填充型聚合物基复合材料的导电和导热性能

研究了高密度聚乙烯为基体、炭黑和炭纤维为填料复合体系的导电和导热性能。发现当导电填料的含量达到渗流阈值时,复合材料的电导率急剧升高;而在渗流阈值附近,其热导率未出现突变。这表明电导渗流现象不完全是由导电粒子通过物理接触生成导电链所致。其导电机制是相当数量的导电粒子相互发生隧道效应。     

碳纤维填充对导电硅橡胶压阻效应及电阻蠕变行为的影响

将导电粒子添加到绝缘硅橡胶中制备出具有压阻效应的导电硅橡胶,它是一种新型压力传感器用材料。选用3种不同长度的碳纤维作为导电填料,高温硫化硅橡胶作为基体制备导电橡胶,同时在100μm长碳纤维填充导电橡胶中引入镍包铝球形粒子形成复合填料。分析了导电硅橡胶的渗流特性、压阻效应与电阻蠕变行为,发现纤维长度和纤维添加量对导电橡胶的压阻行为有显著影响:纤维长度增大,导电橡胶的渗流阈值变小;导电橡胶的压阻效应在渗流区间明显;球形镍包铝可以削弱导电橡胶的电阻蠕变程度。     

导电炭黑填充PP-EAA复合材料的形态及电性能

以聚丙烯(PP) 和乙烯-丙烯酸共聚物( EAA) 的共混物为基体材料, 以导电炭黑为填料, 通过熔融共混的方法制备了导电复合材料。探讨了导电炭黑在两相基体中的分散情况以及聚丙烯结晶度对复合体系导电性能的影响。扫描电镜测试结果表明, 在共混物中炭黑粒子选择性分散在极性EAA 树脂中, 同时EAA 树脂在聚丙烯基体中形成连续网络结构, 从而显著降低了复合体系的渗滤阈值。电性能测试结果表明, 材料在相同导电炭黑含量下的体积电阻率相对于单基体体系有7～8 个数量级的降低, 并且结晶度较高的PP 更有利于降低复合体系的体积电阻率。此外, 炭黑/ PP-EAA 复合材料的拉伸强度相对于炭黑/ PP 体系有所下降, 而断裂伸长率有所提高。      

炭黑填充BST/PVDF复合薄膜的制备与介电性研究

以聚偏氟乙烯(PVDF)为聚合物基体,钛酸锶钡(BST)为陶瓷相,成本低廉的导电炭黑(CB)为导电相。采用流延加低温热处理的方法制备了一系列高介电柔性复合薄膜。利用阻抗分析仪对薄膜的介电性进行了测试,结果表明,炭黑的填充能有效提高复合材料的介电性能,当体积分数接近渗流阈值6.2%时,CB/BST/PVDF复合材料的介电常数、介质损耗、电导率急剧增加。结合经典渗流理论研究了材料在渗流转变时介电性变化特征及微观机理,利用微电容模型、界面极化理论对这一现象进行解释。     

聚苯乙烯/多壁碳纳米管复合丝的制备与性能

采用微型双螺杆挤出共混和熔融纺丝法制备了聚苯乙烯/多壁碳纳米管(PS/MWNTs)复合丝。通过添加改性剂可以提高复合材料的纺丝最大拉伸比。光学显微镜和扫描电镜观察发现,当MWNTs含量较小(<2%)时,MWNTs在基体中的分散比较均匀。随着MWNTs含量的增加,团聚增多,且大多数MWNTs沿纤维轴向取向排列。当MWNTs含量较小时,添加一定量改性剂可以提高复合丝的拉伸强度及尺寸稳定性。电性能结果表明,复合丝的导电渗流阈值出现在2%～5%之间。复合材料的流变渗流阈值与导电渗流阈值具有一致性。     

