Poly(ethylene succinate)/single-walled carbon nanotube composites: a study on crystallization

An investigation on the crystallization of composites based on poly(ethylene succinate) and unmodified single-walled carbon nanotube was made in this report. Both isothermal and non-isothermal modes were studied along with subsequent melting behavior using differential scanning calorimetry. Crystal morphology was then explored using X-ray scattering and infrared spectroscopy. It was observed during isothermal crystallization that carbon nanotube (CNT) could contribute to the crystallization rate through heterogeneous nucleation. Furthermore, nanotubes enhanced the crystallinity within low and high undercooling rather than medium undercooling. Similar findings were obtained in non-isothermal crystallization mode. At lower cooling rates, the crystallization rate was more strongly influenced by the nanotubes, while at higher cooling rates the crystallinity was affected to the greater extent. The onset of the cold crystallization of polymer remained unaffected in presence of the nanotube, while its extent was reduced. X-ray diffraction together with infrared spectroscopy found that the polymer crystalline morphology was of α type, and no transition from α to β occurred in presence of the CNT.     

Enhancement of interfacial adhesion and dynamic mechanical properties of poly(methyl methacrylate)/multiwalled carbon nanotube composites with amine-terminated poly(ethylene oxide)

We have studied the dynamic mechanical behavior of poly(methyl methacrylate) (PMMA)/acidified multiwalled carbon nanotube (MWNT) composites compatibilized with amine-terminated poly(ethylene oxide) (PEO-NH₂). PEO-NH₂ is ionically associated with acidified MWNTs via ionic interaction as shown by XPS and FTIR. The miscibility between PEO and PMMA improves the interfacial adhesion between polymer matrix and MWNTs, leading to an increase in the storage modulus values of the composites. The effects of PEO-NH₂ on storage modulus and glass transition temperature are discussed.     

Rheological and thermal properties of poly(ethylene oxide)/multiwall carbon nanotube composites

Poly(ethylene oxide) (PEO) based nanocomposites were prepared by the dispersion of multiwall carbon nanotubes (MWCNTs) in aqueous solution. MWCNTs were added up to 4 wt % of the PEO matrix. The dynamic viscoelastic behavior of the PEO/MWCNT nanocomposites was assessed with a strain‐controlled parallel‐plate rheometer. Prominent increases in the shear viscosity and storage modulus of the nanocomposites were found with increasing MWCNT content. Dynamic and isothermal differential scanning calorimetry studies indicated a significant decrease in the crystallization temperature as a result of the incorporation of MWCNTs; these composites can find applications as crystallizable switching components for shape‐memory polymer systems with adjustable switching temperatures. The solid‐state, direct‐current conductivity was also enhanced by the incorporation of MWCNTs. The dispersion level of the MWCNTs was investigated with scanning electron microscopy. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Rheological property and curing behavior of poly(amide-co-imide)/multi-walled carbon nanotube composites

Poly(amide-co-imide) (PAI)/multi-walled carbon nanotube (MWCNTs) composites were prepared by using solution mixing with ultrasonication excitation in order to investigate effects of MWCNTs on rheological properties and thermal curing behavior. Steady shear viscosity of the composite showed bell shaped curves with three characteristic patterns: shear thickening, shear thinning, and Newtonian plateau behavior. Both storage modulus and complex viscosity were increased due to higher molecular interaction than that of the pure PAI resin. Especially, hydrogen peroxide treated MWCNT/PAI composites had the highest storage modulus and complex viscosity. Glass transition temperature of the PAI/MWCNT composite was increased with increasing MWCNT content and thermal curing time since the mobility of PAI molecules was reduced as more constraints were generated in PAI molecular chains. It was found that thermal curing conditions of PAI/MWCNT composites are determined by considering effects of weight fraction and surface modification of MWCNTs on internal structure and thermal properties.     

Electrical conductivity of poly(vinylidene fluoride)/carbon nanotube composites with a spherical substructure

Poly(vinylidene fluoride) (PVDF)/multiwalled carbon nanotube (MWCNT) conducting composites were prepared with a percolation threshold as low as 0.07 wt%. The MWCNTs in a PVDF solution can lead to the formation of spherical PVDF/MWCNT composite particles by sonication. The MWCNTs coated on the surfaces of the spherical particles form a conduction network when the spheres coalesce to form a solid composite. The existence of the spherical particles with a substructure results in the reduction in MWCNT content and improves the electrical conductivity of the composites.     

