Effect of the addition of milled carbon fiber as a secondary filler on the electrical conductivity of graphite/epoxy composites for electrical conductive material

In this work, carbon composite bipolar plates consisting of synthetic graphite and milled carbon fibers as a conductive filler and epoxy as a polymer matrix developed using compression molding is described. The highest electrical conductivity obtained from the described material is 69.8 S/cm for the in-plane conductivity and 50.34 S/cm for the through-plane conductivity for the composite containing 2 wt.% carbon fiber (CF) with 80 wt.% filler loading. This value is 30% greater than the electrical conductivity of a typical graphite/epoxy composite with 80 wt.% filler loading, which is 53 S/cm for the in-plane conductivity and 40 S/cm for the through-plane conductivity. The flexural strength is increased to 36.28 MPa compared to a single filler system, which is approximately 25.22 MPa. This study also found that the General Effective Media (GEM) model was able to predict the in-plane and through-plane electrical conductivities for single filler and multiple filler composites.     

Manufacture of a polymer-based carbon nanocomposite as bipolar plate of proton exchange membrane fuel cells

The aim of this paper is to prepare a polymer-based carbon nanocomposite reinforced by carbon fiber cloth (CF) to be utilized as bipolar plate of proton exchange membrane (PEM) fuel cell. For this purpose, some single, double, and triple-filler composites were manufactured by using phenolic resin as polymer (P) and graphite (G), carbon fiber (CF) and expanded graphite (EG) as fillers. The production method was compression-molding technique. The electrical conductivity, flexural strength, toughness, hardness, porosity, and hydrogen permeability tests were then measured to determine the mechanical and physical properties. A triple-filler composite containing 45 wt.% G, 10 wt.% CF, 5 wt.% EG, reinforced by a layer of CF cloth, was selected as composite bipolar plate. The electrical conductivity, thermal conductivity, and flexural strength of this composite were 74 S/cm, 9.6 W/m K, and 74 MPa, respectively, which are higher than the specified value by department of energy in USA (DOE). The composite bipolar plate used in the single fuel cell assembly showed a maximum power density 810 mW/cm². In this paper, a material selection was performed on the different materials of bipolar plates. It can be concluded that the composite bipolar plates are more suitable for high life time stationary applications.     

石墨/酚醛树脂复合材料双极板的制备与性能

双极板是质子交换膜燃料电池的重要组成部分,石墨与聚合物的复合材料双极板是目前研究的重要方向。采用模压热固化二步法,以酚醛树脂为粘结剂、天然鳞片石墨为导电骨料、炭黑为添加剂制备了质子交换膜燃料电池用复合材料双极板。系统研究了不同种类石墨对石墨/酚醛树脂复合材料电性能和抗弯强度的影响。结果表明:以天然鳞片石墨为导电原料时,所制备的石墨/酚醛树脂双极板的性能最好;添加导电炭黑能有效提高石墨/酚醛树脂复合材料的电导率;在复合材料制备中加入4wt%的碳纤维,碳纤维-石墨/酚醛树脂复合材料的抗弯强度提高了29%;碳纤维表面液相氧化处理能有效提高纤维与基体间的结合强度,随着处理时间的延长与处理温度的升高,碳纤维-石墨/酚醛树脂复合材料的电导率和抗弯强度都有很大程度的提高;最终固化温度主要影响酚醛树脂的交联程度,随着最终固化温度的升高,酚醛树脂的交联程度增加,电导率增大,但抗弯强度有一定程度减小。     

Complementary percolation characteristics of carbon fillers based electrically percolative thermoplastic elastomer composites

