CN114633531A - 一种各向异性导热电磁屏蔽尼龙复合膜的制备方法 - Google Patents
一种各向异性导热电磁屏蔽尼龙复合膜的制备方法 Download PDFInfo
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Abstract
本发明公开了一种各向异性导热电磁屏蔽尼龙复合膜的制备方法,通过分层设计和组装策略制备了多功能尼龙复合薄膜,热压成型后连续的顶部的石墨烯导热网络作为各向异性导热层和电磁屏蔽层,中间镀镍尼龙膜作为电磁屏蔽增强层,底部的碳纤维布作为力学性能改善层;通过本发明制得的各向异性导热电磁屏蔽尼龙复合膜能够有效的传导电子设备运行产生的热量以及屏蔽99.99%的电磁波,维护设备正常运行,且复合材料的柔性极好,可广泛应用于各种场景;复合材料制作成本较低,工序简单,适用于工业化生产。
Description
技术领域
本发明属于电磁屏蔽导热材料技术领域,具体涉及一种各向异性导热电磁屏蔽尼龙复合膜的制备方法。
背景技术
如今,随着电子设备集成化、小型化、高性能化的发展,具有各向异性导热性和导电性的柔性聚合物基复合材料引起了广泛关注。为了防止热量聚集影响电子设备正常运行,作为散热器的复合材料应当在面内方向快速耗散废热。同时,为避免相邻热源的影响,要求复合材料的面外热导率不宜太高,可以视为设备之间的隔热板。除此之外,设备之间的电磁波干扰也是很严重的问题,这就要求复合材料具有较好的电磁波屏蔽性能。
石墨烯、碳纳米管等碳材料由于其超高的固有导热导电性能引起了研究人员的广泛关注。但是填料在聚合物基体中的无规分散带来的巨大界面热阻导致复合材料性能远远达不到预期,并且碳材料的粒度极小易团聚,导致复合材料力学性能严重下降。如CN103450674A公开了一种高导热尼龙6石墨烯纳米复合材料及其制备方法,作者将原位聚合石墨烯尼龙母粒和纯尼龙熔融共混密炼制得复合材料,两步法使得填料在聚合物基体中达到良好分散,但是添加10wt%氧化石墨烯的复合材料热导率仅为0.416W/mK,提升率并不理想。大量导热填料的引入容易造成机械性能和加工性能较差,成本和密度较高,对导热性能的提高也相对有限。
为了解决上述问题,本发明通过分层设计再组装成型的方式直接构建了填料的单向热传导通路及电磁损耗通路。石墨烯分散液经过真空抽滤后由于氢键和π-π堆积作用,紧密的贴合在滤膜表面,致密堆叠的石墨烯片层形成了高各向异性的导热通路,电子设备的废热可以从面内迅速传导耗散,且面外几乎绝热更不会影响相邻电子元件。经过化学镀镍后的尼龙滤膜表层沉积了致密的镍层,进一步提高了电磁波的电损耗和磁损耗。底层的碳纤维布提高了材料的整体力学性能,改善了尺寸稳定性。
发明内容
本发明提供了一种各向异性导热电磁屏蔽尼龙复合膜的制备方法。通过分层设计再组装成型的方式将高导电导热石墨烯层、表面镀镍的多孔尼龙树脂层、碳纤维布层复合,构建了填料的单向热传导通路以及电磁损耗通路,最终得到各向异性高导热电磁屏蔽多层尼龙复合膜,该结构赋予膜材料高面向导热、高电磁屏蔽性能的同时,具有较高的力学性能,且制备方法简单有效适宜工业化。
本发明的技术方案如下:
一种各向异性导热电磁屏蔽尼龙复合膜的制备方法,所述制备方法包括如下步骤:
(1)镀镍尼龙滤膜的制备
将经过敏化处理、活化处理的尼龙滤膜浸入镀液中,然后向镀液中滴加还原液,在60℃超声条件下搅拌(300~400rpm)反应5~15min,之后取出滤膜,冲洗,烘干,得到镀镍尼龙滤膜备用;
