WO2018145372A1 - 一种限域空间微纳米精密组装法制备高性能聚合物基导电复合材料的方法 - Google Patents

一种限域空间微纳米精密组装法制备高性能聚合物基导电复合材料的方法 Download PDF

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WO2018145372A1
WO2018145372A1 PCT/CN2017/086039 CN2017086039W WO2018145372A1 WO 2018145372 A1 WO2018145372 A1 WO 2018145372A1 CN 2017086039 W CN2017086039 W CN 2017086039W WO 2018145372 A1 WO2018145372 A1 WO 2018145372A1
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filler
micro
polymer matrix
preparing
nano
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English (en)
French (fr)
Inventor
吴大鸣
高小龙
刘颖
郑秀婷
黄尧
何晓祥
门萨
许红
赵中里
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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Priority to GB1911176.4A priority Critical patent/GB2573914B/en
Priority to US16/483,938 priority patent/US11104037B2/en
Publication of WO2018145372A1 publication Critical patent/WO2018145372A1/zh
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    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
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Definitions

  • the invention relates to a preparation method of a high performance polymer-based conductive composite material, in particular to a method for preparing a high performance polymer-based conductive composite material by a limited space micro-nano precision assembly method, and belongs to the technical field of composite material preparation.
  • polymer-based conductive composites have been widely used in the manufacture of electronic equipment, aircraft parts, personal computers, light-emitting diode chips, electromagnetic interference shielding and sensing materials for antistatic, conductive or thermal conduction requirements in recent years. Medical equipment, intelligent biological materials, auto parts, household appliances, pipes, etc. Most of the polymer matrix itself is not electrically conductive. Therefore, it is necessary to add a conductive filler having a relatively large aspect ratio or specific surface area to the polymer matrix, and a conductive network can be formed to prepare a composite material satisfying the conductive requirement.
  • the commonly used conductive filler is carbon black. Particles, carbon fibers, flake graphite, carbon nanotubes and graphene.
  • the conductivity of the composite can be rapidly increased by increasing the filler content in the conductive percolation zone, the filler is difficult in the polymer matrix due to the high viscosity of the polymer matrix, the repulsive force between the fillers, and the steric hindrance.
  • Self-assembly forms a continuous and tight conductive network, which is far from the expected conductivity.
  • the electrical conductivity of the composite does not change much with the filler content, and there is no way to continue to improve the electrical conductivity of the composite.
  • the invention adopts a new technology path limited space micro-nano precision assembly to achieve the purpose of improving the performance of the composite material.
  • the object of the present invention is to provide a high-performance polymer-based conductive composite material with limited space, and the high-performance polymer-based conductive composite material prepared by the method has a continuous and tight conductive network and has excellent tensile properties. , flexibility and thermal stability.
  • a method for preparing a high performance polymer matrix composite by a space-limited micro-nano precision assembly method comprising the following steps:
  • the conductive filler according to the step (1) is one or a combination of two or more of a micro-nano scale sheet-like filler, a fibrous filler, and a spherical conductive filler.
  • the flaky filler is one or a combination of two or more of flake graphite and graphene;
  • the fibrous filler is one or a combination of two or more of carbon fibers, carbon nanotubes or carbon nanofibers;
  • the conductive filler is one or a combination of one or more of carbon black particles, silver powder or magnesium oxide, and one or a combination of two or more of a flaky filler, a fibrous filler, and a spherical filler.
  • the polymer matrix described in the step (1) is a thermoplastic polymer matrix, a thermosetting matrix or a photocurable matrix.
  • the thermoplastic polymer matrix is one or a combination of two or more of polypropylene, nylon, polypropylene, polycarbonate or polymethyl methacrylate;
  • the thermosetting matrix is phenolic resin, polydimethylsiloxane An alkane or an epoxy resin;
  • the photocurable substrate is an epoxy acrylate, a urethane acrylate or a polyester acrylate.
  • the blending apparatus described in the step (1) includes a high speed agitator, an ultrasonic disperser, an internal mixer, a co-rotating twin screw extruder, a Buss extruder or a planetary extruder.
  • the mechanical compression method described in the step (2) includes flat plate compression, track compression or roll compression.
  • step (2) the homogeneous system first occurs in a conventional manner of self-assembly into a mesh, after which the blend is further compressed until a set feature thickness, in the formation process of the thickness, the self-assembled network
  • the filler on the top is further compacted, the spacing of the filler is reduced to the design value, and the network density is greatly increased.
