CN106758173A - 一种金属修饰的碳纤维及其制备方法 - Google Patents

一种金属修饰的碳纤维及其制备方法 Download PDF

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CN106758173A
CN106758173A CN201611053459.3A CN201611053459A CN106758173A CN 106758173 A CN106758173 A CN 106758173A CN 201611053459 A CN201611053459 A CN 201611053459A CN 106758173 A CN106758173 A CN 106758173A
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周学昌
杨梦嫣
李垚垚
朱德勇
王嘉辉
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Shenzhen University
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Abstract

本发明公开一种金属修饰的碳纤维及其制备方法，方法包括步骤：包括步骤：超声清洗碳纤维1~10分钟；等离子清洗碳纤维1~10分钟；用含双键的硅烷分子溶液浸泡碳纤维10~60分钟；在碳纤维表面进行自由基聚合，长出聚合物刷；在钯液中浸泡10~60分钟；在金属镀液中进行无电沉积。本发明是利用等离子体清洗碳纤维束，以增加它的表面粗糙度，并在其表面接上羟基增加它的亲水性，然后硅烷化，在此基础上长出聚合物刷，以此增加碳纤维束与金属的接触面积，金属在聚合物刷上进行无电沉积，从而获得高导电性高机械强度的碳纤维。

Description

一种金属修饰的碳纤维及其制备方法
技术领域
本发明涉及化学镀金属技术领域，尤其涉及一种金属修饰的碳纤维及其制备方法。
背景技术
可穿戴式电子设备，需求极大的电子新兴领域之一，尤其是在娱乐、军事、体育、太阳能电池和实时健康监测设备等方面。
随着日益庞大的应用需要，高性能柔性导电连接器、触体和电极，可穿戴式电子产品严重依赖于金属涂层纺织品，不仅仅可以提供理想的穿着舒适性，也可以保证功能和应用，如电导率、静电放电、电磁屏蔽和无线电频率干扰保护。
碳纤维具有优良的机械强度，市场对其的需求越来越大，但它的导电性能不如金属，所以要改良它的导电性能。目前，通过在碳纤维表面沉积一层导电金属，以提高其导电性的技术有电镀、原子层沉积、金属无电沉积技术。但是碳纤维与金属的结合力差，镀层金属容易脱落。
因此，现有技术还有待于改进和发展。
发明内容
鉴于上述现有技术的不足，本发明的目的在于提供一种金属修饰的碳纤维及其制备方法，旨在解决现有碳纤维与金属的结合力差，镀层金属容易脱落的问题。
本发明的技术方案如下：
一种金属修饰的碳纤维的制备方法，其中，包括步骤：
A、表面清洗：超声清洗碳纤维1~10分钟；
B、亲水化：等离子清洗碳纤维1~10分钟；
C、硅烷化：用含双键的硅烷分子溶液浸泡碳纤维10~60分钟；
D、自由基聚合：在碳纤维表面进行自由基聚合，长出聚合物刷；
E、离子交换：在钯液中浸泡10~60分钟；
F、金属无电沉积：在金属镀液中进行无电沉积。
所述的金属修饰的碳纤维的制备方法，其中，步骤C中，所述含双键的硅烷分子溶液可以为但不限于乙烯基三甲氧基硅烷溶液。
所述的金属修饰的碳纤维的制备方法，其中，所述乙烯基三甲氧基硅烷溶液的质量分数为1%~5%。
所述的金属修饰的碳纤维的制备方法，其中，步骤D具体包括：碳纤维在甲基丙烯酰氧乙基三甲基氯化铵溶液中浸泡30~180分钟（包括但不限于这个时间），碳纤维表面进行自由基聚合，长出聚合物刷。
所述的金属修饰的碳纤维的制备方法，其中，所述甲基丙烯酰氧乙基三甲基氯化铵溶液的质量分数为15%~25%。
所述的金属修饰的碳纤维的制备方法，其中，步骤E中，所述钯液为含二价钯离子的溶液。
所述的金属修饰的碳纤维的制备方法，其中，所述含二价钯离子的溶液为(NH4)2PdCl4溶液。
所述的金属修饰的碳纤维的制备方法，其中，采用质量浓度1g/L的(NH4)2PdCl4水溶液作为所述(NH4)2PdCl4溶液。
所述的金属修饰的碳纤维的制备方法，其中，步骤F中，所述金属镀液为铜镀液、镍镀液、银镀液或金镀液。
一种金属修饰的碳纤维，其中，采用如上任一所述的金属修饰的碳纤维的制备方法制备而成。
有益效果：本发明是利用等离子体清洗碳纤维束，以增加它的表面粗糙度，并在其表面接上羟基增加它的亲水性，然后硅烷化，在此基础上长出聚合物刷，以此增加碳纤维束与金属的接触面积，金属在聚合物刷上进行无电沉积，从而获得高导电性高机械强度的碳纤维。
附图说明
图1为本发明一种金属修饰的碳纤维的制备方法的流程示意图。
图2为本发明实施例中碳纤维束的SEM图。
图3为本发明实施例中表面有铜沉积的碳纤维束的SEM图。
图4为本发明实施例中表面有镍沉积的碳纤维束的SEM图。
图5为本发明实施例中表面有银沉积的碳纤维束的SEM图。
图6为本发明实施例中表面有金沉积的碳纤维束的SEM图。
具体实施方式
本发明提供一种金属修饰的碳纤维及其制备方法，为使本发明的目的、技术方案及效果更加清楚、明确，以下对本发明进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
结合图1所示，本发明提供一种金属修饰的碳纤维的制备方法较佳实施例，其中，包括步骤：
