In situ microfibrillar morphology and properties of polypropylene/polyamide/carbon black composites prepared through multistage stretching extrusion

Isotactic polypropylene/polyamide/carbon black (PP/PA/CB) composites with microfibrillar morphology were designed and prepared using a multistage stretching extruder with an assembly of laminating-multiplying elements (LMEs). CB was selectively located in PA. With the increase of LME number from zero to seven, the conductive PA/CB phase was found to experience an elongating-breaking-elongating process. This morphological development resulted in the strong dependence of electrical resistivity on the LME number. When no LME was used, PP/PA/CB materials with 2.0, 3.0, or 4.0 wt% (1.0, 1.6, and 2.1 vol%) CB employed were insulators (resistivity: 10¹⁰ Ω cm) due to their droplet morphology. With the introduction of LMEs, a conductive network was formed because of the microfibrillation of the conductive PA/CB phase; these materials became conductors (resistivity: 10⁴–10⁶ Ω cm). The percolation threshold can lower to 1.5 wt% (0.9 vol%). The low resisticity and percolation threshold cannot be obtained through the conventional method.     

Electrical and rheological properties of PMMA/LDPE blends filled with carbon black

Conductive immiscible multiphase blends of PMMA/LDPE filled with carbon black (CB) were studied in this work. Thermo-electrical behavior of the blends was compared with the composites made up of individual polymers in the blend, PMMA and LDPE filled with CB. The conductivity of the immiscible binary blend at different CB content was followed and modeled using a model circuit in which resistors resembling different phases and the interface between them present in the blend. Electrical percolation threshold was measured for the blend and compared with the single component polymers in order to judge the preferred phase for CB distribution in it. Rheological network formation by CB particles in the blend was also studied using dynamic rheology. The effect of CB loading on the morphology of the multiphase blend was also studied using FESEM images. Theoretical models were also used to predict the percolation thresholds for electrical and rheological network formation and compared with the experimental values.     

High-performance conductive materials based on the selective location of carbon black in poly(ether ether ketone)/polyimide matrix

A novel high performance conductive material with excellent comprehensive properties was prepared by melt-blending, and its performances were adjusted by controlling the selective location of carbon black (CB) in poly(ether ether ketone) (PEEK)/thermoplastic polyimide (TPI) matrix. With increasing the CB loadings, the morphology of PEEK/TPI blends changed from sea-island to co-continuous structure, which was owing to the selective location of CB in TPI phase. Notably, with the selective location of CB in the induced co-continuous PEEK/TPI matrix, the electrical percolation threshold was reduced to 5 wt%, which was significantly lower than that of binary PEEK/CB (9 wt%) and TPI/CB (10 wt%) composites. And the electrical conductivity of ternary PEEK/TPI/CB composites was 10⁴ to 10⁶ times higher than that of binary composites at identical 7.5 wt% CB loading, which was attributed to the double percolation effect. Moreover, the incorporation of CB could improve the thermal and mechanical properties effectively.     

Evaluation of thermal,mechanical, and electrical properties of PVDF/GNP binary and PVDF/PMMA/GNP ternary nanocomposites

Graphene nanoplatelet (GNP) was incorporated into poly(vinylidene fluoride) (PVDF) and PVDF/poly(methyl methacrylate) (PMMA) blend to achieve binary and ternary nanocomposites. GNP was more randomly dispersed in binary composites compared with ternary composites. GNP exhibited higher nucleation efficiency for PVDF crystallization in ternary composites than in binary composites. GNP addition induced PVDF crystals with higher stability; however, PMMA imparted opposite effect. The binary composite exhibited lower thermal expansion value than PVDF; the value further declined (up to 28.5% drop) in the ternary composites. The storage modulus of binary and ternary composites increased to 23.1% and 53.9% (at 25 °C), respectively, compared with PVDF. Electrical percolation threshold between 1 phr and 2 phr GNP loading was identified for the two composite systems; the ternary composites exhibited lower electrical resistivity at identical GNP loadings. Rheological data confirmed that the formation of GNP (pseudo)network structure was assisted in the ternary system.     

