CN108368418B - 二维热传导材料及其用途 - Google Patents

二维热传导材料及其用途 Download PDF

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CN108368418B
CN108368418B CN201680070947.7A CN201680070947A CN108368418B CN 108368418 B CN108368418 B CN 108368418B CN 201680070947 A CN201680070947 A CN 201680070947A CN 108368418 B CN108368418 B CN 108368418B
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graphene
filler particles
coating
thermal
nanoflakes
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CN108368418A (zh
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裕裕基·福岛
托马斯·里奇
杰西卡·罗素
王丽雅
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Jie XikaLuosu
Tuo MasiLiqi
Yu YujiFudao
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Tuo MasiLiqi
Yu YujiFudao
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Abstract

热界面材料的开发和制造，其包括用于热界面应用中具有良好通面热传导性的油脂、糊剂、凝胶、粘合剂、衬垫、片材、焊料和相变材料。通过使用涂覆有导热材料的填料，结合涂覆有导热材料的填料和未涂覆的填料，形成传导网络来实现良好的贯通平面热传导性。

Description

二维热传导材料及其用途
其在本说明书中的描述
本申请是为实用专利申请形式，并主张2015年10月9日提交的序列号为62/284,797的美国临时专利申请的优先权。
技术领域
本发明涉及石墨烯基的热界面材料(thermal interface materials)的开发和制造，其包括具有用于热界面应用的良好的贯通平面热传导性(good through-planethermal conductivity)的油脂、糊剂(pastes)、凝胶、粘合剂、衬垫(pads)、片材、焊料和相变材料。通过使用石墨烯和涂覆有石墨烯的填料形成传导网络(conductive network)，可以获得良好的贯通平面热传导性。
背景技术
热界面材料(TIM)用于最小化热源和散热器之间的接触热阻。它被广泛应用于电子和其他行业，从芯片或处理器中去除热量至关重要，因为在高温下集成电路的操作是电子设备故障的主要原因。随着先进电子产品功能的快速增长和功率密度的提高，这种热管理变得越来越重要。产生的热量需要传递或散发到散热器，以保持适当的工作温度。
然而，当两个固体表面如热源和散热器放在一起时，它们之间的真实接触面积是有限的，因为两个表面不是完全平坦的，只有外表面的很小部分实际上是在接触中。因此，这些配合表面之间的热传递也非常有限，导致界面处的显著温差。TIMs的主要作用是填补两个配合表面之间的空隙并增加它们之间的热传递。TIM材料的主要要求是：高热传导性，通过很小的压力就容易变形以填充接触表面之间的空隙，良好的润湿性以及与两个接触表面的亲和性，形成具有最小厚度的层的能力，机械稳定性，不易泄漏，热循环寿命良好，且易于应用。
