Orientation of multiwalled carbon nanotubes in composites with polycarbonate by melt spinning

A conductive polycarbonate (PC) composite containing 2 wt% multiwalled carbon nanotubes (MWNT) and pure PC were melt spun using a piston type spinning device. Different take-up velocities up to 800 m/min and throughputs leading to draw down ratios up to 250 were used. The composite material of PC with MWNT was prepared by diluting a PC based masterbatch consisting of 15 wt% MWNT by melt mixing in an extruder. The alignment of the nanotubes within melt spun fibers with draw down ratios up to 126 was investigated by TEM and Raman spectroscopy. The nanotubes align in their length axis along the fiber axis increasingly with the draw down ratio, however, the curved shape of the nanotubes still exist in the melt spun fibers. At higher draw down ratios, the MWNT started to align by reducing their curvature. Polarized Raman spectroscopy indicated that the D/D and G/G ratios parallel/perpendicular to the fiber axis increase for both MWNT bands in a similar manner with the draw down ratio. Interestingly, with increasing alignment electrical conductivity of the fibers is lost. Mechanical investigations revealed that at low spinning speeds elongation at break and tensile strength of the composite are lower than those of the pure PC. However, at the highest take-up velocity of 800 m/min the elongation at break is higher and true stress at break of the composite fiber is comparable to the pure PC fiber.     

Location-selective incorporation of multiwalled carbon nanotubes in polycarbonate microspheres

In this study, we describe a process to produce polycarbonate (PC) microspheres and incorporate multiwalled carbon nanotubes (MWCNTs) within them location-selectively. The process, an oil-in-water (O/W) emulsion method, entails the formation of an aqueous phase with poly(vinylpyrrolidone) (PVP) and a methylene chloride phase that dissolves PC. Uniform PC microspheres were prepared by forming a stable emulsion using a homogenizer and a steric stabilizer, PVP. With this process, MWCNTs can be location-selectively incorporated in PC microspheres to afford the required properties such as electrical conductivity and thermal stability. When MWCNTs were dispersed in an aqueous phase using PVP, they were incorporated only on the surface of the PC microspheres. However, PC microspheres incorporating MWCNTs inside them were fabricated when the MWCNTs were dispersed in methylene chloride by functionalizing them via alkylation.     

Dielectric properties of epoxy composites with modified multiwalled carbon nanotubes

We report here a high dielectric percolative polymer nanocomposite, fabricated by a combination of triethylene-tetramine (TETA) modified multiwalled carbon nanotube (named as TETA-MWNT) within epoxy resin matrix. In this composite system, with various TETA-MWNT volume fractions, the dielectric constant (K) is well fitted by the scaling law of the percolation theory with the percolation threshold f _c is 0.042 and the critical exponent p is 0.786. At 1,000 Hz of room temperature, the value of the dielectric constant is as high as 421 with the TETA-MWNT content of 4.14vol%, which is almost 60 times higher than that of epoxy resin. In contrast, a simple blend of pristine MWNT in epoxy composite shows evident lower dielectric constant and much higher loss with the same volume fraction.     

Deformation processes of ultrahigh porous multiwalled carbon nanotubes/polycarbonate composite fibers prepared by electrospinning

Mechanical deformation processes of electrospun composite fibers based on polycarbonate with multiwalled carbon nanotubes (MWCNTs) were investigated by in situ tensile tests under transmission electron microscope (TEM) depending on morphology. Using chloroform as solvent and optimizing process conditions, uniform nanoporous composite fibers were generated by electrospinning process. TEM images indicate that the MWCNTs were embedded in the fibers as individual elements, highly aligned parallel to one another along the fiber axis, which makes the mechanical load transfer from the polymer matrix to the MWCNT more favorable. Due to the slippage of individual MWCNTs within the fibers the strain at break of composite fibers is significantly enhanced. In addition, the nanopores on the fiber surface provide the effective sites for stress concentration for the plastic deformation to form nanonecking of fibers under tensile load. Combination of these unique features makes the electrospun composite fibers extremely strong and tough. The results from present work may provide a feasible consideration of such electrospun composite fibers for use as the reinforcing elements in a polymer based composite of a new kind.     

