Conductive polymer tape containing highly oriented carbon nanofillers

The effect of the orientation of carbon fillers with different aspect ratios on the resistivity and morphology of conductive polymer composites (CPCs) based on polypropylene was investigated in this study. Multiwall carbon nanotubes (MWNTs) and carbon black (CB) were used as conductive fillers. The CPCs were made by melt compounding, hot pressing, and solid‐state drawing. The alignment of the filler was observed after solid‐state drawing. The resistivity of the composites increased with the draw ratio at relatively low carbon filler loadings (<20 wt %), whereas it remained unchanged at a high filler loading (20 wt % CB). Orientation‐promoted anisotropy of the conductive network was observed in both the morphology and resistivity. MWNTs were found to be better at maintaining a percolating network under large deformations than CB because of their larger aspect ratio and their entangled network structure. The experimentally obtained resistivity was analyzed with percolation theory, and this indicated that the initial three‐dimensional conductive network was deformed into a two‐dimensional network after solid‐state drawing for the composites containing CB. The three‐dimensional network was found in isotropic CPCs containing MWNTs with the same analysis. Theoretical analysis using excluded volume theory was in good agreement with results obtained experimentally. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Pyroresistivity in conductive polymer composites: a perspective on recent advances and new applications

Conductive polymer composites (CPCs) with pyroresistive behaviour are of interest for a wide variety of applications such as safe batteries, resettable fuses, temperature sensors and self‐regulating heating devices. Due to their ease of processing, low density, tunable electrical properties, good oxidation resistance, and good flexibility and toughness, CPCs have become the preferred choice of pyroresistive materials in a number of applications. The pyroresistive behaviour of CPCs can be tuned to satisfy the specific requirements of different applications. In this perspective paper, recent progress in the use of pyroresistive CPCs is reviewed. In particular, various factors influencing their performance are discussed and compared, in connection with the associated application, with a special focus on reproducibility and positive temperature coefficient intensity levels. Some of the remaining challenges are identified, together with future prospects in this evolving field. © 2018 Society of Chemical Industry     

Dopamine modification of multiwalled carbon nanotubes and its influences on the thermal,mechanical, and tribological properties of epoxy resin composites

A functionalization process with dopamine on multiwalled carbon nanotubes (MWNTs) has been carried out in order to enhance the tribological properties of MWNTs/epoxy resin (EP) composites. Dopamine modification is of signality for the performance of MWNTs/EP composites. The hardness and flexural strength of the composites were significantly improved with the incorporation of dopamine modified MWNTs, owning to the enhanced interfacial bonding between MWNTs and EP. Meanwhile, the thermal characterizations indicated that dopamine played an important role in improving the thermal stability of MWNTs/EP composites. More importantly, the friction and wear properties of dopamine modified MWNTs/EP composites were enhanced considerably and its wear rate was 85.8% lower than that of pure EP. Dopamine modified MWNTs were linked with the matrix by strong covalent bond to form a great network structure and impeded the movement of polymer molecule chains in the composites. Then the friction load transmitted efficiently through the network structure and the plastic deformation was restrained as well as the initiation and growth of cracks on the worn surfaces. POLYM. COMPOS., 38:116–125, 2017. © 2015 Society of Plastics Engineers     

Sensing behaviors of polymer/carbon nanotubes composites prepared in reversed microemulsion polymerization

Polystyrene/carbon nanotubes composites were readily prepared by reversed microemulsion polymerization. Compared with the composites prepared by solution mixing, the uniform dispersion of carbon nanotubes in polymer matrix could be obtained more easily and the thermal and electrical properties of the as‐prepared composites were also enhanced. The as‐prepared composites were deposited onto a microelectrode array to fabricate a vapor sensor. The response for different organic vapors was evaluated by monitoring the change in the resistance of the composites upon exposure to various gases. The change in resistance was of the order of about 10³ for the composites prepared by reversed microemulsion polymerization. The chemical sensors based on the composites prepared by reversed microemulsion polymerization presented excellent reproducibility and reversibility in response. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

