Low percolation threshold in single-walled carbon nanotube/high density polyethylene composites prepared by melt processing technique

A new method was developed to disperse carbon nanotubes (CNTs) in a matrix polymer and then to prepare composites by melt processing technique. Due to high surface energy and strong adsorptive states of nano-materials, single-walled carbon nanotubes (SWNTs) were adsorbed onto the surface of polymer powders by spraying SWNT aqueous suspected solution onto fine high density polyethylene (HDPE) powders. The dried SWNTs/powders were blended in a twin-screw mixture, and the resulting composites exhibited a uniformly dispersion of SWNTs in the matrix polymer. The electrical conductivity and the rheological behavior of these composites were investigated. At low frequencies, complex viscosities become almost independent of the frequency as nanotubes loading being more than 1.5 wt%, suggesting an onset of solid-like behavior and hence a rheological percolation threshold at the loading level. However, the electrical percolation threshold is ∼4 wt% of nanotube loading. This difference in the percolation thresholds is understood in terms of the smaller nanotube-nanotube distance required for electrical conductivity as compared to that required to impede polymer mobility. The measurements of mechanical properties indicate that this processing method can obviously improve the tensile strength and the modulus of the composites.     

Electrical and mechanical properties of polyimide-carbon nanotubes composites fabricated by in situ polymerization

Polyimide (PI)-carbon nanotubes composites were fabricated by in situ polymerization using multi wall carbon nanotubes (MWNT) as fillers. It suggested that in situ polymerization is an ideal technique to make a perfect dispersion of carbon nanotubes into matrixes. Besides it, the pre-treatment of carbon nanotubes in solvent to make the networks untied enough and to let solvent percolated into the networks is very important for forming uniform entanglements between carbon nanotubes and polymer molecular chains. The results imply that the percolation threshold for the electric conductivity of the resultant PI-MWNT composites was ca. 0.15 vol%. The electrical conductivity has been increased by more than 11 orders of magnitude to 10⁻⁴ S/cm at the percolation threshold. The mechanical properties of the polyimide composite were not improved significantly by addition of carbon nanotubes.     

Ultra-low electrical percolation threshold in carbon-nanotube-epoxy composites

Epoxy composites based on aligned CVD-grown multi-wall carbon nanotubes with weight fractions ranging from as low as 0.001 up to 1 wt% were produced. The resulting electrical properties were analysed by AC impedance spectroscopy. The composite conductivity σ follows a percolation scaling law of the form σ∝(p−p_c)^t with the critical mean concentration p_c to form a conductive network of approximately 0.0025 wt% and an exponent, t, of 1.2. The results are compared to previous studies investigating the percolation behaviour of entangled carbon nanotubes and spherical carbon black particles in the same matrix processed under similar conditions. The experimental percolation threshold for the aligned nanotubes used in this study represents the lowest threshold observed for carbon-nanotube-based polymer composites yet reported.     

Correlation of carbon nanotube dispersability in aqueous surfactant solutions and polymers

In order to assess the dispersability of carbon nanotube materials, tubes produced under different synthesis conditions were dispersed in aqueous surfactant solutions and the sedimentation behaviour under centrifugation forces was investigated using a LUMiFuge stability analyzer. The electrical percolation threshold of the nanotubes after melt mixing in polyamide 6.6 was determined and the state of dispersion was studied. As a general tendency, the nanotubes having better aqueous dispersion stability showed lower electrical percolation threshold and better nanotube dispersion in the composites. This indicates that the investigation of the stability of aqueous dispersions is also able to give information about the nanotubes inherent dispersability in polymer melts, both strongly influenced by the entanglement and agglomerate structure of the tubes within the as-produced nanotube materials.The shape of the nanotubes in the aqueous dispersions was assessed using a SYSMEX flow particle image analyzer and found to correspond to the shape observed from cryofractured surfaces of the polymer composites.     