传统的TIMs包括油脂、衬垫、凝胶、粘合剂、焊料(solders)和相变材料等。它们大多数由聚合物基体或有机硅基体制成，并装载有导热填料颗粒。
导热油脂(Thermal greases)是由分散在有机硅或烃油中的导热填料组成的稠浆形式。填料可以是金属的、陶瓷的或碳质材料(carbonaceous materials)。金属基导热油脂通常使用银、铜、或铝颗粒。它们通常具有良好的热传导性，但可能承受高成本。
此外，它们具有导电性，可能会限制其应用而无需额外的电绝缘材料。陶瓷基的导热膏(thermal pastes)通常使用传导性陶瓷颗粒，例如氧化铍、氮化铝、氧化铝、氧化锌和二氧化硅作为填料。它们通常具有良好的热传导性和低成本。碳基导热油脂相对较新。良好的填料包括碳纳米管(CNT)和碳纳米纤维(CNF)。一般而言，导热油脂具有高热传导性、最小的压力的薄粘结线厚度(BLT)、低粘度可填充配合表面之间的空隙、且无需固化。但是，导热油脂容易受到油脂泵出和杂乱施工的影响。泵出(pump-out)通常由配合表面的热膨胀系数(CTE)失配引起，这可能会在热循环期间通过交替挤压和释放系统而迫使TIM流出界面。
导热垫(Thermal pads)是一组衬垫形式的TIMs。它们通常由诸如硅橡胶的弹性体基质和诸如氮化硼、氧化铝或氧化锌的导热填料组成。这种材料经常被制成一个软垫，在压缩时可以与配合表面相匹配。它们易于处理和使用，不易被泵出，并且可以用作振动筛(vibration damper)。他们的主要缺点包括需要较高的接触压力和较低的热传导性以及比导热油脂更高的成本。
导热凝胶(Thermal gels)通常由具有低交联密度的硅树脂(或烯烃)聚合物构成，负载有导热性填料，无论是陶瓷的还是金属的。硅树脂具有低弹性模量、良好的润湿特性和高的热稳定性。这些材料就像油脂，但可以固化。它们具有相当好的热传导性，良好的润湿特性，易于与配合表面匹配，并且不易被泵出。但是，他们需要固化，并在热循环过程中可能分层。
导热粘合剂(Thermal adhesives)是一种通常由粘合树脂和导热填料组成的导热胶类型。一种实施例是在固化的环氧树脂中分散银颗粒。这样的TIMs可以消除恒压的机械附件的需要，并且易于应用。他们不容易泵出，并且可以匹配到配合表面。但是，它们需要固化，并且在使用过程中可能会出现分层的风险。
相变材料(PCM)是一种具有高熔化热的物质，它能够在熔融或凝固时储存或释放大量的能量。相变热界面材料典型地是由高导热悬浮颗粒和基材制成。实例包括分散在有机物基体中的传导性金属氧化物颗粒，有机物基体如完全精制的石蜡、聚合物、共聚物或三者的混合物。在室温时，它们类似于导热垫。当加热到特定温度时，通常＞50℃，它们变为半固体或液体以填充配合表面之间的空隙。当温度降至过渡温度以下时，它们再次凝固。PCM不易泵出，且其应用比油脂更容易。它也不需要固化，也不会分层。主要的缺点是它们与油脂相比传导率较低，并且也需要压力。
商购的TIMs的热传导率约为5W/mK，远低于典型配合表面的热传导率。因此，对寻找更好的TIMs，特别是更有效的填料越来越感兴趣。先进的碳基纳米材料如碳纳米管、石墨烯和石墨烯纳米薄片(graphene nanoplatelets)由于其高固有热传导性而成为有希望的候选材料。例如，单壁碳纳米管(CNT)的热传导率室温下在3000～5000W/mK的范围内，而石墨烯的热传导率甚至更高。尽管CNT在TIM应用方面受到了相当的关注，但由于性能和制造成本问题，它尚未取得商业成功。早期工作的重点是随机分散CNT，结果不尽如人意。近来，注意力转移到CNT的垂直对准和CNT与两个配合表面之间的界面处的边界阻力的减小。但是，由于其高处理成本，将这种技术用于大规模应用将是一个挑战。
