CN116198190A - 一种面内均热导热薄膜及其制备方法 - Google Patents
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Abstract
本发明公开了一种面内均热导热薄膜，包括各向异性导热层和各向同性绝热层，各向同性绝热层附着在各向异性导热层上，各向异性导热层包括各向异性导热填料和高分子基体；各向同性绝热层为多孔复合层，所述多孔复合层由各向同性绝热填料和高分子基体组成；各向异性导热填料为氮化硼、氮化硼纳米片、氧化铝纳米片或氮化硼纳米管。该均热导热薄膜能够实现面内快速均热，且具有较高的绝缘作用。本发明还提供了一种面内均热导热薄膜的制备方法。
Description
技术领域
本发明属于导热薄膜领域，具体涉及一种面内均热导热薄膜及其制备方法。
背景技术
5G时代的到来，使得电子元件越来越小型化和柔性化，电子器件在工作时均会产生一定的热量，使工作器件的温度升高，形成局部热点，且电子器件工作频率急剧增加，导致产生的废热越来越集中，会严重影响电子元件的稳定性和使用寿命，目前，导热材料在各种工业领域中均有广泛的应用，但由于热导率的限制，导热均热效果并不理想，限制了器件或者系统的设计。尤其是在微电子产业中，电子电路设计的集成化、小型化趋势越来越明显，高性能导热均热材料的要求也越来越高，需求也越来越大。因此基于5G的发展，对电子器件均匀散热提出了更高的要求。因此设计高效的均热热管理材料非常重要。
传统散热材料通常选用金属或石墨材料为基础制造复合材料，目前已经不能满足电子产业对于导热均热的需求。进一步出现的石墨烯均热膜可以利用超高面内热导率实现较好的面内热扩散。专利号为CN104070715A的中国专利公开了一种石墨烯导热均热膜的制备方法，是通过化学气相沉积法生长十个原子层厚度的石墨烯膜，再将其与厚度小于100微米的常规导热均热膜的人造石墨膜通过胶粘复合在一起得到复合膜。但上述专利所涉及的胶层结合层的不均匀性会引入更大的界面热阻，从而不利于实现面内的均匀散热。同时常规导热均热膜由于导热填料在基体内内很难达到完全均匀，从而均热效果有限。
如果面外方向完全绝热，热量则可以全部从面内方向扩散，这会在很大程度上提高面内的热扩散均匀性。专利号为CN113307658A的中国专利公开了一种石墨-气凝胶双层均热膜的制备方法，将二氧化硅的硅溶胶涂覆到经过刻蚀后表面呈酸性的石墨片上，加热，获得石墨-改性硅凝胶复合膜，进一步将石墨-改性硅凝胶复合膜进行溶剂交换后干燥，随即获得石墨-气凝胶双层均热膜。该工作借助于二氧化硅气凝胶的绝热性来提高石墨的面内均热性，并且石墨片表面经过刻蚀，使石墨片表面和改性硅溶胶的附着力更强，形成特定的导热和隔热层，通过石墨的面内定向导热和气凝胶的隔热功能来实现了面内快速均热。但上述专利所涉及的石墨导热层是导电材料，限制了其在绝缘电子元器件封装领域的应用，且纵向导热效率依然较高。
发明内容
本发明提供了一种面内均热导热薄膜，该均热导热薄膜能够实现面内快速均热，即横向快速均热，且具有较高的绝缘作用。
一种面内均热导热薄膜，包括：各向异性导热层和各向同性绝热层，所述各向同性绝热层附着在各向异性导热层上，其中：
所述各向异性导热层包括各向异性导热填料和高分子基体；
所述各向同性绝热层为多孔复合层，所述多孔复合层包括各向同性绝热填料；
所述各向异性导热填料为氮化硼或氧化铝，所述氮化硼为氮化硼纳米片或氮化硼纳米管，氧化铝为氧化铝纳米片。
氮化硼纳米片的面内热导率达到2000W m-1K-1，而且氮化硼纳米片呈现优异的电绝缘性和低介电常数，这些性能可使材料应用于复杂且高功率的微电子和集成电路领域。因此，利用氮化硼设计一种面内超级均热的复合薄膜会在下一代电子产品具有优异的应用前景。
本发明通过在各向异性导热层上附着各向同性绝热层，使得热量在纵向传导过程中受到各向同性绝热层的阻碍，从而转向横向传导，由由于各向异性导热层具有较高的导热率从而实现了热量的横向高效传导。
所述各向异性导热填料为沿横向定向排列。通过横向定向排列使得热量能够快速的通过横向传导。