LDPE/EVA/MWCNTs/CF复合材料的电学及流变性能

用熔融共混法制备了低密度聚乙烯(LDPE)/乙烯-醋酸乙烯共聚物(EVA)/多壁碳纳米管(MWCNTs)/碳纤维(CF)复合材料。使用高阻计、扫描电子显微镜、旋转流变仪等研究了导电填料及基体组成对材料的电性能和流变性能的影响。发现MWCNTs与CF共同作为导电填料具有协效作用,使得材料其不仅具有渗滤阈值低的特点,并且当填料含量超过阈值时,材料的导电性能相比于纯MWCNTs填充的复合材料电阻率降低了2个数量级。流变测试发现MWCNTS相比于CF对基体分子链运动的限制更为明显,MWCNTs含量的增多会增加材料的黏度并使材料从"类液"的粘弹行为转变为"类固"的粘弹行为。     

单壁纳米碳管/聚酰亚胺复合材料的制备及导电特性

采用熔融聚合法和反复机械拉伸法,制备出定向排列单壁纳米碳管(SWNTs)/聚酰亚胺(PI)复合材料。研究了纳米碳管在复合体中的排列和分散情况。讨论了填充纳米碳管的质量分数对复合材料导电性能的影响,发现SWNTs填充质量分数很少时,复合体系呈现渗流行为,表现出良好的导电性和各向异性,其电导率随着填充纳米碳管的质量分数增加,电导率增大,而且在其拉伸方向比其垂直方向显示出较高的电导率,沿着其拉伸方向的渗流阈值比其垂直方向要低,说明单壁碳纳米管在复合物材料中呈现出良好的排列和均匀分散。     

增强防静电改性聚丙烯的研究

将预处理的微米导电粉体采用熔融共混法添加于聚丙烯树脂中,制成试样,测试其防静电和力学性能。结果表明经改性后的聚丙烯复合体不但其表面电阻率最低可降至107Ω、而且断裂强力则提高到247N,对粉体表面进行电晕放电和化学修饰后,粒子在基体中的分散性及相容性得到显著改善,该方法可制取兼具力学性能的防静电材料。     

石墨烯/超高分子量聚乙烯导电复合材料的电性能

通过两步法制备了纳米石墨烯(GNS)/超高分子量聚乙烯(UHMWPE)分离结构导电复合材料,通过扫描电子显微镜和透射偏光显微镜研究了导电复合材料的形态结构与电性能的关系。研究表明,GNS粒子能够均匀地涂覆在UHMWPE粒子表面。当GNS的体积分数为0.4%时,复合材料电导率提升了15个量级,渗流阀值为0.028%(体积分数,下同)。GNS/UHMWPE分离结构导电复合材料的正温度系数效应(PTC)研究表明,由于填料分布形态及含量的变化,导致复合材料PTC转变温度发生改变。     

拉伸条件下液态Sn/熔融聚乙烯复合体系中Sn的纤维化及其机制

低熔点金属与聚合物复合不仅可以产生高性能的导电和导热复合材料,还为聚合物多相多组分体系的研究提供了新的模型。为系统认识低熔点金属液体/聚合物熔体复合体系在外场作用下的结构变化,首先通过光学显微镜研究了拉伸条件下液态Sn/熔融聚乙烯复合体系中Sn液滴的纤维化现象;然后,测量了不同拉伸程度下Sn/聚乙烯复合体系中Sn粒子的尺寸,并研究了拉伸程度对Sn粒子尺寸的影响;最后揭示了Sn液滴纤维化的机制。结果表明:在液态Sn/熔融聚乙烯复合体系的拉伸过程中,Sn液滴的直径越大,则越先开始纤维化;纤维状Sn粒子的直径由复合体系的拉伸程度决定,而其长度则由Sn液滴的体积决定。所得结论可为高性能金属/聚合物复合材料的制备提供理论指导。     

