Electrical, mechanical, and glass transition behavior of polycarbonate-based nanocomposites with different multi-walled carbon nanotubes

Five commercially available multi-walled carbon nanotubes (MWNTs), with different characteristics, were melt mixed with polycarbonate (PC) in a twin-screw micro compounder to obtain nanocomposites containing 0.25-3.0 wt.% MWNT. The electrical properties of the composites were assessed using bulk electrical conductivity measurements, the mechanical properties of the composites were evaluated using tensile tests and dynamic mechanical analysis (DMA), and the thermal properties of the composites were investigated using differential scanning calorimetry (DSC). Electrical percolation thresholds (p_cs) were observed between 0.28 wt.% and 0.60 wt.%, which are comparable with other well-dispersed melt mixed materials. Based on measurements of diameter and length distributions of unprocessed tubes it was found that nanotubes with high aspect ratios exhibited lower p_cs, although one sample did show higher p_c than expected (based on aspect ratio) which was attributed to poorer dispersion achieved during mixing. The stress-strain behavior of the composites is only slightly altered with CNT addition; however, the strain at break is decreased even at low loadings. DMA tests suggest the formation of a combined polymer-CNT continuous network evidenced by measurable storage moduli at temperatures above the glass transition temperature (T_g), consistent with a mild reinforcement effect. The composites showed lower glass transition temperatures than that of pure PC. Lowering of the height of the tanδ peak from DMA and reductions in the heat capacity change at the glass transition from DSC indicate that MWNTs reduced the amount of polymer material that participates in the glass transition of the composites, consistent with immobilization of polymer at the nanotube interface.     

Effect of processing techniques on the performance of Epoxy/MWCNT nanocomposites

The aim of this study is to investigate the optimum technique to disperse Multi‐Walled Carbon Nanotubes (MWCNTs) in SC‐1 epoxy uniformly and to evaluate the effect of processing technique on the performance of SC‐1 epoxy. To achieve better dispersion, MWCNT was mixed with SC‐1 resin directly or premixed with a solvent and then mixed with SC‐1 resin after evaporating the solvent using sonication, thinky mixing and three‐roll mill methods either in isolation or combination. Flexural tests were performed to evaluate mechanical performances and results exhibit up to 27.13, 13.51, and 21.99% improvement on flexural strength, flexural modulus, and maximum strain, respectively, over neat epoxy with only 0.2 wt % loading. Dynamic mechanical analysis (DMA), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) indicated improvement in storage modulus, T_g, inflection temperature, and residue content, respectively over neat SC‐1 epoxy. Thermal and mechanical properties at higher loading conditions were seen to either reduce or not significantly improve. This was attributed to high viscosity of nanocomposites as determined by rheological analysis which prevents good dispersion of MWNCTs into epoxy system at 0.4 wt % loading. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Functionalization of MWCNT with P(MMA-co-S) copolymers via ATRP: Influence on localization of MWCNT in SAN/PPE 40/60 blends and on rheological and dielectric properties of the composites

In this work, the localization of functionalized multi-walled carbon nanotubes (MWCNT) with random copolymers of methyl methacrylate and styrene (P(MMA-co-S)) in poly(styrene-co-acrylonitrile)/poly(2, 6-dimethyl-1,4-phenylene ether) blends (SAN/PPE) and its influence on morphological, rheological and dielectric properties of the composites were investigated. P(MMA-co-S) copolymers were grafted onto MWCNT via atom transfer radical polymerization (ATRP). The molecular weight of the copolymers was adjusted by controlling the time of reaction. In SAN/PPE blends, MWCNT grafted with low molecular weight copolymers were predominantly located at the interface of the blend and a few individual tubes were dispersed in the PPE phase. Aggregation of MWCNT was observed nearby the interfacial region because of micellization of grafted copolymers. Aggregation was more pronounced with increasing molecular weight of the grafted P(MMA-co-S) copolymer. In the melt, the composite containing MWCNT with low molecular weight copolymers had higher dynamic moduli than the one with pristine MWCNT. An increasing molecular weight of grafted copolymer led to a softening effect which resulted in a reduction of the moduli of the composite. Although a pronounced enhancement was observed for the composites with pristine MWCNT, only a small increase in electrical conductivity was achieved by adding functionalized MWCNT owing to the poor network formed by functionalized MWCNT in the blends.     