Rheology and properties of melt-processed poly(ether ether ketone)/multi-wall carbon nanotube composites

Poly(ether ether ketone) (PEEK)/multi-wall carbon nanotube (MWNT) composites containing up to 17 wt% filler were prepared using a twin screw extruder. Transmission electron microscopy (TEM) images reveal that the MWNTs were homogeneously dispersed in the PEEK matrix. Linear viscoelastic measurements show that both complex viscosity and moduli increase with increasing MWNT concentration. The storage modulus, G^′ exhibits a dramatic seven order increase in magnitude around 1 wt%, leading to a solid-like low-frequency behaviour at higher loadings; the effect can be attributed to network formation at a rheological percolation threshold. Rheotens measurements show that the melt strength also increases significantly on addition of nanotubes, however, the drawability decreases. An analytical Wagner model was used to calculate the apparent elongational viscosity over a wide range of elongational rates, and to reveal significant increases on addition of MWNTs, with a similar threshold behaviour. The electrical response is also dominated by percolation effects, increasing by nearly 10 orders of magnitude from 10⁻¹¹ to 10⁻¹ S/cm, on the addition of only 2 wt% MWNTs. In contrast, the thermal conductivity and tensile elastic modulus of the composites increased linearly with nanotube content, rising by 130% and 50%, at 17 wt% MWNTs, respectively.     

Cleaning organized single-walled carbon nanotube interconnect structures for reduced interfacial contact resistance

A method is presented for significantly reducing the interfacial contact resistance of single-walled carbon nanotube (SWCNT) interconnects test-structures. Conventional lithographic cleaning steps are insufficient for complete removal of lithographic residues in SWCNT networks, leading to large interfacial contact resistance. Using improved purification procedures and controlled developing time, the interfacial contact resistance between SWCNTs and contact electrodes of Ti/Au were found to reach values below 2% of the overall resistance in two-probe test-structures of SWCNTs, demonstrating the importance of cleaning lithographic residues from the surface of SWCNTs before the fabrication of metal electrodes. These low-resistance contacts are quite stable over a large temperature range, and represent a step towards the implementation of SWCNTs as future interconnects.     

Nano- and microstructural effects on thermal properties of poly (l-lactide)/multi-wall carbon nanotube composites

In this work the thermal properties of poly (l-lactide)/multi-wall carbon nanotube (PLLA/MWCNT) composites have been investigated. Thermal conductivity was determined after measuring specific heat capacity (C_p), thermal diffusivity (D) and bulk density (ρ) of composites. Thermal conductivity rises up to 0.345 W/m K at 5 wt.% after reaching a minimum value of about 0.12 W/m K at 0.75 wt.%. In order to understand the heat-conduction process, experimentally obtained thermal conductivities were fitted to an existing theoretical model. The much lower thermal conductivity of composites compared with the value estimated from the intrinsic thermal conductivity of the nanotubes and their volume fraction could be explained in terms of the obtained large thermal resistance (R_k) of 1.8 ± 0.3 × 10^?8 m² K/W at nanotube–matrix interface. The CNT dispersion in the composites was analyzed by atomic force microscopy (AFM) and transmission electron microscopy (TEM). Although the thermal resistance dramatically reduces the estimated bulk thermal conductivity of composites, the existence of an interconnected conductive nanotube network for thermal diffusion in PLLA/MWCNT composites demonstrates that the addition of carbon nanotubes represents an efficient strategy in order to successfully enhance the thermal conductivity of insulator polymers.     

