CN105729717A - 金属与树脂的复合体的制备方法及由该方法制得的复合体 - Google Patents

金属与树脂的复合体的制备方法及由该方法制得的复合体 Download PDF

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CN105729717A
CN105729717A CN201410741693.XA CN201410741693A CN105729717A CN 105729717 A CN105729717 A CN 105729717A CN 201410741693 A CN201410741693 A CN 201410741693A CN 105729717 A CN105729717 A CN 105729717A
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metal base
metal
resin
complex
articulamentum
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CN105729717B (zh
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姜传华
张保申
王杰祥
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Shenzhen Futaihong Precision Industry Co Ltd
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Shenzhen Futaihong Precision Industry Co Ltd
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Abstract

本发明提供一种金属与树脂的复合体的制备方法，其包括如下步骤：提供一金属基材；对所述金属基材进行化学蚀刻处理，使该金属基材的表面形成若干纳米孔；对该所述经化学蚀刻处理后的金属基材进行表面耦合处理，以在金属基材及其纳米孔的表面形成一连接层；将经表面耦合处理的金属基材置于模具中，用注塑成型的方法在该连接层的表面注塑形成一树脂层。另，本发明还提供一种由上述方法制得的金属与树脂的复合体。

Description

金属与树脂的复合体的制备方法及由该方法制得的复合体
技术领域
本发明涉及一种金属与树脂的复合体的制备方法及由该方法制得的复合体。
背景技术
近年来便携式电子装置、汽车和IT产业产品的制造要求难度愈来愈高，产品如何做到更轻、薄及更多功能化一直是业者的追求目标，其中在保证产品的强度的同时降低产品的重量特别重要。将便携式电子装置、汽车和IT产业产品的各种不同材质构件有效快速粘合在一起，且不占空间，就可降低产品的厚度，且能提高讯号收发能力。
目前，将金属与塑料材料结合在一起的方法有很多种，包括在两者之间加一层粘着剂，或用机械方法固定在一起，或者先将金属的表面经过特殊表面处理后，再把塑料直接结合到金属基材表面。但是，在这些加工工艺中如何使金属基材表面的树脂层层不发生剥离、龟裂(裂纹)、破损等现象，仍然是一个难题。
发明内容
有鉴于此，有必要提供一种金属与树脂的复合体的制备方法及由该方法制得的复合体。
一种金属与树脂的复合体的制备方法，其包括如下步骤：
提供一金属基材；
对所述金属基材进行化学蚀刻处理，使该金属基材的表面形成若干纳米孔；
对该所述经化学蚀刻处理后的金属基材进行表面耦合处理，以在金属基材及其纳米孔的表面形成一连接层；
将经表面耦合处理的金属基材置于模具中，用注塑成型的方法在该连接层的表面注塑形成一树脂层。
一种金属与树脂的复合体，包括金属基材及形成于该金属基材表面的树脂层，该金属基材的表面通过化学蚀刻处理形成有若干纳米孔，所述金属与树脂的复合体进一步包括一连接层，该连接层形成于该金属基材与该纳米孔的表面，该树脂层覆盖于该连接层的表面从而与该金属基材结合。
本发明通过将表面形成有纳米孔的金属基材浸渍于耦合剂溶液中，从而在金属基材及纳米孔的表面形成连接层，使得树脂层与连接层之间以化学键力相结合，从而使树脂层与金属基材之间以化学键力结合，因此，所制备的复合体中金属基材表面的树脂层不易发生剥离、龟裂(裂纹)、破损等现象。