  • the micro/nano structure array according to the step (3) is one or a combination of two or more of a V-Cut structure, a hemispherical structure, a semi-cylindrical structure, a prism structure, a pyramid structure, a pyramid structure or a semi-elliptical ball structure.
  • the thickness of the composite material according to the step (3) is that the homogeneous sample is mechanically compressed to reduce the thickness to be close to or smaller than the characteristic thickness in the process of self-assembly into a net, and the characteristic thickness depends on the average diameter of the network cable of the filler composition. .
  • a homogeneous system of polymer/conductive filler is obtained by a blending method such as a high-speed stirrer, an internal mixer or a twin-screw extruder, and then the planar blend of the homogeneous blend is mechanically restricted under certain thermodynamic conditions. Domain compression. During the compression process, the homogeneous system first undergoes conventional self-assembly into a web; thereafter the blend is further compressed until the set feature thickness, during which the filler on the self-assembled network is further compacted. The spacing of the packing is reduced to the design value and the network density is greatly improved.
  • the micro-nano-structured arrays on the network are used to perform "array anchoring" of the fillers on the network to finally complete the micro-nano precision assembly of the conductive network.
  • the composite material prepared by the invention forms a continuous and tight conductive network, and the gap between the fillers becomes smaller, especially at the anchoring point, the filler spacing is smaller, and the composite material can obtain high conductivity under the low concentration of the conductive filler. .
  • the method can also be used to prepare high thermal conductivity and high reinforced polymer matrix composites.
  • the prepared polymer-based conductive composite material can be applied to antistatic, electromagnetic interference shielding, wearable electronic equipment, curved display, flexible electronic components, intelligent biological materials and the like.
  • Figure 1 shows the geometry and arrangement micrograph of the v-cut microstructure array on the plate
  • Figure 2 is a micro-architecture of the upper semi-elliptical spherical microstructure array of the plate
  • Figure 3 is a schematic view showing the anchoring action of the convex microstructure array on the plate
  • Figure 4 is a physical diagram of a portion of the composite prepared in the experiment.
  • Figure 5 is a cross-sectional scanning electron micrograph of a polydimethylsiloxane/0.5 wt% carbon fiber composite prepared in Example 1.
  • Figure 6 is a cross-sectional scanning electron micrograph of a polydimethylsiloxane/4 wt% carbon fiber composite prepared in Example 2;
  • Figure 7 is a cross-sectional scanning electron micrograph of a polydimethylsiloxane/4 wt% carbon black composite prepared in Example 3;
  • Figure 8 is a cross-sectional scanning electron micrograph of a polydimethylsiloxane / 3 wt% carbon fiber + 1 wt% carbon black composite prepared in Example 4.
  • Figure 9 is a cross-sectional scanning electron micrograph of a polydimethylsiloxane/3 wt% carbon fiber + 1 wt% carbon nanotube composite prepared in Example 5.
  • Figure 10 is a cross-sectional scanning electron micrograph of a polydimethylsiloxane / 3 wt% carbon fiber + 1 wt% graphene composite prepared in Example 6;
  • Figure 11 is a transmission scanning electron micrograph of a polypropylene/5 wt% carbon fiber composite prepared in Example 7.
  • Figure 12 is a cross-sectional scanning electron microscope of the polydimethylsiloxane/60 wt% carbon fiber composite prepared in Example 8.
  • the polydimethylsiloxane/carbon fiber mixture with a carbon fiber concentration of 0.5 wt% was placed and mixed in a Hacker mixer.
  • the mixing parameters were: screw rotation speed 50 r/min, mixing temperature 30 ° C, and mixing time 15 min.
  • the mixed material and the PDMS curing agent are mixed in a ratio of 10:1, and then placed in a vacuum drying oven for 10 minutes to remove bubbles in the material.
  • the PDMS curing agent is octamethylcyclotetrasiloxane, PDMS and curing agent. All are produced by Dow Corning.
  • the carbon fiber geometry is 7um in diameter and 4mm in length.
  • FIG. 5 is a scanning electron micrograph of a cross section of the composite material prepared in Example 1.
  • the composite test conductivity of Example 1 was 0.036 S/m.