Preparation and properties of carbon black/polymer composites with segregated and double-percolated network structures

A carbon black (CB)/low-density polyethylene (LDPE)/ultrahigh-molecular-weight polyethylene (UHMWPE) composite with a segregated and double-percolated structure has been fabricated using the solution mixing and high-speed mechanical mixing method. Structural observations show that the conducting CB/LDPE layers were only dispersed at the interface of UHMWPE granules and formed a well-developed CB conductive network with a percolation threshold of 0.26 vol%. The low percolation threshold in CB/LDPE/UHMWPE composites can be explained by the segregated and double-percolated networks of CB within the polymer matrix. A noticeable double positive temperature coefficient of resistivity can be observed around the melting temperature of LDPE and UHMWPE followed by a negative temperature coefficient of resistivity. The microstructure evolution of CB/LDPE/UHMWPE composites can be observed and explained by in situ optical micrographs.     

炭黑／聚丙烯／聚碳酸酯复合材料导电性能和PTC特性

以聚丙烯（PP）／聚碳酸酯（PC）共混物为基体,采用不同种类炭黑（CB）填充制备导电复合材料并对其导电性能和PTC特性进行研究。结果表明：在常温时,PP／PC共混基体中PP含量大于40wt％时,材料的电阻率急剧下降;共混比为50：50（wt％）复合材料的电阻率达到最小值。加热时,两者均未出现明显NTC现象,说明PP／PC的共混可以有效的消除NTC效应。但PTC强度仅为1个数量级,远低于PP／CB二元复合材料。CB是影响PTC效应的重要因素之一,达到逾渗值时随着体系CB含量减少PTC效应会增强;乙炔炭黑与炉法CB填充的CB／PP／PC复合材料相比较,前者的体积电阻率较低,而两者的逾渗阈值相近,均为6．6％;乙炔CB为填料的CB／PP／PC三元复合材料的阿C突变温度在140℃附近,以炉法CB为填料时,PTC效应突变点出现在150℃（PC的Tg）附近。DSC分析结果表明,复合材料中PP的结晶度随着CB含量增加呈上升趋势,CB含量为15％时,PP的结晶度为32．75％,对于整个PP／PC／CB体系而言结晶部分的含量较低,因此该体系的PTC效应强度较低。     

多壁碳纳米管增强炭黑/聚丙烯导电复合材料导电行为

为了充分利用不同导电粒子的导电作用,在炭黑(CB)/聚丙烯(PP)导电复合体系中引入了多壁碳纳米管(CNTs)。研究发现：引入的CNTs分散在CB粒子间起到“桥梁”作用,使体系的导电性能得到明显改善,并且CB∶CNTs为19∶1时其协同导电效果最好,该复合体系出现逾渗现象,对应的导电填料体积分数明显降低。在导电填料总体积分数为4.76%时,少量CNTs的引入就可使复合体系的体积电阻率从109Ω·cm下降到105Ω·cm;同时少量的CNTs能明显抑制炭黑/聚丙烯导电复合材料的正温度效应(PTC),使PTC强度从6.10降低到1.48,PTC转变峰温度从166℃升高到174℃。少量的 CNTs可以使PP的结晶温度提高12℃,对PP结晶的成核作用比CB更加明显。复合体系力学性能随导电填料体积分数增加而明显降低,但因为体积电阻率一定时CB-CNTs/PP体系所需导电填料体积分数较CB/PP体系明显降低,因此少量CNTs的引入能够使复合体系的力学性能得到更大程度的保持。     

导热绝缘h-BN/MVQ/EVA复合材料的双逾渗效应

将h-BN加入到MVQ和EVA混合物中制备导热绝缘h-BN/MVQ/EVA复合材料,SEM结果表明h-BN选择性分布在EVA,与杨氏方程理论一致.h-BN/MVQ/EVA复合材料中的双逾渗效应,有助于力学性能和导热性能的提升.h-BN/MVQ/EVA复合材料的热导率与h-BN含量和MVQ/EVA比值有关.当EVA质量分数为30%时,h-BN/MVQ/EVA复合材料热导率的相对值最大.h-BN/MVQ/EVA复合材料的拉伸强度和断裂伸长率与EVA含量有关,随着EVA和h-BN含量的增加,复合材料的介电常数降低.     

