CN1551805A - 镀敷颗粒物质的方法 - Google Patents

镀敷颗粒物质的方法 Download PDF

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CN1551805A
CN1551805A CNA028158105A CN02815810A CN1551805A CN 1551805 A CN1551805 A CN 1551805A CN A028158105 A CNA028158105 A CN A028158105A CN 02815810 A CN02815810 A CN 02815810A CN 1551805 A CN1551805 A CN 1551805A
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布瑞德・度肯
布瑞德·度肯
H・摩寇斯
波利·H·摩寇斯
P・贝奇特
当肯·P·贝奇特
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Abstract

本发明公开一种无电镀敷颗粒物质的方法，其中在镀敷容器中通过搅拌将颗粒与无电镀敷溶液(无还原剂组分)混合。如果必要，可将活性剂物种直接加入镀敷溶液中。然后将还原剂组分加入镀敷溶液以引发镀敷。在颗粒上得到可靠的镀敷而无镀敷溶液的不稳定。

Description

镀敷颗粒物质的方法
背景技术
本发明涉及一种将金属敷层镀敷至颗粒物质表面上的方法。颗粒物质因其小尺寸及大表面积而特别难以镀敷。由于对小颗粒难以提供可靠的电接触，因此对颗粒进行电镀通常是不切实际的。另一方面，颗粒物质可使用无电技术进行镀敷，其不需要电接触而是经化学还原进行镀敷。然而，颗粒物质表现的相当大的表面积趋于造成无电镀敷溶液的不稳定性，并因此引起不可靠的镀敷。
通常，如镍、铜或其他金属的金属在金属与非金属表面上的无电沉积是公知的，而且已采用一段时间。最常采用的无电沉积方法涉及化学还原，其中沉积是利用在由固有催化性材料或经某些预处理形式催化的材料所组成的基质存在下，还原剂对溶于镀敷溶液中金属盐的作用而发生的。大部分镀敷基质不是由固有催化性材料组成，因此必须进行预处理以使表面可被后续镀敷溶液的作用催化。进行此活化最常见的手段是在与无电镀敷溶液接触之前，用包括可催化无电镀敷的离子性或胶状物种的活化剂溶液接触镀敷表面。在接触时，离子性或胶状物种吸附于镀敷表面上，因而使这些表面可被后续镀敷溶液催化。
活化剂溶液通常包括离子性或胶状钯、铂、金、银、钌或其他类似的贵重金属作为活化成分。也可存在如锡的其他金属以稳定胶体和/或增加吸附。关于此点，可参考美国专利3,011,920；3,532,518；3,902,908；以及4,863,758；其所提出的全部内容在此并入作为参考。以上专利叙述了各种用以在无电镀敷前活化非催化性表面的组合物及方法。在各情形下，此方法涉及在与无电镀敷溶液接触前，用活化剂溶液将表面进行预处理。
种类广泛的无电镀敷溶液是公知的，其中最主要是无电铜和无电镍。这些镀敷溶液通常包括镍或铜离子源、还原剂、pH控制化合物、以及络合剂和稳定剂。最常见的无电镍镀敷溶液使用次磷酸盐作为还原剂，而无电铜一般使用甲醛。络合剂包括氨、EDTA和类似的胺，以及如柠檬酸、顺丁烯二酸、甜瓜酸和乳酸的有机酸。无电铜组合物通常使用碱金属氢氧化物且在高碱性pH下进行操作，而无电镍组合物通常用氨调节pH且在4～7范围的pH下进行操作。对于无电镍镀敷的讨论，请参考美国专利4,600,609，其所提出的全部在此并入作为参考。
无电镀敷溶液必定是不稳定溶液，其中应加入稳定化合物以控制不稳定性。各种用于此目的的稳定化合物是公知的。然而，即使使用稳定化合物，无电镀敷溶液仍不稳定，而且此不稳定性在任何时候会随着溶液中可镀敷表面积(即，每升镀敷溶液的表面积平方米)的增加而增加。这在镀敷颗粒物质时特别麻烦，因为即使是少量颗粒物质也存在大镀敷表面积。结果，过去难以镀敷颗粒物质，而且镀敷溶液中生成的不稳定性使该镀敷不可用。
