Morphology and tensile properties of polypropylene‐multiwalled carbon nanotubes composite fibers

In this work, we analyzed tensile properties of polypropylene‐multiwalled carbon nonotubes composite fibers. The multiwalled carbon nanotubes (MWCNTS) were used in different contents of 0, 1, 2, 3, 4, and 5 wt %. Dispersing agents were used to disperse MWCNTs in polypropylene matrix. After the dispersing agent was removed, the mixture was melt mixed. The fibers were spun by a home‐made melt spinning equipment and stretching was done at a draw ratio of 7.5. By using 1–5 wt % of MWCNTs, the modulus of composite fibers increased by 69–84% and tensile strength increased about 39% when compared with the virgin polypropylene fibers. In addition, the MWCNTs dispersion in the matrix was monitored by scanning electron microscopy and transmission electron microscopy. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

碳纳米管填充导电橡胶的研究进展

介绍了碳纳米管(CNTs)的处理改性以及CNTs填充导电橡胶的制备方法,分析了CNTs填充导电橡胶的导电机理及导电逾渗行为,并综述了CNTs填充导电橡胶的力敏特性和驰豫现象.     

碳纤维增强酚醛树脂/石墨双极板复合材料性能及其界面结合

以碳纤维、酚醛树脂以及石墨为原料通过热模压成型得到一种质子交换膜燃料电池双极板材料。研究了碳纤维的处理方式、含量以及长度对复合材料导电性能与弯曲强度的影响,以及复合材料的界面结合。结果表明经过液相处理10 h的碳纤维能有效引进羟基等官能团,改善材料间的界面结合,增强效果较为明显;复合材料的性能随碳纤维含量的增加,出现先增大后减小的趋势;随着碳纤维长度的增大,复合材料性能出现最大值时的碳纤维含量有下降的趋势;利用经过液相处理10 h,含量为3%、长度为10~15 mm碳纤维对复合材料进行增强时,复合材料的弯曲强度与电导率最佳,其值分别为63.6 MPa1、75.4 S/cm。     

An electrical approach to monitor wire and cable thermal oxidation aging condition based on carbon black filled conductive polymer composite

Polymeric materials are widely used as insulation and jacketing materials in wire and cable. When such materials are used for long‐term applications, they undergo thermal oxidation aging in the environment. It is necessary to develop an in situ and nondestructive condition monitoring (CM) method to follow the aging of cable materials. The main objective of this work was to investigate low‐density polyethylene/carbon black (LDPE/CB) conductive polymer composites as potential sensor materials for this purpose. LDPE/CB composites with a carbon black loading below the percolation threshold underwent accelerated thermal oxidation aging experiments. The results indicated that the substantial resistivity decreases of the LDPE/CB composites could be directly related to the increases in volume fraction of the conductive carbon black, which was mainly caused by the mass loss of polymer matrix and sample shrinkage during the thermal oxidation aging process. Compared to existing CM method based on density change, the electrical resistivity is more explicit regarding its absolute changes throughout the thermal oxidation aging. The change in resistivity spanned over four orders of magnitude, whereas the composite density only increased 10%. The results offer strong evidence that resistivity measurements, which reflect property changes under thermal aging conditions, could represent a very useful and nondestructive CM approach as well as a more sensitive method than density CM approach. Crystallinity changes in materials investigated by modulated DSC and TGA measurements indicated deterioration of crystalline regions in polymer during the thermal oxidation aging. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 513–520, 2004     

Enhancement in ballistic performance of composite hard armor through carbon nanotubes

The use of carbon nanotubes in composite hard armor is discussed in this study. The processing techniques to make various armor composite panels consisting of Kevlar^®29 woven fabric in an epoxy matrix and the subsequent V50 test results for both 44 caliber soft-point rounds and 30 caliber FSP (fragment simulated projectile) threats are presented. A 6.5% improvement in the V50 test results was found for a combination of 1.65 wt% loading of carbon nanotubes and 1.65 wt% loading of milled fibers. The failure mechanism of carbon nanotubes during the ballistic event is discussed through scanning electron microscope images of the panels after the failure. Raman Spectroscopy was also utilized to evaluate the residual strain in the Kevlar^®29 fibers post shoot. The Raman Spectroscopy shows a Raman shift of 25 cm^?1 for the Kevlar^®29 fiber utilized in the composite panel that had an enhancement in the V50 performance by using milled fiber and multi-walled carbon nanotubes. Evaluating both scenarios where an improvement was made and other panels without any improvement allows for understanding of how loading levels and synergistic effects between carbon nanotubes and milled fibers can further enhance ballistic performance.     