  • the polydimethylsiloxane/carbon fiber mixture with a carbon fiber concentration of 4 wt% was placed and mixed in a Hacker mixer.
  • the mixing parameters were: screw rotation speed 50 r/min, mixing temperature 30 ° C, and mixing time 15 min.
  • the mixed material and the PDMS curing agent are mixed in a ratio of 10:1, and then placed in a vacuum drying oven for 10 minutes to remove bubbles in the material.
  • the PDMS curing agent is octamethylcyclotetrasiloxane, PDMS and curing agent. All are produced by Dow Corning. The diameter is 7um and the length is 4mm.
  • FIG. 6 is a scanning electron micrograph of a cross section of the composite material prepared in Example 2.
  • the composite test conductivity of Example 2 was 95.2 S/m.
  • the polydimethylsiloxane/carbon black mixture with a carbon black concentration of 4 wt% was placed and mixed in a Hacker mixer.
  • the mixing parameters were: screw rotation speed 50 r/min, mixing temperature 30 ° C, and mixing time 15 min.
  • the mixed material and the PDMS curing agent are mixed in a ratio of 10:1, and then placed in a vacuum drying oven for 10 minutes to remove bubbles in the material.
  • the PDMS curing agent is octamethylcyclotetrasiloxane, PDMS and curing agent. All are produced by Dow Corning.
  • Carbon black is produced by ORION ENGINEERED CARBONS, model: XE2-B.
  • Figure 7 is a scanning electron micrograph of a cross section of the composite prepared in Example 3.
  • the composite test conductivity of Example 3 was 182 S/m.
  • the polydimethylsiloxane/carbon fiber+carbon black mixture with carbon fiber concentration of 3wt% and carbon black concentration of 3wt% is arranged and mixed into the Hak mixer.
  • the mixing parameters are: screw speed 50r/min.
  • the mixing time was 30 min at 30 °C.
  • the mixed material and the PDMS curing agent are mixed in a ratio of 10:1, and then placed in a vacuum drying oven for 10 minutes to remove bubbles in the material.
  • the PDMS curing agent is octamethylcyclotetrasiloxane, PDMS and curing agent. All are produced by Dow Corning.
  • Carbon fiber, 7um in diameter and 4mm in length, carbon black is produced by ORION ENGINEERED CARBONS, model: XE2-B.
  • Figure 8 is a scanning electron micrograph of a cross section of the composite prepared in Example 4.
  • the composite test conductivity of Example 4 was 910 S/m.
  • the polydimethylsiloxane/carbon fiber+carbon nanotube mixture with carbon fiber concentration of 3wt% and carbon nanotube concentration of 1wt% is arranged and mixed into the Hak mixer.
  • the mixing parameters are: screw speed 50r/min.
  • the refining temperature is 30 ° C and the mixing time is 15 min.
  • the mixed material and the PDMS curing agent are mixed in a ratio of 10:1, and then placed in a vacuum drying oven for 10 minutes to remove bubbles in the material.
  • the PDMS curing agent is octamethylcyclotetrasiloxane, PDMS and curing agent. All are produced by Dow Corning.
  • Fig. 9 is a scanning electron micrograph of the cross section of the composite material prepared in Example 5. The composite test conductivity of Example 5 was 727 S/m.
  • the polydimethylsiloxane/carbon fiber+graphene mixture with a carbon fiber concentration of 3wt% and a graphene concentration of 1wt% was prepared and mixed in a Hacker mixer.
  • the mixing parameters were: screw speed 50r/min.
  • the mixing time was 30 min at 30 °C.
  • the mixed material and the PDMS curing agent are mixed in a ratio of 10:1, and then placed in a vacuum drying oven for 10 minutes to remove bubbles in the material.
  • the PDMS curing agent is octamethylcyclotetrasiloxane, PDMS and curing agent. All are produced by Dow Corning.
  • Carbon fiber, diameter 7um, length 4mm, graphene is a single layer of graphene powder, geometric size: thickness 1.0-1.77nm, slice diameter 10-50um, Suzhou Hengqiu technology production. Then, the material of the homogeneous system was added to the flat mold, and the material was compressed by a molding machine to a set thickness of 200 um, and the pressure was 5 MPa. The mold is obtained by heating the mold to 100-130 ° C and curing for 10 minutes. The microstructure and dimensions of the raised microstructure array on one of the plates are shown in Fig. 2.
