-50.0％重量，或者可选地占约35.0-45.0％。所述还原组分还可包含金属醋酸盐，例如醋酸钠，其缓冲所述镀液组合物的pH值。按还原组分的重量计，所述金属醋酸盐大致占约0.01-0.2％重量，或者可选地占约0.05-0.1％。
在本发明中所采用的颗粒物可包括金刚石磨料颗粒。所述颗粒的尺寸为在切削工具中的常规应用的尺寸，例如20/80目(美制)。颗粒的尺寸可在约1/1500μm至约150-1000μm的范围内，甚至约200-600μm的范围内大幅变化。常规尺寸的金刚石磨料颗粒足够大以提供工具所需的切削轮廓，而且不会被所施涂的金属涂层过度稀释。
本发明所使用的金刚石磨料颗粒可以为天然或人造的，但通常通过石墨在高压高温(HP/HT)、包含或不含催化剂的条件下转化得到。优选地，所述金刚石的尺寸在约20至约80目(美制)，而且由转化工艺直接获得。然而，所采用的金刚石颗粒可从更大尺寸的材料通过常规技术经碾磨或粉碎获得。
当用于切割或研磨工具中时，经镀覆的金刚石磨料颗粒可通过常规技术浸渍(impregnate)到适合的金属基质中。例如，经镀覆的颗粒与金属颗粒的混合物可在环境温度下压制到所需形状，并加热经压制的物件以烧结其中的金属。合适的金属包括镍、钴等。例如，用于锯片的工具嵌材(tool insert)可包括30-40目大小的涂覆有铬和镍的金刚石颗粒，且通过烧结的镍、钴和/或钴/铜基质结合。这些工具嵌材可为任意形式或形状，特别是用于切削石头和水泥的工具常规采用的形状。
如下实施例阐述了化学镀液组合物的组分以及含量，还有用该化学镀液组合物镀覆颗粒物的方法。这些实施例仅构建为示意性的，并不以任何方式对其余部分的公开内容构成限制。
实施例
实施例1-化学镀液组合物
含金属组分(重量百分比)
Figure BPA0000175363150000041
还原组分(重量百分比)
50.0-70.0％  去离子水
30.0-50.0％  次磷酸钠
0.01-0.2％   醋酸钠
实施例2-化学镀液组合物
含金属组分(重量百分比)
Figure BPA0000175363150000051
还原组分(重量百分比）
55.0-65.0％  去离子水
35.0-45.0％  次磷酸钠
0.05-0.1％   醋酸钠
实施例3-化学镀液组合物
含金属组分(重量百分比)
Figure BPA0000175363150000052
还原组分（重量百分比）
50.0-70.0％  去离子水
30.0-50.0％  次磷酸钠
0.01-0.2％   醋酸钠
实施例4-化学镀液组合物
含金属组分(重量百分比）
Figure BPA0000175363150000061
还原组分(重量百分比)
55.0-65.0％  去离子水
35.0-45.0％  次磷酸钠
0.05-0.1％   醋酸钠
实施例5-化学镀液组合物
含金属组分(重量百分比)
Figure BPA0000175363150000062
还原组分(重量百分比）
50.0-70.0％  去离子水
30.0-50.0％  次磷酸钠
0.01-0.2％   醋酸钠
实施例6-化学镀液组合物
含金属组分(重量百分比）
Figure BPA0000175363150000063
还原组分(重量百分比)
55.0-65.O％  去离子水
35.0-45.0％  次磷酸钠
0.05-0.1％   醋酸钠
实施例7-颗粒物的化学镀覆
在第一化学镀覆周期中，向适用于实施颗粒物的化学镀覆的容器中装载预定量的颗粒物，然后装入温的去离子水用于预漂洗。加热包含所述颗粒物和水的容器至约60℃至约100℃的温度，优选约70℃，随后将水从容器中滗析出来。然后向容器中装入实施例1的含金属组分，随后添加活化组分，然后是还原组分。在一实施方式中，该活化组分包含钯盐如氯化钯在盐酸中的溶液，其活化所述颗粒物的非导电性的表面。该活化组分的浓度可为约2.0-10.0克钯盐/升盐酸。在一实施方式中，所述钯盐为氯化钯。在可选的实施方式中，实施例1的含金属组分和还原组分可替换为实施例2-6的含金属组分和还原组分。
随后将包含含金属组分、还原组分和活化组分的溶液搅拌10-30分钟时间，得到化学镀覆到颗粒物表面上的金属层。在第一周期的金属层镀覆后，将所得溶液从容器中移除，随后可用去离子水洗涤经镀覆的颗粒物，然后将其从容器中移除。所得的金属层包含镍和选自钙、镁、锶和钡的至少一种另外的金属。在一实施方式中，该金属层包含镍和钙。在另一实施方式中，该金属层包含镍和镁。在又一实施方式中，该金属层包含镍、钙和镁。