CNTs/ UHMWPE composites with a two-dimensional conductive network

A low percolation threshold can be achieved for the conductive polymer composites(CPC) materials having a segregated structure in which the conductive particles like carbon black (CB), carbon nanotubes (CNTs), etc. are only located on the interface of the polymer matrix particles instead of being randomly distributed in the whole system. Multiwalled carbon nanotubes (MWNTs) were experienced alcohol-assisted dispersion under ultrasonication and intense mechanical mixing, and only located on the interfaces of the ultrahigh molecular weight polyethylene (UHMWPE) matrix particles to form a segregated structure. The morphological observation and the critical exponent t value obtained from the classical threshold mechanism indicate that the MWNTs/UHMWPE composites form a 2-dimension conductive network, which leads to a very low percolation of 0.072vol%.     

Lowering the percolation threshold of polymer matrix composite by using raspberry-like carbon black/polystyrene composite particles

Our previous studies of raspberry-like carbon black/polystyrene (CB/PS) composite particles suggested that their morphologies could be tailored as the coverage degree of CB on PS microspheres. Morphologies of these composite particles were investigated by scanning electron microscope. The CB/PS composites prepared by using raspberry-like CB/PS particles had lower percolation threshold than that of general CB/PS composites. Optical microscopy photographs indicated that hierarchical structure of composite particles enabled CB particles to form more effective networks within the matrix. Raspberry-like structure dispersed CB particles in the interfaces between polycarbonate (PC) and PS when CB/PS particles were introduced into PC as additives. The effects of concentration of PS, coverage degree of CB, and concentration of CB on electrical properties of CB/PS/PC composite were investigated. The results showed that the percolation threshold of CB/PS/PC composite was improved when PS concentration was at the range of 20–80% and coverage degree of CB was more than 5% simultaneously.     

Ternary nano-CaCO3/poly(ethylene terephthalate) fiber/polypropylene composites: Increased impact strength and reinforcing mechanism

The binary nano-CaCO₃/polypropylene (PP), poly(ethylene terephthalate) (PET) fibers/PP and ternary nano-CaCO₃/PET fibers/polypropylene composites were prepared by melt blending method, and their structure and mechanical properties were investigated. The results show that the ternary nano-CaCO₃/PET fibers/PP composite displays significantly enhanced mechanical properties compared with the binary PET fibers/PP and nano-CaCO₃/PP composites, and neat PP. The X-ray diffraction, dynamic mechanical analysis, scanning electron microscopy and analysis of the non-isothermal crystallization kinetics were used to investigate the reinforcement mechanism of composites. The results indicate that the interfacial action and compatibility between PET fiber and PP are obviously enhanced by the addition of modified nano-CaCO₃ particles in the ternary composites and the mechanical property enhancement in the ternary system may be mainly originated from the formation of β-form crystallites of PP induced by the synergistic effect between PET fibers and nano-CaCO_3.     

Thermal-Diffusivity Measurements of Conductive Composites Based on EVA Copolymer Filled With Expanded and Unexpanded Graphite

In this research, the thermal diffusivity of composites based on ethylene- vinyl acetate (EVA) copolymer filled with two kinds of reinforcement graphite materials was investigated. The reinforcement graphite fillers were untreated natural graphite (UG) and expanded graphite (EG). Composite samples up to 29.3 % graphite particle volumetric concentrations (50 % mass concentration) were prepared by the melt- mixing process in a Brabender Plasticorder. Upon mixing, the EG exfoliates in these films having nanosized thicknesses as evidenced by TEM micrographs. Thus, the thermal diffusivity and electrical conductivity of composites based on the ethylene-vinyl acetate matrix filled with nanostructuralized expanded graphite and standard, micro-sized graphite were investigated. From the experimental results it was deduced that the electrical conductivity was not only a function of filler concentration, but also strongly dependent on the graphite structure. The percolation concentration of the filler was found to be (15 to 17) vol% for micro-sized natural graphite, whereas the percolation concentration of the filler in nanocomposites filled with expanded graphite was much lower, about (5 to 6) vol%. The electrical conductivity of nanocomposites was also much higher than the electrical conductivity of composites filled with micro-sized filler at similar concentrations. Similarly, the values of the thermal diffusivity for the nanocomposites, EG-filled EVA, were significantly higher than the thermal diffusivity of the composites filled with micro-sized filler, UG-filled EVA, at similar concentrations. For 29.3 % graphite particle volumetric concentrations, the thermal diffusivity was 8.23 × 10^?7 m² · s^?1 for EG-filled EVA and 6.14 × 10^?7 m² · s^?1 for UG-filled EVA. The thermal diffusivity was measured by the flash method.     