  • Fig. 10 is a scanning electron micrograph of a cross section of the composite material prepared in Example 6. The composite test conductivity of Example 6 was 97.7 S/m.
  • the carbon fiber concentration was 5 wt% polypropylene/carbon fiber mixture, and the mixture was mixed in a Hacker mixer.
  • the mixing parameters were: screw rotation speed 100 r/min, mixing temperature 170 ° C, and mixing time 15 min.
  • the mixed material and the PDMS curing agent are mixed in a ratio of 10:1, and then placed in a vacuum drying oven for 10 minutes to remove bubbles in the material.
  • the PDMS curing agent is octamethylcyclotetrasiloxane, PDMS and curing agent. All are produced by Dow Corning.
  • Carbon fiber, 7um in diameter and 4mm in length, carbon black is produced by ORION ENGINEERED CARBONS, model: XE2-B.
  • FIG. 1 is a scanning electron micrograph of a cross section of the composite prepared in Example 7.
  • the composite test conductivity of Example 7 was 0.11 S/m.
  • the polydimethylsiloxane/carbon fiber mixture with a carbon fiber concentration of 60 wt% was placed and mixed in a Hacker mixer.
  • the mixing parameters were: screw rotation speed 50 r/min, mixing temperature 30 ° C, and mixing time 15 min.
  • the mixed material and the PDMS curing agent are mixed in a ratio of 10:1, and then placed in a vacuum drying oven for 10 minutes to remove bubbles in the material.
  • the PDMS curing agent is octamethylcyclotetrasiloxane, PDMS and curing agent. All are produced by Dow Corning. The diameter is 7um and the length is 4mm.
  • FIG. 12 is a scanning electron micrograph of a cross section of the composite material prepared in Example 8.
  • the composite test conductivity of Example 8 was 2650 S/m.

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Abstract

