CN107851475A - 由包被粉末制备的传导性复合材料 - Google Patents

由包被粉末制备的传导性复合材料 Download PDF

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CN107851475A
CN107851475A CN201680039405.3A CN201680039405A CN107851475A CN 107851475 A CN107851475 A CN 107851475A CN 201680039405 A CN201680039405 A CN 201680039405A CN 107851475 A CN107851475 A CN 107851475A
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conductive
conductive composites
composites
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particle
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C·雅各布
S·布赫尔
F·普罗斯特
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Hydromecanique et Frottement SAS
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HEF SAS
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Abstract

本发明涉及制造功能复合材料(电导体、热导体等)，所述功能复合材料由包被粉末制备。

Description

由包被粉末制备的传导性复合材料
前言
本发明涉及制造功能复合材料(电导体、热导体等)，该功能复合材料由包被粉末制备。所讨论的复合材料由可以是聚合物的有机相以及热和/或电传导相组成。该传导相使得通常绝缘的有机材料被赋予电和/或热传导性。
目前，这些传导性能通过将传导性填料，特别是金属填料或陶瓷填料与有机基质(base)混合来获得。因此，可以高度可变的比例使用各种类型的填料以产生期望的热和/或电的传导性值。
在现有技术中所使用的制造工艺中，用于获得热和/或电传导性材料的调节参数如下：
-掺入到有机基质中的填料的性质，
-其形貌(形式)，
-其粒度，和
-传导性填料相对于传导性填料和有机基质的混合物的总重量的质量分数。
当需要高传导率值时，待掺入到该有机基质中的填料的质量分数可能非常大。
举例来说，为了在有机材料中获得小于1Ω·cm的电阻率，相对于混合物的总重量，传导性材料的填料(诸如银)的质量分数可能超过50％。
然后，通过在有机基质内形成传导性颗粒的互连网络来降低这种材料的电阻率。因此需要相当大的且必然高的体积分数的、均匀分布的所述传导性颗粒的存在。
本发明的目的是在获得高的传导性的同时大大降低有机基质中传导相的比例。通过使用包被粉末可以实现该目的，其中，粉状有机材料B包覆有传导性材料A，如图1所示。
发明描述
更具体地，本发明提供了一种传导性复合材料，所述传导性复合材料包括传导性颗粒的互连网络，其中，所述传导性颗粒包括包覆有至少一层电和/或热传导材料的有机材料核，
其特征在于，全部所述颗粒在所述成型的传导性复合材料的内部结构内互连，从而形成传导性材料的连续三维网络，且
其特征在于，所述传导性复合材料的传导性包覆材料的质量分数占所述传导性复合材料的总重量的1wt％至30wt％。
就本发明而言，连续三维网络是指通过每个传导性颗粒的传导性涂层之间的接触的存在而形成的网络。
优选地，所述传导性复合材料的传导性包覆材料的质量分数可以占所述传导性复合材料的总重量的5wt％至20wt％。
所述传导性复合材料可以优选为膜或三维物体的形式。
就本发明而言，三维物体指不是膜的有一定体积的物体。(an object in volume)
传导性颗粒各自包括有机材料核和至少一层传导性材料。
一层或多层传导性材料可以有利地由金属材料或陶瓷材料或有机材料制成。
根据第一变型，(包覆到传导性颗粒的有机材料核上的)所述传导性材料可以包括选自银、金、铜、铝、钛、镍、钴和铁的至少一种金属。
根据第二变型，(包覆到传导性颗粒的有机材料核上的)所述传导性材料可以是陶瓷，所述陶瓷选自金属氧化物以及选自氮化物、碳化物、硅基化合物和锡基混合的化合物，例如ITO，其为氧化铟和氧化锡的混合物。