最近，由于其高热传导性，石墨烯成为先进热管理解决方案的新焦点。石墨烯具有独特的导热性质：它具有极高的平面内热传导率(in-plane thermal conductivity)，但石墨烯的贯通平面传导率至少低两个数量级。高平面内热传导率是由碳原子之间的共价sp2键合产生的，而低贯通平面热传导率主要是由于该方向上的弱范德华力偶联。据报道，当通过光学方法测量拉曼G带的偏移时，悬浮的单层石墨烯的热传导率约为5000W/mK。因此，许多研究人员尝试将石墨烯或石墨烯纳米薄片以各种材料或形式用于热应用，包括用于散热的片状产品和用于热界面传热的石墨烯基的糊剂/粘合剂。
例如，本发明人已经开发了可用于将来自热源的热量散布到散热器的石墨烯基片材产品(XG Leaf B)。该材料具有＞500W/mK的高平面内热传导率和＜5W/mK的低贯通平面传导率。该材料利用石墨烯纳米薄片的二维和各向异性特征，使得热量横向散发远离热源，而不是转移到电子器件的其他部分。然而，对于其他一些应用，热量需要通过热源和散热器的两个配合表面传递。例如，图1示出了LED照明装置中的热界面材料的应用。目前，使用银基焊膏(solder paste)将热量从LED芯片传递到散热器。这种热管理解决方案有几个缺点。首先，需要在易于导致芯片损坏的温度下固化该糊剂。其次，一旦固化，很难分开。当一个芯片发生故障时，整个设备都必须更换。第三，银基糊剂是昂贵的。因此，希望用具有高贯通平面热传导率和低成本的薄油脂、凝胶或带(tape)来代替焊膏。一些其他应用要求TIM形式为粘合剂、衬垫、相变材料等。正是在这种情况下，构想了以下发明。
如在WO2015/103435、US2014/328024、以及US2014/120399中发现的，已经将石墨烯和石墨烯基材料用于热界面材料中作为填料。然而，由于它们的二维性质，石墨烯片材或石墨烯纳米薄片倾向平行于热界面排列或取向，特别是在压力下。因此，提高贯通平面热传导率的效果大大降低。因此，建立一个能够有效传导热量的热通道势在必行。本发明对现有技术具有独特的区别。
WO2015/103435涉及一种使用磁功能化和磁场将石墨烯薄片垂直对准于配合基材的方法。这需要昂贵的专用设备来产生磁场。另外，一旦不再施加磁场，石墨烯排列(graphene alignment)可以随着时间流逝在流体系统中降低。在本发明中，可以将石墨烯、石墨烯纳米薄片或诸如氮化硼薄片的导热材料涂覆或锚定在填料表面上。垂直对准于配合基材的部分石墨烯薄片是由石墨烯或其他涂覆填料制造的TIM的固有性质，并且将保持稳定。可以使用标准的工业设备和方法加工这种TIM，并且仍然可以获得对齐的石墨烯和其他热传导性薄片的益处。
US2014/120399描述了将石墨烯添加到用作TIM的基质中的热效益，但没有提到在实际TIM应用中使用的薄粘结线中遇到的薄片对准(platelet alignment)问题。我们的发明解决了对齐问题。
US2013/0221268描述了使用石墨烯薄片结合其他填料材料来产生3D传导网络的导热膏。然而，通过将石墨烯薄片涂覆到其他填料上而不会显著损害它们的结构，本发明实现了类似的热传导性改进，且粘度大大降低，结果是优异的处理和热阻产品。
U.S.7,886,813描述了一种具有涂覆有高热传导率涂层的填料颗粒的TIM材料。这些涂层是金属，并且没有考虑使用石墨或片材来涂覆填料。
U.S.2014/025578描述了用石墨烯涂覆颗粒的方法。没有考虑将这些颗粒用于传热，例如在TIM中。
