CN106183211B - 一种电磁屏蔽复合织物及其制备和应用 - Google Patents
一种电磁屏蔽复合织物及其制备和应用 Download PDFInfo
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Abstract
本发明涉及一种电磁屏蔽复合织物及其制备和应用，包括：碳纳米管/石墨烯复合膜(1)、聚苯胺薄膜(2)、粘合剂(3)、基体织物(4)，其中碳纳米管/石墨烯复合膜中石墨烯复合于碳纳米管膜的上表面，聚苯胺薄膜通过粘合剂粘附于碳纳米管膜的下表面。制备：将石墨烯悬浮液沉积于一层碳纳米管薄膜上，室温自然晾干，得到石墨烯/碳纳米管复合膜；通过粘合剂，将聚苯胺薄膜粘附于碳纳米管薄膜的下表面，得到碳纳米管/石墨烯/聚苯胺复合膜；通过粘合剂，将上述碳纳米管/石墨烯/聚苯胺复合膜的表面粘合基体织物，固化，即得。本发明所制备的电磁屏蔽复合织物的电磁屏蔽性能优良，又能保持织物材料透气、柔韧、可折叠、粘结等特性。
Description
技术领域
本发明属于柔性电磁屏蔽材料及其制备领域，特别涉及一种电磁屏蔽复合织物及其制备和应用。
背景技术
当今社会飞速发展，现代技术日新月异，电器产品越来越普遍，电磁辐射产生的问题也日益严重。屏蔽是抑制电磁干扰的重要手段，在屏蔽材料中电磁屏蔽织物不仅具有屏蔽性好、柔软、易变形等优点，而且利于裁剪缝合，更贴近人民的生活，既满足人们日常生活的需要，又能起到防护的作用。因而，电磁屏蔽织物成为大家研究的热点，在近年来发展迅速，有良好的应用前景。
传统的电磁屏蔽织物可分为镀金属织物、表面涂覆织物、贴金属箔织物、导电纤维混纺织物等。镀金涂覆织物存在金属与织物的结合力较差，容易脱落，镀层容易被刮擦而失去屏蔽性能，制备过程污染严重等问题，至今在电磁屏蔽领域内未得到广泛应用，而金属纤维混纺织物也存在织造过程中易缠绕、金属纤维易断、生产效率低，生产成本高等问题，由此生产的产品屏蔽性能也相对较差。
因此探索高效电磁屏蔽材料尤其是柔性电磁屏蔽织物，对于防止电磁波引起的电磁干扰、提高电子产品、弹药、引信、精密电子武器设备等的安全可靠性及人身安全等具有十分重要的意义。
新型的电磁屏蔽织物材料将向吸波织物材料的方向发展，并且要求屏蔽织物材料具有“薄、轻、宽、强”的特性，碳纳米管是一种新型功能材料，电磁性能优于传统材料，同时又拥有较大的长径比，相对于其它金属颗粒和石墨颗粒，用很少的量就能形成导电网链，且其密度比金属颗粒小得多，不易因重力的作用而聚沉，同时还具有吸收频带宽、多功能、质量轻、厚度薄等特点，有作为优秀电磁屏蔽材料的巨大潜力。
发明内容
本发明所要解决的技术问题是提供一种电磁屏蔽复合织物及其制备和应用，本发明采用基体织物与复合电磁屏蔽膜复合，使得其可应用于智能纺织品中，同时也起到了保护碳纳米管膜的作用，使其不易磨损破坏，电磁屏蔽性能稳定，提高了材料的耐久性；本发明制备方法简单易行，适合产业化推广，具有广泛的应用前景。
本发明的一种电磁屏蔽复合织物，所述电磁屏蔽复合织物包括：碳纳米管/石墨烯复合膜
