CN106003888A - 一种柔性可拉伸电磁屏蔽膜及其制备方法 - Google Patents
一种柔性可拉伸电磁屏蔽膜及其制备方法 Download PDFInfo
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Abstract
本发明提供了一种柔性可拉伸电磁屏蔽膜及其制备方法。所述的柔性可拉伸电磁屏蔽膜的制备方法，包括：选用弹性膜作为弹性附着基体，将其拉伸到一定伸长率后固定，在弹性膜表面涂覆一层液体弹性粘合剂；将柔性纳米电磁屏蔽复合膜压渍在液体弹性粘合剂上，在柔性纳米电磁屏蔽复合膜的上侧涂覆具有保护作用的树脂，形成树脂层，在一定条件下使液体弹性粘合剂和树脂固化；释放施加在弹性附着基体上的拉力，使其带动柔性纳米电磁屏蔽复合膜回缩，即可制得柔性可拉伸电磁屏蔽膜。本发明所制备的柔性可拉伸电磁屏蔽膜具有弹性好、伸长率高(20％‑50％)，电磁屏蔽性能优良(1‑5GHz频率内，电磁波吸收率99％以上)，同时可承受一定弯曲和压缩变形。
Description
技术领域
本发明涉及电磁屏蔽材料领域，更具体地说，涉及柔性可拉伸电磁屏蔽膜领域。
背景技术
随着科技的迅速发展，电磁波在航空、航天、通信、家用电器、军事等领域得到广泛的应用，随之电磁污染问题也日渐突出。电磁波向外辐射的电磁能量正在以每年7％-14％的速度递增，电磁对环境的污染日益严重。在世界各地，各种信息网络传递着数以亿计的军事、政治、经济等方面的重要情报和信息，由于电磁波辐射而导致的信息泄密事件也时有发生，直接威胁到国家政治、经济、军事安全。同时，电磁波还会造成武器***失灵，给作战带来严重的隐患。因此，防止电磁波辐射，以保障信息、武器***安全以及人体健康成为迫切任务。
目前市场上很多电磁屏蔽材料都是通过材料表面金属镀溅、涂覆、贴覆或通过混纺导电纤维等方式，在制备和使用过程中容易出现很多问题，如金属与材料结合能力差，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，而且材料较粗硬，柔韧性差，不透气、手感性较差，不可穿戴，而且很难满足现代电磁屏蔽材料所需的“薄、轻、宽、强”的特性，因此，迫切需要研发一种具有高电磁屏蔽性能、柔韧性好、轻薄、耐久性好且可穿戴的电磁屏蔽材料。
发明内容
本发明所要解决的技术问题是提供一种具有高电磁屏蔽性能、柔韧性好、轻薄、耐久性好且可穿戴的柔性可拉伸电磁屏蔽膜及其制备方法。
为了解决上述技术问题，本发明提供了一种柔性可拉伸电磁屏蔽膜，其特征在于，包括：从下到上依次设置的弹性膜、至少一层柔性纳米电磁屏蔽复合膜和树脂层。
优选地，所述的弹性膜的下侧粘帖有双面粘性胶体。
本发明还提供了上述的柔性可拉伸电磁屏蔽膜的制备方法，其特征在于，包括：
第一步：将碳纳米管膜浸渍在石墨烯悬浮液中，处理一段时间后取出，在室温下自然晾干，得到柔性纳米电磁屏蔽复合膜；
第二步：选用弹性膜作为弹性附着基体，并对其两端施加一定拉力，将其拉伸到一定伸长率后固定，在弹性膜表面涂覆一层液体弹性粘合剂；
第三步：将第一步得到的柔性纳米电磁屏蔽复合膜压渍在液体弹性粘合剂上，在柔性纳米电磁屏蔽复合膜的上侧涂覆具有保护作用的树脂，形成树脂层，在一定条件下使液体弹性粘合剂和树脂固化，或者，在柔性纳米电磁屏蔽复合膜的上侧粘合另一弹性膜；
第四步：释放施加在弹性附着基体上的拉力，使其带动柔性纳米电磁屏蔽复合膜回缩，即可制得柔性可拉伸电磁屏蔽膜。
优选地，所述第一步还包括在柔性纳米电磁屏蔽复合膜的端部黏附电极。
更优选地，所述的电极为铜片、铜丝、导电纤维或其它导电材料。
更优选地，所述的导电纤维为碳纳米管纱线。
更优选地，所述的电极通过导电银胶与柔性纳米电磁屏蔽复合膜相连。