附图说明
图1为本发明较佳实施方式的金属与树脂的复合体的剖视图。
图2为本发明较佳实施方式的金属基材表面形成有连接层时的扫描电子显微镜照片。
主要元件符号说明
金属与树脂的复合体 100
金属基材 10
纳米孔 11
连接层 30
树脂层 50
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
请参阅图1，本发明一较佳实施方式的金属与树脂的复合体100的制备方法，其包括如下步骤：
提供一形状化的金属基材10。该金属基材10可为不锈钢、铝合金、钛合金、铝镁合金或锌合金等。
对该金属基材10进行脱脂处理，以去除金属基材10表面的油污。所述脱脂处理可为将金属基材10浸渍于温度为40~75℃的金属清洗剂中超声清洗3~10min。该金属清洗剂的浓度可为5~20g/L。该金属清洗剂可为市面上常售的金属清洗剂。
对所述经脱脂处理后的金属基材10进行酸洗处理，以除去金属基材10表面的自然氧化物层。所述酸洗处理可为将金属基材10浸渍于温度为50~60℃的酸性溶液中0.5~5min分钟。所述酸性溶液的浓度为5~20g/L。该酸性溶液可为盐酸、磷酸、硫酸、硝酸及氢氟酸等酸性溶液的任意一种或者几种的混合物。所述酸洗处理过程中，酸性溶液可除去金属基材10表面的自然氧化物层，并未对该金属基材10本身进行腐蚀。即，该金属基材10经过该酸洗处理后其表面未形成纳米孔。
对所述经酸洗处理后的金属基材10进行化学蚀刻处理，以于该金属基材10的表面形成纳米孔11，所述纳米孔11的的直径可为10~1000nm，深度可为0.1~20μm。所述化学蚀刻处理可为将金属基材10浸渍于温度为10~120℃的蚀刻液中反应1~120min。该蚀刻液可为浓度为100~980ml/L的硫酸。
对所述经化学蚀刻处理后的金属基材10进行表面耦合处理，以于该金属基材10及纳米孔11的表面形成连接层30，该连接层30的厚度可为0.5~10nm。所述表面耦合处理可为将所述金属基材10浸渍于温度为25~100℃的耦合溶液中1s~5min。所述耦合溶液中含有耦合剂与溶剂。该耦合剂的浓度为10~100ml/L。所述耦合剂可为钛酸酯类耦合剂、锆酸酯类耦合剂、硼酸酯类耦合剂、有机磺酸类耦合剂或硅烷类耦合剂等。所述溶剂可为乙醇或水。
将经所述表面耦合处理的金属基材10的表面进行干燥处理，该干燥处理可为自然晾干或置于烘干机中烘干，该干燥处理的温度为25~140℃。
采用X射线能谱仪（EDS）对该表面形成有连接层30的金属基材10表面进行成分分析，结果显示该表面形成有连接层30的金属基材10的表层含有质量百分含量为2.58~2.87%的C、质量百分含量为1.29~2.08%的O、质量百分含量为0.59~0.72%的Si、质量百分含量为17.78~18.08%的Cr、质量百分含量为0.66~0.75%的Mn、质量百分含量为67.73~69.23%的Fe、质量百分含量为7.79~7.88%的Ni。
请参阅图2，采用扫描式电子显微镜（SEM）对该表面形成有连接层30的金属基材10进行表面形貌观察，结果显示该连接层30覆盖于该金属基材10及该纳米孔11的表面，且连接层30未完全将该纳米孔11填满。该纳米孔11覆盖有连接层30后的直径为10~990nm。
将经干燥处理的金属基材10置于模具（图未示）中，用注塑成型的方法在金属基材10及耦合连接层30的表面注塑树脂层50，控制射出熔融温度为220~320℃，即制得金属与树脂的复合体100。该树脂层50可为聚对苯二甲酸丁二醇酯（PBT）、聚苯硫醚（PPS）、聚对苯二甲酸乙二醇酯（PET）、聚醚醚酮（PEEK）、聚碳酸酯（PC）、聚氯乙烯（PVC）等。该树脂层50直接与耦合连接层30以化学键力相结合，从而使树脂层50与金属基材10之间以化学键力相结合。
请参阅图1，本发明一较佳实施方式金属与树脂的复合体100（以下简称“复合体”），其包括金属基材10及依次形成于该金属基材10表面的连接层30与树脂层50。
该金属基材10的表面通过化学蚀刻处理形成有若干纳米孔11。该纳米孔11的直径可为10~1000nm，深度为0.1~20μm。所述金属基材10的材质可为不锈钢。
所述连接层30覆盖于该金属基材10及该纳米孔11的表面。其中，该连接层30并未完全填满该纳米孔11。该连接层30的厚度可为0.5~10nm。