Characterization and electrical conductivity of poly(ethylene glycol)/polyacrylonitrile/multiwalled carbon nanotube composites

Poly(Lactic acid) (PLA)‐layered silicate nanocomposite films were prepared by solvent casting method. The films were irradiated with Co⁶⁰ radiation facility at dose of 30 kGy. The effect of γ irradiation on mechanical properties of the neat PLA and nanocomposites was evaluated by data obtained from tensile testing measurements. The tensile strength of the irradiated PLA films increased with addition of 1 wt % triallyl cyanurate indicating crosslink formation. Significant ductile behavior was observed in the PLA nanocomposites containing 4 pph of nanoclay. Incorporation of nanoclay particles in the PLA matrix stimulated crystal growth as it was studied by differential scanning calorimetry. The morphology of the nanocomposites characterized by transmission electron microscopy and X‐ray diffraction revealed an exfoliated morphology in the PLA nanocomposite films containing 4 pph of nanoclay. Only very small changes were observed in the chemical structure of the irradiated samples as it was investigated by Fourier transform infrared spectroscopy. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Multi-walled carbon nanotubes covalently attached with poly(3-hexylthiophene) for enhancement of field-effect mobility of poly(3-hexylthiophene)/multi-walled carbon nanotube composites

For the purpose of enhancing the field-effect mobility of poly(3-hexylthiophene) (P3HT), multi-walled carbon nanotubes (MWCNTs) were functionalized by attaching covalently P3HT onto the MWCNT surface to yield P3HT-grafted MWCNTs (g-MWCNTs). When a small amount of g-MWCNTs was added to P3HT, the field-effect mobility of the composite was considerably increased as compared to either P3HT or the composites of P3HT and carboxylated MWCNTs (c-MWCNTs). This is because g-MWCNTs are better dispersed than c-MWCNTs in P3HT matrix and consequently g-MWCNTs act more effectively as conducting bridges connecting the crystallites of P3HT.     

Electrochemical capacitance of well-coated single-walled carbon nanotube with polyaniline composites

Well-coated single-walled carbon nanotube (SWNT) with polyaniline (PANI) composite electrodes with good uniformity for electrochemical capacitors are prepared by the polymerization of aniline containing well-dissolved SWNTs. The capacitance properties are investigated with cyclic voltammetry, charge-discharge tests and ac impedance spectroscopy. The composite electrode shows much higher specific capacitance, better power characteristics and is more promising for application in capacitor than pure PANI electrode. The effect and role of SWNT in the composite electrode are also discussed in detail.     

The effect of temperature on fatigue strength of poly(ether-imide)/multiwalled carbon nanotube/carbon fibers composites for aeronautical application

This work concerns the fatigue behavior at three different temperature conditions (−40, 20, and 80°C) and the addition of multiwalled carbon nanotube (MWCNT) into a carbon-fiber reinforced poly(ether-imide) composite. The incorporation of MWCNT into the composite increased the tensile strength and Young's modulus by up 5 and 2%, respectively. At low temperature, the incorporation of the nanoparticles improved the fatigue strength of the laminates by 15%. The shear strength results obtained by interlaminar shear strength and compression shear test tests have shown an increase of about 16 and 58%, respectively, by the introduction of nanotubes into the laminates. Fractographic observations revealed that the surface of carbon nanotube laminate (PEI/MWCNT/CF) presented a ductile behavior, and differences in the fracture aspects of the material compared to the traditional PEI/CF laminate have been observed.     

Electrical properties of poly(phenylene sulfide)/multiwalled carbon nanotube composites prepared by simple mixing and compression

Poly(phenylene sulfide) (PPS)/multiwalled carbon nanotubes (MWNTs) conductive composites were prepared through the simple mixing of PPS granules with MWNT powder and subsequent compression. The electrical properties as a function of MWNT loading clearly showed a low percolation threshold of about 0.22 vol % and a high critical exponent value of 3.55 for composites prepared by this method. A comparison study with composites prepared via melt mixing was also carried out, where a random dispersion of MWNTs was achieved. There existed a striplike morphology of MWNTs in the PPS matrix and MWNTs were selectively located in strips caused by compression. The effects of temperature and pressure on the conductivity of the PPS/MWNT composites as prepared via simple mixing and compression are discussed. In addition, the conductivity also showed a dependence on the flow direction of the compression, with higher conductivity in the direction parallel to the flow direction than in the direction perpendicular to the flow direction. So the relationship of the processing and morphological properties was investigated in detail. The possible conductive mechanisms of conventional melt blending and preparation via sample mixing and compression are also discussed. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and properties of poly(methyl methacrylate)/carbon nanotube composites covalently integrated through in situ radical polymerization