(1)、聚苯胺薄膜(2)、粘合剂(3)、基体织物(4)，其中碳纳米管/石墨烯复合膜中石墨烯复合于碳纳米管膜的上表面，聚苯胺薄膜通过粘合剂粘附于碳纳米管膜的下表面；碳纳米管/石墨烯复合膜(1)、聚苯胺薄膜(2)总膜厚可根据需要控制在0.5mm-3mm，优选为1mm。
所述粘合剂为液体粘合剂，聚二甲基硅氧烷、丙烯酸、聚氨酯中的一种；基体织物为氨纶弹性织物或尼龙耐磨织物。
本发明的一种电磁屏蔽复合织物的制备方法，包括：
(1)将石墨烯沉积于碳纳米管薄膜的上表面，室温自然晾干，得到碳纳米管/石墨烯复合膜；
(2)通过粘合剂，将聚苯胺薄膜粘附于碳纳米管薄膜的下表面，得到碳纳米管/石墨烯/聚苯胺复合膜；
(3)通过粘合剂，将上述碳纳米管/石墨烯/聚苯胺复合膜的表面粘合基体织物，固化，即得电磁屏蔽复合织物。
所述步骤(1)中石墨烯沉积于碳纳米管薄膜的上表面具体为：将石墨烯悬浮液通过布氏漏斗抽滤沉积于一层碳纳米管薄膜上。
所述石墨烯悬浮液的浓度为1mg/ml-50mg/ml。
所述步骤(1)中碳纳米管薄膜为：可由单壁或多壁碳纳米管制得，碳纳米管直径为10nm-100nm，薄膜厚度为10μm-50μm，孔隙率为35％-75％，拉伸强度为100MPa-500MPa，电导率为104-105S/m。
所述步骤(2)、(3)中粘合剂均为液体粘合剂，聚二甲基硅氧烷、丙烯酸、聚氨酯中的一种。
所述步骤(2)中聚苯胺膜为：通过乙醇助溶分散—溶液浇注成膜/压片成膜的方法制备。具体制备过程：
将聚苯胺研磨10-15min，然后分散到无水乙醇中，接着用细胞粉碎机粉碎5-10min，将得到的溶液超声1-1.5h后，在玻璃板上浇注成膜，在水中浸泡3-10分钟，得到自支撑聚苯胺薄膜；或将聚苯胺研磨10-15min，然后分散到无水乙醇中，接着用细胞粉碎机粉碎5-10min，将得到的溶液超声1-1.5h后，最后水浴加热蒸发多余的乙醇得到聚苯胺粉末，在室温、压强2-3MPa下压制成薄膜。
步骤(2)石墨烯/碳纳米管/聚苯胺复合膜进行裁剪，然后层叠铺放粘合，得到多层石墨烯/碳纳米管/聚苯胺复合膜；其中层数为1-10层。
所述步骤(3)中固化参数(如固化时间、温度等条件)由所选择的树脂决定，一般为温度：25℃-150℃，时间：0.5h-24h。
本发明的一种电磁屏蔽复合制备的应用，其特征在于：用于屏蔽服、屏蔽帐篷、屏蔽室材料。
本发明的复合织物具有使用方向性，将聚苯胺层朝向被屏蔽体，其对电磁波的反射可加强复合膜对电磁波的多次吸收；将石墨烯层朝向被屏蔽体，对电磁波的反射效率增强，可根据使用需求合理安排复合织物的使用方向。
本发明提供了一种柔性电磁屏蔽复合织物，采用了碳纳米管膜作为柔性复合电磁屏蔽膜的主体材料，并将石墨烯、聚苯胺分别复合于碳纳米管膜的上下两表面，再通过粘结复合工艺，制得柔性电磁屏蔽复合织物。本发明制备工艺简单，适合工业化生产，制备得到的电磁屏蔽织物柔韧性好、电磁屏蔽性能优良(1-5GHz频率内，电磁波吸收率99％以上)，还可以对其进行裁剪，选择不同形状和大小，满足不同应用的需求。此外还能保持织物材料透气、柔韧、可折叠、粘结等特性，可制成屏蔽服、屏蔽帐篷及屏蔽室材料等，以保障人身、信息安全等，是理想的电磁屏蔽材料。