特殊形态结构导电高分子复合材料的电学性能

先使聚丙烯接枝马来酸酐(PP-g-MAH)与炭黑(CB)反应,再与聚丙烯/尼龙6(PP/PA6)共混制备出CB位于两相界面处的PP/PA6/PP-g-MAH/CB导电高分子复合材料,研究了材料的特殊结构和电学性能。结果表明,在PP/PA6/CB体系中CB粒子分布在PA6相,体系的逾渗阈值为2%;而在PP/PA6/PP-g-MAH/CB体系中,CB被PP-g-MAH诱导分布在两相界面处。PP/PA6两相为海岛结构时,PP/PA6/PP-g-MAH/CB体系仍可导电。PP/PA6/PP-g-MAH/CB体系的逾渗阈值降至1.6%,低于PP/PA6/CB体系。体系的正温度效应(PTC)强度远高于PP/PA6/CB体系,在90-135℃范围内不出现负温度效应(NTC)。PP/PA6/PP-g-MAH/CB体系的电学性能归结于其特殊的界面形态结构:导电通道由位于共混物界面处的PP-g-MAH和CB构建而成。     

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。     

Synergistic effects in network formation and electrical properties of hybrid epoxy nanocomposites containing multi-wall carbon nanotubes and carbon black

Epoxy nanocomposites including multi-wall carbon nanotubes (MWCNT) and carbon black (CB) were produced and investigated by means of electrical conductivity measurements and microscopical analysis. Varying the weight fraction of the nanoparticles, electrical percolation behaviour was studied. Due to synergistic effects in network formation and in charge transport the inclusion of both MWCNT and CB in the epoxy matrix leads to an identical electrical behaviour of this ternary nanocomposite system compared to the binary MWCNT-epoxy system. For both types of nanocomposites an electrical percolation threshold of around 0.025 wt% and 0.03 wt% was observed. Conversely, the binary CB nanocomposites exhibit a three-times higher percolation threshold of about 0.085 wt%. The difference between the binary MWCNT-epoxy and the ternary CB/MWCNT-epoxy in electrical conductivity at high filler concentrations (e.g. 0.5 wt%) turns out to be less than expected. Thus, a considerable amount of MWCNTs can be replaced by CB without changing the electrical properties.     

Comparison of rheological and electrical percolation phenomena in carbon black and carbon nanotube filled epoxy polymers

Epoxy nanocomposite suspensions including multi-wall carbon nanotubes (MWCNTs) and carbon black (CB) were produced and investigated by means of combined rheological and electrical analysis. The rheological percolation behaviour was compared to the electrical percolation behaviour. Due to similar dynamic agglomeration mechanisms the difference between the rheological and the electrical percolation threshold in the cured state is identical for MWCNT and CB filled systems. Non-covalent matrix–nanoparticle interactions in uncured epoxy suspensions are negligible since the onset of electrical and rheological percolation in the uncured state coincidence. Furthermore, the electrical percolation threshold in the cured state is always lower than in the uncured state because of the high tendency of CB and MWCNTs to form conductive networks during curing. The difference between rheological and electrical percolation threshold is dependent on the curing conditions. Thus, the rheological percolation threshold can be considered as an upper limit for the electrical percolation threshold in the cured state. Due to the formation of co-supporting networks multi-filler (MWCNTs and CB) suspensions exhibit a similar rheological behaviour as the binary MWCNT suspensions. For both types of suspensions a rheological percolation threshold of around 0.2 and 0.25 wt% was determined. Conversely, the binary CB nanocomposites exhibit a four-times higher percolation threshold of about 0.8 wt%. The difference between the binary MWCNT suspension and the ternary CB/MWCNT suspension in storage shear modulus at high filler concentrations (~0.8 wt%) turns out to be less than expected. Thus, synergistic effects in network formation are already present in the epoxy suspension and get more pronounced during curing.     