因此，本发明的目的在于提出一种能够以可靠的方式镀敷大量颗粒物质的方法。这些及其他目的可通过使用以下提供的镀敷方法而实现。
发明概述
本发明在此提出以下方法以镀敷颗粒物质：
1.将颗粒物质装至镀敷容器中；
2.将无电镀敷溶液的所有组分，最好是除了还原剂，搅拌加入镀敷容器；
3.如果颗粒物质对无电镀敷浴没有催化性，则将活化剂溶液加入镀敷容器；
4.逐渐加入还原剂以诱发并持续镀敷，最好是直到经镀敷反应消耗掉镀敷溶液中基本上所有的金属离子为止；
5.现在去除消耗的镀敷溶液，而且如果需要，重复此方法，以建立额外的镀敷厚度或增加不同的镀敷金属层。
最好是，以上述次序进行此方法的步骤，除了步骤1与2可互换，并在整个方法中都使用搅拌。
发明的详细说明
本发明人在此已发现一种可靠地镀敷颗粒物质的方法，其克服了过去无电镀敷溶液稳定性的问题。提出的方法也可活化镀敷溶液本身中的颗粒物质，因而减少了所需的步骤数。因此，本发明人提出一种镀敷颗粒物质的方法，所述方法包括：
1.将颗粒物质装至镀敷容器中；
2.将无电镀敷溶液的所有组分，除了还原剂，搅拌加入镀敷容器；
3.如果颗粒物质对无电镀敷浴没有催化性，则将活化剂溶液加入镀敷容器；
4.将还原剂组分逐渐加入镀敷容器；
5.一旦沉积完成，自镀敷容器去除所消耗的镀敷溶液；以及
6.视情况重复此方法。
提出的方法可用于镀敷各种颗粒物质的表面，包括金刚石、铁硅酸盐氧化物颗粒、金属氧化物颗粒、金属颗粒、塑料颗粒及其他类似的颗粒物质。最好是，镀敷材料中的粒度范围为从分布中的最小颗粒到分布中的最大颗粒不大于约200％。此外，最好是平均粒度大于约10微米且小于约400微米。控制粒度及粒度范围易通过在装入镀敷容器前筛选颗粒物质而实现。在将颗粒物质筛选后及装入镀敷容器前，颗粒物质最好是经碱洗、被熔融和/或在水中反复清洗，以去除任何灰尘或污染物。被熔融是指在如氢氧化钠和硝酸钠的熔盐中进行处理。
镀敷容器是有效容纳颗粒物质和镀敷溶液的槽。镀敷容器最好是具有圆锥形底部的圆柱形槽，如此可易于经圆锥底部的阀来去除镀敷物质。用于镀敷容器适合的构成材料包括聚乙烯、聚丙烯或316不锈钢。镀敷容器必须装有搅拌装置，足以在活化和镀敷过程中始终保持颗粒物质在镀敷溶液中悬浮且移动。搅拌将影响得到的镀敷的均匀性，以及镀敷溶液的整体稳定性和可靠性。本发明人已发现，不管浴体积的大小而以恒定速度操作的推进器型搅拌器是一种有效的搅拌装置，特别是如果结合经镀敷溶液起泡的空气。因此，搅拌提供了颗粒物质在整个镀敷溶液中的均匀分布，因而提高了镀敷的均匀性和镀敷溶液的稳定性。在镀敷容器中可装设挡板以改善搅拌和整个容器的搅拌均匀性。
此方法不受所使用无电镀敷溶液类型的限制，但是通过使用无电镍和无电铜镀敷溶液且较佳。适合的无电铜溶液包括(i)铜离子源，如氯化铜和/或硫酸铜，(ii)螯合剂，(iii)氢氧化钠或钾，以及(iv)作为还原剂的甲醛。适合的无电镍镀敷溶液包括：(i)镍离子源，如硫酸镍和/或氯化镍，(ii)螯合剂，如有机酸，(iii)pH控制剂，如氨，以及(iv)作为还原剂的次磷酸盐。商业无电铜和无电镍溶液还包括其他性能添加剂和稳定剂。如所示，在起初(即，步骤1和2)混合颗粒物质和镀敷溶液时，镀敷溶液最好不包括还原剂。此时无还原剂可防止在此时发生无电镀敷，而且可随后在镀敷溶液中原位活化该颗粒物质。本发明人也已发现，逐渐加入作为分离组分的还原剂的方法步骤大大增强了所完成的镀敷的均匀性和可靠性，以及镀敷溶液的稳定性。颗粒物质和镀敷溶液(无还原剂)应在此时结合搅拌而足以将颗粒物质均匀地分散于整个镀敷溶液中。通常，每千克镀敷颗粒物质需要2至4加仑的镀敷溶液。
许多镀敷颗粒，包括金刚石、铁硅酸盐氧化物、金属氧化物和特定类型的金属，对无电铜或无电镍镀敷溶液本身没有催化性。因此，它们必须通过与活化剂物种接触才具有催化性。直到现在，此活化过程发生在镀敷溶液与镀敷材料接触之前的分离步骤中。然而，发明人在此已发现，通过起初将还原剂从镀敷溶液分离出来，活化剂物种可直接加入镀敷溶液(无还原剂)中，从而在镀敷溶液中原位活化该颗粒物质。如所示，随后加入还原剂从而引发镀敷。