优选地，所述第一步中的碳纳米管膜由单壁或多壁碳纳米管制得，碳纳米管直径为10nm-100nm，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。
更优选地，所述第一步中的碳纳米管膜的尺寸与拉伸后的弹性附着基体相同。
优选地，所述的石墨烯悬浮液的浓度为1mg/ml～50mg/ml，浸渍时间1～5h，浸渍1～3次，可根据需要设计选择。
优选地，所述的弹性膜为聚二甲基硅氧烷薄膜、丙烯酸薄膜、聚氨酯薄膜或高弹橡胶薄膜。
优选地，所述的液体弹性粘合剂为聚二甲基硅氧烷、丙烯酸或聚氨酯。
优选地，所述的具有保护作用的树脂为聚氨酯、聚二甲基硅氧烷或橡胶。树脂的涂覆厚度可根据需要选择。
优选地，所述的第二步中的伸长率为弹性膜的断裂伸长率的5～50％。
所述的固化时间、温度、压力等条件由所选择的粘合剂和树脂决定。
与现有技术相比，本发明的优点是：
(1)本发明采用PDMS膜作为弹性附着基体，并在拉伸的同时与柔性纳米电磁屏蔽膜粘结固化，从而提高了电磁屏蔽膜的柔韧性和弹性。
(2)本发明以高电磁屏蔽吸收率的碳纳米管膜浸渍石墨烯悬浮液得到柔性纳米电磁屏蔽复合膜，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、厚度薄等特点，同时还采用浸渍石墨烯悬浮液的方式进一步提高了其电磁屏蔽性能。
(3)采用涂覆树脂的方式保护碳纳米管膜，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)该制备方法简单易行，适合产业化推广，具有广泛的应用前景。
(5)本发明制备得到的的柔性可拉伸电磁屏蔽膜具有弹性好、伸长率高(20％-50％)，电磁屏蔽性能优良(1-5GHz频率内，电磁波吸收率99％以上)，同时可承受一定弯曲和压缩变形。该弹性电磁屏蔽膜可以用于智能可穿戴服装和多功能电磁防护织物中，在军用和民用的智能防护领域具有广泛的应用。
附图说明
图1是柔性可拉伸电磁屏蔽膜示意图；
图2是超高屏蔽效能的弹性电磁屏蔽膜示意图；
图3是弹性可拉伸的电磁屏蔽粘附膜示意图。
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：超薄弹性可拉伸的电磁屏蔽膜
一种柔性可拉伸电磁屏蔽膜的制备方法，具体步骤为：
第一步：将碳纳米管膜浸渍在石墨烯悬浮液中，浸渍时间3h，浸渍1次，取出，在室温下自然晾干，得到柔性纳米电磁屏蔽复合膜2，并在其两端通过导电银胶黏附铜丝电极；
所述的碳纳米管膜选用尺寸为20×28cm2的碳纳米管膜(中国科学院苏州纳米技术与纳米仿生研究所)，由多壁碳纳米管制得，碳纳米管直径为20nm左右，膜厚度为20um，孔隙率为75％，拉伸强度为约200MPa，电导率约1×105S/m；所述的石墨烯悬浮液的浓度为2mg/ml的石墨烯悬浮液(纽美泰新材料有限公司)。
第二步：选用弹性膜1作为弹性附着基体，并对其两端施加一定拉力，将其拉伸到一定伸长率(断裂伸长率的40％)后固定，在弹性膜1表面涂覆一层液体弹性粘合剂(PDMS粘合剂)，厚度约为0.2mm；
所述的弹性膜1为方形PDMS膜，尺寸为20×20cm2，厚度为0.3mm。PDMS膜采用PDMS树脂(道康宁公司DC184)通过涂膜方法得到。
所述的PDMS粘合剂采用道康宁公司的SYLGARD184，由基本组分(PDMS液体，粘度5.2Pa-sec)和固化剂(粘度3.5Pa-sec)按10∶1的重量比混匀得到。
第三步：将第一步得到的柔性纳米电磁屏蔽复合膜2压渍在液体弹性粘合剂上，在柔性纳米电磁屏蔽复合膜2的上侧涂覆具有保护作用的树脂(水溶性聚氨酯树脂，拜耳科技有限公司，型号：U54)，形成树脂层3，厚度约为0.3mm，保持弹性膜1的拉伸状态，在60℃下使液体弹性粘合剂和树脂固化，时间不低于12小时；
第四步：释放施加在弹性附着基体上的拉力，使其带动柔性纳米电磁屏蔽复合膜2回缩，即可制得柔性可拉伸电磁屏蔽膜。