有益效果
(1)本发明采用碳纳米管膜制备电磁屏蔽材料，电磁性能优于传统材料，同时又拥有较大的长径比，具有纳米尺寸效应，相对于其它金属颗粒和石墨颗粒，具有吸收频带宽、多功能、质量轻、厚度薄、柔性可变形等特点；
(2)本发明采用电磁屏蔽材料的多重复合方法，若聚苯胺朝向被屏蔽体，可以达到超高电磁屏蔽吸收效率：石墨烯加强了碳纳米管膜对电磁波的吸收，同时聚苯胺对电磁波的反射使得复合膜进一步对电磁波加以吸收；
(3)本发明采用基体织物与复合电磁屏蔽膜复合，使得其可应用于智能纺织品中，同时也起到了保护碳纳米管膜的作用，使其不易磨损破坏，电磁屏蔽性能稳定，提高了材料的耐久性；
(4)本发明制备方法简单易行，适合产业化推广，具有广泛的应用前景。
附图说明
图1是超薄柔性电磁屏蔽复合织物示意图；
图2是超高屏蔽效能的电磁屏蔽织物示意图；
图3是防水透气的柔性电磁屏蔽复合织物示意图；
其中，图1-3中，1—碳纳米管/石墨烯复合膜；2—聚苯胺薄膜；3—粘合剂；4—基体织物。
具体实施方式
下面结合具体实施例，进一步阐述本发明。应理解，这些实施例仅用于说明本发明而不用于限制本发明的范围。此外应理解，在阅读了本发明讲授的内容之后，本领域技术人员可以对本发明作各种改动或修改，这些等价形式同样落于本申请所附权利要求书所限定的范围。
实施例1
材料：
(1)选用尺寸为40×40cm2的碳纳米管膜1(中国科学院苏州纳米技术与纳米仿生研究所)，膜厚度为20um，孔隙率为75％，拉伸强度为约200MPa，电导率约1×105S/m；
(2)选用2mg/ml的石墨烯悬浮液(纽美泰新材料有限公司)；
(3)聚苯胺2(阿法埃莎公司)，其电导率为1S/cm。
(4)将PDMS(聚二甲基硅氧烷)液体(道康宁公司DC184)与固化剂按10:1比例混合均匀得到粘合剂3。
(5)选用超细超薄莱卡布4，克重：110g/m2，纱支：20D，成分及含量：锦纶：80％，氨纶：20％，尺寸为40×40cm2。
制备步骤：
将均匀分散的石墨烯悬浮液通过布氏漏斗抽滤沉积在一层超薄碳纳米管膜上，在室温下自然晾干，得到超薄碳纳米管/石墨烯复合膜；其次，采用乙醇助溶分散—溶液浇注成膜的方法：将聚苯胺研磨15min，然后分散到无水乙醇中，接着用细胞粉碎机粉碎5min，将得到的溶液超声1h后，在玻璃板上浇注成膜，在水中浸泡三分钟，得到自支撑聚苯胺薄膜，厚度约为0.1mm；再次，通过一层厚度约为0.2mmPDMS粘合剂，将聚苯胺薄膜粘附于碳纳米管膜的下表面形成碳纳米管/石墨烯/聚苯胺复合膜；最后，在上述复合电磁屏蔽薄膜上下表面各均匀涂覆一层PDMS，厚度约为0.2mm，再粘合一层莱卡布作为保护层，使其在80℃下固化10小时，固化结束后即得到超薄柔性电磁屏蔽复合织物。
该超薄柔性电磁屏蔽复合膜厚度约为0.7mm，可吸收频带宽，电磁屏蔽效能高，在1-5GHz频率内，电磁波吸收率99％以上，屏蔽效能可达35dB，具有“轻、薄、柔、宽、强”的特性，可作为新一代柔性电磁屏蔽材料。