用于本发明的活化剂溶液通常含有如钯、铂、金、银或钌的离子性或胶态贵重物种金属作为活化成分。也可存在如锡的其他金属以稳定胶体和/或增加吸附。最常见的商业可得的活化剂溶液为离子性钯溶液或胶态锡-钯溶液。以上任意一种均可在本发明的方法中使用。如果使用以钯为基础的活性剂，则每千克颗粒物质应使用约25至100毫克活化剂(如钯)。将活化剂溶液搅拌加入含颗粒物质的镀敷溶液(无还原剂)中。
活化之后，将还原剂逐渐搅拌加入镀敷溶液中。加入还原剂使镀敷反应开始。完全地镀敷基本上所有来自镀敷溶液的离子性金属物种所需的还原剂量理论上可基于镀敷反应而计算，其条件为增加5～10％。然后经约15分钟至1小时的时间逐渐加入此还原剂量。最好是，在此期间镀敷基本上所有来自镀敷溶液的镀敷金属物种。用于无电铜镀敷溶液最常见的还原剂为甲醛，而用于无电镍镀敷溶液最常见的还原剂为次磷酸盐，如次磷酸钠。
一旦镀敷完成，自镀敷容器去除耗尽的镀敷溶液。搅拌加入新鲜水以清洗刚镀敷的颗粒。如果需要，可反复清洗。
在需要于颗粒物质上建立多层镀敷金属或得到指定重量增加的情形下，可重复此方法。例如，起初可以用无电镍镀敷颗粒物质。然后用无电铜重复此方法以在镍层上形成镀敷铜层。在此情形下，由于镍对无电铜具有催化性，因此不需要第二活化剂。
在以镀敷金属层封装时，如铁硅酸盐氧化物粉末的颗粒物质是一种用于电磁屏蔽的有效介质。对于许多屏蔽应用，铁硅酸盐氧化物粉末最好用双层镍继而用铜来进行镀敷。然而，对于某些指定应用，以铜的单镀敷层或重量增加可得到所需的电磁波衰减程度。
在镀敷后，镀敷颗粒可用如苯并三唑的防锈剂处理。最后使用溶剂或醇溶液来清洗可以便于干燥。
用下面的实例将对以上发明作进一步的叙述，其应仅视为描述性而绝非限制性。
实例
经不锈钢筛网筛选具有尺寸范围为次微米至约400微米粒度的铁硅酸盐氧化物颗粒，以分离出一部分具有约150微米至约400微米尺寸范围的颗粒。在筛选出被分离的材料(即，150～400微米)之后，将其清洗至清洗水透明为止。然后使用以下步骤镀敷经清洗的颗粒物质：
1.在具有圆锥形底部和搅拌装置的圆柱形聚乙烯镀敷容器中，将1千克颗粒物质与各0.5升的MacDermid Niklad NiCAP-A&B无电镍镀敷溶液浓缩物(无还原剂组分)(得自康乃狄克州Waterbury的MacDermid公司)混合。加入9升去离子水并加热至160°F。以气动式推进器提供搅拌。将颗粒物质均匀地分散于整个镀敷溶液中。
2.将25毫升含有约1.0克钯的MacDermid Niklad 262钯活性剂溶液(得自康乃狄克州Waterbury的MacDermid公司)搅拌加入镀敷溶液中。
3.将300毫升MacDermid Niklad NiCAP-C(即，含有次磷酸钠的用于镀敷溶液的还原剂组分)经约超过1/2小时的时间逐渐加入镀敷溶液中。持续搅拌。此加入引起镀敷反应开始，并将镀敷持续约1/2小时，直到基本上所有的镍被镀敷溶液耗尽为止。
4.关闭搅拌，颗粒沉降，并去除镀敷溶液。
5.搅拌加入水，并去除水以清洗镀敷颗粒。
6.搅拌加入1加仑无还原剂组分的MacDermid Niklad CuCAP-A无电铜镀敷溶液。
7.将100毫升MacDermid Niklad CuCAP-B(即，含有甲醛的用于镀敷溶液的还原剂组分)经约超过1/2小时的时间逐渐加入无电铜镀敷溶液中。持续搅拌。此加入引起镀敷反应开始，并将镀敷持续约1/2小时，直到基本上所有的铜被镀敷溶液耗尽为止。
8.关闭搅拌，颗粒沉降，并去除镀敷溶液。
9.搅拌加入水以清洗镀敷颗粒，然后去除水。
10.用0.5至1.0％体积浓度的防锈材料MacDermid Metex 667清洗镀敷颗粒物质1～2分钟。
11.自容器取出镀敷颗粒并在150°F烘箱内干燥。在烘箱内干燥之前，使用异丙醇来分离清洗有助于加速干燥过程。
经过检验，颗粒铁硅酸盐氧化物被镍和铜有效地镀敷。