如图1所示，所得的柔性可拉伸电磁屏蔽膜包括：从下到上依次设置的弹性膜1、一层柔性纳米电磁屏蔽复合膜2和树脂层3。
该超薄弹性可拉伸的电磁屏蔽膜可吸收频带宽，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“薄、轻、宽、强”的特性，可作为新一代柔性电磁屏蔽材料。
实施例2：超高屏蔽效能的弹性电磁屏蔽膜
一种柔性可拉伸电磁屏蔽膜的制备方法，具体步骤为：
第一步：将3片碳纳米管膜分别浸渍在石墨烯悬浮液中，浸渍时间3h，浸渍1次，取出，在室温下自然晾干，得到3层柔性纳米电磁屏蔽复合膜2，在其中两片的一端通过涂覆导电银胶黏附铜丝电极；
所述的碳纳米管膜选用尺寸为20×30cm2的碳纳米管膜(中国科学院苏州纳米技术与纳米仿生研究所)，由多壁碳纳米管制得，碳纳米管直径为20nm左右，膜厚度为20um，孔隙率为75％，拉伸强度为约200MPa，电导率约1×105S/m；所述的石墨烯悬浮液的浓度为2mg/ml的石墨烯悬浮液(纽美泰新材料有限公司)。
第二步：选用弹性膜1作为弹性附着基体，并对其两端施加一定拉力，将其拉伸到一定伸长率(断裂伸长率的50％)后固定，在弹性膜1表面涂覆一层液体弹性粘合剂(PDMS粘合剂)，厚度约为0.2mm；
所述的弹性膜1为方形PDMS膜，尺寸为20×20cm2，厚度为0.4mm。PDMS膜采用PDMS树脂(道康宁公司DC184)通过涂膜方法得到。
所述的PDMS粘合剂采用道康宁公司的SYLGARD184，由基本组分(PDMS液体，粘度5.2Pa-sec)和固化剂(粘度3.5Pa-sec)按10∶1的重量比混匀得到。
第三步：将第一步得到的3层柔性纳米电磁屏蔽复合膜2依次压渍在液体弹性粘合剂上，带有电极的纳柔性纳米电磁屏蔽复合膜2位于上下两层，相邻两层柔性纳米电磁屏蔽复合膜2之间形成粘合剂层4；
在最上层的柔性纳米电磁屏蔽复合膜2的上侧涂覆具有保护作用的树脂(PDMS粘合剂，同第二步)，形成树脂层3，厚度约为0.3mm，保持弹性膜1的拉伸状态，在80℃下使液体弹性粘合剂和树脂固化，时间不低于12小时；
第四步：释放施加在弹性附着基体上的拉力，使其带动柔性纳米电磁屏蔽复合膜2回缩，即可制得柔性可拉伸电磁屏蔽膜。
如图2所示，所得的柔性可拉伸电磁屏蔽膜包括：从下到上依次设置的弹性膜1、三层柔性纳米电磁屏蔽复合膜2和树脂层3。
该弹性电磁屏蔽膜采用了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％，可作为工业、军事柔性电磁屏蔽材料，有效防止电磁波辐射和泄露，保障人身安全，维护国家信息、政治、军事安全。
实施例3：弹性可拉伸的电磁屏蔽粘附膜
一种柔性可拉伸电磁屏蔽膜的制备方法，具体步骤为：
第一步：将碳纳米管膜浸渍在石墨烯悬浮液中，浸渍时间3h，浸渍1次，取出，在室温下自然晾干，得到柔性纳米电磁屏蔽复合膜2，并在其两端通过导电银胶黏附铜丝电极；
所述的碳纳米管膜选用尺寸为20×30cm2的碳纳米管膜(中国科学院苏州纳米技术与纳米仿生研究所)，由多壁碳纳米管制得，碳纳米管直径为20nm左右，膜厚度为20um，孔隙率为75％，拉伸强度为约200MPa，电导率约1×105S/m；所述的石墨烯悬浮液的浓度为2mg/ml的石墨烯悬浮液(纽美泰新材料有限公司)。
第二步：选用弹性膜1作为弹性附着基体，并对其两端施加一定拉力，将其拉伸到一定伸长率(断裂伸长率的40％)后固定，在弹性膜1表面涂覆一层液体弹性粘合剂(PDMS粘合剂)，厚度约为0.2mm；
所述的弹性膜1为方形PDMS膜，尺寸为20×20cm2，厚度为0.4mm。PDMS膜采用PDMS树脂(道康宁公司DC184)通过涂膜方法得到。