Effect of carbon nanotubes functionalization on properties of their nanocomposites with polycarbonate/poly(acrylonitrile-butadiene-styrene) matrix

In this work, a comparative study evaluating the influence of different functionalization of carbon nanotubes on the properties of nanocomposites with polymeric matrix was performed. A 50/50 wt% polycarbonate (PC)/poly(acrylonitrile-butadiene-styrene) (ABS) blend was used as polymeric matrix of the nanocomposites. The comparison was made between nanocomposites reinforced with covalently functionalized multiwall carbon nanotubes (MWCNTf) and MWCNTf/nanoclay hybrid functionalization. The effect on the mechanical and morphological properties of the nanocomposites was evaluated through tensile and Izod impact tests and scanning electron microscopy and transmission electron microscopy (TEM) analyses. The thermal characterization of PC/ABS blends and nanocomposites was performed by differential scanning calorimetry (DSC). Results showed that both methods of functionalization of MWCNTs increased the stiffness and impact resistance of the nanocomposites. TEM micrographs indicated the preferred location of the reinforcements in the SAN phase of ABS. Results from DSC indicated an increase in the thermal resistance of the nanocomposites.     

Mechanical and electrical properties of electrospun PVDF/MWCNT ultrafine fibers using rotating collector

Poly(vinylidene fluoride) (PVDF) ultrafine fibers with different proportions of multi-walled carbon nanotube (MWCNT) embedded have been fabricated using a modified electrospinning device with a rotating collector. With the increasing of MWCNT content, the β phase was noticeable enhanced, and the fibers became more elastic, which was manifested by Young''s modulus decreased drastically. Furthermore, with adding the amounts of MWCNTs, the density of carbon nanotube (CNT)-CNT junctions among the fibers increased accordingly. When the MWCNT content was of 1.2 wt.%, a stable three-dimensional conducting network was formed. After this percolation threshold, the density of CNT-CNT junctions among the fibers tended to be a constant quantity, leading to a stabilized conductivity consequently. It is hoped that our results can be helpful for the fabrication of flexible devices, piezoelectric devices, force transducer, and so on.

PACS

81.05.Qk; 81.16.-c     

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.     

Electrical conductivity modeling of carbon black/polycarbonate,carbon nanotube/polycarbonate,and exfoliated graphite nanoplatelet/polycarbonate composites

Adding conductive carbon fillers to electrically insulating thermoplastic polymers increases the resulting composite's electrical conductivity, which would enable them to be used in electrostatic dissipative and semiconductive applications. In this study, varying amounts of carbon black (CB: 2 to 10 wt %), multiwalled carbon nanotubes (CNT: 0.5 to 8 wt %), or exfoliated graphite nanoplatelets (GNP: 2 to 15 wt %) were added to polycarbonate (PC) and the resulting composites were tested for electrical conductivity (EC = 1/electrical resistivity). The percolation threshold was ～ 1.2 vol % CNT, ～ 2.4 vol % CB, and ～ 4.6 vol % GNP. In addition, three EC models (Mamunya, additive, and general effective media) were developed for the CB/PC, CNT/PC, and GNP/PC composites. The general effective media (GEM) model showed the best agreement with the experimental results over the entire range of filler concentrations (above and below the percolation threshold) for all three composite systems. In addition, the GEM model can be easily adapted for composites containing combinations of different conductive fillers. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of silane structure on the properties of silanized multiwalled carbon nanotube-epoxy nanocomposites

Multiwalled carbon nanotubes (MWCNTs) were functionalized with aminosilanes via an aqueous deposition route. The size and morphology of siloxane oligomers grafted to the MWCNTs was tuned by varying the silane functionality and concentration and their effect on the properties of a filled epoxy system was investigated. The siloxane structure was found to profoundly affect the thermo-mechanical behavior of composites reinforced with the silanized MWCNTs. Well-defined siloxane brushes increased the epoxy T_g by up to 19 °C and significantly altered the network relaxation dynamics, while irregular, siloxane networks grafted to the MWCNTs had little effect. The addition of both types of silanized MWCNTs elicited improvements in the strength of the nanocomposites, but only the well-defined siloxane brushes engendered dramatic improvements in toughness. Because the silanization reaction is simple, rapid, and performed under aqueous conditions, it is also an industrially attractive functionalization route.     