A convenient route to modified multiwall carbon nanotubes with liquid crystal molecules via covalent functionalization

A novel nanocomposite of the rod‐like liquid crystal (LC) molecules' waist positions anchored on the surface (sidewalls and ends) of multiwall carbon nanotubes (MWNTs) was prepared by using a dissolving metal reduction method for the first time. The MWNTs carbanion complexes of lithium were first synthesized in tetrahydrofuran with an electron transfer from lithium naphthalene radical anion on the surface of MWNTs. Then the novel material (LC‐MWNTs) was obtained by treating the carbanion complexes with bromic liquid crystalline aromatic amide compound. The formation of the LC‐MWNTs was confirmed by both Raman and FTIR spectroscopies. HRTEM demonstrates that the rod‐like LC molecules are anchored on the surface of MWNTs via covalent attachment, with a wrapped thickness approximately 3‐4 nm. The loss‐weight fraction of the LC layers for the LC‐MWNTs can be roughly estimated as 23% by TGA. The experiments of solubility exhibit that the LC‐MWNTs forms a stable suspension solution in polar solvents such as dimethylformamide. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

The morphology and thermal properties of multi‐walled carbon nanotube and poly(hydroxybutyrate‐co‐hydroxyvalerate) composite

Nanocomposites based on poly(hydroxybutyrate‐co‐hydroxyvalerate) (PHBV) and multi‐walled carbon nanotubes (MWNTs) were prepared by solution processing. Ultrasonic energy was used to uniformly disperse MWNTs in solutions and to incorporate them into composites. Microscopic observation reveals that polymer‐coated MWNTs dispersed homogenously in the PHBV matrix. The thermal properties and the crystallization behavior of the composites were characterized by thermogravimetric analysis, differential scanning calorimetry and wide‐angle X‐ray diffraction, the nucleant effect of MWNTs on the crystallization of PHBV was confirmed, and carbon nanotubes were found to enhanced the thermal stability of PHBV in nitrogen. Copyright © 2004 Society of Chemical Industry     

Excellent tensile ductility in highly oriented injection-molded bars of polypropylene/carbon nanotubes composites

Multi-wall carbon nanotubes (MWNTs) grafted with alkyl chain were used for reinforcement of polypropylene (PP). For achieving excellent tensile properties, the as-prepared PP/MWNTs composites were subjected to a unique injection molding, as so-called dynamic packing injection molding, to induce a highly oriented structure with both PP chains and MWNTs aligned along the shear flow direction. Not only Young's modulus and tensile strength were enhanced, as expected for oriented materials, but also more importantly composites containing only 0.1-0.3 wt% MWNTs were much ductile compared with the polymer matrix. The addition of PP-g-MMA made a drop in the elongation at break to only 15%; however, it could be improved to 80-100% after incorporation of small amount of MWNTs. This improvement in ductility could be ascribed to: (1) the increased mobility of both the PP chains and MWNTs, as they are oriented along tensile deformation direction and (2) the bridging effect of the oriented MWNTs on the crack development during tensile failure.     

Freestanding chemiresistive polymer composite ribbons as high-flux sensors

Chemiresistive polymer composite ribbons that function as chemical detectors were produced from solution-cast films of polymers and carbon composites. An array with multiple polymer sensor threads was exposed to dimethyl methyl phosphonate, a nerve agent simulant, and different interferents in the vapor phase. Principal component analysis was used to differentiate between the analytes. The response of the ribbon sensors as a function of the carbon composite and the host polymer source was investigated. The freestanding threads/sensors were mounted into a cell perpendicular to the gas flow to provide little pressure drop and were imbedded into fabrics to provide an example of a small, low-cost, wearable chemical sensor. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Gas sensitivity of carbon black/waterborne polyurethane composites

The synthesis of conductive composites consisting of waterborne polyurethane (WPU) and carbon black (CB) is reported. Besides the low percolation threshold (0.7-0.95 wt%), the composites are quite sensitive to organic solvent vapors regardless of their polarities as characterized by the drastic changes in conductivity. In the case of polar solvents, negative and positive vapor coefficient phenomena of the composites were successively observed with a rise in CB content. It was found that different mechanisms are responsible for the broad applicability of the composites as candidates for gas sensing materials owing to the different interactions among the matrix polymer, the filler particles and the solvent molecules.     