Electrically percolative composites of thermoplastic elastomers (TPE) filled with different concentrations of carbon nanotubes (CNT), carbon black (CB) and (CNT–CB) hybrid fillers were fabricated by melt blending. The effects of filler type and composition on the electrical properties of the percolative TPE composites were studied. Percolation threshold for CB-, CNT- and (CNT–CB)-based composites was found to be 0.06, 0.07 and 0.07 volume fraction respectively. Compared to CB-based composites and earlier reported results, CNT- and (CNT–CB)-based ones revealed an unexpectedly high percolation threshold, which otherwise considered an unwelcome phenomenon, lead to distinct and rare percolation characteristics of CNT filled percolative composites like per-percolation conductivity and a relatively steep percolation curves. CB-based composites showed a comparatively sharp insulator–conductor transition curve complementing the percolation characteristics CNT- and (CNT–CB)-based composites. Percolation threshold conductivity of the fillers was in the order of CB > CNT > (CNT–CB), while maximum attained conductivities followed the order of CNT > (CNT–CB) > CB. Conductivity order of fillers not only denied much reported synergic effect in (CNT–CB) filler but also highlighted the effect of percolation characteristics on the outcome of conductivity values. Results obtained were of theoretical as well as practical importance and were explained in the context of filler morphology and different dispersion characteristics of the carbon based fillers.     

Enhanced conductivity behavior of polydimethylsiloxane (PDMS) hybrid composites containing exfoliated graphite nanoplatelets and carbon nanotubes

Polydimethylsiloxane (PDMS) hybrid composites consisting of exfoliated graphite nanoplatelets (xGnPs) and multiwalled carbon nanotubes functionalized with hydroxyl groups (MWCNTs-OH) were fabricated, and the effects of the xGnP/MWCNT-OH ratio on the thermal, electrical, and mechanical properties of polydimethylsiloxane (PDMS) hybrid composites were investigated. With the total filler content fixed at 4 wt%, a hybrid composite consisting of 75% × GnP/25% MWCNT-OH showed the highest thermal conductivity (0.392 W/m K) and electrical conductivity (1.24 × 10⁻³ S/m), which significantly exceeded the values shown by either of the respective single filler composites. The increased thermal and electrical conductivity found when both fillers are used in combination is attributed to the synergistic effect between the fillers that forms an interconnected hybrid network. In contrast, the various different combinations of the fillers only showed a modest effect on the mechanical behavior, thermal stability, and thermal expansion of the PDMS composite.     

石墨/聚合物复合材料双极板的研究进展

评述了采用石墨/聚合物复合材料制备质子交换膜燃料电池双极板的研究进展,主要分析了原材料、制作工艺对复合材料电导率、力学强度等性能的影响,并介绍了赋予此类双极板内增湿功能的研究概况,预示了燃料电池用双极板的发展方向.     

Rubber composites based on graphene nanoplatelets,expanded graphite,carbon nanotubes and their combination: A comparative study

Solution styrene butadiene rubber (S-SBR) composites reinforced with graphene nanoplatelets (GnPs), expanded graphite (EG), and multiwalled carbon nanotubes (MWCNTs) were prepared and the electrical and various mechanical properties were compared to understand the specific dispersion and reinforcement behaviours of these nanostructured fillers. The electrical resistivity of the rubber composite gradually decreased with the increase of filler amount in the composite. The electrical percolation behaviour was found to be started at 15 phr (parts per hundred rubber) for GnP and 20 phr for EG filled systems, whereas a sharp drop was found at 5 phr for MWCNT based composites. At a particular filler loading, dynamic mechanical analysis and tensile test showed a significant improvement of the mechanical properties of the composites comprised of MWCNT followed by GnP and then EG. The high aspect ratio of MWCNT enabled to form a network at low filler loading and, consequently, a good reinforcement effect was observed. To investigate the effect of hybrid fillers, MWCNT (up to 5 phr) were added in a selected composition of EG based compounds. The formation of a mixed filler network showed a synergistic effect on the improvement of electrical as well as various mechanical properties.     

Microstructural image analysis and structure–electrical conductivity relationship of single- and multiple-filler conductive composites

The electrical conductivity of polypropylene/graphite (PP/G) composites and polypropylene/graphite/carbon black (PP/G/CB) was investigated in this paper. The conductivity experimental data of PP/G composites was correlated to theoretical models, which exist in the literature, and the results showed higher values of the exponent t compared to the expected typical values. Moreover, these analytical models were unable to describe the electrical behaviour for multiple-filler conductive composites such as PP/G/CB composites. A 2D computer simulation to numerically compute the electrical conductivity based on digital image analysis was found to be somewhat useful to describe the mechanism of conduction in PP/G/CB composites and to determine the critical factors in developing high electrically conductive composites.     

