Nonlinear conduction in nylon-6/foliated graphite nanocomposites above the percolation threshold

The nonlinear conduction behavior of composite materials of foliated graphite nanosheets and nylon-6 subjected to a variable direct-current electric field has been studied. Corresponding to the onset of the nonlinearity, there is a crossover current density/electric field (or current–voltage) couple. The current density or current decreases as the foliated graphite concentration decreases. Through discussions of the nonlinearities within the frameworks of the two theoretical models, the nonlinear random resistor network and the dynamic random resistor network, it is shown that neither of these models can explain fully the results obtained for this system. On the basis of the microscopic structures and conduction processes of the nanocomposites, it is found that a combination of the models can generally account for the nonlinear characteristics. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 155–167, 2004     

Reversible nonlinear conduction behavior for high‐density polyethylene/graphite powder composites near the percolation threshold

The reversible nonlinear conduction (RNC) behavior of high‐density polyethylene/graphite powder composites with various graphite powder volume concentrations slightly above the threshold has been studied. The relationships between the current density (J) and electric field (E) of the composites, as shown in J(E) curves, can be well described by the scaling functions of J/J_c ～ (E/E_c) when E < E_c and J/J_c ～ (E/E_c) when E > E_c, where J_c is the crossover current density and E_c is the crossover electric field. The results indicate that J_c scales with the linear conductivity σ₀ as J_c ～ σ. It is believed that the macroscopic RNC is a combined result of the microscopic conduction processes, involving electronic transporting along carbon chains and tunneling or hopping across thin polymer bridges. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2833–2842, 2001     

A new process of fabricating electrically conducting nylon 6/graphite nanocomposites via intercalation polymerization

A new process was developed to fabricate electrically conducting nylon 6/graphite nanocomposites via intercalation polymerization of ϵ‐caprolactam in the presence of expanded graphite. The transition from an electrical insulator to an electrical semiconductor for nylon 6 occurred when the graphite volume content was 0.75, which was much lower than that of conventional conducting polymer composites. The electrical conductivity reached 10⁻⁴ S/cm when the graphite content was 2.0 vol %. The TEM microphotographs suggested that the low percolation threshold and the great improvement of electrical conductivity could be attributed to the high aspect ratio (width‐to‐thickness), the high expansion ratio in c axis of the graphite sheets and the homogeneous dispersion of the nanoscale graphite particles in the nylon 6 matrix. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1626–1633, 2000     

Fabrication and characterization of nylon 6/foliated graphite electrically conducting nanocomposite

In this study, the nylon 6/foliated graphite (FG) electrically conducting nanocomposites with a low percolation threshold of less than 0.75 vol % have been prepared via an in situ polymerization approach in the presence of FG nanosheet filler. Based on laser counting, scanning electron microscopy, transmission electron microscopy, and X‐ray diffraction characterization techniques, the structures and morphologies of the nanoscale filling particles and the resulting nanocomposites were examined. Using percolation theory, the conductivity behavior of the nanocomposite samples were modeled and analyzed. Through the use of mean‐field and excluded volume approaches, it was demonstrated that the experimentally observed percolation threshold values could be approximately estimated, and a correlation between the percolation threshold and the aspect ratio of FG particles could be quasi‐quantitatively established. Also, preliminary studies on the effects of FG nanosheets on the thermal properties of the host nylon 6 were performed. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2844–2856, 2004     

Preparation and characterization of PVC/PANI conductive composite with extremely low percolation threshold

Aniline was polymerized in the presence of poly(vinyl chloride) (PVC) powders in hydrochloric acid to in situ prepare poly(vinyl chloride)/polyaniline (PVC/PANI) composite particles. UV‐vis spectra and FT‐IR spectra indicate PANI in PVC/PANI composite particles possessed a higher oxidation state with decreased aniline content in reactants. Both conductivity and impact strength of the dodecylbenzenesulfonic acid (DBSA) doped PANI composites (PVC/PANI‐DBSA), which were compression molded from the in situ prepared PVC/PANI particles, increase with the pressing temperature and decrease with the increase of DBSA doped PANI (PANI‐DBSA) loading. An excellent electric conductivity of 5.06 × 10^?2 S/cm and impact strength of 0.518 KJ/m² could be achieved for the in situ synthesized and subsequently compression molded composite. Copyright © 2004 John Wiley & Sons, Ltd.     

