石墨烯微片的尺寸和形态对聚丙烯基纳米复合材料导电导热性能的影响

通过熔融共混法制备了5种不同石墨烯微片（GNP）的聚丙烯（PP）/GNP纳米复合材料,采用电子和光学显微镜等仪器和导电导热等性能测试研究了GNP的尺寸和含量对PP基纳米复合材料导电导热性能的影响。结果表明,同一厚度的GNP片径越大,片层间的接触面积也越大,复合材料导电导热性能越好;同一片径的GNP,片层薄的在PP基体中的剥离程度和分散程度好,相应的PP/GNP纳米复合材料的导电导热性能好;而且GNP含量的改变对PG-100、PG-030和PG-G5导电导热性能的影响是不同的;其中PG 030导电网络最先形成,渗流阈值最低,而PG-G5在高含量时导电和导热率最高。     

Conducting bicomponent fibers obtained by melt spinning of PA6 and polyolefins containing high amounts of carbonaceous fillers

Melt spinning of conductive polymer composites (CPCs) is coupled with some difficulties such as a decrease of conductivity upon drawing and a reduced spinnability with increasing filler concentration. Applying bicomponent technology may provide the possibility to produce fibers from CPCs with a high filler concentration. A pilot‐scale bicomponent melt spinning set‐up was used to produce core/sheath fibers with fiber titers between 13 and 47 dtex. The sheath material was polyamide 6 (PA6) or polypropylene (PP) and the core material was a CPC. Two CPCs were used, polypropylene (PP) with carbon black (CB), denoted by PP/CB, and polyethylene (PE) with multiwalled carbon nanotubes (MWNT), denoted by PE/MWNT. The results showed that both materials could be used with a filler concentration of 10 wt % to obtain melt draw ratios up to 195. The volumetric fraction of core material in the bicomponent structure was 28%. A heat treatment of PP/CB fibers restored the conductivity to the level of the undrawn material, corresponding to an increase in conductivity by a factor 5. The same heat treatment had a positive effect on the conductivity of PE/MWNT fibers although the conductivity was not restored. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

纳米石墨片/炭黑/氯醋树脂复合导电膜的制备及性能研究

以氯醋树脂P(VC-Co-VAc)为基体,采用原位还原萃取分散技术制备了纳米石墨片复合导电膜,通过与炭黑填料的对比,考察了导电填料的几何形状以及两相导电填料之间的协同作用对复合膜导电性能的影响.结果表明:纳米石墨片在基体中分散良好,其复合膜的导电性能明显优于炭黑导电膜;当纳米石墨片和炭黑的体积比为4:6时,二者的协同作用最佳,其导电性明显优于相同含量下的单相填料复合导电膜.     

混杂碳质填料对聚丙烯流变性能的影响

为研究多种碳质填料混杂对聚丙烯(PP)流变性能的影响,采用熔融共混法制备了聚丙烯(PP)/石墨烯(GNP)/碳纳米管(CNT)/炭黑(CB)复合材料,采用旋转流变仪研究了复合材料的流变行为。结果表明,加入的碳质填料,显著提高了复合材料的储能模量(G')、损耗模量(G″)以及复数黏度(η*)。在相同含量下,PP/CNT复合材料流变逾渗值最小,其次是PP/CB,最后是PP/GNP。当CNT含量超过0.5%时,PP/GNP/CNT复合材料出现了模量平台;当CB含量超过3%时,PP/GNP/CB复合材料出现模量平台;CNT与CB的协同作用最佳,CNT和CB的加入有利于GNP的分散;GNP与少量的CNT和CB共混能使G'、G″以及η*得到明显提高,同时,能够大幅减小流变逾渗值;纯PP以及PP/GNP复合材料的损耗因子随频率的增加而下降,PP/CNT、PP/CB、PP/GNP/CNT/CB复合材料损耗因子随频率增加呈先升高后下降的趋势。     

Effects of multiple carbon fillers on the rheology of polycarbonate‐based composites