A comparative study on the electrical,thermal and mechanical properties of ethylene–octene copolymer based composites with carbon fillers

Conducting polymer composites (CPC) were prepared with an ethylene–octene copolymer (EOC) matrix and with either carbon fibers (CFs) or multiwall carbon nanotubes (MWCNTs) as fillers. Their electrical and thermal conductivities, mechanical properties and thermal stabilities were evaluated and compared. CF/EOC composites showed percolation behavior at a lower filler level (5 wt.%) than the MWCNT/EOC composites (10 wt.%) did. Alternating current (AC) conductivity and real part of permittivity (dielectric constant) of these composites were found to be frequency-dependent. Dimensions and electrical conductivities of individual fillers have a great influence on the conductivities of the composites. CF/EOC composites possessed higher conductivity than the MWCNT-composites at all concentrations, due to the higher length and diameter of the CF filler. Both electrical and thermal conductivities were observed to increase with increasing filler level. Tensile moduli and thermal stabilities of both (CF/EOC and MWCNT/EOC) composites increase with rising filler content. Improvements in conductivities and mechanical properties were achieved without any significant increase in the hardness of the composites; therefore, they can be potentially used in pressure/strain sensors. Thermoelectric behavior of the composites was also studied. Accordingly, CF and MWCNT fillers are versatile and playing also other roles in their composites than just being conducting fillers.     

Electrical properties of hybrid carbon black/carbon fiber polypropylene composites

The electrical conductivity and morphology of injection molded polypropylene based composites containing two conductive fillers, carbon black (CB) and carbon fibers (CF) were studied. Injection moldings containing both, CB and CF, where the content of each filler was above its own percolation threshold, resulted in similar or lower values of overall composite volume resistivity compared with the resistivity of systems filled only with CB at the corresponding content. However, the resistivity of two-filler systems is always higher than the resistivity of systems filled only with CF at the corresponding content. The morphology and fiber length analysis of the injection molded composites are quite intriguing. Fiber orientation in the injection molded two-filler systems was found to be almost perpendicular to the melt flow direction, with no significant skin-core fiber orientation patterns, contrary to the typically observed fiber orientation in injection molded fiber filled composites. Moreover, the CF breakage in the presence of the CB was found more intense than when just CF is used, resulting in shorter fibers with narrower length distributions. This unexpected fiber behavior is responsible for the unexpected electrical behavior. However, the coexistence of CB and CF electrically conductive networks, supporting each other, was confirmed, in spite of the mechanical disturbances caused by the presence of fibrilar and particulate fillers.     

膨胀石墨/酚醛树脂-聚乙烯醇缩丁醛复合双极板的制备与性能

采用聚乙烯醇缩丁醛（PVB）对酚醛树脂（PF）进行改性,并以膨胀石墨为第一导电填料,用模压成型法制备了新型质子交换膜燃料电池用膨胀石墨/PF-PVB复合材料双极板。研究了PVB与PF质量比、改性树脂含量及炭黑的添加对膨胀石墨/PF-PVB复合材料双极板电导率、抗弯强度等性能的影响。结果表明,当改性树脂质量分数固定为30wt%时,膨胀石墨/PF-PVB复合材料双极板在PVB：PF=0.5时表现出最佳的电导率及抗弯强度,分别为192.3 S/cm、47.25 MPa,与不添加PVB的膨胀石墨/PF复合材料双极板相比,平面内电导率和抗弯强度分别提高了12.3%、14.2%。在PVB含量固定的条件下（PVB：PF=0.5）,当改性树脂的质量分数由25wt%增加至45wt%时,膨胀石墨/PF-PVB复合材料双极板的电导率下降,而抗弯强度增加。进一步添加炭黑提高膨胀石墨/PF-PVB复合材料双极板的导电性能,当改性树脂质量分数固定为45wt%时,炭黑添加量为4wt%的试样表现出最佳的平面电导率和面比电阻,分别为137 S/cm、14.4 mΩ·cm²。     