根据第三变型，(包覆到传导性颗粒的有机材料核上的)所述传导性材料可以是选自聚乙炔(polyacetylene)类、聚吡咯类和聚苯胺类的导电聚合物型有机材料。
就有机材料核而言，它可以有利地选自：
-热塑性塑料，诸如聚乙烯(PE)、聚丙烯(PP)，聚醚醚酮(PEEK)，聚醚酮酮(PEKK)、聚氯乙烯(PVC)、聚偏二氟乙烯(PVDF)、聚四氟乙烯(PTFE)和有机硅塑料(silicone)；及
-热固性塑料，诸如环氧树脂、聚酯、聚氨酯和丙烯酸树脂。
有机材料核可以有利地具有300nm至10mm，优选5μm至300μm的粒度。
为了获得包层的传导性颗粒，通过包覆使具有任何类型的形貌、粒度和性质的有机材料粉末具有涂层。
有机材料核可以有利地为球状式或层状，或为片状，线状或海绵状、不规则形的颗粒。
根据本发明的传导性复合材料可以有利地展现出16.10-9Ω·m至100Ω·m.的电阻率。
根据本发明的传导性复合材料可以有利地表现出2W·m-1·K-1至50W·m-1·K-1，优选地5W·m-1·K-1至10W·m-1·K-1的热导率。
有机材料核可以有利地包括热和/或电传导性填料。
这些热和/或电传导性填料可以包被有类似于以上说明书中所限定的那些的热和/或电传导性材料。
这些热和/或电传导性填料可以优选地包被有石墨、石墨烯、碳纳米管、植物纤维或传导性聚合物型的热和/或电导体材料。
本发明展示了使用包被粉末来制造功能复合材料(电和/或热的传导性)的优点。
由于在颗粒表面存在传导相，传导性的功能性大大增强。
观察到存在相互连接的传导性网络(如一种三维网状物)的理想的微结构。
除了这个概念所代表的经济收益，由于其允许低比例的填料获得高的传导性，这种粉末的使用可以通过避免混合组分时的精密且复杂的操作(这种操作不可避免地导致不均匀的问题)来简化其使用。
此外，根据本发明获得的具有银包覆层粉末的复合材料的热导率优于目前最好的复合材料的热导率值(1W·m-1·K-1至3W·m-1·K-1)且介于2W·m-1·K-1至50W·m-1·K-1,优选地介于5W·m-1·K-1至10W·m-1·K-1。
该复合材料可以被制成成品(烧结、注塑等)或者带状，或者例如通过热成型制成的可变形的膜。
这些粉末本身可以用于通过粉末包被制备功能涂层。包被的复合材料粉末也可以用于浸渍工业纺织品。
还应该注意的是，可以制备吸收雷达波的材料(或RAM：“雷达吸收材料”)。
本发明同样提供了用于制造根据本发明所定义的传导性复合材料的方法，其包括以下步骤：
a)提供和/或制备带电有机颗粒或不带电有机颗粒；
b)给所述有机颗粒包覆上一层或多层至少一种电和/或热传导材料以形成传导性颗粒，
c)使所述传导性颗粒成型以形成传导性膜或形状已预先限定的元件，
所述方法的特征在于，包覆所述有机颗粒的步骤b)按照以下任一种进行：
-利用干表面处理技术，所述颗粒被置于两相流化床中的悬浮液中，或者通过旋转或振动的机械方法；
-或者利用涉及在所述颗粒表面的沉淀或聚合的氧化还原反应的湿表面处理技术，所述颗粒被置于三相流化床中的悬浮液中，或通过机械或磁力搅拌方法。
作为干化学包被方法，可以特别提及的是化学或物理包被方法以及热化学扩散处理。
在所述有机颗粒的包覆(步骤b)之后，使由此获得的传导性颗粒成型(步骤c)。
通过塑料工艺学领域中常用的各种技术来使这些复合颗粒成型，从而制备具有相当特殊结构的成品或半成品。这是因为有机颗粒表面的传导相的存在自然地使得在致密化后获得相互连接的三维传导性网络，如图2所示。
使包覆过的传导性颗粒成型的步骤c)可以有利地通过选自烧结后轧制、原型制作(prototyping)、热成型或热喷涂的技术来进行。
附图说明
通过阅读以下描述，本发明的其他特征和优点将变得更清楚，所述描述是以示例性的并且非限制性的实施例的形式给出，并参考了附图，其中：
-图1示出了根据本发明的传导性颗粒的示意图；
-图2示出了所述传导性颗粒成型之后获得的结构的示意图；
-图3A示出了包覆之前有机聚乙烯核的显微图；
-图3B示出了通过化学包被用银包覆之后的聚乙烯颗粒的显微图；
-图4A示出了包被有20wt％的银的有机聚乙烯核的显微剖视图；
-图4B示出了包被有20wt％的银的有机聚乙烯核的显微剖视图；
-图5A和5B示出了包被有40wt％的银的有机PTFE核的显微剖视图；
-图6A和6B示出了包被有30wt％的氧化锡的有机PEKK核的显微剖视图；
-图7示出了在银包被的聚乙烯(PE)颗粒烧结之后获得的元件；
-图8示出了在银包被的PE颗粒烧结之后获得的元件的微观结构；
-图9示出了由聚乙烯粉末和银粉末的混合物获得的传导性材料的微观结构。
除非另有说明，在这些实施例中所有的百分比和份数均以质量百分比表示。
实施例
实施例1本发明