所述敏化处理是将尼龙滤膜放入敏化溶液中超声15min,所述敏化溶液由氯化亚锡、浓盐酸、去离子水按比例2(g):1(mL):99(mL)混合而成;
所述活化处理是将经过敏化处理的尼龙滤膜放入活化溶液中超声15min,所述活化溶液由氯化钯、浓盐酸、去离子水按比例0.01(g):0.1(mL):99.9(mL)混合而成;
所述镀液由六水合氯化镍、柠檬酸钠、去离子水、氨水按比例2(g):3(g):90(mL):10(mL)混合而成;
所述还原液由次亚磷酸钠、去离子水按比例4(g):10(mL)混合而成;
所述尼龙滤膜的孔径为0.8~0.22μm;
(2)真空抽滤负载石墨烯
将步骤(1)制备的镀镍尼龙滤膜置于滤纸上,通过真空辅助抽滤石墨烯分散液,使石墨烯覆盖于镀镍尼龙滤膜上,得到负载有石墨烯的镀镍尼龙滤膜;
所述石墨烯分散液中石墨烯的浓度为1mg/mL,配制方法为:将十二烷基苯磺酸钠、石墨烯纳米片、去离子水按比例100(mg):100(mg):100(mL)混合,超声处理30min,然后用超声波细胞破碎机处理30min,得到均匀分散且稳定的石墨烯分散液;
所述石墨烯纳米片的尺寸为5~10μm,片层数5~10层;
基于负载有石墨烯的镀镍尼龙滤膜的总质量,石墨烯的负载量为10~20wt%;
(3)铺叠热压
将步骤(2)制备的负载有石墨烯的镀镍尼龙滤膜覆盖于碳纤维布上,负载石墨烯的一面朝上(即负载石墨烯的一面不与碳纤维布接触),使用全自动压片机热压成型;
所述碳纤维布由极性聚合物集束剂包覆碳纤维制成,单丝直径为10~20μm,含碳量高于95%;
所述热压成型的条件为:热压温度200℃,压力10MPa,热压时间10min。
与现有技术相比,本发明的有益效果是:
1、本发明利用通过分层设计再组装成型的方式直接构建了填料的单向热传导通路以及电磁损耗通路,实现了复合材料的高性能化和多功能性,同时避免了填料在基体内部聚集对材料力学性能的负面影响,复合膜的结构示意图如图1所示;
2、本发明通过化学镀镍法,直接在尼龙滤膜基材表层原位沉积纳米镍颗粒,镍颗粒在膜表面形成厚度10微米左右的致密镍层,入射电磁波在镍层导电网络中发生传导损耗及磁损耗,有效增强了电磁屏蔽性能,工艺简便高效,可大规模化制备,镀镍滤膜实物图及断面扫描电镜如图2所示;
3、本发明利用石墨烯分散液真空抽滤负载的方式,在滤膜上表层致密堆叠的石墨烯片层形成了高各向异性的导热通路,避免了填料被基体包覆导致的较大界面热阻,电子设备的废热可以从面内迅速传导耗散,且面外的滤膜泡孔结构几乎绝热更不会影响相邻电子元件;
4、本发明将碳纤维布作为增强基底,提供了复合材料优异的力学性能,以及提升了尺寸稳定性。
附图说明
图1本发明复合膜的结构示意图。
图2实施例4中镀镍滤膜实物图及断面扫描电镜图。
具体实施方式
下面通过具体实施例进一步描述本发明,但本发明的保护范围并不仅限于此。
实施例中使用的尼龙滤膜购自上海新亚公司,直径为50mm;碳纤维布购自嘉兴纳科新材料有限公司,裁成直径50mm的圆片;石墨烯纳米片购自烯碳科技有限公司,片层数5-10层;其余试剂十二烷基苯磺酸钠、氯化亚锡、浓盐酸、氯化钯、六水合氯化镍、柠檬酸钠、氨水、次亚磷酸钠等为分析级纯度,可通过常规途径商购获得。
以下实施例中1mg/mL石墨烯分散液按如下配制:
100mg十二烷基苯磺酸钠、100mg石墨烯纳米片、100mL去离子水。将上述溶液超声处理30分钟,然后用超声波细胞破碎机处理30分钟,得到均匀分散且稳定的石墨烯分散液。
以下实施例中尼龙滤膜化学镀镍前的预处理按如下操作:
取2g氯化亚锡、1mL浓盐酸和99mL的去离子水混合均匀得到敏化溶液,将5-10张尼龙滤膜放入溶液中敏化处理,并超声15分钟。取出滤膜并用去离子水洗涤。再取0.01g氯化钯和0.1mL浓盐酸组成的100mL溶液进行活化处理,超声15分钟。再次取出滤膜用去离子水冲洗。然后配制镀液:2g的六水合氯化镍、3g的柠檬酸钠、90mL去离子水和10mL的氨水。还原液:4g次亚磷酸钠、10mL去离子水。
实施例1
将滤膜浸入镀液中,然后将还原液逐滴加入镀液中,并在60℃超声处理下剧烈搅拌。反应5min后取出滤膜,并用去离子水冲洗,并在60℃的真空烘箱中烘干24小时。量取6ml的石墨烯分散液(1mg/mL),通过镀镍尼龙滤膜和滤纸过滤(镀镍尼龙滤膜位于滤纸上)。将滤膜覆盖在碳纤维布上方,负载石墨烯纳米片的一面朝上。使用全自动压片机在200℃、10MPa热压成型10分钟。具体性能见表一。
实施例2
将滤膜浸入镀液中,然后将还原液逐滴加入镀液中,并在60℃超声处理下剧烈搅拌。反应10min后取出滤膜,并用去离子水冲洗,并在60℃的真空烘箱中烘干24小时。量取6ml的石墨烯分散液(1mg/mL),通过镀镍尼龙滤膜和滤纸过滤(镀镍尼龙滤膜位于滤纸上)。将滤膜覆盖在碳纤维布上方,负载石墨烯纳米片的一面朝上。使用全自动压片机在200℃、10MPa热压成型10分钟。具体性能见表一。
实施例3
将滤膜浸入镀液中,然后将还原液逐滴加入镀液中,并在60℃超声处理下剧烈搅拌。反应5min后取出滤膜,并用去离子水冲洗,并在60℃的真空烘箱中烘干24小时。量取12ml的石墨烯分散液(1mg/mL),通过镀镍尼龙滤膜和滤纸过滤(镀镍尼龙滤膜位于滤纸上)。将滤膜覆盖在碳纤维布上方,负载石墨烯纳米片的一面朝上。使用全自动压片机在200℃、10MPa热压成型10分钟。具体性能见表一。
实施例4
将滤膜浸入镀液中,然后将还原液逐滴加入镀液中,并在60℃超声处理下剧烈搅拌。反应10min后取出滤膜,并用去离子水冲洗,并在60℃的真空烘箱中烘干24小时。量取12ml的石墨烯分散液(1mg/mL),通过镀镍尼龙滤膜和滤纸过滤(镀镍尼龙滤膜位于滤纸上)。将滤膜覆盖在碳纤维布上方,负载石墨烯纳米片的一面朝上。使用全自动压片机在200℃、10MPa热压成型10分钟。具体性能见表一。
实施例5
对照组:纯尼龙滤膜未处理。具体性能见表一。
使用万能试验机(Instron-5966,USA)测试复合材料的力学性能。根据ISO527-2,在23℃和50%相对湿度下使用A型试样及薄膜夹具以50mm/min速度进行拉伸试验。
基于热盘瞬态平面源法,在室温及空气气氛下使用热常数分析仪(HotDiskTPS2500S,Sweden)测量复合材料的导热系数。
使用矢量网络分析仪对复合材料的电磁屏蔽性能进行测试。使用长度为22.86毫米,宽度为10.16毫米,厚度为2毫米的长方形样条在8-12GHz频段的电磁波下测试。
本发明实施例制备的各向异性导热电磁屏蔽尼龙复合膜的导热、电磁屏蔽、力学性能如下表一所示:
表一
相比对照组(纯尼龙),复合膜的面向导热系数、电磁屏蔽性能、力学性能都明显提升。化学镀镍时间越长,表面沉积的镍颗粒越多,对电磁波的损耗作用也更强。石墨烯量提高后,导热网络更加致密,面向导热系数明显提高,电磁屏蔽性能也有显著提升。此外,复合膜的面外导热系数没有很大变化,基本上是绝热的。总体而言,镀镍时间和石墨烯量对力学性能影响不大,复合膜的力学性能都很优异。
相比之下,实施例4化学镀镍时间较长,石墨烯的量也比较多,复合材料的电磁屏蔽性能和面向导热性能最佳,力学性能也较好。证明了分层设计再组装成型方案的可行性。