实施例2
材料：
(1)选用尺寸为60×20cm2的碳纳米管膜1(中国科学院苏州纳米技术与纳米仿生研究所)，膜厚度为20um，孔隙率为75％，拉伸强度为约200MPa，电导率约1×105S/m；
(2)选用2mg/ml的石墨烯悬浮液(纽美泰新材料有限公司)；
(3)聚苯胺2(阿法埃莎公司)，其电导率为1S/cm。
(4)选用水溶性聚氨酯(拜耳科技有限公司)作为粘合剂3。
(5)选用高密锦纶四面弹力布4，克重：168g/m2，成分及含量：锦纶：84％，氨纶：16％，尺寸为20×20cm2。
制备步骤：
将均匀分散的石墨烯悬浮液通过布氏漏斗抽滤沉积在一层超薄碳纳米管膜上，在室温下自然晾干，得到超薄碳纳米管/石墨烯复合膜；其次，采用乙醇助溶分散—溶液浇注成膜的方法：将聚苯胺研磨10min，然后分散到无水乙醇中，接着用细胞粉碎机粉碎5min，将得到的溶液超声1h后，在玻璃板上浇注成膜，在水中浸泡5分钟，得到自支撑聚苯胺薄膜，厚度约为0.1mm；再次，通过一层厚度约为0.2mm聚氨酯粘合剂，将聚苯胺薄膜粘附于碳纳米管膜的下表面形成碳纳米管/石墨烯/聚苯胺复合膜；最后，将上述复合膜裁剪成三块20×20cm2的小块膜，通过聚氨酯粘合剂粘合后层叠铺放，再在三层复合膜上下两表面均匀涂覆一层聚氨酯，厚度约为0.3mm，再粘合一层锦纶四面弹力布作为保护层，使其在60℃下固化12小时；固化结束后即可制得柔性电磁屏蔽复合织物。
该柔性电磁屏蔽复合膜采用了3层纳米电磁屏蔽复合膜，屏蔽测试结果可达到50dB,即屏蔽效率可达99.999％，而且轻便耐磨、垂挺质感及可变形性好，穿着舒适，耐久性好。
实施例3
材料：
(1)选用尺寸为20×20cm2的碳纳米管膜1(中国科学院苏州纳米技术与纳米仿生研究所)，膜厚度为20um，孔隙率为75％，拉伸强度为约200MPa，电导率约1×105S/m；
(2)选用2mg/ml的石墨烯悬浮液(纽美泰新材料有限公司)；
(3)聚苯胺2(阿法埃莎公司)，其电导率为1S/cm。
(4)选用水溶性聚氨酯(拜耳科技有限公司)作为粘合剂3，防水透气。
(5)选用100D涤纶四面弹力布4，克重：125g/m2，成分及含量：涤纶：90％，氨纶：10％，尺寸为40×40cm2。
制备步骤：
将均匀分散的石墨烯悬浮液通过布氏漏斗抽滤沉积在一层超薄碳纳米管膜上，在室温下自然晾干，得到超薄碳纳米管/石墨烯复合膜；其次，采用乙醇助溶分散—压片成膜的方法：将聚苯胺研磨10min，然后分散到无水乙醇中，接着用细胞粉碎机粉碎5min，将得到的溶液超声1h，最后水浴加热蒸发多余的乙醇得到聚苯胺粉末，在室温、压强3MPa下压制成多片厚度约为0.5mm的薄膜；再次，通过一层厚度约为0.2mm聚氨酯粘合剂，将聚苯胺薄膜均匀分布排列并粘附于碳纳米管膜的下表面形成碳纳米管/石墨烯/聚苯胺复合膜；最后，在复合膜上下两表面均匀涂覆一层聚氨酯树脂，厚度约为0.3mm，再粘合一层涤纶四面弹力布作为保护层，使其在60℃下固化12小时；固化结束后即可制得柔性电磁屏蔽复合织物。