采用X射线能谱仪（EDS）对该表面形成有连接层30的金属基材10表面进行成分分析，结果显示该表面形成有连接层30的金属基材10表面含有质量百分含量为2.58~2.87%的C、质量百分含量为1.29~2.08%的O、质量百分含量为0.59~0.72%的Si、质量百分含量为17.78~18.08%的Cr、质量百分含量为0.66~0.75%的Mn、质量百分含量为67.73~69.23%的Fe、质量百分含量为7.79~7.88%的Ni。
请参阅图2，采用扫描式电子显微镜（SEM）对该表面形成有连接层30的金属基材10进行表面形貌观察，结果显示该连接层30覆盖于该金属基材10及该纳米孔11的表面，且连接层30未完全将该纳米孔11填满。该纳米孔11覆盖有连接层30后的直径为10~990nm。
所述树脂层50通过注塑成型形成于所述连接层30的表面并填充于所述纳米孔11未被连接层30填满的的区域。该树脂层50可为聚对苯二甲酸丁二醇酯（PBT）、聚苯硫醚（PPS）、聚对苯二甲酸乙二醇酯（PET）、聚醚醚酮（PEEK）、聚碳酸酯（PC）、聚氯乙烯（PVC）等。该树脂层50直接与连接层30以化学键力相结合，从而使树脂层50与金属基材10之间以化学键力相结合。所述复合体100的拉拔力范围为10~100KgF/cm2，剪切力范围为10~260Kgf/cm2。
下面通过实施例来对本发明进行具体说明。
实施例1
本实施例金属基材10的材质为不锈钢SUS304，树脂层50的材质为PBT。
脱脂处理：将金属基材10浸渍于浓度为20g/L的金属清洗剂中超声波清洗5min，保持清洗剂的温度为75℃。
酸洗处理：将经脱脂的金属基材10浸渍于温度为50℃的盐酸溶液中0.5分钟。盐酸溶液中盐酸的浓度为200g/L。
化学蚀刻处理：将金属基材10浸渍于温度为70℃的硫酸溶液中反应10min。该硫酸溶液中硫酸的浓度为300ml/L。
表面耦合处理：将经化学蚀刻处理后的金属基材10浸渍于温度为25℃的耦合溶液中10s。该耦合溶液中含有锆酸酯耦合剂与乙醇。该耦合溶液中锆酸酯耦合剂的浓度为30ml/L。
烘干处理：将经耦合处理的金属基材10清洗后置于烘箱中进行烘干，烘干温度为60℃，时间为15min。
注塑成型：射出温度为285℃。
实施例2
本实施例金属基材10的材质为不锈钢SUS306，树脂层50的材质为PPS。
脱脂处理：将金属基材10浸渍于浓度为5g/L的清洗剂中超声波清洗10min，保持清洗剂的温度为75℃。
酸洗处理：将经脱脂的金属基材10浸渍于温度为常温的盐酸溶液中5分钟。盐酸溶液中盐酸的浓度为200g/L。
化学蚀刻处理：将金属基材10浸渍于温度为120℃的硫酸溶液中反应10min。该硫酸溶液中硫酸的浓度为980ml/L。
表面耦合处理：将经化学蚀刻处理后的金属基材10浸渍于温度为40℃的耦合溶液中60s。该耦合溶液中含有锆酸酯耦合剂与水。该耦合溶液中锆酸酯耦合剂的浓度为20ml/L。
烘干处理：将经耦合处理的金属基材10清洗后置于烘箱中进行烘干，烘干温度为60℃，时间为15min。
注塑成型，射出温度为320℃。
实施例3
本实施例金属基材10的材质为不锈钢SUS316，树脂层50的材质为PA。
脱脂处理：将金属基材10浸渍于浓度为15g/L的清洗剂中超声波清洗10min，保持清洗剂的温度为60℃。
酸洗处理：将经脱脂的金属基材10浸渍于温度为常温的盐酸溶液中3分钟。盐酸溶液中盐酸的浓度为150g/L。
化学蚀刻处理：将金属基材10浸渍于温度为10℃的硫酸溶液中反应120min。该硫酸溶液中硫酸的浓度为900ml/L。
表面耦合处理：将经化学蚀刻处理后的金属基材10浸渍于温度为25℃的耦合溶液中15s。该耦合溶液中含有硅烷偶合剂与水。该耦合溶液中硅烷偶合剂的浓度为30ml/L。
烘干处理：将经耦合处理的金属基材10清洗后置于烘箱中进行烘干，烘干温度为120℃，时间为5min。
注塑成型，射出温度220℃。
所述金属与树脂的复合体100的制备方法，通过将表面形成有纳米孔11的金属基材10浸渍于耦合剂溶液中，从而在金属基材10及纳米孔11的表面形成连接层30，使得树脂层50与连接层30之间以化学键力相结合，从而使树脂层50与金属基材10之间以化学键力结合，因此，所制备的复合体100中金属基材10表面的树脂层50不易发生剥离、龟裂(裂纹)、破损等现象。