Adding conductive carbon fillers to insulating thermoplastic polymers increases the electrical conductivity of the resulting composite, which could allow them to be used in electrostatic dissipative and semiconductive applications. Adding fillers often increases viscosity, which can make the material more difficult to process. In this study, three different carbon fillers [carbon black (CB), carbon nanotubes (CNT), and exfoliated graphite nanoplatelets (GNP)] were studied via three different combinations of two different fillers (CB/CNT, CB/GNP, and CNT/GNP). These filler combinations were studied via three 3² factorial designs, which considered the following loading levels: CB: 0, 2, and 5 wt%; CNT: 0, 1, and 5 wt%; and GNP: 0, 2, and 5 wt%. These composites were compounded, injection molded, and tested for electrical conductivity and steady shear viscosity. CB and GNP exhibited classic filler behavior, increasing the composite viscosity with increased filler loading. CNT acted differently, lowering the composite viscosity with increased filler loading. When CB and GNP were combined, the viscosity increase was additive. When CNT was combined with either CB or GNP, the resultant composite had a lower viscosity than the corresponding single filler composite with equivalent loadings of CB or GNP. This viscosity lowering effect of CNT, even at loadings as low as 1 wt%, allows for increased filler loadings of CB or GNP with little impact on processability. Five different formulations (four containing two filler combinations) could be used for electrostatic dissipative applications and seven different formulations (six containing two filler combinations) may be used for semiconductive applications. POLYM. COMPOS., 2012. © 2011 Society of Plastics Engineers     

In situ dynamic vulcanization process in preparation of electrically conductive PP/EPDM thermoplastic vulcanizate/expanded graphite nanocomposites: Effects of state of cure

In situ melt dynamic vulcanization process has been employed to prepare electrically conductive polypropylene (PP)/ethylene–propylene–diene rubber (EPDM) (40/60 wt %) thermoplastic vulcanizates (TPVs) incorporated by expanded graphite (EG) as a conductive filler. Maleic anhydride grafted PP (PP‐g‐MAH) was used as compatibilizer and a sulfur curing system was designed and incorporated to vulcanize the EPDM phase during mixing process. Developed microstructures were characterized using scanning electron microscopy (SEM), melt rheomechanical spectroscopy (RMS), X‐ray diffraction (XRD), and transmission electron microscopy (TEM) and were correlated with electrical conductivity behavior. For comparison, another class of TPV/EG nanocomposites was fabricated using a commercially available PP/EPDM‐based TPV via both direct and masterbatch melt mixing process. Conductivity of the nanocomposites prepared by in situ showed no significant change during dynamic vulcanization till the mixing torque reached to the stationary level where micro‐morphology of the cured rubber droplets was fully developed, and conductivity abrupt was observed. In situ cured nanocomposites showed higher insulator to conductor transition threshold (3.15 vol % EG) than those based on commercially available TPV. All electrically conductive in situ prepared TPV nanocomposites exhibited reinforced melt elasticity with pseudosolid‐like behavior within low frequency region in dynamic melt rheometry indicating formation of physical networks by both EG nanolayers and crosslinked EPDM droplets. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synergistic effects of hybrid carbon nanomaterials in room‐temperature‐vulcanized silicone rubber

This work examines nanocomposites based on nanofillers and room‐temperature‐vulcanized silicone rubber. The carbon nanofillers used were conductive carbon black (CB), carbon nanotubes (CNTs) and graphene (GE). Vulcanizates for CB, GE, CNTs as the only filler and hybrid fillers using CNTs, CB and GE were prepared by solution mixing. The elastic modulus for CNT hybrid with CB at 15 phr (4.65 MPa) was higher than for CB hybrid with GE (3.13 MPa) and CNTs/CB/GE as the only filler. Similarly, the resistance for CNT hybrid with CB at 10 phr (0.41 kΩ) was lower than for CB (0.84 kΩ) at 20 phr and CNTs as the only filler. These improvements result from efficient filler networking, a synergistic effect among the carbon nanomaterials, the high aspect ratio of CNTs and the improved filler dispersion in the rubber matrix. © 2016 Society of Chemical Industry     

Blends of polypropylene and ethylene octene comonomer with conducting fillers: Influence of state of dispersion of conducting fillers on electrical conductivity