在向颗粒物上镀覆至少一层金属层的过程中，溶液的pH值可保持在4至13，但优选保持在6至9。而且，在向颗粒物上镀覆金属层的过程中，混合期间的反应混合物的温度可保持在约60℃至约100℃，优选约70℃。
在完成本文所述的在颗粒物上沉积第一金属层的第一周期后，可实施额外的周期以在颗粒物上镀覆另外的金属层。在一实施方式中，所述颗粒物可经受约20个周期，实现向颗粒物上镀覆20层金属层。
基于本文描述的化学镀覆方法的颗粒物镀覆，提供了如图1和图2的扫描电子显微镜图像所示的经镀覆的颗粒物。如这些图中各自所示，经镀覆的颗粒物的表面轮廓得到修饰。虽然不希望受理论所限以及参照图1和图2，认为经镀覆的颗粒物的表面轮廓的修饰为该颗粒物提供了额外的表面积。认为当沉积到适合的切削和打磨工具的表面上之后，该提高的表面面积可以改善所述经镀覆的颗粒物的留存。这进而导致所述切削和打磨工具的耐磨性能增强。
基于上文所披露内容，现在可以明了，本文描述的化学镀液组合物和采用该组合物对颗粒物进行镀覆的方法可以实现上文给出的目标。因此，应该理解，任何明显的变型均落入要求保护的本发明范围之内，因而在不脱离本文公开和描述的本发明精髓的情况下可以确定特定组成要素的选择。

Claims (24)

1.用于镀覆颗粒物的化学镀液组合物，所述镀液组合物包含含金属组分和还原组分，其中所述含金属组分包含：
镍盐；
选自钙盐、镁盐、锶盐和钡盐的至少一种金属盐；
螯合剂；和
水；且
所述还原组分包含：
还原剂；和
水。
2.权利要求1的镀液组合物，其中所述镍盐选白硫酸镍、氯化镍和醋酸镍。
3.权利要求1的镀液组合物，其中所述至少一种金属盐选自硫酸钙、氯化钙、醋酸钙、硫酸镁、氯化镁、醋酸镁、硫酸锶、氯化锶、醋酸锶、硫酸钡、氯化钡和醋酸钡。
4.权利要求3的镀液组合物，其中所述至少一种金属盐为氯化钙。
5.权利要求3的镀液组合物，其中所述至少一种金属盐为氯化镁。
6.权利要求1的镀液组合物，其中所述含金属组分包含镍盐，和选自钙盐、镁盐、锶盐和钡盐的至少两种金属盐。
7.权利要求6的镀液组合物，其中所述至少两种金属盐为钙盐和镁盐。
8.权利要求7的镀液组合物，其中所述至少两种金属盐为氯化钙和氯化镁。
9.权利要求7的镀液组合物，其中所述颗粒物选自天然金刚石和人造金刚石。
10.权利要求1的镀液组合物，其中所述螯合剂为醋酸。
11.权利要求1的镀液组合物，其中所述还原剂选自次磷酸钠、硼氢化钠和氢气。
12.权利要求1的镀液组合物，其中所述含金属组分进一步包含苛性含金属碱，且所述还原组分进一步包含金属醋酸盐，其中所述苛性含金属碱和金属醋酸盐缓冲所述镀液组合物的pH值。
13.对颗粒物进行化学镀覆的方法，所述方法包括步骤：
向容器中装载颗粒物；
向包含颗粒物的容器中装载包含化学镀液组合物和活化组分的溶液，其中所述镀液组合物包含含金属组分和还原组分，
其中所述含金属组分包含：
镍盐；
选自钙盐、镁盐、锶盐和钡盐的至少一种金属盐；
螯合剂；和
水；且
所述还原组分包含：
还原剂；和
水；
在约60℃至约100℃的温度和约4至约13的pH值下，混合所述镀液组合物、活化组分和颗粒物；以及
向所述颗粒物上镀覆至少一层金属层，其中所述金属层包含至少两种金属。
14.权利要求13的方法，其中所述至少一层金属层包含镍和选自钙、镁、锶和钡的至少一种另外的金属。
15.权利要求13的方法，其中所述镍盐选自硫酸镍、氯化镍和醋酸镍。
16.权利要求13的方法，其中所述至少一种金属盐选白硫酸钙、氯化钙、醋酸钙、硫酸镁、氯化镁、醋酸镁、硫酸锶、氯化锶、醋酸锶、硫酸钡、氯化钡和醋酸钡。
17.权利要求16的方法，其中所述至少一种金属盐为氯化钙。
18.权利要求16的方法，其中所述至少一种金属盐为氯化镁。
19.权利要求13的方法，其中所述含金属组分包含选自钙盐、镁盐、锶盐和钡盐的至少两种金属盐。
20.权利要求13的方法，其中所述颗粒物选白天然金刚石和人造金刚石。
21.权利要求13的方法，其中所述活化组分为钯盐与盐酸的溶液。
22.权利要求21的方法，其中所述钯盐为氯化钯。
23.权利要求13的方法，其中首先向包含颗粒物的容器中装入所述含金属组分，接着是所述活化组分，然后是所述还原组分。
24.通过颗粒物的化学镀覆形成的镀覆物品，所述镀覆物品包括：
具有确定的外表面面积的颗粒物，其中所述颗粒物选白天然金刚石和人造金刚石，所述颗粒物具有至少一层金属层，其中所述至少一层金属层镀覆在所述颗粒物的外表面上并且包含镍和选白钙、镁、锶和钡的至少一种另外的金属。
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