Preparation and properties of biodegradable PBS/multi-walled carbon nanotube nanocomposites

In this study, poly(butylene succinate)/multi-walled carbon nanotube (PBS/MWNT) hybrids were prepared by a melt-blending process. The carbon nanotubes (CNTs) were successfully modified using N,N′-dicyclohexylcarbodiimide (DCC) dehydrating agents. As a result, excellent dispersion of the modified carbon nanotubes (CNT-C18) in organic solvents was achieved. Subsequently, the PBS/CNT nanocomposites were prepared through facile melt blending. Mechanical properties, thermal behavior, conductivity of these resultant polymer/CNT composites were investigated. The results obtained show that the PBS/CNT-C18 nanocomposites consisting of well-dispersed nanotubes exhibited enhanced thermal and mechanical properties. With the addition of 3 wt% CNT-C18, T_d of the nanocomposite increased 12.3 °C as compared to that of the pristine PBS sample. Moreover, the increments of E′ and E″ of the nanocomposite at 25 °C were 120 and 55%, respectively. In the aspect of conductivity, the surface resistivity of the PBS/CNT-C18 composite was found to be 7.30 × 10⁶ Ω, which is a decrease of 10⁹ fold in value as compared to that of the pristine PBS sample. Such PBS/CNT-C18 sample exhibits high anti-static efficiency, which would be potentially useful in electronic packaging materials.     

二乙烯三胺改性碳纳米管对环氧树脂纳米复合材料力学性能影响研究

采用二乙烯三胺(DETA)对碳纳米管(MWNTs)进行改性,并用X射线衍射(XRD)和傅里叶变换红外光谱(FTIR)对其进行表征。发现DETA被有效地包覆在MWNTs表面。并将改性前后的MWNTs与环氧树脂进行复合,采用浇铸成型法制备了MWNTs/环氧树脂纳米复合材料,测试其力学性能,并采用透射电镜(TEM)研究其分散性,扫描电镜(SEM)对其断口进行了分析研究。结果表明,少量的改性MWNTs可以使复合材料的力学性能提高,具有明显的增韧作用。当MWNTs的含量为0.6%时,纳米复合材料的冲击强度与纯环氧体系相比,提高幅度达400%以上,弯曲强度和弯曲模量的提高幅度均达到了100%以上。     

Preparation and properties of cyclic olefin copolymers multiwalled carbon nanotube nanocomposites

Nanocomposites of cyclic olefin copolymer (COC) and two types of multiwalled carbon nanotubes (MWCNTs) with different aspect ratios were prepared. The morphology, thermal behavior, and electrical conductivity of the nanocomposites were investigated by scanning electron microscopy, differential scanning calorimetry, thermal gravimetric analysis, and the DC conductivity measurement. It was found that the developed nanocomposite preparation method resulted in good nanotubes dispersion in the polymer matrix for both types of MWCNTs. No appreciable differences in glass transition temperatures were observed between the pure COC and nanocomposites. On the other hand, CNTs significantly improved the thermo‐oxidative stability of the COC. The nanocomposites showed significant delay in onset of degradation and the degradation temperature was ～ 40°C higher than that of the pure COC. The nanocomposites also showed substantially higher DC conductivity, which increased with the nanotube concentration and aspect ratio. An increase of DC electrical conductivity over 10⁹ times can be achieved by the addition of 2 wt % CNTs. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Study on the preparation and characterization of biodegradable polylactide/multi-walled carbon nanotubes nanocomposites

In this study, polylactide/multi-walled carbon nanotubes (PLA/MWNTs) hybrids were prepared by means of a melt blending method. To enhance the compatibility between PLA and MWNTs, the acrylic acid grafted polylactide (PLA-g-AA) and the multihydroxyl-functionalized MWNTs (MWNTs-OH) were used to replace PLA and MWNTs, respectively. The crude MWNTs were chemically oxidized by a mixture of H₂SO₄ and HNO₃ and then reacted with thionyl chloride to functionalize them with chlorocarbonyl groups (MWNTs-COCl). The MWNTs-OH was finally obtained by the reaction of MWNTs-COCl and 1,6-hexanediol. The resulting products have been characterized by FTIR, ¹³C solid-state NMR, TGA, DMA, SEM, TEM, and Instron mechanical tester. Due to the formation of ester groups through the reaction between carboxylic acid groups of PLA-g-AA and hydroxyl groups of MWNTs-OH, results demonstrated dramatic enhancement in thermal and mechanical properties of PLA, for example, 77 °C increase in initial decomposition temperature with the addition of only 1 wt%. Based on the result of thermal and mechanical examinations, it was found that the optimal amount of MWNTs-OH was 1 wt% because excess MWNTs-OH caused separation of the organic and inorganic phases and lowered their compatibility.     