Functional nano-fillers in waterborne polyurethane/acrylic composites and the thermal,mechanical, and dielectrical properties

Modification is mostly used to adjust and increase the performance of polymers by employing organic or inorganic fillers in composites. It is significant to investigate the functions of different fillers in polymer matrix. In this work, we prepared a series of composites by using polyurethane/acrylic dispersions as polymer matrix and nanofillers (cellulose nanocrystals, carbon nanotubes and aluminum oxide nanoparticles) as modifiers to study their micro-structure and applied performance. It is found that the different nanofillers can be dispersed in PUA homogenously, which are inclusive physically. Different nanofillers have a noticeable influence on the T_g for the acrylate copolymers and the T_g of the interphase between the acrylate and polyurethane. The CNTs significantly increases the elongation to 127.29%, and gives the highest dielectric response. We imply that the CNTs may be the most significant fillers to increase the mechanical and electrical properties.     

Rheological,electrical, and microwave properties of polymers with nanosized carbon particles

The rheology, dc‐conductivity, and microwave properties of acrylic, polyurethane, and epoxy composites containing 0–15 vol % of nanosized carbon particles have been investigated. Carbon nanoparticles (1–3 nm) are produced by a shock wave technology. Steady‐state shear and oscillatory flow tests are applied to investigate the rheological properties of dispersions; dc‐conductivity and MW absorption/reflection are investigated for solid composite films. Rheological characteristics are used for the evaluation of agglomeration processes of nanoparticles in dispersions, as controlled by volume fraction and processing technology. The percolation threshold is interpreted as a structural transition from a dispersed to an agglomerated state and it is found to depend significantly on the type of the matrix polymer. Above the percolation threshold, the presence of carbon nanoparticles produces a strong increase in the viscosity of dispersions as well as of the electrical conductivity and microwave properties of solid composites. A good correlation between the three characteristics is found for the systems in a wide range of carbon volume fractions. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2220–2227, 2004     

Dispersion of carbon nanotubes through amphiphilic block copolymers: Rheological and dielectrical characterizations of poly(ethylene oxide) composites

In this article, we report on some properties of polymer nanocomposites prepared from dispersions of multiwall carbon nanotubes (CNT) in aqueous solution prepared using amphiphilic block copolymers. These nanocomposites are made of polyethylene oxide as matrix and CNT wrapped with copolymers as fillers. We investigated the rheological and electrical behavior of such composites with the objectives of underlined the effect of wrapping. Two rheological and only one electrical percolation thresholds have been observed and related to polymer–CNT and CNT–CNT networks. The low values of these percolation thresholds agree with a homogeneous dispersion of CNT in the matrix. We also demonstrated that specific wrapping may induce an increase of electrical conductivity without affecting too much the viscosity of the melt. POLYM. COMPOS., 2012. © 2011 Society of Plastics Engineers     

Electrical,mechanical, and crystallization properties of ethylene‐tetrafluoroethylene copolymer/multiwalled carbon nanotube composites

Multiwalled carbon nanotubes (MWCNTs) were melt‐mixed in a conical twin‐screw extruder with a random copolymer of ethylene and tetrafluoroethylene. Surprisingly, the electrical percolation threshold of the resultant composites was quite low; ～0.9 wt %. In fact, this value is as low or lower than the value for most MWCNT/semicrystalline polymer composites made with roughly equivalent aspect ratio tubes mixed in a similar manner, for example, melt mixing. This low percolation threshold, suggestive of good dispersion, occurred even though the polymer surface energy is quite low which should make tubes more difficult to disperse. Dynamic mechanical measurements confirmed the rather low percolation threshold. The effect of nanotubes on crystallization kinetics was quite small; suggesting perhaps that a lack of nucleation which in turn reduces/eliminates an insulating crystalline polymer layer around the nanotubes might explain the low percolation threshold. Finally, the modulus increased with the addition of nanotubes and the strain at break decreased. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41052.     