Poly(methyl methacrylate) (PMMA)/single‐walled carbon nanotube (SWNT) composites were synthesized by the grafting of PMMA onto the sidewalls of SWNTs via in situ radical polymerization. The free‐radical initiators were covalently attached to the SWNTs by a well‐known esterification method and confirmed by means of thermogravimetric analysis and Fourier transform infrared spectroscopy. Scanning electron microscopy and transmission electron microscopy were used to image the PMMA–SWNT composites; these images showed the presence of polymer layers on the surfaces of debundled, individual nanotubes. The PMMA–SWNT composites exhibited better solubility in chloroform than the solution‐blended composite materials. On the other hand, compared to the neat PMMA, the PMMA–SWNT nanocomposites displayed a glass‐transition temperature up to 6.0°C higher and a maximum thermal decomposition temperature up to 56.6°C higher. The unique properties of the nanocomposites resulted from the strong interactions between the SWNTs and the PMMA chains. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Synthesis and characterization of poly(3‐octylthiophene)/single wall carbon nanotube composites for photovoltaic applications

In situ polymerization of P3OT with SWCNT is carried out in the presence of a FeCl₃ oxidant in a chloroform medium. The characterization of the composites is performed with FTIR, Raman, ¹H‐NMR, UV–Vis, PL spectroscopy, XRD, SEM, TEM, and conductivity measurements. The change (if any) in CC symmetric and antisymmetric stretching frequencies in FTIR, the shift in G band frequencies in Raman, any alterations in λ_max of UV–Vis and PL spectroscopic measurements are monitored with SWCNT loading in the polymer matrix. ¹H‐NMR confirms the wrapping of the polymer on to the SWCNT indicating lack of mobility. The work function values and the optical band gap values also support this view. The in situ polymerization procedure of the donor polymer molecules and the acceptor carbon nanotubes has resulted in enhanced dispersibility and stability of the composites in organic solvents. However, the principal focus of the study is to understand the interaction between the polymer and the SWCNTs, as the interface plays an important role in its application in the photovoltaic cells. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Poly(ethylene terephthalate)/carbon nanotube composites prepared with chemically treated carbon nanotubes

Surfaces of multiwalled carbon nanotubes (CNT) were functionalized by treatment with strong acid mixture (purification) followed by modification with sodium dodecyl sulfate, poly(ethylene glycol) (PEG), and diglycidyl ether of Bisphenol A (DGEBA). Poly(ethylene terephthalate) (PET)‐based conductive polymer composites were prepared by using these CNT by means of melt mixing with a twin screw extruder. Amount of carboxylic acid groups on the CNT surface increased after acid treatment but decreased with surface modification due to the consumption of these groups during the chemical reactions between the surface modifiers and CNT surface. Fourier transformed infrared spectroscopy (FTIR) and nuclear magnetic resonance analyses of the composites revealed the increase in the interactions between PET and CNT surface after treatment with PEG and DGEBA. Mechanical strength of the composites prepared with modified CNT were higher than that of the untreated CNT‐filled composite owing to the enhanced interactions between PET and CNT. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

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.     

Polybenzoxazine/single-walled carbon nanotube nanocomposites stabilized through noncovalent bonding interactions

In this study we prepared a new class of pyrene-functionalized benzoxazines (Py-BZ) through reactions of phenol, paraformaldehyde, and pyren-1-amine (Py-NH₂) in toluene and EtOH. We prepared Py-NH₂ through catalytic reduction of 1-nitropyrene (Py-NO₂), which we had synthesized through electrophilic aromatic substitution of pyrene, using HNO₃ as the nitration agent. ¹H and ¹³C nuclear magnetic resonance spectroscopy and Fourier transform infrared (FTIR) spectroscopy confirmed the chemical structure of this new monomer; differential scanning calorimetry (DSC) and FTIR spectroscopy revealed the curing behavior of the Py-BZ polymers. The presence of the pyrene-functionalized benzoxazine enhanced the solubility of single-walled carbon nanotubes (SWCNTs) in THF, leading to the formation of highly dispersible Py-BZ/SWCNT organic/inorganic hybrid complex materials. Fluorescence emission spectroscopy revealed significant π–π stacking interactions between the Py-BZ and the SWCNTs in these complexes. In addition, differential scanning calorimetry, thermogravimetric analysis, and dynamic mechanical analysis revealed that incorporating the SWCNTs into the Py-BZ matrix significantly enhanced the thermal stability of the polymer after thermal curing.