本发明涉及一种限域空间微纳米精密组装法制备高性能聚合物基导电复合材料的方法，属于复合材料制备技术领域；具体包括如下步骤：(1)将导电填料与聚合物基体加入到共混设备中混合均匀得到均相的聚合物/导电填料物料体系；(2)将均相物料体系加入到由两个平板组成的模具中，通过机械压缩的方式对均相共混物进行平面限域压缩；(3)利用压缩模板上设置的微纳结构阵列，对网络上的填料进行进一步压实，进行"阵列锚固"，实现网络的微纳米精密组装，得到性能优异的复合材料，具有连续紧密的导电网络，同时兼具优良的拉伸性能、柔性和热稳定性。

Description

一种限域空间微纳米精密组装法制备高性能聚合物基导电复合材料的方法 技术领域
本发明涉及一种高性能聚合物基导电复合材料的制备方法，特别是涉及一种限域空间微纳米精密组装法制备高性能聚合物基导电复合材料的方法，属于复合材料制备技术领域。
背景技术
聚合物基导电复合材料作为重要的功能材料之一，近年来广泛的应用于制造抗静电、导电或者导热需求的电子设备、飞机配件、个人电脑、发光二极管芯片、电磁干扰屏蔽和传感材料、医疗设备、智能生物材料、汽车零部件、家用电器、管道等。大部分聚合物基体本身不导电，因此需要向聚合物基体中添加具有相当大长径比或比表面积的导电填料，形成导电网络才能制备出满足导电要求的复合材料，常用的导电填料有炭黑粒子、碳纤维、片状石墨、碳纳米管和石墨烯。原位聚合法、溶液混合法和熔体共混法是制备聚合物基导电复合材料的常用方法，其中熔体共混是制备填料均匀分散的聚合物基复合材料普遍采用的方法。理论与实践表明，形成连续紧密的导电网络是制备超高电导率聚合物基复合材料的关键，现有的提高复合材料导电性能的方法主要通过提高填料含量达到导电渗流阈值后继续添加直至饱和，即便如此，复合材料的电导率与理论值相差甚远，究其原因主要在于传统方法大多是在特定的热力学和流体动力学条件下让填料在基体中自组装形成导电网络，填料间距具有不可控性，虽然在导电渗流区域可以通过提高填料含量快速提升复合材料的导电性能，但是由于大多聚合物基体粘度高，加上填料之间排斥力，位阻等影响，填料在聚合物基体中很难自组装形成连续紧密的导电网络，距离预期的电导率相差甚远，尤其在经过导电渗流区域之后，复合材料的电导率随着填料含量变化不大，继续提高复合材料的导电性能已经无能为力。本发明采用新的技术路径限域空间微纳米精密组装来达到提高复合材料性能的目的。
发明内容
本发明的目的是提供一种限域空间高性能聚合物基导电复合材料的方法，采用该方法制备的高性能聚合物基导电复合材料具有连续紧密的导电网络，同时兼具优良的拉伸性能、柔性和热稳定性。
为实现上述发明的目的，本发明采取的技术方案如下：
一种空间限域微纳米精密组装法制备高性能聚合物基复合材料的方法，包括如下步骤：
(1)将导电填料与聚合物基体按质量比为(0.5～60)：100的比例加入到共混设备中混合均匀，通过共混得到均相的聚合物/导电填料物料体系；
(2)将步骤(1)制备的均相物料体系加入到由两个平板组成的模具中，通过机械压缩的方式对均相共混物进行平面限域压缩；
(3)利用压缩模板上设置的微纳结构阵列，对网络上的填料进行进一步压实，进行“阵列锚固”，实现网络的微纳米精密组装，得到性能优异的复合材料。
步骤(1)所述的导电填料为微纳米尺度的片状填料、纤维状填料、球状导电填料中的一种或两种以上的组合物。所述的片状填料为鳞片石墨、石墨烯中的一种或两种以上的组合物；纤维状填料为碳纤维、碳纳米管或碳纳米纤维中的一种或两种以上的组合物；球状导电填料为炭黑粒子、银粉或氧化镁中的一种或两种以上的组合物以及片状填料、纤维状填料、球状填料的一种或两种以上组合。
步骤(1)所述的聚合物基体为热塑性聚合物基体、热固性基体或光固化类基体。所述的热塑性聚合物基体为聚丙烯、尼龙、聚丙烯、聚碳酸酯或聚甲基丙烯酸甲酯中的一种或两种以上的组合物；热固性基体为酚醛树脂、聚二甲基硅氧烷或环氧树脂；光固化类基体为环氧丙烯酸酯、聚氨酯丙烯酸酯或聚酯丙烯酸树脂。
步骤(1)所述的共混设备包括高速搅拌器、超声分散仪、密炼机、同向双螺杆挤出机、Buss挤出机或行星挤出机。
步骤(2)所述的机械压缩方式包括平板压缩、履带压缩或辊压压缩。
步骤(2)所述的平面限域压缩，均相体系首先发生传统方式的自组装成网，其后共混物被进一步压缩直至设定的特征厚度，在该厚度形成过程中，自组装网络上的填料被进一步压实，填料的间距降低到设计的数值，网络密实度大幅提高。