石墨/ 高铝水泥模压复合材料双极板的特性

采用高铝水泥作为粘结剂, 石墨作为导电填料, 通过室温模压的方法制备了导电复合材料, 拟用于制作质子交换膜燃料电池的双极板。对石墨/ 高铝水泥复合材料双极板的电性能和力学性能的影响因数进行了分析和评价, 并测量了该复合材料双极板的含水量、凝胶毛细孔尺寸分布和氢气渗透性。实验结果表明: 含有60 wt %石墨的石墨/ 高铝水泥模压复合材料双极板的电导率和力学强度基本上可以同时满足质子交换膜燃料电池的使用要求; 并且该复合材料双极板含有凝胶毛细孔, 约具有7 wt %的含水量, 具有自增湿功能; 此外, 氢气渗透率也较低。      

填料种类对炭/石墨材料性能和微观结构的影响

分别利用炭黑、石油焦、针状焦和天然石墨粉为填料,煤沥青为黏结剂,经模压成型(150MPa,10min)、炭化(1300℃,1h)和石墨化(2300℃)制备炭/石墨材料.考察了填料类型对最终炭/石墨材料物理性能和微观结构的影响.研究结果表明:利用炭黑为填料所制材料具有较高的机械强度,但其导热和导电性能相对较差;经石墨化后(2300℃),其抗弯和抗压强度分别达到88.0和173.2MPa.而以天然石墨粉为填料所制材料具有较好的导热和导电性能,在室温下其导热率达到278W/m · K;另外,其抗弯和抗压强度分别达到51.1和90.2MPa.微观结构分析表明,以天然石墨粉为填料所制得的材料具有最大的微晶尺寸和高度的取向性.     

Toward multi-functional polymer composites through selectively distributing functional fillers

The distribution of functional filler is known to have significant influence on various functionalities, yet, not been systematically investigated. Herein, we use a blends system based on PA12/PA6 containing SiC and low-temperature expandable graphite (LTEG) to study it. The effect of filler distribution in such blends on various functionalities including: thermal conductivity, electrical conductivity, and electromagnetic interference (EMI) shielding ability, has been systematically studied. Further study on altering filler distribution with polished PA6-LTEG and PA6-LTEG in different sizes reveals that, polished particle surface results in reduced electrical and thermal conductivity; and smaller particle size leads to enhanced electrical conductivity, thermal conductivity and EMI shielding ability. Finally, theoretical approach on thermal conductivity demonstrates that the system illustrates very effective contribution in thermal conductivity from large PA6-LTEG “filler” comparing to much smaller traditional fillers. Such study could provide a guideline for the processing of functional polymer composites.     

Study on the semi-empirical model for the complex permittivity of carbon nanocomposite laminates in microwave frequency band

A semi-empirical model is proposed for the complex permittivity of composites containing electrical conductive carbon nanomaterials such as carbon black (CB), carbon nanofiber (CNF) and multi-walled carbon nanotube (CNT). The composites were fabricated with E-glass fabric/epoxy prepregs. The model is based on the percolation theory. The model is available for the composite of filler content over the percolation threshold and applicable within the high frequency band in which AC electrical conductivity of the composite is continuously proportional to the frequency. The proposed model is composed of the numerical equations of the scaling law in percolation theory and constants obtained from experiments to quantify the model. The model describes the complex permittivity as a function of frequency and filler content. The model was verified when compared with the measurements. The measurements for the complex permittivities of the composites were performed at the frequency band between 0.5 and 18.0 GHz using a vector network analyzer with a 7 mm coaxial air line.     

Electrostatic self-assembled carbon nanotube/nano carbon black composite fillers reinforced cement-based materials with multifunctionality

Electrostatic self-assembled carbon nanotube (CNT)/nano carbon black (NCB) composite fillers are added into cement mortar to fabricate smart cement-based materials. The grape bunch structure of CNT/NCB composite fillers is beneficial for dispersing CNT/NCB in cement mortar matrix and achieving cooperative improvement effect. The mechanical, electrically conductive, and piezoresistive behaviors of the cement mortar are investigated. The CNT/NCB composite fillers can effectively enhance the flexural strength and electrical conductivity of cement mortars, and endow stable and sensitive piezoresistivity to cement mortar at a low filler content. However, they weaken the compressive strength of cement mortar to some extent. The percolation threshold zone of cement mortar with CNT/NCB composite fillers ranges in the amount of 0.39–1.52 vol.%. The optimal content of CNT/NCB composite fillers is 2.40 vol.% for piezoresistivity and the stress and strain sensitivities can reach 2.69% MPa⁻¹ and 704, respectively.     