Dielectric spectroscopy on melt processed polycarbonate—multiwalled carbon nanotube composites

Complex permittivity and related AC conductivity measurements in the frequency range between 10⁻⁴ and 10⁷ Hz are presented for composites of polycarbonate (PC) filled with different amounts of multiwalled carbon nanotubes (MWNT) varying in the range between 0.5 and 5 wt%. The composites were obtained by diluting a PC based masterbatch containing 15 wt% MWNT by melt mixing using a Micro Compounder. From DC conductivity measurements it was found that for samples processed at a mixing screw speed of 150 rpm for 5 min, the percolation occurs at a threshold concentration (p_c) between 1.0 and 1.5 wt% MWNT. For concentrations of MWNT near the percolation threshold, the processing conditions (screw speed and mixing time) were varied. The differences in the dispersion of the MWNT in the PC matrix could be detected in the complex permittivity and AC conductivity spectra, and have been explained by changes in p_c. The AC conductivity and permittivity spectra are discussed in terms of charge carrier diffusion on percolation clusters and resistor-capacitor composites.     

Dispersion, agglomeration, and network formation of multiwalled carbon nanotubes in polycarbonate melts

Three different industrially available multiwalled carbon nanotube (MWNT) materials were directly incorporated into polycarbonate by melt mixing using a small-scale compounder. Despite of similar aspect ratios the electrical percolation behaviour was different. TEM investigations reveal significant differences in the nanotube dispersion which can be attributed to different dispersability of the raw MWNT materials. It is shown that the investigation of the sedimentation behaviour of aqueous MWNT dispersions is a simple method to estimate the nanotube dispersability.The relationships between melt processing conditions and MWNT dispersion and distribution were studied on polycarbonate samples containing 0.875 wt% MWNT prepared by masterbatch dilution. During melt mixing only high shear forces can provide suitable MWNT dispersion because firstly the MWNT disentanglement is facilitated and secondly secondary agglomeration is prevented. At low shear agglomeration of formerly well dispersed MWNT could be observed. During hot pressing the network or MWNT arrangement and the resulting electrical conductivity can be manipulated by the processing conditions like melt temperature and pressing speed. A certain nanotube agglomeration can enhance the development of an electrical percolated network as shown by dielectric spectroscopy.     

Analysis of agglomerate dispersion mechanisms of multiwalled carbon nanotubes during melt mixing in polycarbonate

Dispersion of primary nanotube agglomerates in polymer melts is one of the difficult tasks when applying melt mixing for nanocomposite preparation. Hence, there is a need for a better understanding of the ongoing processes. Filler agglomerates generally undergo dispersion by rupture and erosion mechanisms, which usually occur simultaneously. To analyse these mechanisms and their corresponding dispersion kinetics 1 wt% multiwalled carbon nanotubes (MWNT) were incorporated into polycarbonate using a microcompounder. Different mixing speeds at constant melt temperature were applied thereby changing the applied stress. The states of MWNT agglomerate dispersion at different mixing times were assessed by quantifying the agglomerate area ratio and particle size distribution using image analysis of optical transmission micrographs. A model is proposed to estimate the fractions of rupture and erosion mechanisms during agglomerate dispersion. At low mixing speeds, the dispersion was found to be governed by both mechanisms, whereas rupture dominance increases with increasing mixing speed. Further, the relationship between electrical resistivity and dispersion was studied indicating a critical behaviour. A dependency on the amount of dispersed nanotubes was found only in a certain range of state of dispersion.     

Rheological and dielectrical characterization of melt mixed polycarbonate-multiwalled carbon nanotube composites

A series of composites of polycarbonate (PC) with 23 different contents of multiwalled carbon nanotubes (MWNT) was produced by melt mixing using the masterbatch dilution method. In dielectric measurements, AC conductivity and complex permittivity data obtained in the frequency range between 10⁻³ and 10⁷ Hz at room temperature indicated the electrical percolation threshold at about 1.0 wt%.

The dynamic mode melt rheological measurements for the same samples at eight temperatures between 170 and 280 °C showed a visible change in the frequency dependence of dynamic moduli and the absolute value of the complex viscosity |η*| particularly at low frequencies. In literature these changes are sometimes related to so called ‘percolation threshold concentration’. Applying this picture to our experimental data we have to assume that the percolation threshold is strongly dependent on the measurement temperature. It changes from about 5 to 0.5 wt% MWNT by increasing the measurement temperature from 170 to 280 °C, respectively. This temperature dependence cannot be explained by a classical liquid-solid transition but may be related to the existence of a combined nanotube-polymer network.     

