Modulation of electrical properties in single-walled carbon nanotube/conducting polymer composites

The preparation and electrical characterization of a new class of composite layers formed by dispersing single-walled carbon nanotubes (SWNT) in 1,8-diaminonaphthalene polymer, the poly(1,8-DAN), are described.The material was grown on the surface of Pt plates by electropolymerization of 1,8-diaminonaphthalene (1,8-DAN) monomer in the presence of nanotubes. This synthesis method allows the simultaneous deposition of both the host polymer matrix and the filler nanotubes. A series of composite films were prepared using untreated nanotubes as well as nanotubes treated with KOH, HNO₃ and HNO₃/H₂SO₄ solutions. The structural features of the nanotubes and of the films produced have been investigated using Raman spectroscopy. Insight into the nature of nanotube dispersion and nanotube-polymer association was gained by AFM and STM analysis and by FE-SEM inspection after removing the outermost portion of composite films.The charge transport in composite films is found to be strongly enhanced by the nanotube insertion. Depending on the SWNTs processing, currents up to 30 mA, higher by a factor of about 140 than those of the pure poly(1,8-DAN) films, were measured with an applied voltage of 250 mV.     

Rheological and electrical properties of polycarbonate/multi-walled carbon nanotube composites

Rheological and electrical properties of the polycarbonate (PC)/multi-walled carbon nanotube (MWNT) were studied. The MWNT was funtoinalized by treating with the hydrogen peroxide (H₂O₂). The H₂O₂ treated MWNT was dried by thermal and freeze drying methods. From the morphological studies, the degree of entanglement of the MWNT was decreased after treating with the H₂O₂. For the H₂O₂ treated MWNT (thermal drying), the length of the MWNT was shortened compared that of the H₂O₂ treated MWNT (freeze drying). The rheological and electrical properties of the PC/MWNT (H₂O₂ treated) composites increased compared that of the PC/MWNT (untreated) composites. Also, the electrical conductivity showed higher value for the PC/MWNT (H₂O₂ treated, freeze drying) composites compared that of the PC/MWNT (H₂O₂ treated, thermal drying) composites. From the results of the morphological, rheological, and electrical properties of the PC/MWNT composites, it is suggested that the electrical and rheological properties of the PC/MWNT composites are affected by the MWNT-MWNT network structure, which is related with the MWNT morphologies such as the degree of aggregation and aspect ratio of the MWNT.     

Conductivity spectroscopy on melt processed polypropylene-multiwalled carbon nanotube composites: Recovery after shear and crystallization

Frequency dependent investigations of conductivity and dielectric permittivity have been performed on composites of polypropylene (PP) containing different amounts of 2, 3.5, and 5 wt% of multiwalled carbon nanotubes (MWNTs) in the melt and during crystallization. The experiments were performed in a measurement slit die containing two dielectric sensors in plate-plate geometry, which was flanged to the outlet of a single screw laboratory extruder. AC conductivity and the related complex permittivity were measured in the frequency range from 20 Hz to 10⁶ Hz after stopping the extruder (recovery after shearing) and during cooling (non-isothermal crystallization). For a sample with a MWNT content of 2 wt% the AC conductivity shows a tremendous increase with time after shearing was stopped. This conductivity recovery is explained by the reorganization of the conducting network-like filler structure, which was partially destroyed by the shear. The reformation kinetics of filler clusters is assumed to be due to a cooperative aggregation. For conductive fillers in a thermoplastic matrix the kinetics of cooperative aggregation is coupled to the electrical percolation. The reorganization of the percolation network can be related to reformation of (i) the local contact regions between the nanotubes (separated by polymer chains) and (ii) to the reorientation of nanotubes oriented in the shear flow. The conductivity recovery is less pronounced for samples with MWNT concentrations well above the percolation threshold. During cooling of the melt to temperatures below crystallization a significant decrease in the conductivity and permittivity was detected. This is consistently expressed in the conductivity and permittivity spectra and can be explained by reduction of the amorphous phase (high ion mobility) on expense of the crystalline phase and/or by crystalline regions in the contact region between tubes.     