Study of the effective parameters on mechanical and electrical properties of carbon black filled PP/PA6 microfibrillar composites

In this study the electrical and mechanical properties of microfibrillar polypropylene (PP)/polyamide6 (PA6) blend filled with super conductive carbon black (CB) have been investigated. In situ microfibrillar PP/PA6 composites filled with CB are produced using a single screw extruder equipped with a spinneret. Glycidyl methacrylate (GMA) grafted polypropylene (PP-g-GMA) is used as the compatibilizer. To investigate the effects of extensional flow on the microstructure, electrical and mechanical properties, three adaptors with various convergence angles were designed, prepared and applied between the extruder and the spinneret. To optimize the effects of processing and material parameters on the electrical and mechanical properties, the Taguchi method of experimental design is used. Material and processing factors which are studied include: concentration of PA6, compatibilizer level, CB concentration, drawing speed of melt spinning line, adaptor angle, order of mixing and temperature profile along the extruder. The results show an increase in DC conductivity of up to 10¹¹ times in comparison with pure PA6, by increasing the concentration of CB, drawing speed, adaptor angle and optimizing other parameters. By optimizing processing and material factors studied here, strength of microfibrillar structured composites is increased of up to 80% in comparison to pure PP.     

Electromagnetic interference shielding of carbon nanotube/ethylene vinyl acetate composites

Single-walled carbon nanotube (SWCNT) and ethylene vinyl acetate (EVA) composites were synthesized in an internal mixer by melt mixing. The electrical conductivity as well as electromagnetic interference (EMI) shielding effectiveness (SE) over the X-band (8–12 GHz) and microwave (200–2,000 MHz) frequency ranges of these composites were investigated. It was observed that the electrical conductivity of composites increases with increasing SWCNT loading. A percolation threshold of about 3.5 wt.% was obtained and the electrical conductivity of EVA was increased by ten orders of magnitude, from 10⁻¹⁴ to 10⁻⁴ Ω⁻¹ cm⁻¹. The effect of sample thickness on SE was investigated. The correlation between SE and conductivity of the composites is discussed. The experimental data showed that the SE of the composites containing higher carbon nanotube loadings (above 10 wt.%) could be used as an EMI shielding material and lower SWCNT loadings could be used for the dissipation of electrostatic charge.     

Assessment of percolation and homogeneity in ABS/carbon black composites by electrical measurements

In this study, composites consisting of an insulating poly(acrylonitrile-co-butadiene-co-styrene) polymer matrix and a conducting carbon black (CB) additive were produced by twin-screw extrusion. Both direct current and alternating current electrical measurements were used to evaluate the electrical properties of the composite and to assess whether sufficient mixing was achieved. Electrical measurement results and scanning electron micrographs show that once-extruded composites had a porous structure and poor conductivity while twice-extruded composites were much more homogeneous and had higher conductivity. The percolation threshold of the twice-extruded poly(acrylonitrile-co-butadiene-co-styrene)/CB composites was found to be between 8 and 10% CB. Electrical measurements provided a feedback loop for improving processing of the composite material.     

导电聚苯胺纳米纤维对聚乙烯/炭黑复合体系电阻行为的影响

采用水溶液氧化聚合和热掺杂相结合的技术制备十二烷基苯磺酸掺杂的聚苯胺(PANI-DBSA)纳米纤维,并将PANI-DBSA纳米纤维与低密度聚乙烯(LDPE)和炭黑(CB)进行熔融共混制得PANI-DBSA/LDPE/CB导电复合材料,研究了PANI-DBSA纤维的引入对导电复合材料电阻行为的影响。结果表明,添加PANI-DBSA纳米纤维,复合材料的逾渗阀值移向较低炭黑含量,复合材料的PTC强度得到一定程度的提高,复合材料的电阻率-温度曲线的热循环稳定性得以改善。