Cationic polymerization of styrene on the surface of graphite expanded

Cationic polymerization of styrene initiated by the CO⁺ClO group on the surface of expanded graphite (EG) was carried out for modifying the surface properties of graphite. The initiating sites were achieved by the reaction of EG with SOCl₂ and followed by AgClO₄. Subsequently, the cationic polymerization of styrene was conducted to afford polystyrene brush on EG. The influence factors, such as polymerization time and temperature, on the polymerization including the grafting ratio and efficiency were investigated. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2715–2721, 2003     

Thermal conductive PS/graphite composites

Polystyrene (PS) was compounded with graphite that possesses high thermal conductivity and layer structures, and the PS/graphite thermal conductive nano‐composites were prepared. Thermal conductivity of PS improved remarkably in the presence of the graphite, and a much higher thermal conductivity of 1.95 W/m K can be achieved for the composite with 34 vol% of colloidal graphite. The Maxwell‐Eucken model and the Agari model were used to evaluate the thermal conductivity of the composites. For the purpose of improving the interfacial compatibility of PS/graphite, realizing the exfoliation and nano‐dispersion of graphite in the PS matrix, three intercalation methods, including rolling intercalation, solvent intercalation, and pan milling intercalation, were applied to prepare the composites, and the morphologies, thermal conductivities, and mechanical properties of the composites were investigated. It should be noted that the one prepared by pan milling intercalation not only had excellent thermal conductivity but also much higher mechanical properties, resulting from a high degree of layer exfoliation of the graphite, the formation of the chain structure agglomerates of the graphite, and the creation of more conductive paths under the strong shear stress of pan milling. Copyright © 2008 John Wiley & Sons, Ltd.     

Nonuniversal transport behavior in heterogeneous high‐density polyethylene/graphite nanosheet composites

The direct‐current resistivity of high‐density polyethylene/graphite nanosheet composites above the percolation threshold has been measured and fitted to a power law, which gives a conductivity critical exponent (0.10 ± 0.01) and a percolation threshold (2.97 ± 0.03). These fitted parameters are in disagreement with universal theoretical predictions, and plausible explanations of the observed discrepancies are given. The sample‐to‐sample fluctuations in the relative resistivity seem to obey a power law. This fluctuation behavior, if interpreted in terms of correlation‐length fluctuations, yields a correlation‐length critical exponent, 0.52 ± 0.06, that is consistent with the mean‐field value of 1/2. Interpretations of these experimental results imply that nonuniversal transport behavior in disordered composites is caused by composites being in a nonuniversal scaling regime. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1846–1852, 2006     

Influence of polymer particle size on the percolation threshold of electrically conductive latex‐based composites

Monodispersed copolymer emulsions, each with a different polymer particle size, were used to investigate the effect of particle size on the electrical and thermomechanical properties of carbon black (CB)‐filled segregated network composites. These emulsions were synthesized with equal moles of methyl methacrylate and butyl acrylate, with latex particle size ranging from 83 to 771 nm. The electrical percolation threshold was found to decrease from 2.7 to 1.1 vol % CB as the latex particle size was increased. Microstructural images reveal diminished latex coalescence, and improved CB segregation, with increasing latex particle size. In general, coalescence is shown to increase for all systems with increasing CB concentration. Furthermore, all systems exhibited a similar maximum electrical conductivity plateau of 0.7 S cm^?1, albeit at lower concentration for larger latex particle size. This ability to tailor percolation threshold with latex particle size provides an important tool for manipulating electrical and mechanical properties of polymer nanocomposites. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 49: 1547–1554, 2011     

Phase‐separated,conducting composites from polyaniline and benzobisthiazole rigid‐rod polymer

As an alternative method for processing polyaniline (PANI) from its conducting (protonated) state, vacuum casting of PANI from a methanesulfonic acid (MSA) solution provided films with electrical conductivity values of about 130–150 S/cm. In addition, we similarly prepared blended films of PANI · MSA and poly(p‐phenylene benzobisthiazole) (PBZT). This process eliminated the need for a subsequent protonation step and had the additional advantage that the conjugated PBZT may provide alternative conducting pathways. Conductivity values of the composite films ranged from 100 pS/cm to 124 S/cm, and the films displayed critical concentration behavior with a PANI threshold concentration of 2.75% and a critical exponent of 4. Transmission electron micrographs displayed phase‐separated regions with PANI forming a continuous network at high concentrations. Thermogravimetric analysis results demonstrated the thermal and thermooxidative stability advantage of the blends due to the PBZT component. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2539–2548, 2001     

The role of interfacial compatibilization upon the microstructure and electrical conductivity threshold in polypropylene/expanded graphite nanocomposites