Comparative study on electrical properties of copper nanowire/polypropylene and carbon nanotube/polypropylene composites

Nanocomposites using copper nanowires (CuNWs) or carbon nanotubes (CNTs) as fillers with polypropylene (PP) as matrix were prepared by miscible solution mixing and precipitation method. Comparative studies on electrical conductivity and electromagnetic interference shielding properties were reported. On the conductivity curve, a plateau was found for both CuNW/PP composite and CNT/PP composite. The plateaus are located at a different concentration range for each composite type: for CuNW/PP composite, it is between 0.8 and 1.7 vol %, while for CNT/PP composite the plateau occurs in a narrower range between 0.4 and 0.6 vol %. The shielding effectiveness (SE) increases with increased concentration of fillers. CNT/PP composite has higher SE at concentrations less than 2 vol %; the two curves cross near 10 dB at this point and at concentrations higher than 2 vol %, CuNW/PP composite has higher SE. © 2014 American Institute of Chemical Engineers AIChE J, 61: 296–303, 2015     

Improved mechanical properties of carbon nanotube/polymer composites through the use of carboxyl-epoxide functional group linkages

Single-walled and multi-walled carbon nanotubes (CNTs) were functionalized with carboxyl groups and dispersed in a polymer containing an epoxide group. We have then observed experimentally that mutual chemical reaction between the functional groups on the CNTs with the polymer epoxide group can enhance, two-fold, both the tensile strength and elastic modulus, E, of single walled CNT/polymer composites. A simple model was formulated to understand the variation of E with CNT volume fraction, considering agglomeration effects as well. An increase in the work of fracture, obtained from the experimental stress-strain curves, was seen at low nanotube filling fractions and is presumably due to crack bridging of the polymer matrix by CNTs. The influence of CNT length and geometry on mechanical properties, along with the influences of electrical and mechanical percolation thresholds was considered.     

Conductivity of carbon black-based polymer composites under creep in the molten state

The mechanical deformation of conductive polymer composites during melt processing affects their final electrical properties considerably. To get an insight in this relationship, simultaneous electrical-rheological measurements can be used to follow the changes in composite phase structure induced by defined deformation. In this work, the evolution of electrical conductivity was investigated during and after shear deformation at constant stress. From the experiments performed it can be concluded, that the flow-induced build-up mechanism leads to the formation of conductive pathways with enhanced stability compared to the structures build-up under quiescent conditions. This finding can be explained by the orientation of particle structures in the shear direction. Therefore, materials with different deformation history but the same electrical conductivity can display markedly different electrical behaviour under deformation.     

A representative and comprehensive review of the electrical and thermal properties of polymer composites with carbon nanotube and other nanoparticle fillers

In this review we present the results of our literature investigation into the electrical and thermal properties of carbon nanotube polymer composites. A short selection of data relating to conductive polymer composites with various fillers is provided for comparison. The effects of filler properties such as type and size, the use of hybrid fillers, fabrication methods for polymer composites and the importance of the modeling of the electronic and thermal transport mechanisms are discussed, as are more general factors influencing the properties of these composites. This review represents a comprehensive survey and constructive study and should serve as a useful reference tool for industrial and academic researchers working in this field. © 2017 Society of Chemical Industry     

Highly conductive and high-strength carbon nanotube film reinforced silicon carbide composites