所述高分子基体为纤维素、聚乙烯醇、水性聚氨酯、水性环氧树脂或乙烯醇缩丁醛酯。
所述各向同性绝热填料为二氧化硅或中空玻璃微珠。
所述各向异性导热层的面内热导率为大于60W m-1K-1。面内热导率太低则无法高效的将热集中区域的热量扩散。
所述各向同性绝热层的热导率低于0.05W m-1K-1，绝热层的热导率太高则会促使热量的面外扩散从而放大导热薄膜的不均匀性，从而无法实现面内的均匀散热。
所述多孔复合层为各向同性绝热气凝胶，所述各向同性绝热气凝胶为无机气凝胶、有机气凝胶或有机无机复合气凝胶，所述无机气凝胶为二氧化硅气凝胶，所述有机气凝胶为聚氨酯泡棉。
进一步的，所述各向异性导热填料为氮化硼纳米片，所述高分子基体材料为纤维素，所述各向同性绝热层为二样化硅气凝胶薄膜。
本发明还提供了一种面内均热导热薄膜的制备方法，包括：
步骤1：将所述各向异性导热填料和所述高分子基体溶液混合、超声得到混合溶液，将所述混合溶液进行第一次抽滤得到第一悬浮液，第一次抽滤时间为20-40min；
步骤2：将各向同性绝热气凝胶放置于所述第一悬浮液的表面，进行第二次抽滤去除水分得到面内均热导热薄膜。
本发明利用步骤1的第一次抽滤使得各向异性导热填料与带有高分子的水溶液分离，带有高分子的水溶液位于上层，各向异性导热层位于下层，然后通过第二次抽滤将剩余的水分去除，从而通过在水溶液中的高分子将各向异性导热层与各向同性绝热气凝胶紧密粘结起来，与直接通过粘结料粘结相比尽快可能减小由于粘结介质而形成的不均匀的区域，降低热阻。
所述高分子基体溶液的浓度为1wt％。
所述各向异性导热填料和所述高分子基体的质量比为9.5:1-8.5:1，质量比过低，导热填料之间无法构建有效的导热通路，质量比过高，制备的材料易脆。
与现有技术相比，本发明的有益效果为：
本发明制备的薄膜背面覆有绝热层，良好的面外隔热效果使热量优先通过面内扩散，而弥补了导热层的面内不均匀性，从而实现均热的效果。本发明制备的导热薄膜的面内导热率约为60W m-1K-1，绝热膜的面外导热率为0.03W m-1K-1，其中复合薄膜的面外热导率降低到0.05W m-1K-1。
附图说明
图1为本发明实施例1制备的面内超级均热导热膜的SEM图；
图2为本发明实施例1制备的面内超级均热导热膜的红外热像图；
图3为本发明对比例1制备的面内超级均热导热膜的SEM图；
图4为本发明对比例1制备的面内超级均热导热膜的红外热像图；
具体实施方式
下面结合实施例与附图对本发明作进一步详细描述，需要指出的是，以下所述实施例旨在便于对本发明的理解，而对其不起任何限定作用。
本发明通过ASTM E1461-2013测试方法测量各个实施例中制备的导热薄膜的导热率。
实施例1
原料：纤维素溶液(1wt％)1.5g，水100g，氮化硼纳米片0.135g，二氧化硅气凝胶0.5g。
首先，将纤维素溶液1.5g，纤维素为0.015g，氮化硼纳米片0.135g，水100mL混合均匀，并在100W的水浴超声1h，混合均匀得到100mL混合溶液，并取出20mL混合溶液加入到抽滤瓶中抽滤20min之后得到第一悬浮液，在第一悬浮液表面放置0.5g二氧化硅气凝胶，继续抽滤并抽干水分得到面内均热薄膜，如图1所示，上层为二氧化硅气凝胶层，下层为高导热氮化硼薄膜层，得到的面内均热薄膜外热导率，即纵向导热率为0.05W m-1K-1,面内热导率，即横向导热率为65W m-1K-1，如图2所示，超级匀热膜用于点热源散热时，薄膜面内导热效果均匀一致。
实施例2
原料：PVA水溶液(1wt％)1.5g，水100g，氮化硼纳米片0.135g，二氧化硅气凝胶0.5。
首先，将PVA水溶液1.5g，PVA为0.015g，氮化硼纳米片0.135g，水100mL混合均匀，并在100W的水浴超声1h，混合均匀得到100mL混合溶液，并取出20mL混合溶液加入到抽滤瓶中抽滤25min之后得到第一悬浮液，在第一悬浮液表面放置0.5二氧化硅气凝胶，继续抽滤并抽干水分得到面内均热薄膜，得到的面内均热薄膜外热导率，即纵向导热率为0.05W m- 1K-1,面内热导率，即横向导热率为55W m-1K-1。
实施例3