Attempts have been made to evaluate the effect of interface and degree of interfacial interaction upon electrical conductivity threshold in polypropylene/expanded graphite (PP/EG) nanocomposites, and dispersion state of graphite nanosheets. For this purpose, maleic anhydride grafted polypropylene (PPgMA) and maleic anhydride grafted EPDM (EPDMgMA) were used as compatibilizer. Nanocomposite samples containing 1–5 vol% of EG were prepared by melt mixing method using laboratory scale internal mixer. Characterization was carried out by using X‐ray diffraction (XRD), differential scanning calorimeter (DSC), thermo‐gravimetric analysis (TGA), scanning electron microscope (SEM), transmission electron microscope (TEM), and rheo‐mechanical spectroscopy (RMS). The conductivity measurements were carried out by using four point probe method according to ASTM D991. Results showed that the conductivity threshold is controlled by the extent of interfacial interaction between PP and EG. So, better conductivity was obtained using PPgMA as compatibilizer which causes higher level of interaction between PP and EG, and therefore better dispersion of the EG nanolayers in the polymer matrix. On the other hand, high levels of compatibilizers, especially EPDMgMA, caused formation of separated aggregates of EG shelled with the compatibilizer, which results in the reduction of conductivity of the nanocomposites. This finding has been verified by SEM, RMS, and conductivity measurements. Effects of EG nanolayers on crystalline structure and thermal decomposition temperature of the nanocomposites have also been investigated by DSC and TGA, respectively. Copyright © 2009 John Wiley & Sons, Ltd.     

Synthesis and characterization of polyaniline/graphite conducting nanocomposites

A new method for the synthesis of exfoliated graphite and polyaniline (PANI)/graphite nanocomposites was developed. Exfoliated graphite nanosheets were prepared through the microwave irradiation and sonication of synthesized expandable graphite. The nanocomposites were fabricated via the in situ polymerization of the monomer at the presence of graphite nanosheets. The as-synthesized graphite nanosheets and PANI/graphite nanocomposite materials were characterized with Fourier transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, and thermogravimetric analysis (TGA). The conductivity of the PANI/graphite nanocomposites was dramatically increased over that of pure PANI. TGA indicated that the incorporation of graphite greatly improved the thermal stability of PANI. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1972–1978, 2004     

Fabrication of highly ordered polymer/graphite flake composite with eminent anisotropic electrical property

Highly ordered polyester/graphite flake composite has been fabricated via orienting the graphite flakes within a polymer matrix. The randomly dispersed graphite flakes in a polyester prepolymer were induced twice along the electric field direction, followed by the cross‐linking of the prepolymer. Scanning electron microscopy (SEM), X‐ray diffraction (XRD) analysis showed that the graphite flakes in the resulting composites were aligned parallel to each other. This structure anisotropy of the composite appeared to be a significant electrical anisotropic property with five to six orders of magnitude. Analysis showed that field‐induced torque caused by the polarization of graphite flakes undergone at electric field was a main force inducing the orientation of the graphite flakes. Copyright © 2008 John Wiley & Sons, Ltd.     

溶液共混法制备聚苯乙烯/多壁碳纳米管复合导电材料

碳纳米管(CNTs)自从1991年被发现以来,以其特有的力学、电学和化学性能以及独特的准一维管状分子结构和在未来高科技领域中所具有的许多潜在应用价值,迅速成为化学、物理及材料科学领域的研究热点[1]。碳纳米管的C-C共价键链段结构与高分子链段结构相似,能通过配位键作用与高分     

Electrical conductivity of carbon fibres/polyester resin composites in the percolation threshold region

The electrical conductivity of composites of a polyester resin filled with short carbon fibres has been investigated with a special attention to the properties in the percolation threshold region. A very low percolation threshold (0.7-0.8 vol% of the filler) was confirmed. In contrast to S-shaped curves calculated according to the percolation theory of composites of globular particles, the experimental conductivity vs. fibre content dependence, after a steep increase in the percolation region, increased almost linearly. This atypical behaviour was explained by a different mechanism of formation of fibrous and globular conducting structures above the percolation threshold. An increase in scatter of conductivity values observed at percolation threshold as a consequence of great fluctuation of fibre arrangement manifested itself also in the conductivity-temperature dependences.     