Film formed by carbon nanotubes is usually called carbon nanotube film (CNT_f). In the present study, CNT_f fabricated by floating catalyst method was used to prepare CNT_f/SiC ceramic matrix composites by chemical vapor infiltration (CVI). Mechanical and electrical properties of the resulting CNT_f/SiC composites with different CVI cycles were investigated and discussed, and the results revealed that the CNT_f has a good adaptability to CVI method. Tensile test demonstrated an excellent mechanical performance of the composites with highest tensile strength of 646 MPa after 2 CVI cycles, and the strength has a decline after 3 CVI cycles for an excessively dense matrix. While, the elastic modulus of the composite increased with the CVI cycles and reached 301 GPa after 3 CVI cycles. Tensile fracture morphologies of the composites were analyzed by scanning electron microscope to study the performance change laws with the CVI cycles. With SiC ceramic matrix infiltrated into the CNT_f, enhanced electrical conductivity of the CNT_f/SiC composite compared to pure CNT_f was also obtained, from 368 S/cm to 588 S/cm. Conductivity of the SiC matrix with free carbon forming in the CVI process was considered as the reason.     

Processing-structure-multi-functional property relationship in carbon nanotube/epoxy composites

The novel properties of carbon nanotubes have generated scientific and technical interest in the development of nanotube-reinforced polymer composites. In order to utilize nanotubes in multi-functional material systems it is crucial to develop processing techniques that are amenable to scale-up for high volume, high rate production. In this research we investigate a scalable calendering approach for achieving dispersion of CVD-grown multi-walled carbon nanotubes through intense shear mixing. Electron microscopy was utilized to study the micro and nanoscale structure evolution during the manufacturing process and optimize the processing conditions for producing highly-dispersed nanocomposites. After processing protocols were established, nanotube/epoxy composites were processed with varying reinforcement fractions and the fracture toughness and electrical/thermal transport properties were evaluated. The as-processed nanocomposites exhibited significantly enhanced fracture toughness at low nanotube concentrations. The high aspect ratios of the carbon nanotubes in the as-processed composites enabled the formation of a conductive percolating network at concentrations below 0.1% by weight. The thermal conductivity increased linearly with nanotube concentration to a maximum increase of 60% at 5 wt.% carbon nanotubes.     

Thermoelectric properties of carbon nanotube reinforced cement-based composites fabricated by compression shear

Carbon nanotubes (CNTs) with weight percent of 5.0%, 10.0% and 15.0% were added into the cement matrix to fabricate CNT reinforced cement-based composites (CNTs/CC) by mixing and dry compression shear methods. Seebeck coefficient, electrical conductivity and thermal conductivity of the as-received CNTs/CC were measured and analyzed in detail. The CNTs/CC exhibits the thermoelectric behavior of p-type semiconductor. CNTs were dispersed uniformly in cement matrix by compression shear stress, which promoted a relatively high electrical conductivity (0.818 S/cm) and Seebeck coefficient (57.98 μV/°C) of CNTs/CC. Combining with their lower thermal conductivity ranged from 0.734 to 0.947 W m^?1 K^?1, the CNTs/CC shows the highest thermoelectric figure of merit (ZT) has reached 9.33 × 10^?5, Which is benefit to the applications in large-scale energy harvesting in the buildings and pavements with low cost in the future cities.     

Experimental and numerical investigations of the interlaminar shear properties of carbon/carbon composites

Experimental tests and numerical simulations were implemented to investigate the interlaminar shear properties of carbon/carbon composites (C/Cs). A unit‐cell model, according to the microstructure of the C/Cs, was used to predict material properties of the C/Cs. A three‐dimensional finite element model was established to investigate the damage behavior of C/Cs on the basis of Linde failure criterion and damage evolution. Good agreement, in terms of the load force history and failure modes, was observed between the experimental and numerical results; this provided the applicability of the numerical simulation. The test results show that the interlaminar shear strength of the C/Cs was 10.52 MPa and the value of the simulation result was 10.89 MPa, with the relative error being less than 4%. Damage contours and stress distribution analysis of the simulation results are discussed. Fiber damage occurred at the bottom of the specimen, and matrix damage was found in the upper half of the specimen; this was similar to the appearance of the tested specimens. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44783.     

