CN106903306A - 一种缺陷诱导化学镀工艺制备3d打印用金属颗粒/聚合物复合粉体的方法 - Google Patents
一种缺陷诱导化学镀工艺制备3d打印用金属颗粒/聚合物复合粉体的方法 Download PDFInfo
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Abstract
一种缺陷诱导化学镀工艺制备3D打印用金属颗粒/聚合物复合粉体的方法，涉及化学镀及复合材料制备领域，首先将聚合物粉体加入酸性刻蚀液中浸泡，清洗、离心；然后将刻蚀后的聚合物粉体进行化学镀，水洗干燥即可。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。采用酸刻蚀聚合物粉体，形成缺陷诱导化学镀，制备工艺简单，成本低，可以实现连续化生产。制备的产品中金属颗粒均匀包覆在聚合物粉体表面，且包覆的粉体附着力强，易分散。得到的复合粉体材料可提高3D打印制件的力学性能，且润湿性和流动性好。其选择性烧结性能优异，在3D打印领域有着广泛的应用。
Description
技术领域
本发明涉及化学镀及复合材料制备领域，特别涉及到一种缺陷诱导化学镀工艺制备3D打印用金属颗粒/聚合物复合粉体的方法。
背景技术
近些年来，化学镀作为表面强化的途径，因其操作简单和成本低等优点已引起广泛重视和不断发展。化学镀金属包覆聚合物粉体是指以聚合物粉体为核心，以金属包覆其表面而得到的金属颗粒/聚合物复合粉体。这种金属颗粒/聚合物复合粉体由于具有优良的导电性能、良好的力学性能、以及电磁学和光学等方面的优异性质，在3D打印行业有着广泛的应用价值。
目前金属包覆聚合物粉体制备金属颗粒/聚合物复合粉体的制备方法有机械混合法、溶胶凝胶法、化学镀法、非均相沉淀法等，而化学镀法由于其制备工艺简单，流程易于控制，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受到了广泛的关注。
目前应用较广的粉体表面化学镀工艺主要是化学镀液中的金属离子在还原剂的作用下沉积到聚合物表面，从而实现聚合物表面区域选择性化学镀。例如，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，且聚合物同粉体表面缩合反应很难实现粉体表面完全包裹，用该种方法得到的复合粉体附着力差。
再如专利：02131262.1公开了粉体表面金属化的方法。此方法首先粉体经过铬酐的溶液粗化；然后经氯化亚锡盐酸溶液敏化，氯化钯溶液活化；最后进行粉体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，该种工艺不能实现如粉煤灰、碳酸钙、碳酸镁等粉体的表面化学镀。因此现有聚合物粉体表面化学镀还存在着很多不足之处，化学镀制备金属颗粒/聚合物复合粉体方法有待改善。
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聚合物粉体、工艺简单且环保的缺陷诱导化学镀工艺制备3D打印用金属颗粒/聚合物复合粉体的方法。
为了实现上述目的，本发明的技术方案如下：
一种缺陷诱导化学镀工艺制备3D打印用金属颗粒/聚合物复合粉体的方法，包含以下步骤：
(1)将聚合物粉体加入80～110℃的酸性刻蚀液中浸泡10～50min，清洗、离心；
(2)将步骤(1)所得刻蚀后的聚合物粉体采用辅助工艺进行化学镀，化学镀时间为20～60min，化学镀镀液的温度为30～60℃，化学镀后水洗，60℃干燥40min，得到3D打印用金属颗粒/聚合物复合粉体。
优选地，制备方法中，所述步骤(1)中聚合物粉体为尼龙粉体、聚丙烯粉体、聚乙烯粉体、聚亚苯基硫醚粉体、丙烯腈/丁二烯/苯乙烯共聚物粉体中的至少一种。
优选地，制备方法中，所述步骤(1)中酸性刻蚀液为醋酸、甲酸和硫酸中的至少一种。
优选地，制备方法中，所述步骤(2)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。
优选地，制备方法中，所述步骤(2)中化学镀的辅助工艺包括超声、微波加热、水热法中的至少一种。
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，本发明的优点表现在：
1、本发明采用酸刻蚀聚合物粉体，形成缺陷诱导化学镀，制备工艺简单，成本低，可以实现连续化生产。
2、本发明制备的产品中金属颗粒均匀包覆在聚合物粉体表面，且包覆的粉体附着力强，易分散。
3、本发明方案得到的复合粉体材料可提高3D打印制件的力学性能，且润湿性和流动性好。其选择性烧结性能优异，在3D打印领域有着广泛的应用。
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
