CN110549542A - 复合体及其制作方法 - Google Patents

复合体及其制作方法 Download PDF

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Publication number
CN110549542A
CN110549542A CN201810552682.5A CN201810552682A CN110549542A CN 110549542 A CN110549542 A CN 110549542A CN 201810552682 A CN201810552682 A CN 201810552682A CN 110549542 A CN110549542 A CN 110549542A
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China
Prior art keywords
nano
bonding layer
holes
metal substrate
composite
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CN201810552682.5A
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姜传华
戴祯仪
郑增茂
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FIH Precision Electronics Lang Fang Co Ltd
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Foxconn Precision Electronic Langfang Co Ltd
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Priority to CN201810552682.5A priority Critical patent/CN110549542A/zh
Priority to TW107121029A priority patent/TW202003231A/zh
Priority to US16/177,383 priority patent/US20190366603A1/en
Publication of CN110549542A publication Critical patent/CN110549542A/zh
Pending legal-status Critical Current

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    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
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    • B29C45/14311—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles using means for bonding the coating to the articles
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    • B29C45/1418—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles the inserts being deformed or preformed, e.g. by the injection pressure
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Abstract

一种复合体，包括金属基材及形成于所述金属基材表面的塑料件，所述金属基材的材质为钛或钛合金，所述基材表面形成有多个纳米孔洞，所述复合体还包括结合层，所述结合层形成于所述金属基材表面与所述塑料件之间，且所述纳米孔洞被所述结合层部分填充。本发明还公开了一种复合体的制作方法。

