CN106947960A - 一种3d打印用聚合物/金属复合粉体材料的制备方法 - Google Patents
一种3d打印用聚合物/金属复合粉体材料的制备方法 Download PDFInfo
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- C23C18/31—Coating with metals
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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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Abstract
一种3D打印用聚合物/金属复合粉体材料的制备方法，涉及化学镀及复合材料制备领域，制备方法为：(a)聚合物粉体材料表面改性；(b)改性聚合物粉体表面敏化和活化；(c)聚合物粉体表面化学镀。将制备的复合粉体进行分级，选择粒径为50～80μm的粉体作为原料可进行3D产品的打印。制备的复合粉体采用金属包裹，能够避免聚合物粉体在敏化和活化过程中同酸反应，可以实现聚合物粉体表面化学镀。制备的复合粉体中金属层均匀包覆在聚合物粉体表面，且包覆不受粉体形貌限制。金属颗粒分散均匀且金属颗粒与聚合物粉体表面具有良好的润湿性，烧结性能优异，可广泛应用于3D打印领域。
Description
技术领域
本发明涉及化学镀及复合材料制备领域，特别涉及到一种3D打印用聚合物/金属复合粉体材料的制备方法。
背景技术
金属包覆无机粉体是指以无机粉体为核心，以金属为外壳的复合粉体。这种复合粉体由于具有优异的电磁学、光学、化学催化以及可以改善金属和陶瓷之间的润湿性等优异的性质，近年来广泛应用于3D打印领域。
金属包覆无机粉体复合粉体的制备方法有溶胶凝胶法、机械混合法、化学镀法、非均相沉淀法等，其中化学镀法由于可以在任何基体表面都能制备出均匀、孔隙率低、厚度可控的金属镀层，且工艺易于控制、设备简单受到广泛的关注。
目前粉体表面化学镀工艺为：(1)粉体表面引入活性基团；(2)活性基团吸附催化剂；(3)吸附催化剂的粉体表面通过化学镀沉积金属粒子。例如，专利：02131262.1公开了无机粉体表面金属化的方法。此方法首先无机粉体经过铬酐的溶液粗化；然后经氯化亚锡盐酸溶液敏化，氯化钯盐酸溶液活化；最后进行表面化学镀覆金属层。其中粗化、敏化和活化过程均在酸性条件下，这种工艺不能实现如碳酸钙、粉煤灰、碳酸镁等粉体的表面化学镀。再如专利200780011903.8公开了导电性非电解电镀粉体及其制造方法。此方法是将芯材粉体与三聚氰胺树脂的初期缩合物接触，进行该初期缩合物的聚合反应，利用三聚氰胺树脂中的氨基吸附催化剂，从而实现化学镀。该方法是采用聚合物单体通过聚合反应在粉体表面引入活性基团，工艺复杂，另外聚合物同粉体表面缩合反应很难实现粉体表面完全包裹。因此，现有无机粉体化学镀的方法有待改善。
发明内容
本发明的目的在于克服现有粉体表面化学镀方法的不足，提供一种适用于各种无机粉体、工艺简单和环保的3D打印用聚合物/金属复合粉体材料的制备方法。
为了实现上述目的，本发明的技术方案如下：
一种3D打印用聚合物/金属复合粉体材料的制备方法，包含以下步骤：
(1)将聚合物粉体浸泡在水解的硅烷溶液中30min，清洗、离心；
(2)将步骤(1)所得聚合物粉体浸入pH为1～3的敏化液中进行敏化，敏化温度为30～60℃，敏化时间为10～50min，水洗至中性；
(3)将步骤(2)所得敏化聚合物粉体浸入pH为1～4的活化液中进行活化，活化温度为30～60℃，活化时间为10～50min，水洗至中性；