A、表面清洗：超声清洗碳纤维1~10分钟（包括但不限于此时间）；
具体地，将碳纤维用溶剂（如乙醇）在超声清洗机里清洗1~10分钟（包括但不限于此时间），优选3~5分钟。然后将清洗后的碳纤维放入70~90℃（包括但不限于此温度）鼓风烘箱烘干，例如80℃。
B、亲水化：等离子清洗碳纤维1~10分钟（包括但不限于此时间）；
具体地，将烘干的碳纤维放入等离子体清洗机里等离子处理1~10分钟，优选3~5分钟（如4分钟），在碳纤维的表面接上羟基等亲水基团。本发明利用等离子清洗碳纤维，以增加它的表面粗糙度，并在其表面接上羟基增加它的亲水性。
C、硅烷化：用含双键的硅烷分子溶液浸泡碳纤维10~60分钟（包括但不限于此时间）；
具体地，将经过亲水处理的碳纤维浸泡在含双键的硅烷分子溶液中10~60分钟，优选13~17分钟（如15分钟），然后用去离子水冲洗干净。其中，所述含双键的硅烷分子溶液可以为但不限于VTMS溶液（乙烯基三甲氧基硅烷溶液），所述VTMS溶液的质量分数为1%~5%（如2%），所述VTMS溶液可以为VTMS的乙醇溶液。
D、自由基聚合：在碳纤维表面进行自由基聚合，长出聚合物刷；
具体地，将硅烷化后的碳纤维在温度70~90℃（如80℃）的甲基丙烯酰氧乙基三甲基氯化铵溶液（含KPS 60g/L）中浸泡30~180分钟，优选50~70分钟（如60分钟），碳纤维表面进行自由基聚合，在碳纤维的表面长出聚合物刷，然后用去离子水冲洗干净。其中，所述甲基丙烯酰氧乙基三甲基氯化铵溶液的质量分数为15%~25%（包括但不限于此浓度），优选18%~22%（如20%）。本发明通过在碳纤维表面长出聚合物刷，以此增加碳纤维与金属的接触面积。
E、离子交换：在钯液中浸泡10~60分钟；
具体地，将经过自由基聚合后的碳纤维浸泡在钯液中10~60分钟，优选13~17分钟（如15分钟），进行离子交换。其中，所述钯液可以为但不限于含二价钯离子的溶液，所述含二价钯离子的溶液可以为但不限于为(NH4)2PdCl4溶液。优选地，采用质量浓度1g/L的(NH4)2PdCl4水溶液作为所述(NH4)2PdCl4溶液。
F、金属无电沉积：在金属镀液中进行无电沉积。
具体地，将经过离子交换的碳纤维放入金属镀液中进行无电沉积，所述金属镀液可以为但不限于铜镀液、镍镀液、银镀液或金镀液。
本发明还提供一种金属修饰的碳纤维，其中，采用如上任一所述的金属修饰的碳纤维的制备方法制备而成。本发明金属修饰的碳纤维具有高导电性高机械强度，有效解决了现有碳纤维与金属的结合力差，镀层金属容易脱落的问题。
下面通过实施例对本发明进行详细说明。
金属修饰碳纤维的具体步骤为：
（1）、表面清洗：将碳纤维束用乙醇在超声清洗机里清洗4分钟；
（2）、烘干：将清洗后的碳纤维束放入80℃鼓风烘箱烘干；
（3）、亲水化：将烘干的碳纤维束放入等离子体清洗机里等离子处理4分钟，在碳纤维束的表面接上羟基等亲水基团；
（4）、硅烷化：将经过亲水处理的碳纤维束浸泡在2%（wt%）的VTMS的乙醇溶液中15分钟，然后用去离子水冲洗干净；
（5）、自由基聚合：将硅烷化后的碳纤维束浸泡在20%（wt%）的METAC溶液中（含KPS 60g/L），80℃条件下反应60分钟，在碳纤维束的表面长出聚合物刷，然后用去离子水冲洗干净；
（6）、离子交换：将经过自由基聚合后的碳纤维束浸泡在1g/L的(NH4)2PdCl4水溶液中15分钟进行离子交换；
（7）、金属无电沉积：将经过离子交换的碳纤维束放入金属镀液中进行无电沉积。
a）、所用金属镀液为铜镀液时，铜镀液的组成见下表1，但不限于此组成。进行无电沉积时，将A液和B液按1:1的比例（体积比）混合均匀，再加入混合液3倍体积的水进行稀释，然后将碳纤维束放入铜镀液中进行无电沉积。
表1、铜镀液的组成
b）、所用金属镀液为镍镀液时，镍镀液的组成见下表2，但不限于此组成。进行无电沉积时，将A液和B液按4:1的比例（体积比）混合均匀，再用氨水调pH值为8，然后将碳纤维束放入镍镀液中进行无电沉积。
表2、镍镀液的组成
c）、所用金属镀液为银镀液时，银镀液的组成见下表3，但不限于此组成。进行无电沉积时，先要在碳纤维束上镀上一层铜，然后将银镀液的A液和B液按1:1的比例（体积比）混合均匀，将镀上铜的碳纤维束放入银镀液中进行无电沉积。
表3、银镀液的组成
d）、所用金属镀液为金镀液时，金镀液的组成见下表4，但不限于此组成。进行无电沉积时，先要在碳纤维束上镀上一层铜，然后将金镀液的B液按用量混合均匀，慢慢将A液滴加到混合均匀的B液中，将镀上铜的碳纤维束放入金镀液中进行无电沉积。
表4、金镀液的组成
测试结果：
图2为碳纤维束的SEM图，图3为本发明实施例中表面有铜沉积的碳纤维束的SEM图，图4为本发明实施例中表面有镍沉积的碳纤维束的SEM图，图5为本发明实施例中表面有银沉积的碳纤维束的SEM图，图6为本发明实施例中表面有金沉积的碳纤维束的SEM图。
碳纤维束在金属修饰前后的电阻对比见下表5。由下表5可知，通过本发明方法修饰后，金属的电阻明显下降，导电性得到明显提高。
表5、金属修饰前后的电阻
金属 无 Cu Ni Ag Au
电阻Ω/cm 11 0.6 6 0.24 1
综上所述，本发明提供的一种金属修饰的碳纤维及其制备方法。本发明是利用等离子体清洗碳纤维束增加它的表面粗糙度，并在其表面接上羟基增加它的亲水性，然后硅烷化，在此基础上长出聚合物刷，以此增加碳纤维束与金属的接触面积，金属在聚合物刷上进行无电沉积，从而获得高导电性高机械强度的碳纤维。
应当理解的是，本发明的应用不限于上述的举例，对本领域普通技术人员来说，可以根据上述说明加以改进或变换，所有这些改进和变换都应属于本发明所附权利要求的保护范围。