粒径对Ni/硅橡胶复合材料压敏性及介电性质的影响

采用不同粒径的Ni粉与硅橡胶(110型)按质量比2.4∶1.0制成Ni/硅橡胶复合材料, 分别测量了其压敏导电性及介电性质, 并结合扫描电镜照片对其微观导电机制进行了分析。结果表明随着填料Ni粉粒径的减小, Ni/硅橡胶复合材料的直流电阻率对外加压强更加敏感: 在低压强下, 粒径为74、48和18 μm的样品的电阻率随压强的变化率分别为1.73×104、2.59×104和3.71×10 4 Ω·m/kPa。样品直流电阻率陡降的区域随粒径的减小向压强较小的方向移动, 显示出复合材料的渗流阈值与填充粒子的粒径有关: 粒径越小, 渗流阈值也越小。Ni/硅橡胶复合材料的交流电导率、介电常数、介电损耗均随填料Ni粉粒径的减小而变大: Ni粉粒径为18 μm的Ni/硅橡胶复合材料的电导率约为10-2 S·m-1, 比74 μm粒径样品的电导率(约10-7 S·m-1)提高了5个数量级; 对应的介电常数由约102提高到约103。改变填料Ni粉粒径可以有效地调节复合材料的弹性和压敏、电输运特性。      

Ti3C2Tx MXene/聚乙烯醇复合材料的介电性能

以二维过渡金属碳化物Ti₃C₂T_x MXene作为填料,非铁电、可生物降解的高分子物质聚乙烯醇(PVA)作为基体,通过溶液涂膜法制备了具有高介电常数的Ti₃C₂T_x MXene/PVA柔性复合材料。研究了Ti₃C₂T_x MXene充填量对复合材料介电性能的影响。Ti₃C₂T_x MXene/PVA复合材料的介电性能变化遵循逾渗规律,随着Ti₃C₂T_x MXene充填量的增加,Ti₃C₂T_x MXene/PVA复合材料的介电常数呈先增加后减小的变化规律,Ti₃C₂T_x MXene充填量为20wt%的Ti₃C₂T_x MXene/PVA复合材料介电常数在20 Hz时高达577.3,比纯PVA的介电常数(10.5)提升了5 398%。但是,当Ti₃C₂T_x MXene充填量超过20wt%后,Ti₃C₂T_x MXene/PVA复合材料的介电常数急剧下降,介电损耗快速上升,表现出明显的逾渗行为。      

Non-ohmic I–V behaviour of random metal-insulator composites near their percolation threshold

A large increase in electrical conductivity has been observed when a direct current voltage is applied to random metal-insulator composites near their percolation threshold. This reversible non-ohmic I-V behaviour, which is similar to that observed in zinc oxide varistors, has been studied in three metal/insulator systems including silver particles in a matrix of potassium chloride, and two different systems of nickel particles in a matrix of polypropylene. These composites have all been prepared by mechanically mixing metal particles with an insulator host in predetermined volume fractions. A physical model with a semi-phenomenological equation has been proposed to describe this non-ohmic I–V behaviour. The non-ohmic effect is postulated to arise from a localized reversible dielectric breakdown between narrowly separated metal clusters in the metal/insulator composite.     

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.     

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.     

All-organic PANI–DBSA/PVDF dielectric composites with unique electrical properties

Novel all-organic polymer high-dielectric permittivity composites of polyaniline (PANI)/poly (vinylidene fluoride) (PVDF) were prepared by solution method and their dielectric and electric properties were studied over the wide ranges of temperatures and frequencies. To improve the interface bonding between two polymers, dodecylbenzenesulfonic acid (DBSA), a bulky molecule containing a polar head and a long non-polar chain was used both as a surfactant and as dopant in polyaniline (PANI) synthesis. Synthesized conducting PANI–DBSA particles were dispersed in poly(vinylidene fluoride) (PVDF) matrix to form an all-organic composite with different PANI–DBSA concentrations. Near the percolation threshold, the dielectric permittivity of the composites at 100 Hz frequency and room temperature was as high as 170, while the dielectric loss tangent value was as low as 0.9. Like typical percolation system, composites experienced high dielectric permittivity at low filler concentrations. However, their dielectric loss tangent was low enough to match with non-percolative ceramic filler-based polymer composites. Maximum electrical conductivity at 24 wt% of PANI–DBSA was mere 10^?6 S/cm, a remarkably low value for percolative-type composites. Increase in the dielectric permittivity of the composites with increase in temperature from 25 to 115 °C for different PANI–DBSA concentrations was always in the same range of 50–60 %. However, the degree of increase in the electrical conductivity with the temperature was more prominent at low filler concentrations compared with high filler concentrations. Distinct electrical and their unique thermal dependence were attributed to an improved interface between the filler and the polymer matrix.     