Combined effects of nanotube aspect ratio and shear rate on the carbon nanotube/polymer composites

We use fiber-level simulations to investigate the combined effects of carbon nanotube (CNT) aspect ratio and shear rate on the microstructure and electrical properties of CNT/polymer composites. In our previous studies, we studied the effects of aspect ratio at a constant shear rate as well as the effects of shear rate for a constant aspect ratio. In this study electrical properties and microstructure changes (e.g. agglomeration/deagglomeration, network strength, nanotube orientation) of CNT/polymer composites are investigated for varying aspect ratios at different shear rates. When shear rate is increased, we observe a decrease in the electrical conductivity and an increase in the anisotropy factor due to the deagglomeration and flow induced orientation. Increasing aspect ratio shifts the conductivity vs. shear rate curve to larger values and anisotropy vs. shear rate curve to lower values showing that there is a tendency for tube agglomeration when high aspect ratio nanotubes are used. On the other hand when low aspect ratio nanotubes are used, conductive networks can be more easily destroyed by the shear forces because networks formed by low aspect ratio nanotubes have lower strength than those formed by high aspect ratio nanotubes. Our results show that electrical conductivity is anisotropic with a larger component in the flow direction. The critical shear rate defined as the shear rate where the conductive network is destroyed and all components of the composite conductivity decrease to the matrix conductivity, shifts to higher values when the aspect ratio is increased. Reduced alignment and increased entanglement are the reasons of this decrease.     

Electrical and dielectric properties of multiwall carbon nanotube/polyaniline composites

In this paper, electrical and dielectric properties of multiwall carbon nanotubes (MWCNTs)/insulating polyaniline (PANI) composites were studied. A mixture of MWCNTs and insulating polyaniline was dispersed in an ethanol solution by ultrasonic process, subsequently dried, and was hot-pressed at 200 °C under 30 MPa. Electrical and dielectric properties of the composites were measured. The experimental results show that the dc conductivities of the composites exhibit a typical percolation behavior with a low percolation threshold of 5.85 wt.% MWCNTs content. The dielectric constant of the composites increases remarkably with the increasing MWCNTs concentration, when the MWCNTs concentration was close to percolation threshold. This may be attributed to the critical behavior of the dielectric constant near the percolation threshold as well as to the polarization effects between the clusters inside the composites.     

Effect of phase transitions on the electrical properties of polymer/carbon nanotube and polymer/graphene nanoplatelet composites with different conductive network structures

Multi‐walled carbon nanotube (MWCNT)‐ and graphene nanoplatelet (GNP)‐filled high‐density polyethylene (HDPE) composites with dispersed and segregated network structures were prepared by solution‐assisted mixing. Simultaneous DC conductivity and differential scanning calorimetry were used to measure electrical conductivity during composite thermal phase transitions. It was found that the conductive network is deformed during melting and rebuilt again during annealing due to the re‐agglomeration of nanofillers. The rebuilding of the structure is significantly affected by the original network structure and by the shape and loading of the nanofillers. Both deformation and reorganization of the network lead to drastic changes in the conductivity of the composites. The crystallization process also affects the conductive network to some extent and the subsequent volume shrinkage of the polymeric matrix after crystallization results in a further decrease in the resistivity of HDPE/GNP composites. Classical electrical percolation theory combined with a kinetic equation is used to describe the conductivity recovery of composites during annealing, and the results are found to be in good agreement with experimental data. © 2017 Society of Chemical Industry     

PPS/recycled PEEK/ carbon nanotube composites: Structure,properties and compatibility

