PEDOT‐PSS/singlewall carbon nanotubes composites

Poly(3,4‐ethylenedioxythiophene)‐single wall carbon nanotube (SWNT) composites were prepared via coating methods for improving electrical conductivity and flexibility, minimizing loss of transparency. Three types of surface modified SWNTs were prepared through different modification methods: carboxylated SWNT treated with nitric acid to form carboxylic acid group on their surfaces, 1‐pyrenebutyric acid wrapped SWNT, and 1‐pyrenebutyric acid, lithium salt wrapped SWNT. The surface modifiers had influence on the dispersion states of the SWNTs in 2‐propanol. The dispersion states had influence of aggregate concentrations of surface modified SWNTs in polymer matrix, showing lower aggregate concentration for the carboxylated SWNT than those of the other surface modified SWNTs. The dispersion behaviors of SWNTs were also related with transparency and electrical resistance, and flexibility of composite films. Based on the layer‐by‐layer coating method, SWNT composite film properties such as thickness, transparency, and electrical conductivity could be controlled and would be a good example for improving contradictory properties. POLYM. ENG. SCI., 48:1–10, 2008. © 2007 Society of Plastics Engineers     

New carbon nanotube–conducting polymer composite electrodes for drug delivery applications

A novel drug delivery system (DDS) based on a carbon nanotube (CNT)–poly(3,4‐ethylenedioxythiophene) (PEDOT) composite was constructed via a layering method. Single‐walled CNTs (SWNTs) were immobilized on a gold electrode using a layer‐by‐layer technique. In particular, cysteamine (Cys) was firstly bonded to the gold surface through the strong S? Au association and SWNTs were subsequently linked onto the Cys layer through condensation reaction of ? NH₂ and carboxyl groups by 1‐ethyl‐3‐(3‐dimethylaminopropyl)carbodiimide/N‐hydroxysuccinimide coupling. X‐ray photoelectron spectroscopy and Raman spectroscopy demonstrate that this is a facile route for immobilizing CNTs on gold electrodes. Finally PEDOT was electropolymerized on the SWNT‐functionalized electrode to make a SWNT–PEDOT composite, and the modified electrode was applied as a DDS. Dexamethasone, as a model drug, was incorporated into PEDOT in the electropolymerization. Investigations of the electrochemical properties of SWNT–PEDOT demonstrate that SWNTs greatly improve the conductivity and increase the charge capacity of PEDOT. The composite exhibits a petal‐like surface structure, 20–30 nm thick and 100–200 nm wide. Compared to a DDS based on pure PEDOT synthesized under the same conditions, SWNT–PEDOT has the merits of higher drug release rate and larger release amount. The average mass release for every five voltammetry cycles increases from 1.4126 to 1.8864 mg cm^?2. Copyright © 2011 Society of Chemical Industry     

Interfacial modification of single‐walled carbon nanotubes for high‐loading‐reinforced polypropylene composites

In this article, we present a strategy for fabricating polypropylene (PP)/polypropylene‐regrafted single‐walled carbon nanotube (PP‐re‐g‐SWNT) composites with a high loading of single‐walled carbon nanotubes (SWNTs; 20 wt %). The PP‐re‐g‐SWNTs were characterized by X‐ray photoelectron, Fourier transform infrared spectroscopy, transmission electron microscopy, and thermogravimetric analysis (TGA). The PP‐re‐g‐SWNTs showed excellent interfacial adhesion and dispersion. Furthermore, PP molecules, about 72 wt % by mass, were homogeneously bonded onto the surface of the SWNTs according to TGA. In this hybrid nanocomposite system, the PP‐re‐g‐SWNTs were covalently integrated into the PP matrix and became part of the conjugated network structure (as evidenced by differential scanning calorimetry and dynamic mechanical analysis) rather than just a separate component. Accordingly, the PP/PP‐re‐g‐SWNT composites presented obvious improvements in mechanical properties and conductivity (from 10^?10 to 10^?2). Most importantly, the tensile and flexural strength of the PP/PP‐re‐g‐SWNT composites did not exhibit an obvious downturn with the addition of 20 wt % SWNTs; this was contrary to documented results. We believe that these new observations were due to the novel structure of the PP‐re‐g‐SWNTs. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39817.     

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     

Fabrication of surfactant‐removed polymer composites with single‐walled carbon nanotube networks

Polystyrene (PS) composites with a network of single‐walled carbon nanotubes (SWNTs) were fabricated by using monodispersed PS micospheres. First, PS spheres and surfactant‐dispersed SWNTs were mixed in water, then a hybrid cake was obtained by filtration via a microporous membrane and the SWNTs were filled within the spaces of packed polymer spheres. At this stage, the surfactants for dispersing SWNTs were totally removed from the composites by a thorough washing. Then the composite films with SWNT networks were obtained by compression molding at 160°C. Structure of the composites had been characterized by transmission electron microscopy and scanning electron microscopy. The present SWNT composites showed a low percolation threshold of electrical conductivities. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of polyethylene‐graft‐maleic anhydride as a compatibilizer on the mechanical and tribological behaviors of ultrahigh‐molecular‐weight polyethylene/copper composites