对具有50至500μm的粒度和不规则的形貌的低密度聚乙烯粉末进行银包覆测试。在自催化化学浴(三相流化床)中进行银包被。
将相对于聚乙烯+银的混合物的总重量的10wt％(实施例1B)和20wt％(实施例1A)的银以均匀的涂层的形式施加到聚乙烯(PE)颗粒的表面，如图3A、3B、4A和4B中的图像所示。
在包被有20wt％银的颗粒的截面分析之后，发现在聚乙烯颗粒的表面上存在约1μm的致密且连续的银涂层(图4A和4B)。
根据塑料工艺学中的常规分类，这些包被粉末可以用作任何成分。通过诸如挤出、注塑、烧结、原型制作等技术使这些粉末成型来制备半成品或成品。应该注意的是，对于获得最佳的导电性能，对材料产生高剪切应力的成型技术不是最适合的。
随后如上所述的包被的聚乙烯颗粒通过在负载下烧结(模塑)成型，得到直径为30mm、厚度为5mm的盘状体。对于聚乙烯，在160℃的温度下进行成型。这些初步测试的目的一方面是表征材料的结构，另一方面是表征其电阻率(及其电导率)。获得的元件如图7所示。
在对其表面进行抛光之后，通过光学显微镜分析材料的微观结构。图像如图8所示。由于聚乙烯基材料的弹性导致在抛光操作过程中发生塑性流动现象，使得对聚乙烯基材料进行抛光较为困难。因此不容易显示出清晰的微观结构。然而，可以辨认出银存在于颗粒的外周，并且其还形成了三维互连网络。
实施例2比较例
为了比较，由聚乙烯粉末和银粉末的常规混合物制备传导性复合材料。银粉末的质量百分比设定为相对于混合物的总重量的70％。这种混合物制备出这样的传导性复合材料：它具有与根据本发明制备的(即包含银包被的有机颗粒的)复合材料相当的传导性能，但是具有非常大比例的银粉末。这种材料的微观结构如图9所示。显而易见的是，存在相当大比例的粉状的银。这样的体积比的银容许形成银颗粒的充分连续的网络，从而在材料内产生低电阻率。
实施例1和比较例的传导性复合材料的性能的比较
使用微欧姆计测量电阻，其中，电极间距离为2cm且没有接触压力。所得的结果记录在下表1中：
表1
材料 实施例 电阻(欧姆)
PE/Ag20％复合物 实施例1A 0.04
PE/Ag10％复合物 实施例1B 0.15
PE/Ag70％混合物 实施例2比较例 0.05
下面的表2以举例的形式列出了一些材料的电阻率值和热导率值：
表2
材料 电阻率(μohm·cm) 热导率(W·m-1·K-1)
Ag 1.59 429
Cu 1.67 394
Al 2.65 234
Fe 9.71 80.4
C/金刚石 . 25-470
表1示出了对各种导电材料(本发明或其他)的电阻测量结果。
注意到，测试材料的电阻(或电阻率)非常低。我们观察到，对于由包被粉末制备的复合材料，非常低比例的银足以确保最大的电导率。通过比较，在由粉末混合物制备的传统材料(实施例2)中需要根据本发明的复合材料(实施例1)中所用银量3.5倍的银方能获得相同量级的电阻率。此外，还可以注意到，这些复合材料在密度方面获得了非常显著的改进，这是银的比例较低的直接结果。对于给定的电阻率，密度从复合材料相对应的3.1g/cm3变化到粉末混合物相对应的6.3g/cm3。
最后，对于复合材料，聚乙烯的机械柔韧性仅受到轻微影响，而通过混合获得的材料趋于变得相当硬。
应该指出的是，还可以考虑使用不同的担体粉末用于涂覆，以使复合材料(具有各种分子量和各种密度的热塑性塑料、热固性塑料和弹性体，例如，PE、PP、PEEK、PEKK、PVC、PVDF、PTFE、有机硅塑料、环氧树脂、聚酯、聚氨酯等)弹性增加/减小和/或硬度增加/减小。
除了Ag外，Cu、Nb、SnO2、AlN、Ti等在颗粒上的各种涂层都是可能的。
由此制备的复合材料中的一些非常适合机械加工。
实施例3本发明
银包覆测试是在具有10-100μm的粒度和不规则形貌的PTFE粉末上进行的。在自催化化学浴(三相流化床)中进行银的施用。
施用相对于PTFE+银的混合物的总重量的40wt％的银，从而在PTFE颗粒表面上形成致密且连续的、厚度为约1μm的涂层，如图5A和5B中的截面分析所示。
如上所述，通过诸如烧结的技术使这些包被颗粒成型，使该材料不仅被赋予与银相关的导电性，而且被赋予PTFE固有的自润滑和不粘连的特性。
实施例4本发明
氧化锡包覆试验在具有50μm至300μm的粒度和海绵状形貌的PEKK(聚醚酮酮)粉末上进行。通过湿沉淀法(三相流化床)施用氧化锡。
施用相对于PEKK+氧化锡的混合物的总重量的30wt％的氧化锡，从而在PEKK颗粒表面上形成均匀的、厚度为1μm至2μm的涂层，如图6A和6B中的截面分析所示。
如上所述，通过诸如烧结的技术使这些包被颗粒成型，使得该材料被赋予与氧化锡的存在相关的抗静电特性，并且使得该材料被赋予PEKK的固有特征之一的非常高的最大允许使用温度(～250℃连续地)。