步骤(3)所述的微纳结构阵列为V-Cut结构、半球型结构、半圆柱结构、棱镜结构、金字塔结构、棱锥结构或半椭圆球结构中的一种或两种以上的组合。
步骤(3)所述的复合材料的厚度为对均相样品进行机械压缩，使其厚度压缩至接近或小于自组装成网过程中的特征厚度，而特征厚度取决于填料组成网络网线的平均直径。
本发明的有益效果是：
(1)通过高速搅拌器、密炼机或者双螺杆挤出机等共混的方法得到聚合物/导电填料均相体系，然后在一定热力学条件下通过机械方式对均相共混物进行平面限域压缩。在压缩过程中，均相体系首先发生传统的自组装成网；其后对共混物进一步压缩直至设定的特征厚度，在该厚度形成过程中，自组装网络上的填料被进一步压实，填料的间距降低到设计的数值，网络密实度大幅度提高。
(2)在压缩过程的后期，通过压缩模板上设置的微纳结构阵列，对网络上的填料进行“阵列锚固”最终完成导电网络的微纳米精密组装。通过这两个步骤可获得强迫组装的连续紧密的导电网络，得到导电性能优异的复合材料。
(3)采用本发明制备的复合材料中填料形成连续紧密的导电网络，填料之间缝隙变小，尤其在锚固点，填料间距更小，在导电填料低浓度条件下复合材料可获得高电导率。该方法还可以用于制备高导热和高增强聚合物基复合材料。所制备的聚合物基导电复合材料可应用于防静电、电磁干扰屏蔽、可穿戴电子设备、弯曲显示器、柔性电子元件，智能生物材料等。
附图说明
图1平板上v-cut微结构阵列几何尺寸与排布显微图；
图2平板上半椭圆球微结构阵列几何尺寸与排布显微图；
图3平板上凸起微结构阵列的锚固作用示意图；
图4实验中制备的复合材料部分样品实物图；
图5实施例1制备的聚二甲基硅氧烷/0.5wt％碳纤维复合材料的断面扫描电镜图片；
图6实施例2制备的聚二甲基硅氧烷/4wt％碳纤维复合材料的断面扫描电镜图片；
图7实施例3制备的聚二甲基硅氧烷/4wt％炭黑复合材料的断面扫描电镜图片；
图8实施例4制备的聚二甲基硅氧烷/3wt％碳纤维+1wt％炭黑复合材料的断面扫描电镜图片；
图9实施例5制备的聚二甲基硅氧烷/3wt％碳纤维+1wt％碳纳米管复合材料的断面扫描电镜图片；
图10实施例6制备的聚二甲基硅氧烷/3wt％碳纤维+1wt％石墨烯复合材料的断面扫描电镜图片；
图11实施例7制备的聚丙烯/5wt％碳纤维复合材料的透射扫描电镜图片；
图12实施例8制备的聚二甲基硅氧烷/60wt％碳纤维复合材料的断面扫描电镜。
具体实施方式
下面通过实例对本发明做进一步详细说明，这些实例仅用来说明本发明，并不限制本发明的范围。
实施例1
配置碳纤维浓度为0.5wt％的聚二甲基硅氧烷/碳纤维混合物料，加入哈克密炼机中混合，密炼参数为：螺杆转速50r/min密炼温度30℃密炼时间15min。将混合好的物料与PDMS固化剂按照10:1的比例混合后放入真空干燥箱中抽真空10分钟去除物料中的气泡，PDMS固化剂为八甲基环四硅氧烷，PDMS与固化剂均为道康宁公司生产。碳纤维几何尺寸为：直径7um，长度4mm。然后将均相体系的物料加入平板模具中，利用模压机压缩物料至设定厚度200um，压力为5Mpa。加热模具至100-130℃，固化10分钟，即可得到复合材料。其中一个平板上凸起的微结构阵列几何机构和尺寸如图1，图5为实施例1制备的复合材料的横截面的扫描电镜图片。实施例1的复合材料测试电导率为0.036S/m。
实施例2
配置碳纤维浓度为4wt％的聚二甲基硅氧烷/碳纤维混合物料，加入哈克密炼机中混合，密炼参数为：螺杆转速50r/min密炼温度30℃密炼时间15min。将混合好的物料与PDMS固化剂按照10:1的比例混合后放入真空干燥箱中抽真空10分钟去除物料中的气泡，PDMS固化剂为八甲基环四硅氧烷，PDMS与固化剂均为道康宁公司生产。直径7um，长度4mm，然后将均相体系的物料加入平板模具中，利用模压机压缩物料至设定厚度200um，压力为5Mpa。加热模具至100-130℃，固化10分钟，即可得到复合材料。其中一个平板上凸起的微结构阵列几何机构和尺寸如图1，图6为实施例2制备的复合材料的横截面的扫描电镜图片。实施例2的复合材料测试电导率为95.2S/m。
实施例3