Claims (9)

1.一种金属与树脂的复合体的制备方法，其包括如下步骤：
提供一金属基材；
对所述金属基材进行化学蚀刻处理，使该金属基材的表面形成若干纳米孔；
对该所述经化学蚀刻处理后的金属基材进行表面耦合处理，以在金属基材及其纳米孔的表面形成一连接层；
将经表面耦合处理的金属基材置于模具中，用注塑成型的方法在该连接层的表面注塑形成一树脂层。
2.如权利要求1所述的金属与树脂的复合体的制备方法，其特征在于：所述化学蚀刻处理为将金属基材浸渍于温度为10~120℃的蚀刻液中1~120min，该蚀刻液为浓度为100~980ml/L的硫酸。
3.如权利要求1所述的金属与树脂的复合体的制备方法，其特征在于：所述表面耦合处理为将所述金属基材浸渍于温度为25~100℃的耦合溶液中1s~5min，所述耦合溶液中含有耦合剂与溶剂。
4.一种金属与树脂的复合体，包括金属基材及形成于该金属基材表面的树脂层，该金属基材的表面通过化学蚀刻处理形成有若干纳米孔，其特征在于：所述金属与树脂的复合体进一步包括一连接层，该连接层形成于该金属基材与该纳米孔的表面，该树脂层覆盖于该连接层的表面从而与该金属基材结合。
5.如权利要求4所述的金属与树脂的复合体，其特征在于：所述纳米孔的的直径为10~1000nm，深度为0.1~20μm。
6.如权利要求4所述的金属与树脂的复合体，其特征在于：所述连接层的厚度为0.5~10nm。
7.如权利要求4所述的金属与树脂的复合体，其特征在于：所述连接层未完全将所述纳米孔填满，所述纳米孔表面覆盖有连接层后的直径为10~990nm。
8.如权利要求5所述的金属与树脂的复合体，其特征在于：所述金属基材为不锈钢、铝合金、钛合金、铝镁合金或锌合金。
9.如权利要求5所述的金属与树脂的复合体，其特征在于：所述树脂层为聚对苯二甲酸丁二醇酯、聚苯硫醚、聚对苯二甲酸乙二醇酯、聚醚醚酮、聚碳酸酯或聚氯乙烯，该树脂层与耦合连接层以化学键力相结合，使该树脂层与金属基材之间以化学键力相结合。
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CN109130041A (zh) * 2017-06-28 2019-01-04 洛阳尖端技术研究院 一种防覆冰膜及其制备方法
CN108018555A (zh) * 2017-10-17 2018-05-11 广东长盈精密技术有限公司 一种金属的表面处理方法、金属制品及金属塑料复合体
CN107745477A (zh) * 2017-12-03 2018-03-02 无锡市恒利弘实业有限公司 一种金属表面纳米注塑成型的方法及其应用
CN108297893A (zh) * 2017-12-13 2018-07-20 浙江大学 一种涡流轨道制动系统磨耗板、系统及其制造方法
CN108313087A (zh) * 2017-12-13 2018-07-24 浙江大学 一种涡流轨道制动系统用磨耗板及其制造方法
CN108297893B (zh) * 2017-12-13 2020-03-13 浙江大学 一种涡流轨道制动系统磨耗板、系统及其制造方法
CN108321315A (zh) * 2018-03-16 2018-07-24 常州斯威克光伏新材料有限公司 新型动力锂电池铝塑膜
CN110549542A (zh) * 2018-05-31 2019-12-10 富智康精密电子（廊坊）有限公司 复合体及其制作方法
CN110549543A (zh) * 2018-05-31 2019-12-10 富智康精密电子（廊坊）有限公司 复合体及其制作方法
CN108995126A (zh) * 2018-06-20 2018-12-14 北京航数车辆数据研究所有限公司 一种金属塑料混合结构的制造方法
CN110653993A (zh) * 2018-06-29 2020-01-07 富智康精密电子（廊坊）有限公司 壳体及其制备方法

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