胶原蛋白/PVA/碳纳米管复合纤维的结构与性能

在胶原蛋白与聚乙烯醇(PVA)复合后的溶液中加入少量质量分数为0.05%~0.25%的碳纳米管,通过湿法纺丝制得PVA/胶原蛋白/碳纳米管复合纤维,研究了复合纤维的结构和性能。结果表明:碳纳米管与PVA和胶原蛋白有较好的相容性,在复合纤维中分散比较均匀。添加质量分数为0.25%碳纳米管时,复合纤维结晶度提高了37.62%,水中软化点提高了5℃,回潮率从11.50%下降到10.83%;加入质量分数为0.05%的碳纳米管时,复合纤维的断裂强度提高57.07%。     

Use of carbon nanotubes for strain and damage sensing of epoxy-based composites

The interest in structural health monitoring of carbon fiber-reinforced polymers using electrical methods to detect damage in structures is growing because once the material is fabricated the evaluation of strain and damage is simple and feasible. In order to obtain the conductivity, the polymer matrix must be conductive and the use of nanoreinforcement seems to be the most feasible method. In this work, the behavior of nanoreinforced polymer with carbon nanotubes (CNTs) and composites with glass and carbon fibers with nanoreinforced matrices was investigated. These composites were evaluated in tensile tests by simultaneously measuring stress, strain and resistivity. During elastic deformation, a linear increase in resistance was observed and during fracture of the composite fibers, stronger and discontinuous changes in the resistivity were observed. Among other factors, the percentage of nanotubes incorporated in the matrix turned out to be an important factor in the sensitivity of the method.     

Ethylene–(vinyl acetate) copolymer/carbon fiber conductive composite: effect of polymer–filler interaction on its electrical properties

Ethylene–(vinyl acetate) (EVA)/carbon fibre (CF) composites were prepared by changing the content of CF in the composite. To investigate the effect of the interaction between EVA and CF on the electrical properties of the composite, the CF was treated in nitric acid. The interaction between EVA and CF was examined by a solvent-extraction method. It was found that the interaction of EVA with CF was enhanced due to the chemical absorption of EVA on CF. The correlation of CF content, electrical properties and the formation of polymer–filler gel for the composite with oxidized CF was studied. Although the composites filled with treated CF exhibit a slightly higher resistivity than those filled with untreated CF at room temperature, they show the improved electrical properties, including elimination of the negative-temperature-coefficient (NTC) effect, high electrical reproducibility after thermal cycles, and independence of the conductivity on time, which improves the practical applications of positive-temperature-coefficient (PTC) materials. Copyright © 2004 Society of Chemical Industry     

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     

Stress-relaxation behavior of unidirectional polyethylene–carbon fibers: PMMA hybrid composite laminates

Unidirectional composite laminates based on carbon fibers (CF) and high-performance polyethylene fibers (PEF) and their hybrids were prepared with partially polymerized methyl methacrylate (MMA) at room temperature, followed by heating at 55°C (well below the softening point of PEF, 147°C) for 2 h. The stress-relaxation behavior of the composites were determined and analyzed. It was found that at all strain levels the rate of stress relaxation decreased by the loading of CF in CF-reinforced composite laminates (CFRC); however, the reverse behavior was found in the case of PEF-reinforced composite laminate (PEFRC). An interesting observation of the study was that the rate of stress relaxation decreased linearly in two steps in the case of PEFRC, whereas in the case of CFRC, it decreased in a single step. In the case of hybrid composites, the stress relaxation decreases in two steps as in PEFRC. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1925–1929, 1998     

Electrical and electromagnetic shielding behavior of laminated epoxy–carbon fiber composite

This paper reports results on the electrical properties of laminated epoxy composite containing 25 layers of carbon fibers in the form of mats. The dependence of the activation energy (calculated from DC resistivity measurements) on temperature reveals two independent conduction processes. The AC impedance is independent of the applied frequency below 75°C, and the real componet of the dielectric constant is also independent of temperature at high frequencies. The determined shielding effectiveness is dominated by the insertion loss. The observed optimum shielding effectiveness occurs at 30 mm spacing and applied frequency 9 GHz.     

Lowering the percolation threshold of conductive composites using particulate polymer microstructure

The percolation thresholds of carbon black–polymer composites have been successfully lowered using particulate polymer starting materials (i.e., latex and water‐dispersible powder). Composites prepared using carbon black (CB) and commercial poly(vinyl acetate) (PVAc) latex exhibit a percolation threshold near 2.5 vol % CB. This threshold value is significantly lower than that of a comparable reference composite made from poly(N‐vinylpyrrolidone) (PNVP) solution and the same CB, which exhibits a sharp rise in electrical conductivity near 15 vol % CB. This dramatic difference in critical CB concentration results from the segregated microstructure induced by the latex during composite film formation. Carbon black particles are forced into conductive pathways at low concentration because of their inability to occupy volume already claimed by the much larger latex particles. There appears to be good qualitative agreement between experimental findings and current models dealing with conductive behavior of composites with segregated microstructures. Lack of quantitative agreement with the models is attributed to the polydispersity of the polymer particles in the latex. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 692–705, 2001     