Preparation and thermal properties of multiwalled carbon nanotube/polybenzoxazine nanocomposites

In this study, we prepared nanocomposites comprising multiwalled carbon nanotubes (MWCNTs) and polybenzoxazine (PBZ). The MWCNTs were purified through microwave digestion to remove most of the amorphous carbon and metal impurities. After purification, MWCNTs were treated with H₂SO₄/HNO₃ (3 : 1) to introduce hydroxyl and carboxyl groups onto their surfaces. Raman spectroscopy revealed the percentage of nanotube content improved after prolonged microwave treatment, as evidenced by the decrease in the ratio of the D (1328 cm^?1) and G (1583 cm^?1) bands. For the untreated MWCNTs, the I_D/I_G ratio was 0.56. After microwave treatment for 40 min, the value decreased to 0.29, indicating that the percentage of nanotube content improved. Dynamic mechanical analyses (DMAs) revealed that the storage moduli and the T_gs of the MWCNTs/PBZ nanocomposites were higher than that of the pristine PBZ. This is due to the nanometer‐scale MWCNTs restricting the motion of the macromolecular chains in the nanocomposites. Transmission electron microscopy (TEM) image revealed that the MWCNTs were well dispersed within the PBZ matrix on the nanoscale when the MWCNT content was less than 2.0 phr. The coefficient of thermal expansion (CTE) of the nanocomposites decreased on increasing the MWCNTs content. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Mechanical properties and rheological behavior of poly(butylene terephthalate)/clay nanocomposites with different organoclays

Poly(butylene terephthalate)–clay nanocomposites with three different organically modified clays were prepared via melt blending in a twin‐screw extruder. Decyl triphenylphosphonium bromide, hexadecyl triphenylphosphonium bromide, and cetyl pyridinium chloride were used to modify the naturally occurring montmorillonite clay. The organically modified clays were characterized with X‐ray diffraction for the d₀₀₁‐spacing and with thermogravimetric analysis to determine the thermal stability. The prepared nanocomposites were injection‐molded and examined for the dispersion quality of the clay, the mechanical properties, and the rheological behavior. The tensile strength of the nanocomposites increased with a 1% addition of clay; however, more clay decreased the tensile strength. Nanocomposites with finely dispersed clay platelets and nanocomposites with poorly dispersed clay platelets showed very different rheological behaviors. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preparation,structure and properties of thermoplastic olefin nanocomposites containing functionalized carbon nanotubes

The morphology and properties of multiwalled carbon nanotube modified polypropylene (PP)/ethylene–octene copolymer blends were studied. Polypropylene chains are covalently grafted onto the surface of carbon nanotubes (CNTs) in order to improve their interaction with the polymer matrix. It is observed that functionalization of CNTs improves their dispersion and increases the interfacial bonding between CNTs and polymer matrix. The functionalized CNTs are selectively distributed in the continuous polypropylene phase. The size of the dispersed elastomer phase decreases after the addition of CNTs. Functionalized CNTs act as a nucleating agent and increase the crystallinity of the polypropylene. More importantly, an important increase in impact strength, stiffness and toughness can be achieved through introducing functionalized CNTs. Copyright © 2011 Society of Chemical Industry     

Effects of functionalized MWNTs with GMA on the properties of PMMA nanocomposites

The acid modification of multiwall carbon nanotubes (MWNTs) was performed by an HNO₃/H₂SO₄ solution. The glycidyl methacrylate (GMA) undergoing an opening‐ring was grafted onto the surface of acid‐modified MWNTs. The surface properties of MWNTs were investigated by Fourier transform infrared spectrometer (FTIR), Raman spectra, transmission electron microscopy (TEM), X‐ray diffraction, and thermogravimeric analysis. Then the MWNTs/ poly(methyl methacrylate) (PMMA) nanocomposites were prepared by in situ polymerization. The tribological and dielectric properties of nanocomposites were studied. As a result, GMA was grafted on the surface of MWNTs. The tribological and dielectric properties of MWNTs/ PMMA nanocomposites were improved as the content of the surface‐modified MWNT increased. The marked improvement in tribological and dielectric properties were attributed to the good dispersion of MWNTs that were bonded with C?C on the surface that participated in the polymerization of MMA. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Effect of annealing treatment on the structure and properties of polyurethane/multiwalled carbon nanotube nanocomposites