Carbon nanotubes/cyanate ester composites with low percolation threshold,high dielectric constant and outstanding thermal property

A novel kind of multi-walled carbon nanotubes (MWCNTs)/cyanate ester (CE) composites with low percolation threshold, high dielectric constant and excellent thermal property was developed. In order to investigate the effect of the surface nature of MWCNTs on the morphology and properties of the composites, MWCNTs and surface treated carbon nanotubes (MWCNTs–OH) were used to prepare two sorts of composites, coded as M/CE and M–OH/CE, respectively. Results show that increasing the content of MWCNTs or MWCNTs–OH, the dielectric constant of both kinds of composites initially increases until reaches the maximum value, and then decreases. In addition, when the percolation occurs, dielectric constant and loss of both kinds of composites decrease quickly with the increase of the tested frequency. The addition of MWCNTs into CE decreases the glass transition temperature and thermal stability, while the incorporation of MWCNTs–OH significantly improves the thermal stability of CE resin.     

炭黑/聚丙烯-聚(苯乙烯-乙烯/丁烯-苯乙烯)复合材料的介电性能和压阻性能

为了制备柔性较好的聚合物基压阻材料,利用熔融共混法制备了炭黑/聚丙烯-聚(苯乙烯-乙烯/丁烯-苯乙烯)(CB/PP-SEBS)复合材料,并研究了CB含量对CB/PP-SEBS复合材料介电性能和压阻性能的影响。结果表明:随着CB含量的增加,CB/PP-SEBS复合材料的介电常数、介电损耗及电导率均提高;CB/PP-SEBS复合材料发生导电逾渗时,CB的含量为12.2wt%;在CB/PP-SEBS复合材料发生弹性形变时,由于外力破坏了CB的导电网络,复合材料的电阻随着应变的增大而增大;循环压阻测试结果显示,在弹性变形区CB/PP-SEBS复合材料的电阻随着应变呈现周期性变化。研究结果可为制备具有稳定电阻变化的聚合物基压阻材料提供借鉴。     

Electrical properties of polyvinylidene fluoride (PVDF)/multi-walled carbon nanotube (MWCNT) semi-transparent composites: Modelling of DC conductivity

Transparent conductive composites can be achieved from PVDF–MWCNT at very low concentration of MWCNT. These composites show different degree of UV–Visible radiation absorption depending on MWCNT concentration in composites. The composition dependent dielectric properties and AC conductivity were also measured for these composites. Properties like AC conductivity, dielectric constant and loss are increasing with filler concentration. The variations of DC conductivity against composition and temperature are also reported. The electrical hysteresis and electrical set are observed for PVDF–MWCNT composites when subjected to heating–cooling cycle. The validity of different theoretical models depicting percolation threshold with respect to DC conductivity was tested for these composites.     

Preparation and properties of hollow glass microsphere-filled epoxy-matrix composites

Hollow glass microsphere (HGM)–filled epoxy composites, with filler content ranging from 0 to 51.3 vol.%, were prepared in order to modify the dielectric properties of the epoxy. The results showed that the dielectric constant (D_k) and dielectric loss (D_f) of the composites decreased simultaneously with increasing HGM content, which was critical for the provision of superior high-frequency device performance. Other properties of the composite, such as the coefficient of thermal expansion (CTE) and the glass transition temperature (T_g), were also improved. The improvement in these properties was related to strong interaction between the HGM and epoxy, which was indicated by the formation of an interphase between the HGM and epoxy-matrix. It was unsatisfactory in this study that the thermal conductivity of the composites also decreased with HGM content. In order to obtain relatively high thermal conductivity and a low dielectric constant simultaneously, this paper suggests further adding other filler.