Description

复合体及其制作方法
技术领域
本发明涉及一种复合体及其制作方法。
背景技术
目前，市场上的金属和塑料的复合体大多采用电化学方法在金属基材表面形成纳米孔洞，然后注塑形成复合体。然而，由于金属基材本身的性质，在对其进行电化学处理时容易产生电火花现象，较危险。另外，金属和塑料的复合体的结合力度亦不高。
发明内容
有鉴于此，有必要一种具有强结合力的复合体。
本发明还提供了一种复合体的制作方法。
一种复合体，包括金属基材及形成于所述金属基材表面的塑料件，所述金属基材的材质为钛或钛合金，所述基材表面形成有多个纳米孔洞，所述复合体还包括结合层，所述结合层形成于所述金属基材与所述塑料件之间，且所述纳米孔洞被所述结合层部分填充。
一种复合体的制作方法，其包括如下步骤：
提供一金属基材，所述金属基材的材质为钛或钛合金；
于所述金属基材表面形成多个纳米孔洞；
对形成有纳米孔洞的金属基材表面进行表面处理，以形成结合层，其中，所述纳米孔洞被所述结合层部分填充；
于所述结合层表面形成塑料件。
综上所述，所述复合体通过在所述金属基材表面形成多个纳米孔洞来提高所述金属基材和所述塑料件之间的结合力。另外，所述金属基材和所述塑料件之间还形成有结合层，以进一步增强所述塑料件与所述金属基材的结合力。其中，所述结合层为单层或多层的表面处理剂。同时，本技术方案操作简单，且无需在高温环境下实施，还提高了操作的安全性能。
附图说明
图1为本发明一较佳实施例的复合体的剖面示意图。
图2为图1所述复合的部分剖面示意图。
主要元件符号说明
复合体 10
金属基材 101
纳米孔洞 1011
突起 1012
结合层 103
塑料件 105
如下具体实施方式将结合上述附图进一步说明本发明。
具体实施方式
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
除非另有定义，本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。本文中在本发明的说明书中所使用的术语只是为了描述具体的实施例的目的，不是旨在于限制本发明。
参阅图1，本发明较佳实施例提供一种复合体10。
所述复合体10包括金属基材101、结合层103和塑料件105。
所述金属基材101的材质为钛或钛合金。其中，所述钛合金为TAD、TA0、TA1、TA2、TA3、TA4、TA5、TA6、TA7、TA9、TA10、TB2、TB3、TB4、TC1、TC2、TC3、TC4、TC6、TC9、TC10、TC11、或TC12。
在本实施例中，所述金属基材101的表面形成有多个纳米孔洞1011。其中，所述纳米孔洞1011的孔径为几十到几百纳米。所述纳米孔洞1011为不规则的凹洞。一实施例中，所述纳米孔洞1011大致呈蜂窝状。
请一并参阅图2，所述纳米孔洞1011旁边伴有若干不规则的突起1012。当然，所述突起1012不限于形成于所述纳米孔洞1011旁边，还可以形成于所述纳米孔洞1011内或所述金属基材101的任一部位。其中，所述突起1012属于所述金属基材101的一部分。
在本实施例中，所述纳米孔洞1011是通过对所述金属基材101进行酸处理而形成。具体地，将所述金属基材101放入一酸洗液中，于15-45℃下酸洗2-30分钟，从而于所述金属基材101表面形成多个纳米孔洞1011。所述酸洗液的配比为：4-22％的酸溶液，0.7-2.8％的添加剂，0.6-3.7％的双氧水和76-94％的纯水。其中，所述酸溶液为乙酸、甲酸、草酸、氢氟酸、氨基磺酸中的一种或多种。所述添加剂为氟化钾、氟化钠、氟化镁、硫酸铜中的一种或多种。
所述结合层103形成于具有纳米孔洞1011的金属基材101表面。其中，所述金属基材101表面包括纳米孔洞1011的表面。在本实施例中，所述纳米孔洞1011被所述结合层103部分填充。
在本实施例中，所述结合层103是通过对形成有纳米孔洞1011的金属基材101进行表面处理而形成。具体地，将所述金属基材101浸渍于表面处理剂中，并于15-50℃下反应1-3min，进而形成所述结合层103。所述结合层103的厚度为1-200nm。
一实施例中，所述表面处理剂为一水解液，包括硅烷偶联剂与溶剂。在浸渍过程中，所述硅烷偶联剂中可水解的基团在溶剂中被水解以形成硅醇键。该硅醇键能与金属基材101反应，以使所述结合层103牢固地形成于所述金属基材101的表面。其中，所述硅烷偶联剂可以为2-(3，4-环氧环己基)乙基三甲氧基硅烷、3-(3，4-环氧环己基)丙基三甲氧基硅烷、或4-(3，4-环氧环己基)丁基三甲氧基硅烷等。所述溶剂可为乙醇或水。
所述塑料件105通过注塑成型形成于所述结合层103的表面。在本实施例中，所述塑料件105形成于所述结合层103表面，且所述纳米孔洞1011中未被所述结合层103填充的区域被所述塑料件105填满。其中，所述塑料件105为结晶型热塑性塑料，例如聚酰胺、聚亚苯基硫醚、聚对苯二甲酸丁二醇酯、聚碳酸酯、或聚氯乙烯等常见纳米注塑塑料。
本发明还提供了所述复合体10的制作方法，其包括如下步骤：
提供一金属基材101。在本实施例中，所述金属基材101的材质为钛或钛合金。其中，所述钛合金可为TAD、TA0、TA1、TA2、TA3、TA4、TA5、TA6、TA7、TA9、TA10、TB2、TB3、TB4、TC1、TC2、TC3、TC4、TC6、TC9、TC10、TC11、或TC12。
清洗金属基材101。在本实施例中，利用脱脂剂对所述金属基材101进行脱脂处理后，再利用纯水冲洗所述金属基材101，以清洁所述金属基材101表面的灰尘与油渍。
配置酸洗液。在本实施例中，所述酸洗液的配比为：所述酸洗液的配比为：4-22％的酸溶液，0.7-2.8％的添加剂，0.6-3.7％的双氧水和76-94％的纯水。其中，所述酸溶液为乙酸、甲酸、草酸、氢氟酸、氨基磺酸中的一种或多种。所述添加剂为氟化钾、氟化钠、氟化镁、硫酸铜中的一种或多种。
对清洗后的金属基材101进行酸处理，以于所述金属基材101表面形成多个纳米孔洞1011。具体地，将清洗后的所述金属基材101放入上述酸洗液中，于15-45℃下酸洗2-30分钟，从而于所述金属基材101表面形成多个纳米孔洞1011。其中，所述纳米孔洞1011为不规则的凹洞。所述纳米孔洞1011大致呈蜂窝状。