Polyelectrolyte-functionalized multiwalled carbon nanotubes: preparation, characterization and layer-by-layer self-assembly

Two kinds of polyelectrolyte: polyacrylic acid (PAA) and poly(sodium 4-styrenesulfonate) (PSS), were grafted onto the convex surfaces of multiwalled carbon nanotubes (MWNTs) by surface-initiating ATRP (atom transfer radical polymerization) from the initiating sites previously anchored onto the convex surfaces of MWNTs. The grafted polyelectrolyte can be efficiently quantified by the feed ratio of monomer to MWNT-based macroinitiator, and the maximum amount of grafted polymer is higher than 55 wt%. The polyelectrolyte-coated MWNTs resembled core-shell structures justified by the TEM images of the samples obtained, which provided direct evidence for the covalent modification of MWNT. FTIR, ¹H NMR and TGA were used to determine the chemical structure of the resulting products. Comparison of UV-Vis spectra demonstrated that the products were water-soluble, and that PSS was more effective for improving the water solubility of carbon nanotubes. Using the polyelectrolyte- and carboxylic acid-functionalized MWNTs as templates, and poly(2-(N,N-dimethylaminoethyl) methacrylate (PDMAEMA)/hyperbranched polysulfone amine (HPSA) and PSS as polycation and polyanion, respectively, layer-by-layer (LbL) electrostatic self-assembly was conducted in order to explore the application of the functionalized nanotubes. It was found that the functionalized MWNTs have a high efficiency for loading polyelectrolytes by the LbL approach (the adsorbed polymer quantity is higher than 10 wt% in one assembling step). TEM observations showed that the assembled polymer shell on the MWNT surfaces was very even and flat.     

Cellulose acetate/multiwalled carbon nanotube nanocomposites with improved mechanical,thermal, and electrical properties

Cellulose acetate (CA)‐based nanocomposites with various contents of neat multiwalled carbon nanotube (MWCNT) or acid‐treated one (MWCNT‐COOH) are prepared via melt‐compounding method and investigated their morphology, thermal stability, mechanical, and electrical properties. SEM microphotographs reveal that MWCNT‐COOHs are dispersed uniformly in the CA matrix, compared with neat MWCNTs. FTIR spectra support that there exists a specific interaction between carboxyl groups of MWCNT‐COOHs and ester groups of CA, indicating good interfacial adhesion between MWCNT‐COOHs and CA matrix. Accordingly, thermal stability and dynamic mechanical properties of CA/MWCNT‐COOH nanocomposites were higher than those of CA/MWCNT composites. On the contrary, electrical volume resistivities of CA/MWCNT‐COOH nanocomposites are found to be somewhat higher than those of CA/MWCNT composites, which is because of the deterioration of graphene structures for MWCNT‐COOHs and the good dispersion of MWCNT‐COOHs in the CA matrix. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Multiwalled carbon nanotube/polybenzoxazine nanocomposites: Preparation, characterization and properties

A novel nanocomposite composed of polybenzoxazine (PBZ) and multiwalled carbon nanotubes (MWNT) was prepared successfully. The surface modification of MWNT, including nitric acid modification followed by toluene-2,4-diisocyanate (TDI) treatment, introduced hydroxyl, carboxyl, and isocyanate groups on the MWNT surface. The surface carboxyl groups catalyzed the ring-opening reaction of benzoxazine and thus decreased the curing temperature of the system. The isocyanate groups reacted with the phenolic hydroxyl groups generated by the ring opening of benzoxazine resulting in the significant improvement of the adhesion between PBZ and MWNT. Dynamic mechanical analyses indicated the increase of storage modulus as well as T_g by the addition of MWNT into PBZ. A well dispersed modified-MWNT on nanoscale level inside PBZ matrix was observed by TEM and SEM.     

Morphology and electrical resistivity of melt mixed blends of polyethylene and carbon nanotube filled polycarbonate

Blends were prepared from a high density polyethylene (PE) material and a conductive polycarbonate (PC) composite containing multiwalled carbon nanotubes (MWNT). The PC composite contained 2 wt% MWNT and was prepared by diluting a PC masterbatch consisting of 15 wt% MWNT by melt mixing in an extruder. The aim of blending a conductive PC composite with PE was to obtain a conductive blend at lower amounts of MWNT than required for the pure PC component. The blend morphology was found to be co-continuous over a broad composition range of 30–80 vol.% of the filled PC phase as verified by selective extraction of PC and morphological investigations. The co-continuous structure is very fine with ligaments in the range of 1 μm. Significantly reduced volume resistivity values, i.e. in the range of 10⁷ Ω cm, could be achieved in the same composition range of that of the continuous PC phase, i.e. starting at compositions of 30 vol.% filled PC. Here, the total MWNT content in the blend was only 0.41 vol.%. Interestingly, even if the MWNT had been incorporated in the PC phase, the tubes are still visible in the blends after selective extraction of PC. Scanning electron microscopy investigations revealed that the MWNT bridge the PC and PE phases, at least with their ends. This can be understood by the length dimensions of the tubes, which is higher than the phase sizes in the blends.     