Charge transport properties in carbon black/polymer composites

The charge transport properties of polymer matrix–carbon black composites are investigated in this study. Direct current conductivity is examined with varying parameters: the temperature and the conductive filler content. Conductivity data are analyzed by means of percolation theory, and both percolation threshold and critical exponent are determined at each of the examined temperatures. The temperature dependence of conductivity and the agreement of experimental results with the variable range hopping model reveal hopping conduction as the predominant transport mechanism, below and in the vicinity of the critical concentration of carbon black particles. At higher concentrations, the contribution of hopping transport to the overall conductivity is reduced and a balance between hopping and conduction via geometrical contact occurs. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2535–2545, 2007     

New melt mixing polyethylene multiwalled carbon nanotube nanocomposites with very low electrical percolation threshold

The present work focuses on the study of the electrical properties of high‐density polyethylene (HDPE)/multiwalled carbon nanotube (MWCNT) nanocomposites. The samples were produced by melt mixing by diluting a masterbatch of HDPE/MWCNT using two types of mini‐extruders in order to see the influence of the shear processing on the electrical properties. The dielectric relaxation spectroscopy was used for the investigation of the electrical properties in the studied samples. The composites dc conductivity (σ_dc) follows the scaling low derivate from the percolation theory of the form σ_dc ~ (p ? p_c)^t. A low electrical percolation (p_c ≈ 0.3 ? 0.4 vol. %) was found in both cases. The critical exponent t had a value very close to the theoretical one for a percolation network in three dimensions (t ≈ 2). The analysis of the morphology of the nanocomposites showed a good and homogeneous dispersion of the fillers in the PE matrix. The effect of the incorporation of MWCNTs on the dynamic mechanical and thermal behaviors was also presented. The MWCNTs have improved the mechanical properties of the polyethylene matrix and increased the crystallization temperatures. Copyright © 2013 John Wiley & Sons, Ltd.     

Preparation and characterization of polyfuran/poly(2‐fluoroaniline) conducting composites

This article deals with the chemical synthesis and characterization of poly(2‐fluoroaniline) (P2FAn) and polyfuran (PFu) homopolymers and PFu/P2FAn and P2FAn/PFu composites. P2FAn and PFu homopolymers were synthesized using ammonium persulfate and antimony (III) chloride as catalyst, respectively. These homopolymers and composites were studied in the doped state using Fourier transform infrared spectroscopy and ultraviolet–visible absorption spectroscopy, thermogravimetric analysis, scanning electron microscopy, four‐probe conductivity technique, and Gouy Scale measurements. PFu/P2FAn and P2FAn/PFu composites were found to possess different thermal, conductivity, electronic, and morphological properties from each other when synthesis order of guest and host polymers was varied. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3359–3367, 2004     

基于纳米碳填料可拉伸导电聚合物复合材料的制备

碳系材料具有导电性强、稳定性好、价格低廉等优点,被广泛用于制备可拉伸导电复合材料,并且在可拉伸、可穿戴电子设备等领域有巨大的应用潜力,引起了研究者的密切关注。本文介绍了碳系材料的种类,主要有炭黑、碳纳米管和石墨烯等;总结了3种纳米复合材料的主要制备工艺:原位聚合法、熔融共混法和溶液混合法,并介绍了传统印刷技术和新型打印技术。分析了复合材料的导电机理,介绍了渗流阈值理论;并重点探讨了其在可拉伸传感器和可拉伸能量储存设备领域的应用。针对基于纳米碳填料制备的可拉伸导电聚合物复合材料指出目前研究的不足之处:导电填料分散性差、导电网络不稳定和无法大规模生产等,并提出了多种解决方案。对基于纳米碳填料制备的可拉伸导电聚合物复合材料在微型化、可拉伸、可穿戴电子设备领域的应用前景作出了展望。     

Thermal conductivity anisotropy of expanded graphite/ chlorate salt composites for thermal energy storage

ABSTRACT

Expanded graphite (EG)/LiCl-NaCl phase change composites are prepared by aqueous solution method with different EG amount and forming pressure to enhance heat conduction for high-temperature latent heat thermal energy storage application. Their microstructure and thermal conductivity are characterized. Results indicate that the composites are uniform and the LiCl-NaCl eutectic is well dispersed in the graphite flakes. Thermal conductivity of the LiCl-NaCl can increase to as much as 40.51 W/(m·K), which is 46 times higher than that of pure eutectic salt. With forming pressure, the thermal conductivities of the samples show anisotropy because of a flattened irregular honeycomb network of graphite. Within certain limits, the greater the forming pressure is, the more pronounced the anisotropy performs. In addition, the formulas to calculate the thermal conductivity in the axial direction and the radial direction are given based on the average rotation angle φ of EG basal plane, and experimental data show that the formula in the radial direction is especially useful for calculating the thermal conductivity.