Claims (9)

1.一种镀敷颗粒物质的方法，该方法包括：
a)在镀敷容器中通过搅拌将颗粒物质与无还原剂组分的无电镀敷溶液混合；
b)视情况将用于无电镀敷的活化剂加入镀敷溶液中；以及
c)将还原剂组分加入镀敷溶液中。
2.如权利要求1所述的方法，其特征在于，镀敷溶液选自无电铜镀敷溶液和无电镍镀敷溶液，而还原剂组分选自甲醛和次磷酸盐。
3.如权利要求1所述的方法，其特征在于，活化剂包括离子性钯或胶态钯。
4.如权利要求1所述的方法，其特征在于，颗粒物质的平均尺寸范围为约10微米至约400微米。
5.如权利要求1所述的方法，其特征在于，颗粒物质选自金属氧化物、铁硅酸盐氧化物和金刚石。
6.如权利要求2所述的方法，其特征在于，活化剂包括离子性钯或胶态钯。
7.如权利要求2所述的方法，其特征在于，颗粒物质的平均尺寸范围为约10微米至约400微米。
8.如权利要求2所述的方法，其特征在于，颗粒物质选自金属氧化物、铁硅酸盐氧化物和金刚石。
9.如权利要求4所述的方法，其特征在于，颗粒物质选自金属氧化物、铁硅酸盐氧化物和金刚石。
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