附图说明
图1为示出AIN板1、LED芯片2、热界面材料3、硅4、AIN板5、热界面材料6和散热器7上的衬垫的热界面材料的示例性应用图。
图2为纳米薄片涂覆的填料颗粒的示意图，显示了石墨烯涂层8和填料颗粒9和9'。
图3为用导热纳米薄片和纳米薄片涂覆的填料制成的热界面材料的示意图，其示出了树脂基体10、石墨烯涂覆的填料颗粒11、石墨烯片材或石墨烯纳米薄片12。
图4为用于热界面材料的石墨烯纳米薄片涂覆的氧化铝填料的显微照片。
图5为现有技术的氧化铝与本发明的涂覆氧化铝相比的热传导率曲线图。
图6为现有技术的氧化铝与本发明的涂覆氧化铝相比的耐热性图。
图7为显示干涂覆氧化铝与湿涂覆氧化铝的热传导率图。
图8为显示氧化铝“A”相对于根据本发明处理的氧化铝“B”和涂覆氧化铝“C”、以及涂覆氧化铝和纳米薄片混合物“D”的热传导率图。
图9为显示干涂覆氧化铝与湿涂覆氧化铝的热阻图。
图10为显示氧化铝和湿涂覆氧化铝的热阻图。
图11为显示氧化铝和湿涂覆氧化铝的热传导率图。
具体实施方式
因此，在本发明的一个实施方案中，存在包括选自由填料、石墨烯涂覆填料以及填料和石墨烯涂覆填料的混合物组成的组合的材料的热界面材料。
在另一个实施例中，为一种提供热界面复合材料的方法，该方法包括提供作为散热器的第一基材并提供作为热源的第二基材，并且将如本文所述的热界面材料放置在第一基材和第二基材之间。
还有一个实施例，它是一种复合材料结构，包括固体热源的；固体散热器，以及如本文所述的包含在固体热源与固体散热器之间的热界面材料。
在本发明中，可以通过两种方法实现贯通平面热通道(through-plane thermalpathway)：
1、使用纳米薄片涂覆的填料颗粒(nanoplatelet-coated filler particles)。例如，陶瓷颗粒可以由高传导性纳米薄片材料涂覆，如石墨烯纳米薄片和氮化硼薄片。涂层有助于确保垂直导热通道，并添加最少量的石墨烯纳米薄片。图2说明了这个概念。
2、使用不同大小(sizes)和形态的填料。例如，在一个实施方案中，与单独使用球形颗粒相比，纳米薄片涂覆的球形填料颗粒与石墨烯纳米薄片一起使用以形成3-D传导网络。如图3所示，由于石墨烯纳米薄片的二维和柔性特征，附加的石墨烯纳米薄片有助于更好地桥接填料以改善接触。例如，两个球之间的接触在理论上是单点接触。引入的柔性和片状石墨烯纳米薄片可显著增加传导性填料的接触面积。
在一个实施方案中，本发明包含用石墨烯纳米薄片涂覆的氧化铝填料制成的TIM油脂。氧化铝填料通过使用机械研磨机的方法制成的石墨烯纳米薄片涂覆。涂覆工艺被设计成将石墨烯纳米薄片有效地附着到氧化铝填料上而不用显著粉碎石墨烯纳米薄片或产生无定形碳涂层。图4中示出了涂覆的氧化铝填料。与裸露的氧化铝相比，由石墨烯涂覆的氧化铝填料制成的TIM显示出热传导率的显著增加(图5)且热阻率(thermal resistivity)降低(图6)。
在另一个实施方案中，填料的石墨烯涂层通过湿法来实现。将石墨烯纳米薄片和氧化铝在合适的有机溶剂溶液中混合在一起，其中它们通过超声混合分散并搅拌5分钟。然后，蒸发溶剂，留下均匀的粉末。将粉末分散到硅油中以形成导热油脂。如图7和图8所示，与采用相同量的未改性氧化铝制成的油脂相比，所得到的导热油脂显示出提高的热传导性。
在又一个实施方案中，将石墨烯纳米薄片与石墨烯涂覆的氧化铝填料一起添加到TIM油脂中。由于石墨烯纳米薄片的2-D和柔性特征，附加的石墨烯纳米薄片有助于更好地桥接填料。如图3所示，柔性和片状石墨烯纳米薄片可显著增加传导性填料的接触面积。
本发明中使用的术语石墨烯应该包括从完全剥落的石墨到厚度小于100nm和/或层数小于300且优选厚度小于20nm和/或层数小于60的颗粒的石墨烯纳米薄片。