配置炭黑浓度为4wt％的聚二甲基硅氧烷/炭黑混合物料，加入哈克密炼机中混合，密炼参数为：螺杆转速50r/min密炼温度30℃密炼时间15min。将混合好的物料与PDMS固化剂按照10:1的比例混合后放入真空干燥箱中抽真空10分钟去除物料中的气泡，PDMS固化剂为八甲基环四硅氧烷，PDMS与固化剂均为道康宁公司生产。炭黑为ORION ENGINEERED CARBONS公司生产，型号为：XE2-B。然后将均相体系的物料加入平板模具中，利用模压机压缩物料至设定厚度200um，压力为5Mpa。加热模具至100-130℃，固化10分钟，即可得到复合材料。其中一个平板上凸起的微结构阵列几何机构和尺寸如图1，图7为实施例3制备的复合材料的横截面的扫描电镜图片。实施例3的复合材料测试电导率为182S/m。
实施例4
配置碳纤维浓度3wt％，炭黑浓度为3wt％的聚二甲基硅氧烷/碳纤维+炭黑混合物料，加入哈克密炼机中混合，密炼参数为：螺杆转速50r/min密炼温度30℃密炼时间15min。将混合好的物料与PDMS固化剂按照10:1的比例混合后放入真空干燥箱中抽真空10分钟去除物料中的气泡，PDMS固化剂为八甲基环四硅氧烷，PDMS与固化剂均为道康宁公司生产。碳纤维，直径7um，长度4mm，炭黑为ORION ENGINEERED CARBONS公司生产，型号为：XE2-B。然后将均相体系的物料加入平板模具中，利用模压机压缩物料至设定厚度200um，压力为5Mpa。加热模具至100-130℃，固化10分钟，即可得到复合材料。其中一个平板上凸起的微结构阵列几何机构和尺寸如图1，图8为实施例4制备的复合材料的横截面的扫描电镜图片。实施例4的复合材料测试电导率为910S/m。
实施例5
配置碳纤维浓度3wt％，碳纳米管浓度为1wt％的聚二甲基硅氧烷/碳纤维+碳纳米管混合物料，加入哈克密炼机中混合，密炼参数为：螺杆转速50r/min密炼温度30℃密炼时间15min。将混合好的物料与PDMS固化剂按照10:1的比例混合后放入真空干燥箱中抽真空10分钟去除物料中的气泡，PDMS固化剂为八甲基环四硅氧烷，PDMS与固化剂均为道康宁公司生产。碳纤维，直径7um，长度4mm，碳纳米管几何尺寸为：直径20-30nm，长度10-30um，电导率大于10000S/m，北京德金岛生产。然后将均相体系的物料加入平板模具中，利用模压机压缩物料至设定厚度200um，压力为5Mpa。加热模具至100-130℃，固化10分钟，即可得到复合材料。其中一个平板上凸起的微结构阵列几何机构和尺寸如图2，图9为实施例5制备的复合材料的横截面的扫描电镜图片。实施例5的复合材料测试电导率为727S/m。
实施例6
配置碳纤维浓度3wt％，石墨烯浓度为1wt％的聚二甲基硅氧烷/碳纤维+石墨烯混合物料，加入哈克密炼机中混合，密炼参数为：螺杆转速50r/min密炼温度30℃密炼时间15min。将混合好的物料与PDMS固化剂按照10:1的比例混合后放入真空干燥箱中抽真空10分钟去除物料中的气泡，PDMS固化剂为八甲基环四硅氧烷，PDMS与固化剂均为道康宁公司生产。碳纤维，直径7um，长度4mm，石墨烯为单层石墨烯粉末，几何尺寸为：厚度1.0-1.77nm，片层直径10-50um，苏州恒球科技生产。然后将均相体系的物料加入平板模具中，利用模压机压缩物料至设定厚度200um，压力为5Mpa。加热模具至100-130℃，固化10分钟，即可得到复合材料。其中一个平板上凸起的微结构阵列几何机构和尺寸如图2，图10为实施例6制备的复合材料的横截面的扫描电镜图片。实施例6的复合材料测试电导率为97.7S/m。
实施例7
配置碳纤维浓度为5wt％聚丙烯/碳纤维混合物料，加入哈克密炼机中混合，密炼参数为：螺杆转速100r/min密炼温度170℃密炼时间15min。将混合好的物料与PDMS固化剂按照10:1的比例混合后放入真空干燥箱中抽真空10分钟去除物料中的气泡，PDMS固化剂为八甲基环四硅氧烷，PDMS与固化剂均为道康宁公司生产。碳纤维，直径7um，长度4mm，炭黑为ORION ENGINEERED CARBONS公司生产，型号为：XE2-B。然后将均相体系的物料加入平板模具中，利用模压机压缩物料至设定厚度200um，压力为5Mpa。加热模具至100-130℃，固化10分钟，即可得到复合材料。其中一个平板上凸起的微结构阵列几何机构和尺寸如图2，图11为实施例7制备的复合材料的横截面的扫描电镜图片。实施例7的复合材料测试电导率为0.11S/m。