Blending ultrahigh‐molecular‐weight polyethylene and poly(ethylene/10‐undecen‐1‐ol) in one nascent particle

Ultrahigh‐molecular‐weight polyethylene (UHMWPE)/polar polyethylene (PE) composites were blended in one nascent particle by in situ polymerization with a hybrid catalyst. Polystyrene‐coated SiO₂ particles were used to support the hybrid catalyst. Fe(acac)₃/2,6‐bis[1‐(2‐isopropylanilinoethyl)] was supported on SiO₂ for the synthesis of UHMWPE, whereas [PhN?C(CH₃)CH?C(Ph)O]VCl₂ was immobilized on a polystyrene layer to prepare a copolymer of ethylene and 10‐undecen‐1‐ol (polar PE). Importantly, the core part of the supports (the polystyrene layer) exhibited pronounced transfer resistance to 10‐undecen‐1‐ol; this provided an opportunity to keep the inside iron active sites away from the poisoning of 10‐undecen‐1‐ol. Therefore, UHMWPE was simultaneously synthesized with polar PE by in situ polymerization. Interestingly, the morphological results show that UHMWPE and the polar PE were successfully blended in one nascent polymer. This improved the miscibility of the composites, where most of the chains were difficult to crystallize because of the strong interactions between the PE chains and polar chains. The blends showed an extremely low crystallinity, that is, 9.9%. Finally, the hydrophilic properties of the polymer composites were examined. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46652.     

High thermal conductive m‐xylylenediamine functionalized multiwall carbon nanotubes/epoxy resin composites

In this study, multiwall carbon nanotubes (MWNTs) functionalized by m‐xylylenediamine is used as thermal conductive fillers to improve their dispersibility in epoxy resin and the thermal conductivity of the MWNTs/bisphenol‐A glycidol ether epoxy resin composites. Functionalization with amine groups of MWNTs is achieved after such steps as carboxylation, acylation and amidation. The thermal conductivity, impact strength, flexural strength, and fracture surfaces of MWNTs/epoxy composites are investigated with different MWNTs. The results show that m‐xylylenediamine is successfully grafted onto the surface of the MWNTs and the mass fraction of the organic molecules grafted onto MWNTs is about 20 wt %. The thermal conductivity of MWNTs/epoxy composites is further enhanced to 1.236 W/mK with 2 wt % m‐MWNTs. When the content of m‐MWNTs is 1.5 wt %, the impact strength and flexural strength of the composites are 25.85 KJ/m², 128.1 MPa, respectively. Scanning electron microscope (SEM) results show that the fracture pattern of composites is changed from brittle fracture to ductile fracture. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41255.     

A new approach to functionalize multi-walled carbon nanotubes by the use of functional polymers

A new method to graft a large number of long polymer chains or small functional molecules onto multi-walled carbon nanotubes (MWNTs) indirectly is reported. First, MWNTs were slightly functionalized by reversible addition-fragmentation chain transfer (RAFT) copolymerization of styrene and maleic anhydride using the dithioester groups attached to MWNTs as RAFT agents. The highly reactive maleic anhydride groups could further react with a large number of long polymer chains or small functional molecules with hydroxyl or amino group easily. The resulted MWNTs have good solubility in organic solvents and water; the perfect structure of MWNTs is altered very little from the information of Raman spectra.     