(4)将步骤(3)所得活化后聚合物粉体化学施镀，化学镀时间为20～60min，化学镀镀液的温度为30～60℃，水洗，60℃干燥40min，得到3D打印用聚合物/金属复合粉体材料。
优选地，制备方法中，所述步骤(1)中聚合物粉体为尼龙、聚丙烯、聚乙烯、聚苯硫醚、丙烯腈/苯乙烯/丁二烯共聚物中的至少一种。
优选地，制备方法中，所述步骤(1)中水解的硅烷溶液为硅烷偶联剂KH550、硅烷偶联剂KH560中的至少一种。硅烷偶联剂分子中含有两种不同的活性基因——氨基和氧基，用来偶联有机高分子和无机填料，增强其粘结性，提高产品的机械、电气、耐水、抗老化等性能。
优选地，制备方法中，所述步骤(2)中的敏化液为氯化亚锡溶液。
优选地，制备方法中，所述步骤(3)中所述活化液为包含金属胶体催化剂的硼酸溶液，其中所述金属胶体催化剂为钯、铂、银和金中的至少一种。
优选地，制备方法中，所述步骤(4)中化学镀包括化学镀铜、化学镀镍、化学镀钴和化学镀银中的至少一种。
同时，将上述方法制备的复合粉体进行分级，选择粒径为50～80μm的粉体作为原料可进行3D产品的打印。
与现有技术相比，本发明的有益效果表现在：
1、本发明聚合物粉体采用金属包裹，能够避免聚合物粉体在敏化和活化过程中同酸反应，可以实现聚合物粉体表面化学镀。
2、本发明采用的制备工艺简单，成本低廉，可以实现连续化生产。
3、本发明制备的产品中金属层均匀包覆在聚合物粉体表面，且包覆不受粉体形貌限制。
4、本发明方案得到的改性聚合物粉体，金属颗粒分散均匀且金属颗粒与聚合物粉体表面具有良好的润湿性，烧结性能优异，可广泛应用于3D打印领域。
具体实施方式
以下对本发明实施做进一步详述，以下实施例只是描述性的，不是限定性的，不能以此限定本发明的保护范围。该领域的技术人员根据上述本发明内容对本发明作出一些非本质的改进和调整，均视为本发明的保护范围之内。
实施例1
将干燥后的尼龙浸泡在KH550(20％，其中水为40％，乙醇为40％)溶液中，时间30min，温度为60℃，取出后用净化水清洗一次，再离心。采用改性后的尼龙浸泡在5g/L的SnCl2(用盐酸调pH至1)溶液中敏化10分钟，温度60℃。取出后用去离子水清洗后浸入含有0.15g/L的PdCl2和20g/L的H3BO3(用盐酸调pH至2)溶液中10分钟进行活化，温度60℃，活化后的尼龙用去离子水冲洗。
配置化学镀镍镀液，镀液组分为：NiSO4·7H2O(15g/L)、NaH2PO2·H2O(15g/L)、Na3C6H5O7·2H2O(8g/L)、NH4Cl(18g/L)。将活化后的尼龙浸入60℃的化学镀镍镀液中施镀20分钟。化学镀镍后，用去离子水清洗，在烘箱中60℃干燥40分钟，即得表面包覆镍的尼龙粉体。
以粒径为50～80μm的镍/尼龙复合粉体为原料，采用3D打印技术制备成型件，材料中金属颗粒分散均匀且金属颗粒与聚合物粉体表面具有良好的润湿性，烧结性能优异。
实施例2
将干燥后的聚丙烯浸泡在KH560(20％，其中水为40％，乙醇为40％)溶液中，时间30min，温度为60℃，取出后用净化水清洗一次，再离心。采用改性后的聚丙烯浸泡在5g/L的SnCl2(用盐酸调pH至1)溶液中敏化,50分钟，温度30℃。取出后用去离子水清洗后浸入含有0.15g/L的PdCl2和20g/L的H3BO3(用盐酸调pH至2)溶液中50分钟进行活化，温度30℃，活化后的聚丙烯用去离子水冲洗。
配置化学镀钴镀液，镀液组分为：CoCl2(25g/L)、NaH2PO2·H2O(25g/L)、Na3C6H5O7·2H2O(55g/L)、NH4Cl(45g/L)、H3BO3(25g/L)。将活化后的聚丙烯浸入30℃的化学镀钴镀液中施镀60分钟。化学镀钴后，用去离子水清洗，在烘箱中60℃干燥40分钟，即得表面包覆钴的聚丙烯粉体。