进一步地，所述纳米孔洞1011旁边伴有若干不规则的突起1012。当然，所述突起1012不限于形成于所述纳米孔洞1011旁边，还可以形成于所述纳米孔洞1011内或所述金属基材101的任一部位。其中，所述突起1012属于所述金属基材101的一部分。
对经酸处理的金属基材101进行第一次水洗。具体地，利用纯水，对上述经酸处理的金属基材101进行冲洗，以去除金属基材101表面的酸洗液。
对形成有纳米孔洞1011的金属基材101进行表面处理，以形成结合层103。具体地，将所述金属基材101浸渍于表面处理剂中，并于温度为15～50℃下反应1-3min，以使所述结合层103形成于所述金属基材101表面，且所述纳米孔洞1011被所述结合层103部分填充。其中，所述结合层103的厚度为1-200nm。
一实施例中，所述表面处理剂为一水解液，包括硅烷偶联剂与溶剂。如此，在浸渍过程中，所述硅烷偶联剂中可水解的基团在溶剂中被水解以形成硅醇键，该硅醇键可与金属基材101反应，进而使得所述结合层103牢固地形成于所述金属基材101表面。其中，所述硅烷偶联剂可以为2-(3，4-环氧环己基)乙基三甲氧基硅烷、3-(3，4-环氧环己基)丙基三甲氧基硅烷、或4-(3，4-环氧环己基)丁基三甲氧基硅烷等。所述溶剂可为乙醇或水。
对经表面处理的金属基材101进行第二次水洗。具体地，利用纯水，对上述经表面处理的金属基材101进行冲洗，以去除金属基材101表面的表面处理剂。
于所述结合层103表面注塑成型以形成塑料件105。具体地，将该形成有结合层103的所述金属基材101置入注塑成型模具(图未示)中。向该注塑成型模具内注射熔融的纳米注塑塑料，以使所述纳米注塑塑料覆盖于所述结合层103表面，并与所述结合层103结合，经硬化后形成金属基材101与塑料件105接合为一体的复合体10。其中，所述塑料件105为结晶型热塑性塑料，例如聚酰胺、聚亚苯基硫醚、聚对苯二甲酸丁二醇酯、聚碳酸酯、或聚氯乙烯等常见纳米注塑塑料。
在本实施例中，所述纳米孔洞1011未被所述结合层103填充的区域被所述塑料件105填满，以增强所述塑料件105与所述金属基材101的结合力。同时，由于所述结合层103的成分为表面处理剂，所述表面处理剂中所带的有机官能团，例如羟基、羧基、氨基、或环氧基可与所述塑料件105上的活性官能团以化学键力相结合，以进一步增强所述塑料件105与所述金属基材101的结合力。
下面通过实施例来对本发明进行具体说明。
实施例1
本实施例所使用的金属基材101为钛合金。
清洗基材：在45℃下，采用除油脱脂剂对所述金属基材101进行脱脂处理2分钟，再经利用纯水清洗所述金属基材101，以清洁所述金属基材101表面的灰尘与油渍。
配置酸洗液：所述酸洗液的配比为：4％的氨基磺酸，1％的甲酸、1％的氟化钾、2％的双氧水和92％的纯水。
对清洗后的金属基材101进行酸处理：将清洗后的所述金属基材101放入上述配置好的酸洗液中，于室温下酸洗16分钟，从而于所述金属基材101表面形成多个纳米孔洞1011。
第一次水洗：利用纯水，对上述经酸处理的所述金属基材101进行冲洗，以去除所述金属基材101表面的酸洗液。
表面处理：将形成有纳米孔洞1011的所述金属基材101置于表面处理剂中，并于室温下浸渍3分钟，以使所述结合层103形成于所述金属基材101表面，且所述纳米孔洞1011被所述结合层103部分填充。
第二次水洗：利用纯水，对上述经表面处理的金属基材101进行冲洗，以去除金属基材101表面的表面处理剂。
注塑成型：将该形成有结合层103的所述金属基材101嵌入注塑成型模具(图未示)中，向该注塑成型模具内注射熔融的聚苯硫醚树脂，以使所述聚苯硫醚树脂覆盖于所述结合层103表面，并与所述结合层103结合，经硬化后形成塑料件105，进而获得金属基材101和塑料件105接合为一体的复合体10。其中，所述纳米孔洞1011未被所述结合层103填充的区域被所述聚苯硫醚树脂填满。
测试结果：
拉伸测试：利用万能材料测试机对所述复合体10进行测试，测得结合面积0.5平方厘米的结合力为1300-1600N。
实施例2
本实施例所使用的金属基材101为钛合金。
清洗基材：在45℃下，采用除油脱脂剂对所述金属基材101进行脱脂处理2分钟，再利用纯水清洗所述金属基材101，以清洁所述金属基材101表面的灰尘与油渍。
配置酸洗液：所述酸洗液的配比为：5％的乙酸，1.5％的草酸、1.2％的氟化钠、2％的双氧水和90.3％的纯水。
对清洗后的金属基材101进行酸处理：将清洗后的所述金属基材101放入上述配置好的酸洗液中，于室温下酸洗10分钟，从而于所述金属基材101表面形成多个纳米孔洞1011。
第一次水洗：利用纯水，对上述经酸处理的金属基材101进行冲洗，以去除所述金属基材101表面的酸洗液。
表面处理：将形成有纳米孔洞1011的金属基材101浸渍于表面处理剂中，并于室温下浸渍3分钟，以使所述结合层103形成于所述金属基材101表面，且所述纳米孔洞1011被所述结合层103部分填充。
第二次水洗：利用纯水，对上述经表面处理的金属基材101进行冲洗，以去除金属基材101表面的表面处理剂。
注塑成型：将该形成有结合层103的金属基材101嵌入注塑成型模具(图未示)中，向该注塑成型模具内注射熔融的聚酰胺树脂，以使所述聚酰胺树覆盖于所述结合层103表面，并与所述结合层103结合，经硬化后形成塑料件105，进而获得金属基材101和塑料件105接合为一体的复合体10。其中，所述纳米孔洞1011未被所述结合层103填充的区域被所述聚酰胺树脂填满。
拉伸测试：利用万能材料测试机对所述复合体10进行测试，测得结合面积0.5平方厘米的结合力为1400-1700N。
综上所述，所述复合体10通过在所述金属基材101表面形成多个纳米孔洞1011来提高所述金属基材101和所述塑料件105之间的结合力。其中，所述纳米孔洞1011为不规则的凹洞。所述纳米孔洞1011大致呈蜂窝状。另外，所述金属基材101和所述塑料件105之间还形成有结合层103，以进一步增强所述塑料件105与所述金属基材101的结合力。同时，本技术方案操作简单，且无需在高温环境下实施，还提高了操作的安全性能。
以上实施例仅用以说明本发明的技术方案而非限制，尽管参照较佳实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解，可以对本发明的技术方案进行修改或等同替换，而不脱离本发明技术方案的精神和实质。