PVDF/BaTiO3/carbon nanotubes ternary nanocomposites prepared by ball milling: Piezo and dielectric responses

Nanocomposites based on poly(vinylidene fluoride) (PVDF) filled with barium titanate, BaTiO₃, (BT) particles, and multiwalled carbon nanotubes (MWCNTs) were prepared by high-energy ball milling (HEBM) and subsequent hot pressing. This method of materials preparation allowed obtaining uniform dispersions of the nanofillers. The influence of the particles on the polymer structure and morphology was studied. To understand the origin of changes in the PVDF properties, thermal and electrical behaviors of the PVDF/BT/MWCNT nanocomposites were studied as a function of composition. The addition of BT, MWCNT, or its mixture had not any influence on the PVDF polymorphism. However, calorimetric results pointed out that the presence of the nanofillers exerted nucleation mainly ascribed to the surface to volume ratio of the nanoparticles. The capacitance of the composites increased as the nanofiller content increased, being the effect mainly dependent on the surface to volume ratio of the nanoparticles. The dielectric behavior of the materials as a function of frequency was modeled by a Debye equivalent circuit only below the percolation threshold respect to the amount of MWCNT. The piezoelectric behavior of the ternary nanocomposites was highly affected by the incorporation of the nanofillers only when high dielectric losses occurred above the percolation threshold. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47788.     

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.     

Enhanced positive temperature coefficient in amorphous PS/CSPE-MWCNT composites with low percolation threshold

In this work, amorphous polystyrene/chlorosulfonated polyethylene composites doped with multiwalled carbon nanotubes (PS/CSPE-MWCNT) were constructed by in situ polymerization to form semi-interpenetrating networks. The MWCNTs showed excellent dispersion and selective location in the PS regions. High electrical conductivity and low percolation threshold (0.89 wt %) for the composites were achieved. An enhanced positive temperature coefficient (PTC) behavior for amorphous PS/CSPE-MWCNT composites was first reported, nearly without a negative temperature coefficient (NTC) effect when the conductive fillers were beyond the percolation threshold, similar to those of crystalline polymer composites. Moreover, a PTC intensity of more than five orders of magnitude and excellent repeatability of the PTC effect were achieved. This study offers new insight into the development of novel PTC materials with low percolation threshold. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47053.     

Chitosan/MWCNTs‐decorated with silver nanoparticle composites: Dielectric and antibacterial characterization

The dielectric and biological properties of chitosan (CTS)‐based nanocomposites were analyzed by dielectric spectroscopy, and antibacterial and antifungal assays. Carbon nanotubes (CNT) and CNT decorated with silver nanoparticles (AgnP) were incorporated into a CTS matrix at different concentrations to obtain bionanocomposite thin films. The conductivity of pristine CTS is considerably enhanced, by six orders of magnitude, with the inclusion of CNT; however, with the addition of CNT decorated with AgnP it only increases by two orders of magnitude because of strong chemical interactions between the CNT and AgnP that also affect the antibacterial activity of the composite. The percolation threshold in the CTS/CNT composites is ca. 1.3 wt %, while in CTS/CNT‐AgnP composites the strong CNT‐AgnP chemical interactions give a percolation threshold of ca. 2.2 wt % of CNT‐AgnP. In both cases, DC conductivity exhibits a three‐dimensional hopping conductivity, and the σ‐ and α‐relaxation processes are disclosed in agreement with the pristine CTS relaxation processes previously reported; however, these two relaxations vanish in the vicinity of the saturation concentration. Finally, the antifungal activity of the CTS/CNT‐AgnP composites is comparable with the activity of other composites, while their antibacterial activity seems to be competitive with respect to commercial antibiotics, indicating the effectiveness of these composites in potential hygienic applications. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40214.     