将醋酸加热到80℃，将干燥的聚乙烯粉体加入醋酸溶液中浸泡，时间为10min，取出后用去离子水清洗一次，再离心。
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)。将离心后的聚乙烯粉体浸入30℃的化学镀镍镀液中超声施镀20min。化学镀镍后，用去离子水清洗，在烘箱中60℃干燥40min，即得到缺陷诱导化学镀工艺制备3D打印用镍颗粒/聚乙烯复合粉体。
以粒径为50～80μm的镍颗粒/聚乙烯复合粉体为原料，采用3D打印技术制备的成型件外观颜色均匀、力学性能优良，拉伸强度为3MPa。
实施例2
将甲酸加热到90℃，将干燥的聚丙烯粉体加入甲酸溶液中浸泡，时间为20min，取出后用去离子水清洗一次，再离心。
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)。将离心后的聚丙烯粉体浸入40℃的化学镀铜镀液中微波加热施镀30min。化学镀铜后，用去离子水清洗，在烘箱中60℃干燥40min，即得到缺陷诱导化学镀工艺制备3D打印用铜颗粒/聚丙烯复合粉体。
以粒径为50～80μm的铜颗粒/聚丙烯复合粉体为原料，采用3D打印技术制备的成型件外观颗粒均匀、力学性能优良，拉伸强度为4MPa。
实施例3
将醋酸加热到100℃，将干燥的尼龙粉体加入醋酸溶液中浸泡，时间为30min，取出后用去离子水清洗一次，再离心。
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)。将离心后的尼龙粉体浸入50℃的化学镀镍镀液中超声施镀40min。化学镀镍后，用去离子水清洗，在烘箱中60℃干燥40min，即得到缺陷诱导化学镀工艺制备3D打印用镍颗粒/尼龙复合粉体。
以粒径为50～80μm的镍颗粒/尼龙复合粉体为原料，采用3D打印技术制备的成型件外观颗粒均匀、力学性能优良，拉伸强度为4MPa。
实施例4
将硫酸加热到100℃，将干燥的聚亚苯基硫醚粉体加入硫酸溶液中浸泡，时间为40min，取出后用去离子水清洗一次，再离心。
配制化学镀银镀液，镀液组分为：AgNO3(29g/L)、NH3·H2O(4g/L)、和HCHO(55g/L)。将离心后的聚亚苯基硫醚粉体浸入60℃的化学镀银液中水热施镀50min。化学镀银后，用去离子水清洗，在烘箱中60℃干燥40min，即得到缺陷诱导化学镀工艺制备3D打印用银颗粒/聚亚苯基硫醚复合粉体。
以粒径为50～80μm的银颗粒/聚亚苯基硫醚复合粉体为原料，采用3D打印技术制备的成型件外观颗粒均匀、力学性能优良，拉伸强度为4MPa。
实施例5
将醋酸加热到110℃，将干燥的丙烯腈/丁二烯/苯乙烯共聚物粉体加入醋酸溶液中浸泡，时间为50min，取出后用去离子水清洗一次，再离心。
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)。将离心后的丙烯腈/丁二烯/苯乙烯共聚物粉体浸入60℃的化学镀钴镀液中超声施镀60min。化学镀钴镀后，用去离子水清洗，在烘箱中60℃干燥40min，即得到缺陷诱导化学镀工艺制备3D打印用钴颗粒/丙烯腈/丁二烯/苯乙烯共聚物复合粉体。
以粒径为50～80μm的钴颗粒/丙烯腈/丁二烯/苯乙烯共聚物复合粉体为原料，采用3D打印技术制备的成型件外观颗粒均匀、力学性能优良，拉伸强度为4MPa。
Claims (6)
1.一种缺陷诱导化学镀工艺制备3D打印用金属颗粒/聚合物复合粉体的方法，其特征在于：包含以下步骤：
(1)将聚合物粉体加入80～110℃的酸性刻蚀液中浸泡10～50min，清洗、离心；
(2)将步骤(1)所得刻蚀后的聚合物粉体采用辅助工艺进行化学镀，化学镀时间为20～60min，化学镀镀液的温度为30～60℃，化学镀后水洗，60℃干燥40min，得到3D打印用金属颗粒/聚合物复合粉体。
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粉体、聚丙烯粉体、聚乙烯粉体、聚亚苯基硫醚粉体、丙烯腈/丁二烯/苯乙烯共聚物粉体中的至少一种。
3.如权利要求1所述的制备方法，其特征在于：所述步骤(1)中酸性刻蚀液为醋酸、甲酸和硫酸中的至少一种。
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。
5.如权利要求1所述的制备方法，其特征在于：所述步骤(2)中化学镀的辅助工艺包括超声、微波加热、水热法中的至少一种。
6.如权利要求1～5任一项所述方法制备的金属颗粒/聚合物复合粉体在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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