实施例
实施例1：研磨
将石墨烯纳米薄片和氧化铝一起加入具有研磨介质的罐中，且球磨20分钟。将所得的均匀粉末分散到硅油中以形成导热油脂。与用相同量的未改性氧化铝制成的油脂相比，所得到的导热油脂表现出显著增加的热传导性和较低的热阻。与由相同的石墨烯纳米薄片和氧化铝混合物的简单混合物制成的油脂相比，所述油脂也表现出相等的热传导率和更低的耐热性和粘度。
实施例2：溶液处理
将石墨烯纳米薄片和氧化铝在合适的有机溶剂溶液中混合在一起，其中它们通过超声混合分散并搅拌5分钟。
将溶剂蒸发，留下均匀的粉末。将粉末分散到硅油中以形成导热油脂。与用相同量的未改性的氧化铝制成的油脂相比，所得的导热油脂表现出增强的热传导率。
实施例3：
如实施例1中所述，制备石墨烯纳米薄片涂覆的氧化铝粉末。将该粉末与未加工的石墨烯纳米薄片粉末一起分散到硅油中。如表Ⅰ所示，与用相同填料含量的未改性氧化铝、未改性氧化铝和具有相同石墨烯纳米薄片与氧化铝比率的未加工石墨烯纳米薄片粉末的混合物、或具有相同石墨烯纳米薄片与氧化铝比率的石墨烯纳米薄片涂覆的氧化铝制备的导热油脂相比，所得到的导热油脂表现出优异的热传导率。
表Ⅰ
Figure BDA0001683679120000061
Figure BDA0001683679120000071

Claims (11)

1.一种材料，包括：
陶瓷填料颗粒；
石墨烯或氮化硼中的至少一种，其中石墨烯或氮化硼中的至少一种包围陶瓷填料颗粒并在其上形成涂层；以及
硅油或烃油中至少一种的树脂基体，所述的陶瓷填料颗粒分散在所述的树脂基体中以形成油脂，在所述的陶瓷填料颗粒上的涂层和所述的树脂基质之间不存在空隙。
2.根据权利要求1所述的材料，其特征在于，所述的陶瓷填料颗粒选自于包含以下组成的组合：
a. 氧化物，
b. 碳化物，
c. 硼化物，以及
d. 氮化物。
3.根据权利要求1所述的材料，其特征在于，所述的陶瓷填料颗粒选自于包括以下组成的组合：
a. 氧化铝，
b. 氧化锌，
c. 二氧化硅，
d. 氮化硼，
e. 氮化硅，
f. 氮化铝，
g. 二氧化锡，
h. 氧化镁，
i. 二氧化钛，以及
j. 氧化铍。
4.根据权利要求1所述的材料，其特征在于，还包括纳米薄片，所述的纳米薄片由石墨烯或氮化硼中的至少一种形成，在所述的陶瓷填料颗粒上形成涂层的石墨烯或形成所述的纳米薄片的石墨烯中的至少一种的石墨烯源选自包括以下组成的组合：
a. 石墨，
b. 炭黑，
c. 活性炭，以及
d. 沥青。
5.根据权利要求4所述的材料，其特征在于，石墨烯纳米薄片具有低于100nm的厚度。
6.根据权利要求4所述的材料，其特征在于，石墨烯纳米薄片具有低于50nm的厚度。
7.根据权利要求4所述的材料，其特征在于，石墨烯纳米薄片具有低于25nm的厚度。
8.根据权利要求4所述的材料，其特征在于，石墨烯纳米薄片具有小于500nm的大小。
9.根据权利要求4所述的材料，其特征在于，石墨烯纳米薄片具有低于100nm的大小。
10.一种材料，其特征在于，包括:
球形填料颗粒；
石墨烯或氮化硼中的至少一种，其中石墨烯或氮化硼中的至少一种包围球形填料颗粒并在其上形成涂层；
与球形填料颗粒混合的多个石墨烯纳米薄片；以及
硅油或烃油中至少一种的树脂基体，所述的球形填料颗粒和所述的多个石墨烯纳米薄片分散在所述的树脂基体中以形成油脂，在所述的球形填料颗粒和所述的树脂基质上的涂层之间不存在空隙。
11.根据权利要求10所述的材料，其特征在于，所述的石墨烯纳米薄片为二维的。
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