Blends of polypropylene/ethylene octene comonomer (PP/EOC) with conducting fillers viz., carbon black (CB) and multiwall carbon nanotubes (MWNT) were prepared using melt mixing technique with varying filler concentration and blend compositions. Thermo gravimetric analysis studies indicated that presence of filler enhanced the thermal stability of PP/EOC blends. Morphological analysis revealed the formation of matrix‐dispersed droplet and co‐continuous type of morphology depending on the blend compositions. Significant reduction in droplet size and finer ligament thickness in co‐continuous structure were observed in the blends with filler due to compatibilization action. Fillers were found to be aggregated in the EOC phase irrespective of blends compositions and could be related to the affinity of the fillers toward EOC phase. The electrical conductivity of PP/EOC blends with CB and MWNT was found to be highest for 80/20 composition and decreased as EOC content increased. The percolation threshold of CB was between 10 and 15 wt% for the 80/20 and 70/30 blends whereas it was 15–20 wt% for blends with EOC content higher than 30 wt%. The percolation threshold was 2–3 wt% MWNT for PP/EOC blends. This was attributed to the aggregated filler network preferentially in the EOC phase. The melt‐rheological behavior of PP/EOC blends was significantly influenced in presence of both the fillers. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Electrical,rheological and electromagnetic interference shielding properties of thermoplastic polyurethane/carbon nanotube composites

Electrically conducting rubbery composites based on thermoplastic polyurethane (TPU) and carbon nanotubes (CNTs) were prepared through melt blending using a torque rheometer equipped with a mixing chamber. The electrical conductivity, morphology, rheological properties and electromagnetic interference shielding effectiveness (EMI SE) of the TPU/CNT composites were evaluated and also compared with those of carbon black (CB)‐filled TPU composites prepared under the same processing conditions. For both polymer systems, the insulator–conductor transition was very sharp and the electrical percolation threshold at room temperature was at CNT and CB contents of about 1.0 and 1.7 wt%, respectively. The EMI SE over the X‐band frequency range (8–12 GHz) for TPU/CNT and TPU/CB composites was investigated as a function of filler content. EMI SE and electrical conductivity increased with increasing amount of conductive filler, due to the formation of conductive pathways in the TPU matrix. TPU/CNT composites displayed higher electrical conductivity and EMI SE than TPU/CB composites with similar conductive filler content. EMI SE values found for TPU/CNT and TPU/CB composites containing 10 and 15 wt% conductive fillers, respectively, were in the range ?22 to ?20 dB, indicating that these composites are promising candidates for shielding applications. © 2013 Society of Chemical Industry     

Effects of ultrasound vibration on the structure and properties of polypropylene/graphene nanoplatelets composites

An ultrasound‐assisted extrusion system was added to melt extrusion process to prepare polypropylene (PP) nanocomposites reinforced with graphene nanoplatelets (GNPs). The relationships among the ultrasound vibration, exfoliation, and dispersion morphology of GNPs in PP matrix, the crystallinity, and the macroscopic properties of nanocomposites were investigated. The properties measurement results showed that the present of ultrasound vibrations increased the conductive properties, decreased the apparent viscosity and crystallinity of PP/GNPs nanocomposites. FESEM results revealed that the ultrasound vibration increased the exfoliation and dispersion of GNPs in PP matrix. This morphology was benefit for forming electrical and thermal network, therefore the electrical conductivity and thermal conductivity of PP/GNP nanocomposites were increased. But the powerful vibration that provided by 300 W ultrasound power would reduce the diameter of GNPs, then reduce its conductive properties. FTIR and TGA results showed that ultrasound vibration had less effect on the chemical bond and the degradation of PP/GNPs nanocomposites. POLYM. ENG. SCI., 58:377–386, 2018. © 2017 Society of Plastics Engineers     

Elasticity and structure of weak graphite nanoplatelet (GNP) networks in polymer matrices through viscoelastic analyses

The elasticity and structure of graphite nanoplatelets networks in polymer matrices are studied through linear viscoelastic analyses. GNPs-filled polystyrene nanocomposites at different filler content are prepared through a combination of solution and melt mixing techniques. Electrical volume conductivity experiments prove that a continuous path of conductive nanoplatelets builds up across the matrix above a critical filler content. GNP networks, however, are too tenuous to be detected through conventional dynamic-mechanical spectroscopy in the melt state. Nevertheless, we are able to estimate their elasticity by exploiting the predictive feature of a simple two-phase rheological model. Our approach, validated through the building of a master curve of the elastic modulus of samples at different composition, allows to isolate the elastic contribution of the bare GNP network, whose dynamics reveal that its elasticity follows critical behaviour as predicted by percolation theory.     