Claims (17)

1.一种传导性复合材料，所述传导性复合材料包括传导性颗粒的互连网络，所述传导性颗粒包括有机材料核，所述有机材料核包覆有至少一个电和/或热的传导性材料层，其特征在于，
全部所述颗粒在所述传导性复合材料的内部结构内相互连接，从而形成传导性材料的连续三维网络，
所述传导性复合材料的传导性包覆材料的质量百分比占所述传导性复合材料的总重量的1wt％至30wt％。
2.如权利要求1所述的传导性复合材料，其中，所述传导性复合材料的传导性包覆材料的质量百分比占所述传导性复合材料的总重量的5wt％至20wt％。
3.如权利要求1和2中任一项所述的传导性复合材料，其中，所述传导性复合材料为膜或三维物体的形式。
4.如权利要求1至3中任一项所述的传导性复合材料，其中，所述传导性材料层由金属材料或陶瓷材料或有机材料制成。
5.如权利要求4所述的传导性复合材料，其中，所述传导性材料包括选自银、金、铜、铝、钛、镍、钴和铁的至少一种金属。
6.如权利要求4所述的传导性复合材料，其中，所述传导性材料是陶瓷，所述陶瓷选自金属氧化物以及选自氮化物、碳化物、硅基化合物和锡基混合的化合物。
7.如权利要求4所述的传导性复合材料，其中，所述传导性材料是选自聚乙炔类、聚吡咯类及聚苯胺类的导电聚合物型有机材料。
8.如权利要求1至7中任一项所述的传导性复合材料，其中，所述有机材料核选自：
-热塑性塑料，诸如聚乙烯(PE)、聚丙烯(PP)，聚醚醚酮(PEEK)，聚醚酮酮(PEKK)、聚氯乙烯(PVC)、聚偏二氟乙烯(PVDF)、聚四氟乙烯(PTFE)和有机硅塑料；及
-热固性塑料，诸如环氧树脂、聚酯、聚氨酯和丙烯酸树脂。
9.如权利要求1至8中任一项所述的传导性复合材料，其中，所述有机材料核具有300nm至10mm，优选5μm至300μm的粒度。
10.如权利要求1至9中任一项所述的传导性复合材料，其中，所述有机材料核为球状或层状，或为片状，膜状或具有海绵状、不规则形状的颗粒。
11.如权利要求1至10中任一项所述的传导性复合材料，其中，所述传导性复合材料展现出16.10-9Ω·m至100Ω·m的电阻率。
12.如权利要求1至11中任一项所述的传导性复合材料，其中，所述传导性复合材料展现出2W·m-1·K-1至50W·m-1·K-1的热导率。
13.如权利要求12所述的传导性复合材料，其中，所述传导性复合材料显示出5W·m-1·K-1至10W·m-1·K-1的热导率。
14.如权利要求1至13中任一项所述的传导性复合材料，其中，所述有机材料核包括热和/或电的传导性填料。
15.如权利要求14所述的传导性复合材料，其中，所述传导性填料包被有电和/或热的传导性材料，所述电和/或热的传导性材料为石墨、石墨烯、碳纳米管、植物纤维或传导聚合物。
16.一种用于制造如权利要求1至15中任一项所述的传导性复合材料的方法，所述方法包括以下步骤：
a)提供和/或制备带电有机颗粒或不带电有机颗粒；
b)给所述有机颗粒包覆上一层或多层至少一种电和/或热传导性材料以形成传导性颗粒，
c)使所述传导性颗粒成型以形成传导性膜或形状已预先限定的元件，
所述方法的特征在于，包覆所述有机颗粒的步骤b)按照以下任一种进行：
-利用干表面处理技术，所述颗粒被置于两相流化床中的悬浮液中，或者通过旋转或振动的机械方法；
-或者利用涉及在所述颗粒表面沉淀或聚合的氧化还原反应的湿表面处理技术，所述颗粒被置于三相流化床中的悬浮液中，或通过机械或磁力搅拌方法。
17.如权利要求16所述的用于制造传导性复合材料的方法，其中，使所述传导性颗粒成型的步骤c)通过选自烧结后轧制、原型制作、热成型或热喷涂的技术来进行。
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