Claims (10)

1.一种复合体，包括金属基材及形成于所述金属基材表面的塑料件，其特征在于：所述金属基材的材质为钛或钛合金，所述基材表面形成有多个纳米孔洞，所述复合体还包括结合层，所述结合层形成于所述金属基材与所述塑料件之间，且所述纳米孔洞被所述结合层部分填充。
2.根据权利要求1所述的复合体，其特征在于：所述纳米孔洞的孔径为几十到几百纳米的不规则的凹洞。
3.根据权利要求2所述的复合体，其特征在于：所述纳米孔洞呈蜂窝状，且所述纳米孔洞旁边或所述纳米孔洞内伴有若干不规则的突起。
4.根据权利要求1所述的复合体，其特征在于：所述纳米孔洞未被所述结合层填充的区域被所述塑料件填充。
5.一种复合体的制作方法，其特征在于，所述方法包括如下步骤：
提供一金属基材，所述金属基材的材质为钛或钛合金；
于所述金属基材表面形成多个纳米孔洞；
对形成有纳米孔洞的金属基材表面进行表面处理，以形成结合层，其中，所述纳米孔洞被所述结合层部分填充；
于所述结合层表面形成塑料件。
6.根据权利要求5所述的复合体的制作方法，其特征在于：所述纳米孔洞是通过酸洗液对所述基材的表面进行酸处理形成，其中，所述酸洗液的配比为：4-22％的酸溶液，0.7-2.8％的添加剂，0.6-3.7％的双氧水和76-94％的纯水。
7.根据权利要求6所述的复合体的制作方法，其特征在于：所述酸溶液为乙酸、甲酸、草酸、氢氟酸、氨基磺酸中的一种或多种，所述添加剂为氟化钾、氟化钠、氟化镁、硫酸铜中的一种或多种。
8.根据权利要求5所述的复合体的制作方法，其特征在于：所述表面处理是指将形成有纳米孔洞的金属基材浸泡于表面处理剂中0.1-3分钟，以使所述表面处理剂覆盖于所述金属基材表面，进而形成所述结合层，其中，所述纳米孔洞被所述表面处理剂部分填充。
9.根据权利要求5所述的复合体的制作方法，其特征在于：所述纳米孔洞未被所述结合层填充的区域被所述塑料件填充。
10.根据权利要求5所述的复合体的制作方法，其特征在于：所述纳米孔洞呈蜂窝状，且所述纳米孔洞旁边或所述纳米孔洞内伴有若干不规则的突起。
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