Claims (8)
1.一种各向异性导热电磁屏蔽尼龙复合膜的制备方法,其特征在于,所述制备方法包括如下步骤:
(1)镀镍尼龙滤膜的制备
将经过敏化处理、活化处理的尼龙滤膜浸入镀液中,然后向镀液中滴加还原液,在60℃超声条件下搅拌反应5~15min,之后取出滤膜,冲洗,烘干,得到镀镍尼龙滤膜备用;
所述镀液由六水合氯化镍、柠檬酸钠、去离子水、氨水按比例2(g):3(g):90(mL):10(mL)混合而成;
所述还原液由次亚磷酸钠、去离子水按比例4(g):10(mL)混合而成;
(2)真空抽滤负载石墨烯
将步骤(1)制备的镀镍尼龙滤膜置于滤纸上,通过真空辅助抽滤石墨烯分散液,使石墨烯覆盖于镀镍尼龙滤膜上,得到负载有石墨烯的镀镍尼龙滤膜;
(3)铺叠热压
将步骤(2)制备的负载有石墨烯的镀镍尼龙滤膜覆盖于碳纤维布上,负载石墨烯的一面朝上,使用全自动压片机热压成型。
2.如权利要求1所述各向异性导热电磁屏蔽尼龙复合膜的制备方法,其特征在于,步骤(1)中,所述敏化处理是将尼龙滤膜放入敏化溶液中超声15min,所述敏化溶液由氯化亚锡、浓盐酸、去离子水按比例2(g):1(mL):99(mL)混合而成。
3.如权利要求1所述各向异性导热电磁屏蔽尼龙复合膜的制备方法,其特征在于,步骤(1)中,所述活化处理是将经过敏化处理的尼龙滤膜放入活化溶液中超声15min,所述活化溶液由氯化钯、浓盐酸、去离子水按比例0.01(g):0.1(mL):99.9(mL)混合而成。
4.如权利要求1所述各向异性导热电磁屏蔽尼龙复合膜的制备方法,其特征在于,步骤(1)中,所述尼龙滤膜的孔径为0.8~0.22μm。
5.如权利要求1所述各向异性导热电磁屏蔽尼龙复合膜的制备方法,其特征在于,步骤(2)中,所述石墨烯分散液中石墨烯的浓度为1mg/mL,配制方法为:
将十二烷基苯磺酸钠、石墨烯纳米片、去离子水按比例100(mg):100(mg):100(mL)混合,超声处理30min,然后用超声波细胞破碎机处理30min,得到石墨烯分散液;
所述石墨烯纳米片的尺寸为5~10μm,片层数5~10层。
6.如权利要求1所述各向异性导热电磁屏蔽尼龙复合膜的制备方法,其特征在于,步骤(2)中,基于负载有石墨烯的镀镍尼龙滤膜的总质量,石墨烯的负载量为10~20wt%。
7.如权利要求1所述各向异性导热电磁屏蔽尼龙复合膜的制备方法,其特征在于,步骤(3)中,所述碳纤维布由极性聚合物集束剂包覆碳纤维制成,单丝直径为10~20μm,含碳量高于95%。
8.如权利要求1所述各向异性导热电磁屏蔽尼龙复合膜的制备方法,其特征在于,步骤(3)中,所述热压成型的条件为:热压温度200℃,压力10MPa,热压时间10min。
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Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103466603A (zh) * | 2013-08-09 | 2013-12-25 | 中国科学院苏州纳米技术与纳米仿生研究所 | 石墨烯分散液以及石墨烯薄膜的制备方法 |
CN104210168A (zh) * | 2014-09-10 | 2014-12-17 | 浙江碳谷上希材料科技有限公司 | 一种石墨烯金属复合电磁屏蔽膜的制备方法 |
CN108312680A (zh) * | 2018-03-27 | 2018-07-24 | 华南理工大学 | 一种层压超薄高性能电磁屏蔽薄膜及其制备方法 |