以粒径为50～80μm的钴/聚丙烯复合粉体为原料，采用3D打印技术制备成型件，材料中金属颗粒分散均匀且金属颗粒与聚合物粉体表面具有良好的润湿性，烧结性能优异。
实施例3
将干燥后的聚乙烯浸泡在KH550(20％，其中水为40％，乙醇为40％)溶液中，时间30min，温度为60℃，取出后用净化水清洗一次，再离心。采用改性后的聚乙烯浸泡在5g/L的SnCl2(用盐酸调pH至1)溶液中敏化30分钟，温度50℃。取出后用去离子水清洗后浸入含有0.15g/L的PdCl2和20g/L的H3BO3(用盐酸调pH至2)溶液中30分钟进行活化，温度50℃，活化后的聚乙烯用去离子水冲洗。
配置化学镀镍镀液，镀液组分为：NiSO4·7H2O(15g/L)、NaH2PO2·H2O(15g/L)、Na3C6H5O7·2H2O(8g/L)、NH4Cl(18g/L)。将活化后的聚乙烯浸入50℃的化学镀镍镀液中施镀40分钟。化学镀镍后，用去离子水清洗，在烘箱中60℃干燥40分钟，即得表面包覆镍的聚乙烯粉体。
以粒径为50～80μm的镍/聚乙烯复合粉体为原料，采用3D打印技术制备成型件，材料中金属颗粒分散均匀且金属颗粒与聚合物粉体表面具有良好的润湿性，烧结性能优异。
实施例4
将干燥后的聚苯硫醚浸泡在KH560(20％，其中水为40％，乙醇为40％)溶液中，时间30min，温度为60℃，取出后用净化水清洗一次，再离心。采用改性后的聚苯硫醚浸泡在5g/L的SnCl2(用盐酸调pH至1)溶液中敏化40分钟，温度60℃。取出后用去离子水清洗后浸入含有0.15g/L的PdCl2和20g/L的H3BO3(用盐酸调pH至2)溶液中40分钟进行活化，温度60℃，活化后的聚苯硫醚用去离子水冲洗。
配制化学镀银镀液，镀液组分为：AgNO3(29g/L)、NH3·H2O(4g/L)、和HCHO(55g/L)。将活化后的聚苯硫醚浸入60℃的化学镀银镀液中施镀50分钟。化学镀银后，用去离子水清洗，在烘箱中60℃干燥40分钟，即得表面包覆银的聚苯硫醚粉体。
以粒径为50～80μm的银/聚苯硫醚复合粉体为原料，采用3D打印技术制备成型件，材料中金属颗粒分散均匀且金属颗粒与聚合物粉体表面具有良好的润湿性，烧结性能优异。
实施例5
将干燥后的丙烯腈/苯乙烯/丁二烯共聚物浸泡在KH550(20％，其中水为40％，乙醇为40％)溶液中，时间30min，温度为60℃，取出后用净化水清洗一次，再离心。采用改性后的丙烯腈/苯乙烯/丁二烯共聚物浸泡在5g/L的SnCl2(用盐酸调pH至1)溶液中敏化50分钟，温度60℃。取出后用去离子水清洗后浸入含有0.15g/L的PdCl2和20g/L的H3BO3(用盐酸调pH至2)溶液中50分钟进行活化，温度60℃，活化后的丙烯腈/苯乙烯/丁二烯共聚物用去离子水冲洗。
配制化学镀铜镀液，镀液组分为：NiSO4·7H2O(1g/L)、CuSO4·5H2O(24g/L)、NaH2PO2·H2O(55g/L)、Na3C6H5O7·2H2O(1.5g/L)、H3BO3(70g/L)。将活化后的丙烯腈/苯乙烯/丁二烯共聚物浸入60℃的化学镀铜镀液中施镀60分钟。化学镀铜后，用去离子水清洗，在烘箱中60℃干燥40分钟，即得表面包覆铜的丙烯腈/苯乙烯/丁二烯共聚物粉体。
以粒径为50～80μm的铜/丙烯腈/苯乙烯/丁二烯复合粉体为原料，采用3D打印技术制备成型件，材料中金属颗粒分散均匀且金属颗粒与聚合物粉体表面具有良好的润湿性，烧结性能优异。