所述的PDMS粘合剂采用道康宁公司的SYLGARD184，由基本组分(PDMS液体，粘度5.2Pa-sec)和固化剂(粘度3.5Pa-sec)按10∶1的重量比混匀得到。
第三步：将第一步得到的柔性纳米电磁屏蔽复合膜2压渍在液体弹性粘合剂上，在柔性纳米电磁屏蔽复合膜2的上侧涂覆具有保护作用的树脂(水溶性聚氨酯树脂，拜耳科技有限公司，型号：U54，厚度约为0.3mm，保持弹性膜1的拉伸状态，在60℃下使液体弹性粘合剂和树脂固化，时间不低于12小时；
第四步：释放施加在弹性附着基体上的拉力，使其带动柔性纳米电磁屏蔽复合膜2回缩，在弹性膜1的下表面粘附一层双面粘性胶体5，即可制得柔性可拉伸电磁屏蔽膜。
所述的双面胶4选用厚度为0.5mm的亚克力透明双面胶(上海璨兴复合材料有限公司)。
如图3所示，所得的柔性可拉伸电磁屏蔽膜包括：从下到上依次设置的弹性膜1、一层柔性纳米电磁屏蔽复合膜2和树脂层3。所述的弹性膜1的下侧粘帖有双面粘性胶体5(尺寸为20×30cm2)。
该电磁屏蔽粘附膜可以迅速粘附在需要屏蔽的结构(如帐篷，电磁发生装置等)表面，形成快速的电磁屏蔽效果。
本发明并不局限于上述实施方式，上述实施方式仅是示意性的，而非限制性，本领域的技术人员在本发明的启示下，在不脱离本发明宗旨和权利要求所保护范围下，还可以做出很多种形式，这些均属于本发明的保护范围之中。
Claims (10)
1.一种柔性可拉伸电磁屏蔽膜，其特征在于，包括：从下到上依次设置的弹性膜(1)、至少一层柔性纳米电磁屏蔽复合膜(2)和树脂层(3)。
2.如权利要求1所述的柔性可拉伸电磁屏蔽膜，其特征在于，所述的弹性膜(1)的下侧粘帖有双面粘性胶体(5)。
3.权利要求1或2所述的柔性可拉伸电磁屏蔽膜的制备方法，其特征在于，包括：
第一步：将碳纳米管膜浸渍在石墨烯悬浮液中，处理一段时间后取出，在室温下自然晾干，得到柔性纳米电磁屏蔽复合膜(2)；
第二步：选用弹性膜(1)作为弹性附着基体，并对其两端施加一定拉力，将其拉伸到一定伸长率后固定，在弹性膜(1)表面涂覆一层液体弹性粘合剂；
第三步：将第一步得到的柔性纳米电磁屏蔽复合膜(2)压渍在液体弹性粘合剂上，在柔性纳米电磁屏蔽复合膜(2)的上侧涂覆具有保护作用的树脂，形成树脂层(3)，在一定条件下使液体弹性粘合剂和树脂固化，或者，在柔性纳米电磁屏蔽复合膜(2)的上侧粘合另一弹性膜(1)；
第四步：释放施加在弹性附着基体上的拉力，使其带动柔性纳米电磁屏蔽复合膜(2)回缩，即可制得柔性可拉伸电磁屏蔽膜。
4.如权利要求3所述的柔性可拉伸电磁屏蔽膜的制备方法，其特征在于，所述第一步还包括在柔性纳米电磁屏蔽复合膜(2)的端部黏附电极。
5.如权利要求4所述的柔性可拉伸电磁屏蔽膜的制备方法，其特征在于，所述的电极通过导电银胶与柔性纳米电磁屏蔽复合膜(2)相连。
6.如权利要求3所述的柔性可拉伸电磁屏蔽膜的制备方法，其特征在于，所述第一步中的碳纳米管膜由单壁或多壁碳纳米管制得，碳纳米管直径为10nm-100nm，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。
7.如权利要求3所述的柔性可拉伸电磁屏蔽膜的制备方法，其特征在于，所述的石墨烯悬浮液的浓度为1mg/ml～50mg/ml，浸渍时间1～5h，浸渍1～3次。
8.如权利要求3所述的柔性可拉伸电磁屏蔽膜的制备方法，其特征在于，所述的弹性膜(1)为聚二甲基硅氧烷薄膜、丙烯酸薄膜、聚氨酯薄膜或高弹橡胶薄膜。
9.如权利要求3所述的柔性可拉伸电磁屏蔽膜的制备方法，其特征在于，所述的液体弹性粘合剂为聚二甲基硅氧烷、丙烯酸或聚氨酯。
10.如权利要求3所述的柔性可拉伸电磁屏蔽膜的制备方法，其特征在于，所述的具有保护作用的树脂为聚氨酯、聚二甲基硅氧烷或橡胶。
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