Block Copolymer Composite Synthesis in a Mechanistic Approach

Carbon nanotubes-block copolymer composites were synthesized via reversible addition–fragmentation chain transfer living emulsion mechanism, based on zero–one and pseudo-bulk kinetics. In conjunction with multiwalled carbon nanotubes, ab initio reversible addition–fragmentation chain transfer homopolymerization of styrene and butyl acrylate, respectively, was carried out using xanthate-based reversible addition–fragmentation chain transfer agent through ultrasonified macroemulsion and miniemulsion. Then, the second and third monomer were applied at stage II and III, respectively, to produce multiwalled carbon nanotube diblock and triblock copolymer composites such as multiwalled carbon nanotube-b-poly(styrene)-co-polybutyl acrylate-co-polymethyl acrylate and multiwalled carbon nanotube-b-polybutyl acrylate-co-polymethyl acrylate-co-poly(styrene). As multiwalled carbon nanotube-homopolymer proceeds to diblock and triblock, thermal resistance of multiwalled carbon nanotube block composite products is enhanced. A mechanistic approach of reversible addition–fragmentation chain transfer living macroemulsion and miniemulsion polymerizations, with the purified multiwalled carbon nanotubes enables us to control the composite properties such as thermal degradation, mechanical strength, and glass transition temperature of multiwalled carbon nanotube-block copolymer composites, in conjunction with reaction conditions, monomer type, blocking sequence, particle size, and molecular weight.     

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.     

Electrical,rheological, and mechanical properties copolymer/carbon black composites

This work aims to evaluate the electrical conductivity and the rheological and mechanical properties of copolymer/carbon black (CB) conductive polymer composites (CPCs). The copolymers, containing ethylene groups in their structure, used as matrix were polyethylene grafted with maleic anhydride (PEgMA), ethylene-methyl acrylate–glycidyl methacrylate (EMA-GMA), and ethylene-vinyl acetate (EVA). For comparison purposes, bio-based polyethylene (BioPE)/CB composites were also studied. The electrical conductivity results showed that the electrical percolation threshold of BioPE/CB composite was 0.36 volume fraction of CB, whereas the rheological percolation threshold was 0.25 volume fraction of CB. The most conductive CPC was BioPE/CB. Among the copolymer/CB CPCs, PEgMA/CB showed the highest conductivity, which can be attributed to the fact that the PEgMA copolymer had higher crystallinity. It also has a higher amount of ethylene groups in its structure. Torque rheometry analysis indicated that EMA-GMA copolymer may have reacted with CB. Rheological measurements under oscillatory shear flow indicated the formation of a percolated network in BioPE/CB and copolymer/CB composites. Morphology analysis by scanning electron microscopy (SEM) indicated the formation of a percolated network structure in BioPE/CB composite and finely dispersed CB particles within the PEgMA copolymer. Wetting of CB particles/agglomerates by the copolymer matrix was observed in EVA/CB and EMA-GMA/CB composites. Conductive CB acted as reinforcing filler as it increased the elastic modulus and tensile strength of BioPE and the copolymers.     

Electrical conductivity of chemically modified multiwalled carbon nanotube/epoxy composites

The electrical conductivity of oxidized multiwalled carbon nanotubes (MWNT)/epoxy composites is investigated with respect to the chemical treatment of the MWNT. The oxidation is carried out by refluxing the as-received MWNT in concentrated HNO₃ and H₂O₂/NH₄OH solutions, respectively, under several different treatment conditions. The oxidized MWNT are negatively charged and functionalized with carboxylic groups by both solutions. The MWNT oxidized under severe conditions are well purified, but their crystalline structures are partially damaged. It is recognized that the damage to the MWNT has considerable influence on the electrical properties of the MWNT composites, causing the electrical conductivity to be lowered at a low content of MWNT and the percolation threshold to be raised. The MWNT oxidized by the mixture of H₂O₂ and NH₄OH solution provides epoxy composites with a higher conductivity than those produced with the MWNT oxidized by nitric acid over the whole range of MWNT, independently of the oxidation conditions.     