Improved fracture toughness of immiscible polypropylene/ethylene-co-vinyl acetate blends with multiwalled carbon nanotubes

Functionalized multiwalled carbon nanotubes (f-MWCNTs) have been introduced into immiscible polypropylene/ethylene-co-vinyl acetate (PP/EVA) blends. Two different compositions, one (PP/EVA = 80/20) exhibits the typical sea-island morphology and the other (PP/EVA = 60/40) exhibits the cocontinuous morphology, have been prepared with different contents of f-MWCNTs. The impact measurement shows that f-MWCNTs induce the great improvement of fracture toughness of cocontinuous PP/EVA blends. The results based on the morphologies and the rheological properties of the composites suggest that, a local “single-network structure” of f-MWCNTs exists in PP/EVA (80/20) system whereas a “dual-network structure” of f-MWCNTs and EVA phase exists in PP/EVA (60/40) system, and the latter structure accounts for the largely improved fracture toughness of the composites.     

Morphology and properties of melt-spun polycarbonate fibers containing single- and multi-wall carbon nanotubes

Polycarbonate fibers based single wall and multi-wall nanotubes (SWNT and MWNT) were prepared by first dispersing the nanotubes via solvent blending and/or melt extrusion followed by melt spinning the composites to facilitate nanotube alignment along the fiber axis. Morphological studies involving polarized Raman spectroscopy and wide angle X-ray scattering using a synchrotron radiation source show that reasonable levels of nanotube alignment are achievable. Detailed transmission electron microscopy (TEM) investigations on the polymer-extracted composite fibers reveal that MWNT more readily disperse within the PC matrix and have higher aspect ratios than do SWNT; extraction of the polymer from the composite prior to TEM imaging helps overcome the common issue of poor atomic contrast between the CNT and the organic matrix. Stress-strain analysis on the composites fibers show that MWNT, in general, provide greater stiffness and strength than those based on SWNT. Despite significant reinforcement of the polycarbonate, the level of reinforcement is far below what could be achieved if the nanotubes were completely dispersed and aligned along the fiber axis as predicted by composite theory.     

Dynamic mechanical and morphological properties of polycarbonate/multi-walled carbon nanotube composites

Dynamic mechanical and morphological properties of the polycarbonate (PC)/multi-walled carbon nanotube (MWNT) composites were studied by dynamic mechanical thermal analysis (DMTA) and X-ray diffractometry, respectively. For the without annealed PC/MWNT composites containing the higher content of the MWNT (≥7.0 wt%), double tan δ peaks were observed, which could be explained by the phase separation morphology model. For the annealed PC/MWNT composites, a broad single tan δ peak was observed. From the X-ray diffraction of the annealed PC/MWNT composites, it was observed that more regular structure of the PC was obtained, which was consistent with the result of the thermal analysis of the annealed PC/MWNT composites. From the dynamic mechanical properties, thermal analysis, and X-ray diffraction of the annealed PC/MWNT composites, it is suggested that PC/MWNT composites show a broad single tan δ peak and partially crystalline structure of the PC in the PC/MWNT composites by annealing.     

Synthesis and properties of new polyamide/multiwalled carbon nanotube nanocomposites containing a pyridine group

The effects of multiwalled carbon nanotubes (MWCNTs) on the thermal properties and flame retardancy of a new polyamide (PA) derived from glutaric acid and aromatic diamine were investigated in this work. The synthesized PA containing pyridine and trialkylamine groups was characterized by ¹H NMR and SEC. The PA unit structure was geometrically optimized at the B₃LYP/6‐311⁺⁺G(d, p) level of theory. PA showed a glass transition temperature of 151 ºC. PA nanocomposites containing two different amounts of MWCNTs were prepared via the solution intercalation technique with the solvent N,N‐dimethylacetamide. Transmission electron microscopy showed that MWCNTs were exfoliated in the polymer matrix, resulting in well‐dispersed morphologies at 3 wt% MWCNT content. The redox behaviors of PA and the nanocomposites were examined using cyclic voltammetry (CV). PA showed a reversible oxidation process in the CV scan. Thermal and flammability properties of the nanocomposites were studied by TGA in nitrogen and air, DSC and with a microscale combustion calorimeter. The TGA results showed that the addition of MWCNTs resulted in a substantial increase in the thermal stability and char yields of the nanocomposites compared with neat PA. The heat release rate and total heat release were significantly reduced in the presence of MWCNTs. © 2013 Society of Chemical Industry     