Claims (10)

1.一种金属修饰的碳纤维的制备方法，其特征在于，包括步骤：
A、表面清洗：超声清洗碳纤维1~10分钟；
B、亲水化：等离子清洗碳纤维1~10分钟；
C、硅烷化：用含双键的硅烷分子溶液浸泡碳纤维10~60分钟；
D、自由基聚合：在碳纤维表面进行自由基聚合，长出聚合物刷；
E、离子交换：在钯液中浸泡10~60分钟；
F、金属无电沉积：在金属镀液中进行无电沉积。
2.根据权利要求1所述的金属修饰的碳纤维的制备方法，其特征在于，步骤C中，所述含双键的硅烷分子溶液为乙烯基三甲氧基硅烷溶液。
3.根据权利要求2所述的金属修饰的碳纤维的制备方法，其特征在于，所述乙烯基三甲氧基硅烷溶液的质量分数为1%~5%。
4.根据权利要求1所述的金属修饰的碳纤维的制备方法，其特征在于，步骤D具体包括：碳纤维在甲基丙烯酰氧乙基三甲基氯化铵溶液中浸泡30~180分钟，碳纤维表面进行自由基聚合，长出聚合物刷。
5.根据权利要求4所述的金属修饰的碳纤维的制备方法，其特征在于，所述甲基丙烯酰氧乙基三甲基氯化铵溶液的质量分数为15%~25%。
6.根据权利要求1所述的金属修饰的碳纤维的制备方法，其特征在于，步骤E中，所述钯液为含二价钯离子的溶液。
7.根据权利要求6所述的金属修饰的碳纤维的制备方法，其特征在于，所述含二价钯离子的溶液为(NH4)2PdCl4溶液。
8.根据权利要求7所述的金属修饰的碳纤维的制备方法，其特征在于，采用质量浓度1g/L的(NH4)2PdCl4水溶液作为所述(NH4)2PdCl4溶液。
9.根据权利要求1所述的金属修饰的碳纤维的制备方法，其特征在于，步骤F中，所述金属镀液为铜镀液、镍镀液、银镀液或金镀液。
10.一种金属修饰的碳纤维，其特征在于，采用如权利要求1~9任一所述的金属修饰的碳纤维的制备方法制备而成。
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