Hybrid particulate and fibrous injection molded composites: Carbon black/carbon fiber/polypropylene systems

The electrical properties of injection molded composite systems based on a polypropylene matrix and two types of carbonaceous fillers—carbon black (CB) and carbon fibers (CF)—were investigated. In addition to conductivity as a function of system compositions, conductivity profiles were studied. Inhomogeneous spatial distribution of CB particles in moldings containing either CB as a single filler or in combination with CF was found. Furthermore, unexpected fiber orientation transverse to the melt flow direction and disappearance of skin‐core orientation pattern, typical for injection molded fiber filled composites, were observed in the two filler samples. An amplification of the shear‐thinning behavior, characteristic for the polypropylene (PP) matrix, imposed by the inhomogeneity of the CB distribution resulting in flattening of the advancing melt front and velocity profile is suggested as underlying the observed phenomena. POLYM. COMPOS., 26:454–464, 2005. © 2005 Society of Plastics Engineers     

Synergistic effects of conductive carbon nanofillers based on the ultrahigh-molecular-weight polyethylene with uniform and segregated structures

To discuss the synergistic effects of mixed conductive filler on nanocomposites, different structural carbon nanofiller/ultrahigh-molecular-weight polyethylene (UHMWPE) hybrid nanocomposites with uniform and segregated structure were prepared by using ethanol-assisted dispersion, hydrazine reduction, and hot-pressing methods. Scanning electron microscopy and polarized optical microscopy images of the nanocomposites fracture showed that the complete conductive channels could be formed in segregated nanocomposites prepared by powder mixing method. By contrast, the discontinuous electric path could be observed in the homogeneous nanocomposites prepared by the solution method. The test of conductivity performance demonstrated that the percolation threshold of carbon black (CB)/UHMWPE and multiwalled carbon nanotubes (MWCNTs)-CB/UHMWPE nanocomposites with segregated structure were 0.42 and 0.18 vol %, which were lower than those of the nanocomposites with uniform structure (4.91 and 2.62%). The electrical conductivity of MWCNTs-CB/UHMWPE nanocomposites with segregated structure reached to 3.0 × 10⁻² S m⁻¹ with the filler content of 1.5 vol %. In addition, the results of differential scanning calorimetry indicated that the crystallinity of UHMWPE decreased slightly with the addition of mixed filler. All of the study showed that the conductivity of MWCNTs-CB/UHMWPE nanocomposites with segregated structure has better electrical conductivity than the uniform. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47317.     

聚合物原位复合纳米碳酸钙增韧PP研究

通过有机单体原位聚合包覆的CaCO3与PP熔融混合制备了PP／CaCO3纳米复合材料，经过正交实验研究了填料饱覆聚合物比、接枝聚丙烯以及复合填料含量对PP缺口冲击强度的影响，结果表明：复合纳米CaCO3只需填加5％就可以将缺口冲击强度提高为原树脂的2倍左右。     

Electrical conductivity and electromagnetic interference shielding effectiveness of carbon black/sisal fiber/polyamide/polypropylene composites

The effects of hybrid fillers on the electrical conductivity and electromagnetic interference (EMI) shielding effectiveness (SE) of polyamide 6 (PA6)/polypropylene (PP) immiscible polymer blends were investigated. Carbon black (CB) and steam exploded sisal fiber (SF) were used as fillers. CB was coated on the surface of SF, and this was exploded by water steam to form carbon black modified sisal fiber (CBMSF). CB/SF/PA6/PP composites were prepared by melt compounding, and its electromagnetic SE was tested in low‐frequency and high‐frequency ranges. We observed that SF greatly contributed to the effective decrease in the percolation threshold of CB in the PA6/PP matrix and adsorbed carbon particles to form a conductive network. Furthermore, an appropriate CB/SF ratio was important for achieving the best shielding performance. The results indicate that CBMSF was suitable for use as electronic conductive fillers and the CB/SF/PA6/PP composites could be used for the purpose of EMI shielding. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42801.     