Influence of conductive network composite structure on the electromechanical performance of ionic electroactive polymer actuators

The influence of the nanostructure of the conductive network composite (CNC) on the performance of ionic electroactive polymer (IEAP) actuators has been examined in detail. We have studied IEAP actuators consisting of CNCs with different volume densities of gold nanoparticles (AuNPs) and the polymer network. Varying the concentration of AuNPs in CNC thin films was used as a means to control the CNC–ion interfacial area and the electrical resistance of the CNC, with minimum effect on the mechanical properties of the actuator. Increasing the interfacial area and reducing the resistance, while maintaining porosity of the composite, provide means for generating motion of more ions into the CNC at a significantly shorter time, which results in generation of strain at a faster rate. We have demonstrated that cationic strain in actuators with denser CNCs is improved by more than 460%. Denser CNC structures have larger interfacial areas, which results in attraction/repulsion of more ions in a shorter time, thus generation of a larger mechanical strain at a faster rate. Also, time-dependent response to a square-wave voltage was improved by increasing the AuNP concentration in the CNC. Under 0.1 Hz frequency, the cationic strain was increased by 64% when the AuNP concentration was increased from 4 to 20 ppm.     

Heat treatment‐induced multiple melting behavior of carbon black‐filled polymer blends in relation to the conductive performance stabilization

Polymer blend‐based electrical conductive composites are provided with more possibilities for tailoring the performance in comparison with single polymer systems. To find an optimum heat treatment temperature of the composites, which is critical to practical applications, detailed thermal analyses of the related materials were carried out as a function of different annealing conditions. Based on the discussion of the morphological variation during treatment in terms of multiple melting behavior, it was found that an annealing temperature of 75°C is able to stabilize the resistivity of the composites within a reasonable period of time, as only solid‐state crystallization of LDPE and uniformization of EVA crystalline size are involved. In contrast to treatment at a temperature higher than 75°C, the ultimate equilibrium resistivity resulting from the above annealing procedure approaches the resistivity of the composites as‐manufactured. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1267–1273, 2001     

Improvement of conductive network quality in carbon black‐filled polymer blends

Heat treatment of polymer‐based composites is critical for the enhancement of both stability and long‐term service life, especially when the materials function under an inconstant temperature environment. The present article discusses the effect of heat‐treatment conditions on the electrically conductive properties of carbon black (CB)‐filled low‐density polyethylene (LDPE) and ethylene–vinyl acetate copolymer (EVA) composites, which are candidates for positive temperature coefficient (PTC) materials. It was found that the dispersion mode of CB particles changes as a function of the matrix morphology. When the composites are irradiated to form crosslinked networks in the matrix for the elimination of negative temperature coefficient (NTC) behavior, some of the produced free radicals are also entrapped for quite a long time after the irradiation treatment. These residual radicals further enhance the interaction between CB and the matrix and further induce the crosslinking of the matrix so that the composites' conductivity changes with time as a result of the continuous variation in the contacts between the conductive fillers. To improve the quality of the conduction paths in the composites, appropriate post‐heat treatment should be carried out, which speeds up the formation of the above‐mentioned two kinds of crosslinked structures within a limited time. Annealing at 75°C for more than 10 h is believed to be an effective way. After the treatment, a balanced performance characterized by reduced room‐temperature resistivity and improved PTC intensity was obtained. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2768–2775, 2002     

Matrix mediated alignment of single wall carbon nanotubes in polymer composite films

Alignment of single wall carbon nanotubes (SWNT) in liquid crystalline (LC) polymer matrix imparting orientation to the nanotubes along the nematic director was studied by atomic force microscopy, measurements of electrical conductivity and Raman spectroscopy of the composite in the directions parallel and perpendicular to the nematic director. The composites were prepared through dispersion of SWNT with LC monomer in a common solvent, their alignment in nematic monomer and consequent UV polymerization of the monomer. The anisotropy of electrical and optical properties of the system depends strongly on the concentration of the nanotubes in the range of 1-10% SWNT being especially strong for smaller concentrations and negligible at higher loads. A simple semi-quantitative model is suggested to account for the orientational behavior of nanotubes in nematic matrices. It successfully describes the observed anisotropy of physical properties at microscale (up to 200 μm) in terms of anchoring of the polymer chains to the nanotubes surface and adjustment of the nanotubes orientation to the nematic direction due to such coupling. The increasing disorientation of the nematic domains at higher nanotubes loads is explained as a development of larger number of LC defects induced by the nanotubes in the nematic matrix due to their intrinsic nature of aggregation. The anisotropy of physical properties at macro scale (several millimeters) is much smaller and less dependable on SWNT concentration because differently oriented LC domains effectively wash out the anisotropy.     