Progress on the morphological control of conductive network in conductive polymer composites and the use as electroactive multifunctional materials

Since the emergence of large aspect ratio and multifunctional conductive fillers, such as carbon nanotubes, graphene nanoplates, etc., conductive polymer composites (CPCs) have attracted increasing attention. Although the morphological control of conductive networks in CPCs has been extensively investigated as an important issue for the preparation of high performance CPCs, recent extensive progress has not been systematically addressed in any review. It has been observed that the morphological control of conductive networks during the preparation of CPCs has crucial influence on the electrical properties of these composites. Several methods have been shown to be able to control the network structure, and thus, tune the electrical properties of CPCs, including the use of shear, polymer blends, thermal annealing, mixed filler, latex particle etc. Moreover, many novel and exciting applications have been extensively investigated for CPCs, such as stretchable conductor, electroactive sensors, shape memory materials and thermoelectric materials, etc. Therefore, the morphological control of conductive network in CPCs is reviewed here. Issues regarding morphology characterization methods, morphological control methods, resulted network morphology and electrical properties are discussed. Furthermore, the use of CPCs as electroactive multifunctional materials is also reviewed.     

Functionalization of multiwalled carbon nanotubes with amphiphilic poly(aspartic acid)

A new method to functionalize multiwalled carbon nanotubes (MWNTs) with amphiphilic poly(aspartic acid) was investigated. The amphiphilic polymer (PASP‐C16) was synthesized by thermal condensation and aminolysis by hexadecylamine, followed by hydrolysis of the remaining succinimide units in the polymer backbone. The functionalization of MWNTs was achieved by physical adsorption of the biopolymer onto the surfaces of MWNTs. Ultraviolet‐visible ( UV‐vis) spectra showed that the functionalized MWNTs had a good aqueous dispersity and solubility. The interaction of PASP‐C16 with MWNTs was investigated by analyzing X‐ray diffraction (XRD) patterns, circular dichroism (CD), spectra and high‐resolution transmission electron microscopy ( HRTEM ). From the XRD patterns, it can be known that the aggregate of PASP‐C16 due to intermolecular interaction between hexadecyl chains has been reduced when the polymer interacting with MWNTs. CD spectra indicated that the interaction of hexadecyl chains of PASP‐C16 with the wall of MWNTs is the major interaction between PASP‐C16 and MWNTs, and MWNTs were covered by the poly(aspatic acid) backbone. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

复合型导电高分子材料的液体敏感行为研究进展

综述了复合型导电高分子材料(CPCs)在有机溶剂中的液体敏感响应行为特性和CPCs液体敏感行为的影响因素。基于上述响应特性和影响因素,概括了CPCs液体敏感响应行为的发生机制。对CPCs液体敏感器件在化工、炼油、食品、船舶、环境等领域的应用进行了总结和展望。     

Miscibility of styrene/unsaturated polyester quasibinary systems: Unsaturated polyester chemical composition and molecular weight influence

Unsaturated polyester prepolymers were synthesized with different chemical compositions and molecular weights. Cloud‐point curves (CPC) were measured in St‐UP quasibinary solutions, showing UCST behavior in all cases. The miscibility of the first UP samples series in St comonomer was enhanced when AA chemical comonomer concentration in UP prepolymer increased. In the second series, UP prepolymer miscibility increased with the molecular weight up to a maximum and, after that, the miscibility decreased. A thermodynamic analysis of experimental CPCs was performed using the Flory‐Huggins (F‐H) theory for polydisperse polymer solutions. A simple relationship between the interaction parameter and the temperature inverse could fit the measured CPCs in wide concentrations and molecular weight ranges. In the temperature interval where this fit took place, the positive enthalpic contribution to the interaction parameters determined the miscibility dependence with temperature in both UP sample series. The St‐UP miscibility behavior was also correlated with UPs structural chemical parameters as: (a) the final HO? and HOOC? high polar groups concentration, (b) the chain backbone polar adipate and phthalate groups concentration, and (c) the UP size dependent mixing entropy. All these parameters are molecular weight dependent. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 6064–6073, 2006     