Electrical conductivity modeling of carbon black/polycarbonate,carbon nanotube/polycarbonate,and exfoliated graphite nanoplatelet/polycarbonate composites

Adding conductive carbon fillers to electrically insulating thermoplastic polymers increases the resulting composite's electrical conductivity, which would enable them to be used in electrostatic dissipative and semiconductive applications. In this study, varying amounts of carbon black (CB: 2 to 10 wt %), multiwalled carbon nanotubes (CNT: 0.5 to 8 wt %), or exfoliated graphite nanoplatelets (GNP: 2 to 15 wt %) were added to polycarbonate (PC) and the resulting composites were tested for electrical conductivity (EC = 1/electrical resistivity). The percolation threshold was ～ 1.2 vol % CNT, ～ 2.4 vol % CB, and ～ 4.6 vol % GNP. In addition, three EC models (Mamunya, additive, and general effective media) were developed for the CB/PC, CNT/PC, and GNP/PC composites. The general effective media (GEM) model showed the best agreement with the experimental results over the entire range of filler concentrations (above and below the percolation threshold) for all three composite systems. In addition, the GEM model can be easily adapted for composites containing combinations of different conductive fillers. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Melt spinning of β‐phase poly(vinylidene fluoride) yarns with and without a conductive core

When poly(vinylidene fluoride) (PVDF) is to be used as a piezoelectric material, the processing must include the formation of polar β‐phase crystallites, as well as the application of electrically conducting charge collectors, that is, electrodes. In this article, results from the melt spinning of PVDF yarns and a novel bicomponent PVDF‐yarn with a conductive carbon black/polypropylene (CB/PP) core are presented. Melt spinning has been done under conditions typical for industrial large‐scale fiber production. The effects on the resulting crystalline structure of varying the spinning velocity, draw rate, and draw temperature are discussed. The results show that, for maximum α‐to‐β phase transformation, cold drawing should take place at a temperature between 70 and 90°C, and both the draw ratio and the draw rate should be as high as possible. It was observed that the cold drawing necessary to form β‐phase crystallinity simultaneously leads to a decrease in the core conductivity of the bicomponent yarns. In this work, the melt spinning of bicomponent fibers with high‐β‐phase PVDF in the sheath and a CB/PP core was successfully accomplished. The core material remained electrically conductive, paving the way for the use of a CB‐polymer compound as inner electrode in the melt spinning of piezoelectric bicomponent fibers. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of carbon nanoparticle type,content, and stress on piezoresistive polyethylene nanocomposites

This study examines the piezoresistive behavior of polyethylene (PE) composites containing different types of carbon nanoparticle fillers. The fillers investigated are single‐wall carbon nanotube (SWCNT), multi‐wall carbon nanotube (MWCNT), and graphene nanoplatelets (GNP), which were dispersed in PE through melt blending in concentrations ranging between 0.5 and 10 wt%. The dispersion and nanocomposite morphology were investigated using scanning electron microscopy and X‐ray diffraction with strong evidence found for shear‐induced orientation of GNP nanoparticles during the compression molding process. The conductivity and permittivity of the composite materials was investigated using impedance spectroscopy and the lowest percolation threshold and highest electrical conductivity was observed for SWCNT composites, followed by MWCNT and GNP. The compressive piezoresistance of the nanocomposites was measured and the initial, elastic, and plastic deformation regions were all identifiable by the resistance measurements. The main finding of this study is that the piezoresistance of MWCNT nanocomposites is more sensitive to the effects of varying stress and composition than SWCNT nanocomposites. This indicates an evolving filler network in the case for MWCNT, while a static network for SWCNT, which is explained by the higher aspect ratio and surface area of the latter. POLYM. ENG. SCI., 55:1643–1651, 2015. © 2014 Society of Plastics Engineers     

Melt spinning of conducting polymeric composites containing carbonaceous fillers

Fibers produced by melt spinning of conductive polymer composites are attractive for several applications; the main drawback is however reduced processability at high filler concentrations. Carbon nanotubes (CNTs) are considered suitable fillers for conductive polymer composites, replacing conductive grades of carbon black (CB). In this study, the fiber‐forming properties of conductive polymer composites based on a conductive grade of CB and two masterbatches with CNT in a polyethylene matrix were investigated. The CB was also used in a polypropylene matrix for comparison. The rheological properties of the filler‐containing melts in shear and their extensional behavior were evaluated. A piston‐driven device was used to extrude the molten materials through a capillary; different capillary geometries were tested. Fibers were produced at various draw ratios, and their conductivity was determined. To assess the ultimate extensibility, a modified Rheotens method was used. The results showed that a conductive CB grade can have a lower percolation threshold and higher conductivity than a material with CNT. Conductivity decreased with increasing melt draw ratio for both types of fillers. The spinnability of the materials decreased with increasing concentration of filler material and correlations were found between spinnability and melt elasticity. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011