Carbon black/graphite nanoplatelet/rubbery epoxy hybrid composites for thermal interface applications

Hybrid composites were developed by dispersing carbon black (CB) nanoparticles and graphite nanoplatelets (GNPs) at 4–6 and 12–14 wt%, respectively, into rubbery epoxy resin. SEM analysis showed that CB particles improved the dispersion of GNPs in the hybrid composite. The thermal conductivity of 4 wt% CB/14 wt% GNP-15/rubbery epoxy hybrid composite, 0.81 W/m K, is ca. four times higher than that of rubbery epoxy. When silane-functionalised, the fillers reduced the viscosity of the hybrid dispersion and made the hybrid composite highly electrically insulating. Nevertheless, filler functionalisation decreased the composite’s thermal conductivity by only 16.6%. Compression testing showed that the hybrid fillers increased the compressive modulus and strength of rubbery epoxy by nearly two and three times, respectively. Overall, the hybrid composites with their thermal paste-type morphology, low viscosity, high compliance, improved thermal conductivity and, when fillers are functionalised, low electrical conductivity makes them promising materials as thermal interface adhesives.     

CF/EP composite laminates with carbon black and copper chloride for improved electrical conductivity and interlaminar fracture toughness

An experimental study was conducted to improve the electrical conductivity of continuous carbon fibre/epoxy (CF/EP) composite laminate, with simultaneous improvement in mechanical performance, by incorporating nano-scale carbon black (CB) particles and copper chloride (CC) electrolyte into the epoxy matrix. CF/EP laminates of 65 vol.% of carbon fibres were manufactured using a vacuum-assisted resin infusion (VARI) technique. The effects of CB and the synergy of CB/CC on electrical resistivity, tensile strength and elastic modulus and fracture toughness (K_IC) of the epoxy matrix were experimentally characterised, as well as the transverse tensile modulus and strength, Mode I and Mode II interlaminar fracture toughness of the CF/EP laminates. The results showed that the addition of up to 3.0 wt.% CB in the epoxy matrix, with the assistance of CC, noticeably improved the electrical conductivity of the epoxy and the CF/EP laminates, with mechanical performance also enhanced to a certain extent.     

Synergetic effects of carbon nanotubes and carbon fibers on electrical and self-heating properties of high-density polyethylene composites

High-density polyethylene (HDPE) composite films filled with carbon fibers (CF), carbon nanotubes (CNT) as well as hybrid filler of CF and CNT were prepared by melt mixing. The electrical and self-heating properties of the composite films were investigated. Results showed that: when the total content of filler was the same, (i) the electrical resistivity of composite films filled with hybrid fillers was lower than those with single filler; (ii) the composite films filled with hybrid fillers displayed more excellent self-heating performance such as a higher surface temperature (T _s), a more rapid temperature response, and a better thermal stability. This indicates the synergetic effect of combination of CNT and CF on improvement of the electrical and self-heating properties of HDPE-based composite films. The synergy can be considered to be the result of the fibrous filler CF acting as long distance charge transporters and the CNT serving as an interconnection between the fibers by forming local conductive paths.     

炭黑填充多组分高分子导电复合材料的研究进展

基体为多组分高分子的填充型导电复合材料中存在“双逾渗”行为,能有效地降低导电填料的逾渗阈值,克服由填料含量过高而导致的材料加工性和力学性能下降的缺点,并能削弱材料的负温度系数(NTC)效应。本文基于国内外炭黑(CB)填充多组分高分子导电复合材料的研究进展,对CB分布、多组分高分子基体对材料体系导电性的影响、导电机理以及电导-温度依赖性等方面进行评述。