The thermoplastic polyurethane/multiwalled carbon nanotube (TPU/CNT) nanocomposites with high conductivity and low percolation threshold value were prepared by melting blending and annealing treatment. The effect of annealing process on the microphase structure and the properties of TPU/CNT nanocomposites was studied. It has been shown that CNT flocculation can occur in TPU/CNT nanocomposites during the annealing process. At a critical CNT content, which defined the percolation threshold, CNTs could form conductivity network. The conductive percolation threshold value of TPU/CNT nanocomposites was decreased from 10 to 4% after annealing process, and the conductivity of TPU/CNT nanocomposites with 10 vol % of CNT could reach 1.1 S/m after an annealing time of 1 h. The significant enhancement of electrical conductivity was influenced by the annealing time and the content of CNTs. The formation of CNT networks was also verified by dynamic viscoelastic characterization. The results of X‐ray diffraction and differential scanning calorimetry indicated that annealing process reinforced the microphase separation of the nanocomposites. Mechanical properties test showed that the annealing treatment was in favor of improving the mechanical properties; however, further increase in the annealing time has negative effect on the mechanical properties. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation and thermoelectric properties of MoS2/Bi2Te3 nanocomposites

MoS₂ nanosheets with size of several-hundred nanometers were prepared by a hydrothermal intercalation/exfoliation method, then MoS₂/Bi₂Te₃ composite nanopowders were prepared by a microwave-assisted wet chemical method using the MoS₂ nanosheets, TeO₂, Bi(NO₃)₃·5H₂O, KOH and ethylene glycol as raw materials. Bulk MoS₂/Bi₂Te₃ nanocomposites were prepared by hot pressing the MoS₂/Bi₂Te₃ composite nanopowders with MoS₂ nanosheet content ranging from 0 to 17 wt% at 80 MPa and 648 K in vacuum. X-ray photoelectron spectroscopy and X-ray diffraction analyses indicate that MoS₂ and Bi₂Te₃ did not react each other during the hot pressing. FESEM observation reveals that the MoS₂/Bi₂Te₃ composite samples had a more compact microstructure than the pristine Bi₂Te₃ bulk sample. The MoS₂ phase was relatively randomly dispersed in the composite. At a given temperature, the electrical conductivity of the composites increases first then decreases as the MoS₂ content increases, whereas the Seebeck coefficient of the bulk nanocomposites does not change much. A highest power factor, ~18.3 μW cm⁻¹ K⁻² which is about 30% higher than that of pristine Bi₂Te₃ sample, at 319 K has been achieved from a nanocomposite sample containing 6 wt% MoS₂.     

Preparation and characterization of alkylated carbon nanotube/polyimide nanocomposites

BACKGROUND: The development of carbon nanotube‐reinforced composites has been impeded by the difficult dispersion of the nanotubes in polymers and the weak interaction between the nanofiller and matrices. Efficient dispersion of carbon nanotubes is essential for the formation of a functional nanotube network in a composite matrix. RESULTS: Multiwalled carbon nanotubes (MWNTs) were incorporated into a polyimide matrix to produce MWNT/polyimide nanocomposites. To disperse well the MWNTs in the matrix and thus improve the interfacial adhesion between the nanotubes and the polymer, ‘branches’ were grafted onto the surface of the nanotubes by reacting octadecyl isocyanate with carboxylated MWNTs. The functionalized MWNTs were suspended in a precursor solution, and the dispersion was cast, followed by drying and imidization to obtain MWNT/polyimide nanocomposites. CONCLUSION: The functionalized MWNTs appear as a homogeneous dispersion in the polymer matrix. The thermal stability and the mechanical properties are greatly improved, which is attributed to the strong interactions between the functionalized MWNTs and the polyimide matrix. Copyright © 2009 Society of Chemical Industry     

Copolyester nanocomposites based on carbon nanotubes: reinforcement effect of carbon nanotubes on viscoelastic and dielectric properties of nanocomposites

Nanocomposites based on an amorphous copolyester, poly(ethylene glycol‐co‐cyclohexane‐1,4‐dimethanol terephthalate) and carbon nanotubes were fabricated using a simple melt processing technique. The reinforcement effect of carbon nanotubes in the copolyester was investigated experimentally using different approaches based on dynamic mechanical analysis, rheology and dielectric analysis. The nanocomposites show a mechanical reinforcement effect with significant increase in the stiffness especially in the rubbery regime with increasing nanotube content. An increase in T_g and a decrease in damping are seen, which are derived from the presence of a percolating superstructure of the filler. Rheological experiments show an increase in storage modulus up to four orders of magnitude. Viscolelastic characterization shows that the percolation threshold is at 3 wt% of nanotubes. Dielectric relaxation spectroscopy confirms the presence of this percolating structure. We conclude that the responses of both rheological and electrical properties are different, although both are related to the formation of a percolating network superstructure of the filler. Copyright © 2007 Society of Chemical Industry