Thermomechanical properties and deformation behavior of a unidirectional carbon-fiber-reinforced shape memory polymer composite laminate

A shape memory polymer (SMP) demonstrates large reversible deformation functionality upon exposure to heating stimuli. In this study, the thermomechanical properties and deformation behavior of a unidirectional carbon-fiber-reinforced SMP composite (SMPC) laminate were studied. The findings can be used as a basis to design angle-ply laminated plates, woven laminated plates, or special laminated structures used for space deployment. The fundamental static and dynamic mechanical properties of SMP and SMPC were characterized. The fiber-reinforced SMPC exhibited local postmicrobuckling behavior and obtained a high-reversible macroscale strain of 9.6%, which enabled the high-reversible deformation to be used for foldable structures in space. The state of critical failure of bending deformation was determined through microscale morphology observations and provided the upper limit in the design of SMPC structures. The evolution of the key shape memory properties (e.g., recovery speed and recovery ratio) during deformation cycles was characterized, and it offered the general recovery performance of a space deployable structure. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48532.     

Improving delamination resistance of carbon fiber reinforced polymeric composite by interface engineering using carbonaceous nanofillers through electrophoretic deposition: An assessment at different in-service temperatures

In this article, modification of carbon fiber surface by carbon based nanofillers (multi-walled carbon nanotubes [CNT], carbon nanofibers, and multi-layered graphene) has been achieved by electrophoretic deposition technique to improve its interfacial bonding with epoxy matrix, with a target to improve the mechanical performance of carbon fiber reinforced polymer composites. Flexural and short beam shear properties of the composites were studied at extreme temperature conditions; in-situ cryo, room and elevated temperature (−196, 30, and 120°C respectively). Laminate reinforced with CNT grafted carbon fibers exhibited highest delamination resistance with maximum improvement in flexural strength as well as in inter-laminar shear strength (ILSS) among all the carbon fiber reinforced epoxy (CE) composites at all in-situ temperatures. CNT modified CE composite showed increment of 9% in flexural strength and 17.43% in ILSS when compared to that of unmodified CE composite at room temperature (30°C). Thermomechanical properties were investigated using dynamic mechanical analysis. Fractography was also carried out to study different modes of failure of the composites.     

碳纤维复合炭黑导电砂浆导电性能及其电热功能研究*

本研究介绍了碳纤维复合炭黑导电砂浆的制备方法、导电性能和电热功能研究。导电砂浆作为一种新型的功能性建筑材料，具有导电性能和电热功能，可以应用于感应加热、防冰除雪等多种场景。为了改善导电砂浆的性能，试验探究了采用碳纤维和炭黑复合的制备方法，并分析了碳纤维掺量对导电砂浆电阻率和电热功能的影响。实验结果表明，最佳的碳纤维掺量为胶凝材料质量分数的1%，炭黑掺量为胶凝材料质量分数的0.4%，在通入10 V交流电压下1 h后，试样温度升高13.3℃。电性能测试还证实了碳纤维复合炭黑导电砂浆具有低电阻率和高发热功率密度，具有较强的融雪或除冰能力。然而，为了将这一试验成果应用于更大的场景，还需要进一步研究导电砂浆试样。     

Preparation and characterization of multi‐walled carbon nanotubes/polymer gradient composite films

BACKGROUND: Recently, much work has focused on the efficient dispersion of carbon nanotubes (CNTs) throughout a polymer matrix for mechanical and/or electrical enhancement. However, there are still only few reports about gradient distribution of CNTs in polymer matrices. In the work reported here, CNTs embedded in a polymer film with a gradient distribution were successfully obtained and studied. RESULTS: For composite films with gradient distributions of CNTs, the upper surface behaves as an intrinsic insulator, while the lower one behaves as a semiconductor, or even as a conductor. It is also found that with an increase of 1 wt% CNTs, the resistance of the bottom surface decreases by 2–3 orders of magnitude, as compared with pure polyarylene ether nitrile; furthermore, when the proportion of CNTs increases up to 5 wt%, the resistance of the bottom surface shows only very little change. As a result, sufficient matrix conductivity of the bottom surface could be achieved at a lower filler concentration with CNTs in a gradient distribution. Meanwhile, the thermal stability, glass transition temperature and tensile properties of the matrix are maintained. CONCLUSION: There is considerable interest in such gradient composite films, which could be applied in the electrical engineering, electronics and aerospace fields, for their excellent mechanical properties, thermal stability and novel electrical properties. Copyright © 2008 Society of Chemical Industry