Conductivity and mechanical properties of composites based on MWCNTs and styrene‐butadiene‐styrene block™ copolymers

Composites based on multiwall carbon nanotubes (MWCNTs) and the block copolymer styrene‐butadiene‐styrene with two different contents of styrene have been investigated and their electrical conductivity and mechanical properties have been evaluated. The composites were prepared by a solution casting procedure, using a dispersant agent for the MWCNTs. Conductivity values of 10^?4 and 1.6 S cm^?1 have been obtained for samples containing 1 and 12 wt % of MWCNTs, respectively. The percolation threshold achieved for these systems was ～0.25 wt %. According to dynamic mechanical analysis, the MWCNTs interact with both phases of the copolymers, acting as a reinforcement filler, whereas the dispersant agent acts as a plasticizer. However, it was shown that the reinforcing effect of the MWCNTs overcomes the latter, resulting in an overall improvement of mechanical properties of the composites. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Mechanical properties and electrical conductivity of carbon-nanotube filled polyamide-6 and its blends with acrylonitrile/butadiene/styrene

Composites of polyamide-6 and carbon nanotubes (NT) have been prepared on a corotating twinscrew extruder. It is shown by transmission electron microscopy (TEM) that the nanotubes are dispersed homogeneously in the polyamide-matrix. The electrical conductivity of these composites was analyzed and compared to carbon black filled polyamide-6. It is found that the NT-filled polyamide-6 shows an onset of the electrical conductivity at low filler loadings (4-6 wt%). In agreement with rheological measurements this onset in the conductivity is attributed to a percolation of nanotubes in the insulating matrix polymer. Tensile tests of the NT-composites show a significant increase of 27% in the Young's modulus, however the elongation at break of these materials dramatically decreases due to an embrittlement of the polyamide-6. Blends of these composites and Acrylonitrile/butadiene/styrene (ABS) have been prepared by extrusion. It is shown by TEM measurements that the nanotubes are selectively located in the polyamide-6. These selectively filled polyamide-6/ABS-blends show a highly irregular, cocontinuous morphology. Due to the confinement of the conductive filler to one blend component these materials show an onset in the electrical conductivity at very low filler loadings (2-3 wt%). These findings are explained by a double percolation effect. The NT-filled blends show superior mechanical properties in the tensile tests and in IZOD notched impact tests.     

The role of non-covalent interactions and matrix viscosity on the dispersion and properties of LLDPE/MWCNT nanocomposites

Linear low density polyethylene (LLDPE)/multi-walled carbon nanotube (MWCNT) composites were prepared by melt compounding, following two different compatibilization strategies that involved non-covalent interactions between the matrix and the filler. The first approach involved grafting pyridine aromatic moieties on the maleated polyolefin backbone, which are able to interact by π–π stacking with the surface of the nanotubes. The second method implemented non-covalent/non-specific surface functionalization of the MWCNTs with a hyperbranched polyethylene (HBPE). The enhanced interfacial interactions established in the composites containing LLDPE functionalized with pyridine grafts improved the dispersion of the nanotubes within the polymer matrix. Dispersion was also favoured by higher matrix viscosity. Composites containing finely dispersed MWCNTs exhibited an increase in the rheological and electrical percolation thresholds, and a significant improvement in mechanical properties. On the contrary the composites based on the low viscosity matrix contained large amounts of aggregates, which promoted lower percolation thresholds. Manipulation of matrix viscosity and compatibilization resulted in composites with good mechanical properties, and low percolation thresholds.     

Structural characterization and electrical properties of carbon nanotubes/epoxy polymer composites

The purpose of this study is to identify the relationship between the electrical and structural characteristics of multiwalled carbon nanotubes dispersed into the polymer matrix of a resin. In a first step, the composites were characterized by small‐angle neutron scattering, which provide information about the bulk dispersion of nanotubes in the matrix and form three‐dimensional networks with a surface fractal behavior. In the second step, a dielectric and electrical study was carried out in the frequency range between 1 Hz and 10 MHz at room temperature. We have found that the electric and dielectric behavior of these composites can be described by Jonscher's universal dielectric response. We show that the critical exponents describing the concentration dependence of the conductivity and the dielectric constant, obtained in the vicinity of the percolation threshold, are in good agreement with the theoretical values. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44514.