Claims (7)
1.一种3D打印用聚合物/金属复合粉体材料的制备方法，其特征在于：包含以下步骤：
(1)将聚合物粉体浸泡在水解的硅烷溶液中30min，清洗、离心；
(2)将步骤(1)所得聚合物粉体浸入pH为1～3的敏化液中进行敏化，敏化温度为30～60℃，敏化时间为10～50min，水洗至中性；
(3)将步骤(2)所得敏化聚合物粉体浸入pH为1～4的活化液中进行活化，活化温度为30～60℃，活化时间为10～50min，水洗至中性；
(4)将步骤(3)所得活化后聚合物粉体化学施镀，化学镀时间为20～60min，化学镀镀液的温度为30～60℃，水洗，60℃干燥40min，得到3D打印用聚合物/金属复合粉体材料。
2.如权利要求1所述的制备方法，其特征在于：所述步骤(1)中聚合物粉体为尼龙、聚丙烯、聚乙烯、聚苯硫醚、丙烯腈/苯乙烯/丁二烯共聚物中的至少一种。
3.如权利要求1所述的制备方法，其特征在于：所述步骤(1)中水解的硅烷溶液为硅烷偶联剂KH550、硅烷偶联剂KH560中的至少一种。
4.如权利要求1所述的制备方法，其特征在于：所述步骤(2)中的敏化液为氯化亚锡溶液。
5.如权利要求1所述的制备方法，其特征在于：所述步骤(3)中所述活化液为包含金属胶体催化剂的硼酸溶液，其中所述金属胶体催化剂为钯、铂、银和金中的至少一种。
6.如权利要求1所述的制备方法，其特征在于：所述步骤(4)中化学镀包括化学镀铜、化学镀镍、化学镀钴和化学镀银中的至少一种。
7.如权利要求1～6任一项所述方法制备的聚合物/金属复合粉体材料在3D产品打印中的应用，其特征在于：将制备的复合粉体进行分级，选择粒径为50～80μm的粉体作为原料进行3D产品的打印。
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104911568A (zh) * | 2015-07-06 | 2015-09-16 | 合肥学院 | 一种选择性化学镀的方法 |
| CN104995335A (zh) * | 2013-02-13 | 2015-10-21 | 埃托特克德国有限公司 | 将第一金属层沉积在非导电聚合物上的方法 |
| CN105296973A (zh) * | 2015-12-01 | 2016-02-03 | 中北大学 | 一种超高分子量聚乙烯粉末表面化学镀镍方法 |
| CN106119818A (zh) * | 2016-08-30 | 2016-11-16 | 合肥乐凯科技产业有限公司 | 一种无机粉体表面化学镀的方法及其薄膜 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104911568A (zh) * | 2015-07-06 | 2015-09-16 | 合肥学院 | 一种选择性化学镀的方法 |
| CN105296973A (zh) * | 2015-12-01 | 2016-02-03 | 中北大学 | 一种超高分子量聚乙烯粉末表面化学镀镍方法 |
| CN106119818A (zh) * | 2016-08-30 | 2016-11-16 | 合肥乐凯科技产业有限公司 | 一种无机粉体表面化学镀的方法及其薄膜 |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108251823A (zh) * | 2018-01-15 | 2018-07-06 | 杭州和韵科技有限公司 | 一种塑料电镀预处理方法 |
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