石墨烯/聚合物泡沫压阻式应变传感器研究进展

基于石墨烯和聚合物的三维多孔结构的导电聚合物基复合材料（CPCs）具有轻量化、高灵敏度、宽应变检测范围、低成本和可扩展性等优点，已成为可穿戴柔性应变传感器的理想选择。首先，总结了柔性压阻式泡沫应变传感器的裂纹扩展机制、重叠-断开机制和隧穿效应机制；其次，介绍了3种具有多孔结构的石墨烯/聚合物柔性应变传感器的构筑工艺，包括基于聚合物泡沫、基于石墨烯/聚合物混合分散液、基于石墨烯泡沫的方法；然后，综述了通过上述3种工艺制备的柔性多孔应变传感器的传感性能，并列举了其在人体运动监测领域中的应用实例；最后，对基于石墨烯和聚合物的柔性多孔应变传感器面临的挑战和发展前景进行了展望。     

Partially miscible poly(lactic acid)‐ blend‐poly(propylene carbonate) filled with carbon black as conductive polymer composite

BACKGROUND: Conductive polymer composites (CPCs) can be obtained by filling polymer matrices with electrically conductive particles, and have a wide variety of potential applications. In the work reported, the biodegradable polymer poly(lactic acid) (PLA) as a partially miscible blend with poly(propylene carbonate) (PPC) was used as a polymer matrix. Carbon black (CB) was used as the conducting filler. RESULTS: Fourier transform infrared spectroscopy revealed interactions between matrix and CB filler; this interaction was stronger in PPC‐blend‐CB than in PLA‐blend‐CB composites. A rheology study showed that low‐viscosity PPC could improve the fluidity of the CPCs, but decrease that of CB. With increasing CB content, the enforcement effect, storage modulus and glass transition temperature increased, but the elongation at break decreased. CPCs exhibited the lowest electrical percolation thresholds of 1.39 vol.% CB when the content of PPC in PLA‐blend‐PPC was 40 wt%. The conductivity of CPCs containing 5.33 vol.% CB and 40 wt% PPC reached 1.57 S cm^?1. Scanning electron microscopy revealed that CB exhibits a preference for dispersion in the low‐viscosity phase (PPC) of the multiphase matrix. CONCLUSION: In the presence of CB, partially miscible PLA‐blend‐PPC could form multi‐percolation CPCs. Moreover, the combination of PLA and PPC with CB broadens novel application of both renewable polymers and CPCs. Copyright © 2008 Society of Chemical Industry     

以聚乳酸为基体的导电高分子复合材料研究进展

概括了导电填料种类、结构及成型方法、工艺条件等因素对单相聚乳酸(PLA)基导电高分子复合材料(CPCs)电学性能的影响,介绍了PLA基多相CPCs中导电填料选择性分布机制和较低逾渗值的机理,总结了PLA基CPCs在有机溶剂中的响应行为,并对材料的应用前景进行了展望。     

Incorporation of 4‐aminobenzene functionalized multi‐walled carbon nanotubes in polyaniline for application in formic acid electrooxidation

Incorporation of carbon nanotubes (CNTs) in conducting polymer can lead to new composites with enhanced electrical and mechanical properties. However, the development of such composites has been hampered by the inability to disperse CNTs in polymer matrix due to the lack of chemical compatibility between polymers and CNTs. Covalent sidewall functionalization of carbon nanotube provides a feasible route to incorporate carbon nanotube in polymer. In this work, 4‐aminobenzene groups were grafted onto the surface of multi‐walled carbon nanotube (MWNT) via C? C covalent bond. Polyaniline (PANI)/MWNT composites were fabricated by electrochemical polymerization of aniline containing well‐dissolved functionalized MWNTs. The obtained composites can be used as catalyst supports for electrooxidation of formic acid. Cyclic voltammogram results show that platinum particles deposited in PANI/MWNT composite films exhibit higher electrocatalytic activity and better long‐term stability towards formic acid oxidation than that deposited in pure PANI films. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010