Flammability properties of polymer nanocomposites with single-walled carbon nanotubes: effects of nanotube dispersion and concentration

The effects of the dispersion and concentration of single walled carbon nanotube (SWNT) on the flammability of polymer/SWNT nanocomposites were investigated. The polymer matrix was poly (methyl methacrylate) (PMMA) and the SWNT were dispersed using a phase separation (‘coagulation’) method. Dispersion of SWNTs in these nanocomposites was characterized by optical microscopy on a micrometer scale. Flammability properties were measured with a cone calorimeter in air and a gasification device in a nitrogen atmosphere. In the case where the nanotubes were relatively well-dispersed, a nanotube containing network structured layer was formed without any major cracks or openings during the burning tests and covered the entire sample surface of the nanocomposite. However, nanocomposites having a poor nanotube dispersion or a low concentration of the nanotubes (0.2% by mass or less) formed numerous black discrete islands with vigorous bubbling occurring between these islands. Importantly, the peak heat release rate of the nanocomposite that formed the network layer is about a half of those, which formed the discrete islands. It is proposed that the formation of the discrete islands is due to localized accumulation of the nanotubes as a result of fluid convection accompanying bubble formation and rise of the bubbles to the surface through the molten sample layer and bursting of the bubbles at the surface. The network layer acts as a heat shield to slow the thermal degradation of PMMA.     

Fabrication of hybrid nanocomposites with polystyrene and multiwalled carbon nanotubes with well-defined polystyrene via multiple atom transfer radical polymerization

The PS-grafted multiwalled carbon nanotubes (MWNTs) were produced by the bromo-ended PS (PS-Br) and pristine MWNTs in 1,2-dichlorobenzene at 110 °C for 72 h via atom transfer radical polymerization (ATRP). Bromo-ended PS (PS-Br) used as an initiator for the functionalization of MWNTs was synthesized with styrene by ATRP conditions using CuBr and N,N,N′,N′,N″-pentamethyldiethylenetriamine as catalyst. The PS-grafted MWNTs were fully characterized by ¹H-NMR, FT-IR, DSC, TGA, and SEM. The PS-grafted MWNTs were found to be highly soluble in a variety of organic solvents. The PS was chemically attached to the surfaces of MWNTs via ATRP approach, and the grafting amount of PS was 40–90%. From TGA and DSC measurements, the PS-grafted MWNTs were decomposed at lower temperature compared to that of PS-Br, and the functionalization of MWNTs increased the glass-transition temperature (T_g) of the grafted PS. The PS/PS-grafted MWNTs nanocomposites were prepared with PS and PS-grafted MWNTs by solution mixing in dimethylformamide (DMF). The resulting nanocomposites were found to be the homogeneous dispersion of PS-grafted MWNTs in PS matrix via aromatic (π–π) interactions between PS and PS-grafted MWNTs as determined by SEM and TEM.     

Fabrication and characterization of homogeneous composites of polypropylene and multiwalled carbon nanotubes

The polypropylene‐grafted multiwalled carbon nanotubes (PP‐MWCNTs) were produced from the reaction of PP containing the hydroxyl groups and MWCNTs having 2‐bromoisobutyryl groups. The PP‐MWCNTs had a significantly rougher surface than the original MWCNTs. PP‐MWCNTs had PP layers of thickness 10–15 nm on the outer walls of the MWCNTs. PP/PP‐MWCNT composites and PP/MWCNT composites were prepared by solution mixing in o‐xylene. Unlike PP/MWCNT composites, PP‐MWCNTs were homogeneously dispersed in the PP matrix. As a consequence, the thermal stability and conductivity of PP/PP‐MWCNT composites were dramatically improved even if only 1 wt % of PP‐MWNTs was added to the PP matrix. The good miscibility of PP and PP‐MWCNTs plays a critical role in the formation of the homogeneous composites and leads the high thermal stability and conductivity. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012