Blends of poly(phenylene sulfide) (PPS) and recycled poly(ether ether ketone) (r‐PEEK) were prepared using a twin‐screw extruder. The carbon nanotube (CNT) added to the blends not only improved the compatibility of the two polymers, but also affected the morphology of the immiscible PPS/r‐PEEK blends. R‐PEEK always forms the dispersed phase and PPS the continuous phase in such blends. In the composite, CNT particles were observed in the PPS phase, mostly distributes in the interface between PPS and PEEK. The results show that r‐PEEK improves the impact and tensile strength of PPS, but does not provide nucleation effect on PPS. However, CNT improved the flexural modulus of PPS/r‐PEEK blends and promoted the crystallization of r‐PEEK rather than that of PPS. The prepared PPS/r‐PEEK blends provided larger electrical conductivity than neat polymers. Adding 20 wt % CNT to blend resulted in composite with the minimum volume resistivity, a reduction of four orders of magnitude, compared with that of the neat blend. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42497.     

Modeling and characterization of the electrical conductivity of carbon nanotube-based polymer composites

In this research, we investigate both analytically and experimentally the electrical properties of carbon nanotube (CNT)-based polymer composites. An analytical model was developed to predict the electrical conductivity of CNT-based composites. The micro/nanoscale structures of the nanocomposites and the electrical tunneling effect due to the matrix material between CNTs were incorporated within the model. Electrical conductivity measurements were also performed on CNT/polycarbonate composites to identify the dependence of their electrical transport characteristics on the nanotube content. The analytical predictions were compared with the experimental data, and a good correlation was obtained between the predicted and measured results. In addition, the effect of nanotube geometry on the nanocomposite electrical properties at the macroscale was examined.     

Rheological behavior of multiwalled carbon nanotube/polycarbonate composites

The rheological behavior of compression molded mixtures of polycarbonate containing between 0.5 and 15 wt% carbon nanotubes was investigated using oscillatory rheometry at 260 °C. The nanotubes have diameters between 10 and 15 nm and lengths ranging from 1 to 10 μm. The composites were obtained by diluting a masterbatch containing 15 wt% nanotubes using a twin-screw extruder. The increase in viscosity associated with the addition of nanotubes is much higher than viscosity changes reported for carbon nanofibers having larger diameters and for carbon black composites; this can be explained by the higher aspect ratio of the nanotubes. The viscosity increase is accompanied by an increase in the elastic melt properties, represented by the storage modulus G′, which is much higher than the increase in the loss modulus G″. The viscosity curves above 2 wt% nanotubes exhibit a larger decrease with frequency than samples containing lower nanotube loadings. Composites containing more than 2 wt% nanotubes exhibit non-Newtonian behavior at lower frequencies. A step increase at approximately 2 wt% nanotubes was observed in the viscosity-composition curves at low frequencies. This step change may be regarded as a rheological threshold. Ultimately, the rheological threshold coincides with the electrical conductivity percolation threshold which was found to be between 1 and 2 wt% nanotubes.     

碳纳米管的制备及其聚合物基复合材料的研究进展

本文综述了单壁碳纳米管的制备方法,重点阐述了化学气相沉积法的合成运用,并对目前碳纳米管在聚合物基纳米复合材料方面的研究做了综合阐述。     

Morphology,thermal expansion,and electrical conductivity of multiwalled carbon nanotube/epoxy composites

Multiwalled carbon nanotube/epoxy composites loaded with up to 0.5 wt % multiwalled carbon nanotubes were prepared and characterized. Infrared microscopy, scanning electron microscopy, thermogravimetry, differential scanning calorimetry, thermomechanical analysis, and electrical conductivity measurements of the composites were performed. Infrared microscopy and scanning electron microscopy images showed that the debundled nanotubes were well dispersed. The thermal expansion coefficients, before and after the glass transition, remained approximately constant with the addition of nanotubes, whereas the electrical conductivity at room temperature increased approximately 5 orders of magnitude. This result was attributed to the thermal expansion coefficients of the intertube gap on the carbon nanotube bundles, which were in the same range as that of the epoxy resin. Therefore, nanocomposites capable of electrostatic dissipation can be processed as neat epoxy materials with respect to the volume changes with temperature. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008