原料：纤维素溶液(1wt％)1.6g，水100g，氮化硼纳米片0.135g，聚氨酯气凝胶0.7g。
首先，纤维素溶液1.6g，纤维素0.016g，氮化硼纳米片0.135g，水100mL混合均匀，并在100W的水浴超声1h，混合均匀得到100mL混合溶液，并取出20mL混合溶液加入到抽滤瓶中抽滤35min之后得到第一悬浮液，在第一悬浮液表面放置0.7g聚氨酯气凝胶，继续抽滤并抽干水分得到面内均热薄膜，得到的面内均热薄膜外热导率，即纵向导热率为0.06W m-1K-1,面内热导率，即横向导热率为50W m-1K-1。
对比例1
原料：纤维素溶液1.5g(1wt％)，水100g，氮化硼纳米片0.135g。
首先，将纤维素溶液1.5g，氮化硼纳米片0.135g，水100mL混合均匀，在100W的水浴超声在超声1h，经超声后再次混合均匀，并取出20mL加入到抽滤瓶中抽滤，待抽滤瓶中的水分抽干后得到导热薄膜，如图3所示，氮化硼片在横向呈现整齐的排列。制备薄膜的热导率为65W m-1K-1，如图4所示，薄膜用于点热源的散热时，热量在面内分布不均匀，容易在薄膜内造成热点集中。
以上所述，仅是本申请的几个实施例，并非对本申请做任何形式的限制，虽然本申请以较佳实施例揭示如上，然而并非用以限制本申请，任何熟悉本专业的技术人员，在不脱离本申请技术方案的范围内，利用上述揭示的技术内容做出些许的变动或修饰均等同于等效实施案例，均属于技术方案范围。
Claims (10)
1.一种面内均热导热薄膜，其特征在于，包括：各向异性导热层和各向同性绝热层，所述各向同性绝热层附着在各向异性导热层上，其中：
所述各向异性导热层包括各向异性导热填料和高分子基体；
所述各向同性绝热层为多孔复合层，所述多孔复合层包括各向同性绝热填料；
所述各向异性导热填料为氮化硼或氧化铝，所述氮化硼为氮化硼纳米片或氮化硼纳米管，氧化铝为氧化铝纳米片。
2.根据权利要求1所述的面内均热导热薄膜，其特征在于，所述各向异性导热填料为沿横向定向排列。
3.根据权利要求1所述的面内均热导热薄膜，其特征在于，所述高分子基体为纤维素、聚乙烯醇、水性聚氨酯、水性环氧树脂或乙烯醇缩丁醛酯。
4.根据权利要求1所述的面内均热导热薄膜，其特征在于，所述各向同性绝热填料为二氧化硅或中空玻璃微珠。
5.根据权利要求1所述的面内均热导热薄膜，其特征在于，所述各向异性导热层的面内热导率为大于60W m-1K-1；所述各向同性绝热层的热导率低于0.05W m-1K-1。
6.根据权利要求1所述的面内均热导热薄膜的制备方法，其特征在于，所述多孔复合层为各向同性绝热气凝胶，所述各向同性绝热气凝胶为无机气凝胶、有机气凝胶或有机无机复合气凝胶，所述无机气凝胶为二氧化硅气凝胶，所述有机气凝胶为聚氨酯泡棉。
7.根据权利要求1所述的面内均热导热薄膜，其特征在于，所述各向异性导热填料为氮化硼纳米片，所述高分子基体材料为纤维素，所述各向同性绝热层为二样化硅气凝胶薄膜。
8.根据权利要求1-7任一项所述的面内均热导热薄膜的制备方法，其特征在于，包括：
步骤1：将所述各向异性导热填料和所述高分子基体溶液混合、超声得到混合溶液，将所述混合溶液进行第一次抽滤得到第一悬浮液，第一次抽滤时间为20-40min；
步骤2：将各向同性绝热气凝胶放置于所述第一悬浮液的表面，进行第二次抽滤去除水分得到面内均热导热薄膜。
9.根据权利要求7所述的面内均热导热薄膜的制备方法，其特征在于，所述高分子基体溶液的浓度为0.5-1.5wt％。
10.根据权利要求7所述的面内均热导热薄膜的制备方法，其特征在于，所述各向异性导热填料和所述高分子基体的质量比为9.5:1-8.5:1。
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| CN117551335B (zh) * | 2024-01-12 | 2024-04-19 | 沈阳欧施盾新材料科技有限公司 | 一种用于超低温液氧环境的低粘度高液氧相容性树脂体系及其制备方法和应用 |
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