CN109205607A (zh) * | 2018-11-06 | 2019-01-15 | 西安交通大学 | 一种使石墨烯水平平铺自组装形成石墨烯膜的方法 |
CN110258106A (zh) * | 2019-07-19 | 2019-09-20 | 中南林业科技大学 | 一种基于碳纤维织物、金属镍纳米颗粒和石墨烯的夹层式柔性电磁屏蔽材料的制备方法 |
US20190292675A1 (en) * | 2018-03-20 | 2019-09-26 | Nanotek Instruments, Inc. | Process for graphene-mediated metallization of polymer films |
CN111232966A (zh) * | 2020-03-18 | 2020-06-05 | 北京石墨烯研究院 | 一种石墨烯分散液及其制备方法 |
CN210694780U (zh) * | 2019-09-14 | 2020-06-05 | 山东天厚新材料科技有限公司 | 一种坡莫合金低频电磁场屏蔽带 |
-
2022
- 2022-03-01 CN CN202210194634.XA patent/CN114633531A/zh active Pending
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103466603A (zh) * | 2013-08-09 | 2013-12-25 | 中国科学院苏州纳米技术与纳米仿生研究所 | 石墨烯分散液以及石墨烯薄膜的制备方法 |
CN104210168A (zh) * | 2014-09-10 | 2014-12-17 | 浙江碳谷上希材料科技有限公司 | 一种石墨烯金属复合电磁屏蔽膜的制备方法 |
US20190292675A1 (en) * | 2018-03-20 | 2019-09-26 | Nanotek Instruments, Inc. | Process for graphene-mediated metallization of polymer films |
CN108312680A (zh) * | 2018-03-27 | 2018-07-24 | 华南理工大学 | 一种层压超薄高性能电磁屏蔽薄膜及其制备方法 |
CN109205607A (zh) * | 2018-11-06 | 2019-01-15 | 西安交通大学 | 一种使石墨烯水平平铺自组装形成石墨烯膜的方法 |
CN110258106A (zh) * | 2019-07-19 | 2019-09-20 | 中南林业科技大学 | 一种基于碳纤维织物、金属镍纳米颗粒和石墨烯的夹层式柔性电磁屏蔽材料的制备方法 |
CN210694780U (zh) * | 2019-09-14 | 2020-06-05 | 山东天厚新材料科技有限公司 | 一种坡莫合金低频电磁场屏蔽带 |
CN111232966A (zh) * | 2020-03-18 | 2020-06-05 | 北京石墨烯研究院 | 一种石墨烯分散液及其制备方法 |
Non-Patent Citations (1)
Title |
---|
许亚东: "三明治结构电磁屏蔽复合薄膜的快速制备与性能研究", 中国博士学位论文全文数据库工程科技I辑, no. 8, pages 43 - 57 * |
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