该防水透气的电磁屏蔽织物电磁屏蔽效能高，在1-5GHz频率内可达35dB,而且轻便、透气性好，符合人体皮肤的生理要求，光滑、凉爽、清新透气、柔软，而且也能保持服装的外形美。
Claims (9)
1.一种电磁屏蔽复合织物的制备方法，包括：
(1)将石墨烯沉积于碳纳米管薄膜的上表面，室温自然晾干，得到碳纳米管/石墨烯复合膜，其中石墨烯沉积于碳纳米管薄膜的上表面具体为：将石墨烯悬浮液通过布氏漏斗抽滤沉积于一层碳纳米管薄膜上；
(2)通过粘合剂，将聚苯胺薄膜粘附于碳纳米管薄膜的下表面，得到石墨烯/碳纳米管/聚苯胺复合膜；
(3)通过粘合剂，将上述石墨烯/碳纳米管/聚苯胺复合膜的表面粘合基体织物，固化，即得电磁屏蔽复合织物。
2.根据权利要求1所述的一种电磁屏蔽复合织物的制备方法，其特征在于：所述步骤(1)中石墨烯悬浮液的浓度为1mg/ml-50mg/ml。
3.根据权利要求1所述的一种电磁屏蔽复合织物的制备方法，其特征在于：所述步骤(1)中碳纳米管薄膜为：碳纳米管直径为10nm-100nm，薄膜厚度为10μm-50μm，孔隙率为35％-75％，拉伸强度为100MPa-500MPa，电导率为104-105S/m。
4.根据权利要求1所述的一种电磁屏蔽复合织物的制备方法，其特征在于：所述步骤(2)、(3)中粘合剂均为聚二甲基硅氧烷、聚氨酯中的一种。
5.根据权利要求1所述的一种电磁屏蔽复合织物的制备方法，其特征在于：所述步骤(2)中聚苯胺膜为：通过乙醇助溶分散—溶液浇注成膜或压片成膜的方法制备。
6.根据权利要求1所述的一种电磁屏蔽复合织物的制备方法，其特征在于：所述步骤(2)中石墨烯/碳纳米管/聚苯胺复合膜进行裁剪，然后层叠铺放粘合，得到单层或多层石墨烯/碳纳米管/聚苯胺复合膜；其中层数为1-10层。
7.根据权利要求1所述的一种电磁屏蔽复合织物的制备方法，其特征在于：所述步骤(3)中电磁屏蔽复合织物包括：碳纳米管/石墨烯复合膜(1)、聚苯胺薄膜(2)、粘合剂(3)、基体织物(4)，其中碳纳米管/石墨烯复合膜中石墨烯复合于碳纳米管膜的上表面，聚苯胺薄膜通过粘合剂粘附于碳纳米管膜的下表面；电磁屏蔽复合织物具有使用方向性，将聚苯胺层朝向被屏蔽体，其对电磁波的反射加强复合膜对电磁波的多次吸收；将石墨烯层朝向被屏蔽体，对电磁波的反射效率增强，根据使用需求合理安排复合织物的使用方向。
8.根据权利要求7所述的一种电磁屏蔽复合织物的制备方法，其特征在于：所述粘合剂为聚二甲基硅氧烷、聚氨酯中的一种；基体织物为氨纶弹性织物或尼龙耐磨织物。
9.根据权利要求1所述的一种电磁屏蔽复合织物的制备方法，其特征在于：所述步骤(3)中电磁屏蔽复合织物用于屏蔽服、屏蔽帐篷和屏蔽室材料。
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| CN105330857A (zh) * | 2015-11-19 | 2016-02-17 | 浙江大学 | 聚苯胺-氧化石墨烯-碳纳米管复合电磁屏蔽材料的制备方法 |
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