实施例8
配置碳纤维浓度为60wt％的聚二甲基硅氧烷/碳纤维混合物料，加入哈克密炼机中混合，密炼参数为：螺杆转速50r/min密炼温度30℃密炼时间15min。将混合好的物料与PDMS固化剂按照10:1的比例混合后放入真空干燥箱中抽真空10分钟去除物料中的气泡，PDMS固化剂为八甲基环四硅氧烷，PDMS与固化剂均为道康宁公司生产。直径7um，长度4mm，然后将均相体系的物料加入平板模具中，利用模压机压缩物料至设定厚度200um，压力为5Mpa。加热模具至100-130℃，固化10分钟，即可得到复合材料。其中一个平板上凸起的微结构阵列几何机构和尺寸如图1，图12为实施例8制备的复合材料的横截面的扫描电镜图片。实施例8的复合材料测试电导率为2650S/m。

Claims (10)

  1. 一种空间限域微纳米精密组装法制备高性能聚合物基复合材料的方法，其特征在于：包括如下步骤：
    (1)将导电填料与聚合物基体按质量比为0.5～60：100的比例加入到共混设备中混合均匀，通过共混得到均相的聚合物/导电填料物料体系；
    (2)将步骤(1)制备的均相物料体系加入到由两个平板组成的模具中，通过机械压缩的方式对均相共混物进行平面限域压缩；
    (3)利用压缩模板上设置的微纳结构阵列，对网络上的填料进行进一步压实，进行“阵列锚固”，实现网络的微纳米精密组装，得到性能优异的复合材料。
  2. 根据权利要求1所述的一种空间限域微纳米精密组装法制备高性能聚合物基复合材料的方法，其特征在于：步骤(1)所述的导电填料为微纳米尺度的片状填料、纤维状填料、球状导电填料中的一种或两种以上的组合物。
  3. 根据权利要求1所述的一种空间限域微纳米精密组装法制备高性能聚合物基复合材料的方法，其特征在于：步骤(1)所述的聚合物基体为热塑性聚合物基体、热固性基体或光固化类基体。
  4. 根据权利要求1所述的一种空间限域微纳米精密组装法制备高性能聚合物基复合材料的方法，其特征在于：步骤(1)所述的共混设备包括高速搅拌器、超声分散仪、密炼机、同向双螺杆挤出机、Buss挤出机或行星挤出机。
  5. 根据权利要求1所述的一种空间限域微纳米精密组装法制备高性能聚合物基复合材料的方法，其特征在于：步骤(2)所述的机械压缩方式包括平板压缩、履带压缩或辊压压缩。
  6. 根据权利要求1所述的一种空间限域微纳米精密组装法制备高性能聚合物基复合材料的方法，其特征在于：步骤(2)所述的平面限域压缩，均相体系首先发生传统方式的自组装成网，其后共混物被进一步压缩直至设定的特征厚度，在该厚度形成过程中，自组装网络上的填料被进一步压实，填料的间距降低到设计的数值，网络密实度大幅提高。
  7. 根据权利要求1所述的一种空间限域微纳米精密组装法制备高性能聚合物基复合材料的方法，其特征在于：步骤(3)所述的微纳结构阵列为V-Cut结构、半球型结构、半圆柱结构、棱镜结构、金字塔结构、棱锥结构或半椭圆球结构中的一种或两种以上的组合。
  8. 根据权利要求1所述的一种空间限域微纳米精密组装法制备高性能聚合物基复合材料的方法，其特征在于：步骤(3)所述的复合材料的厚度为对均相样品进行机械压缩，使其厚度压缩至接近或小于自组装成网过程中的特征厚度，而特征厚度取决于填料组成网络网线的平均直径。
  9. 根据权利要求2所述的一种空间限域微纳米精密组装法制备高性能聚合物基复合材料的方法，其特征在于：所述的片状填料为鳞片石墨、石墨烯中的一种或两种以上的组合物；纤维状填料为碳纤维、碳纳米管或碳纳米纤维中的一种或两种以上的组合物；球状导电填料为炭黑粒子、银粉或氧化镁中的一种或两种以上的组合物以及片状填料、纤维状填料、球状填料的一种或两种以上组合。
  10. 根据权利要求3所述的一种空间限域微纳米精密组装法制备高性能聚合物基复合材料的方法，其特征在于：所述的热塑性聚合物基体为聚丙烯、尼龙、聚丙烯、聚碳酸酯或聚甲基丙烯酸甲酯中的一种或两种以上的组合物；热固性基体为酚醛树脂、聚二甲基硅氧烷或环氧树脂；光固化类基体为环氧丙烯酸酯、聚氨酯丙烯酸酯、聚酯丙烯酸树脂。
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