Ultrahigh‐molecular‐weight polyethylene/copper (UHMWPE/Cu) composites compatibilized with polyethylene‐graft‐maleic anhydride (PE‐g‐MAH) were prepared by compression molding. The effects of the compatibilizer on the mechanical, thermal, and tribological properties of the UHMWPE/Cu composites were investigated. These properties of the composites were evaluated at various compositions, and worn steel surfaces and composite surfaces were examined with scanning electron microscopy and X‐ray photoelectron spectroscopy. The incorporation of PE‐g‐MAH reduced the melting points of the composites and increased their crystallinity to some extent. Moreover, the inclusion of the PE‐g‐MAH compatibilizer greatly increased the tensile rupture strength and tensile modulus of the composites, and this improved the wear resistance of the composites. These improvements in the mechanical and tribological behavior of the ultrahigh‐molecular‐weight‐polyethylene‐matrix composites with the PE‐g‐MAH compatibilizer could be closely related to the enhanced crosslinking function of the composites in the presence of the compatibilizer. Moreover, the compatibilizer had an effect on the transfer and oxidation behavior of the filler Cu particulates, which could be critical to the application of metallic‐particulate‐filled polymer composites in engineering. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 948–955, 2004     

Investigation of molecular interaction between single‐walled carbon nanotubes and conjugated polymers

Single‐walled carbon nanotubes (SWNTs) have unique properties such as high electrical conductivity and high tensile strength. Their composites with polymers have a great role in new sciences such as organic solar cells and ultrastrong lightweight materials. In this article, molecular dynamic simulations with polymer consistent force field are performed to study the interaction between SWNTs and conjugated polymers including poly(2‐methoxy‐5‐(3‐7‐dimethyloctyloxy)‐1,4‐phenylenevinylene) (MDMO‐PPV), poly(3‐hexythiophene) (P3HT), and poly[(9,9′‐dioctylfluorenyl‐2,7‐diyl)‐co‐bis(N,N′‐(4,butylphenyl))bis(N,N′‐phenyl‐1,4‐phenylene)diamine] (PFB). We computed the interaction energy and morphology of polymers adsorbed to the surface of SWNTs was studied by the radius of gyration (Rg). The influence of important factors such as SWNT radius, chirality, and the temperature on the interfacial adhesion of SWNT–polymer and Rg of polymers were studied. We found that the strongest interaction between the SWNTs and these polymers was, first observed for P3HT, then MDMO‐PPV, and finally PFB. Our results showed that the interaction energy is influenced by SWNT radius and the specific monomer structure of the polymers, but the effects of chirality and temperature are very weak. In addition, we found that the temperature, chirality, and radius have not any important effect on the radius of gyration. POLYM. COMPOS.,, 2012. © 2012 Society of Plastics Engineers     

Synthesis and properties of water soluble single‐walled carbon nanotube graft ionic polyacetylene nanocomposites

Water‐soluble single‐walled carbon nanotube‐polyacetylene [SWNT‐PA, SWNT‐P(2EPy‐MeTf)] nanocomposites have been synthesized by using the surface initiated “grafting‐from” method. The FT‐IR spectra confirmed the formation of an amide bond between the functionalized SWNTs and the initiator, 4‐(2‐Aminoethyl) pyridine, to polymerize N‐Methyl‐2‐ethynlypyridinium triflate (2EPy‐MeTf). UV‐vis spectroscopy indicated that the degree of polymerization of P(2EPy‐MeTf) in the SWNT‐polyacetylene composites is 15, based on the Lewis‐Calvin equation. The SWNT‐polyacetylene composites have been characterized by TGA, AFM, and TEM. From TGA analysis, the loading of SWNTs in the SWNT grafted ionic polyacetylenes is estimated to be 22%. AFM and TEM images clearly showed that the nanotube is wrapped with the PA. The SWNT‐polyacetylene composites displayed high water solubility (8 mg/ml). The room temperature electrical conductivity of the doped SWNT‐polyacetylene composites was found to be in the range of 10⁻³ to 10⁻⁴ S/cm, an order of magnitude of increase over neat P(2EPy‐MeTf) and a two order of magnitude increase over Dendrimer‐polyacetylen composites. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Carbon nanotube core–polymer shell nanofibers

Single‐walled carbon nanotube (SWNT)/poly(methyl methacrylate) and SWNT/polyacrylonitrile composite nanofibers were electrospun with SWNT bundles as the cores and the polymers as the shells. This was a novel approach for processing core (carbon nanotube)–shell (polymer) nanofibers. Raman spectroscopy results show strain‐induced intensity variations in the SWNT radial breathing mode and an upshift in the tangential (G) and overtone of the disorder (G′) bands, suggesting compressive forces on the SWNTs in the electrospun composite fibers. Such fibers may find applications as conducting nanowires and as atomic force microscopy tips. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1992–1995, 2005     

Starch‐filled ternary polymer composites. II: Room temperature tensile properties

The room temperature tensile properties of granular starch‐filled low‐density polyethylene (PE) and starch‐filled blends of PE and poly(hydroxy ester ether) (PHEE) are presented. At low filler contents (?_f), the filled PE:PHEE blend has a higher yield stress and tensile strength than either the starch/PE composites or the unfilled matrix. The increase in the yield stress indicates that matrix yielding occurs before debonding. At high filler contents, the tensile strength of the filled blend is again greater than the strength of the starch/PE composites. This increase in strength is the result of higher debonding stresses in the ternary composite. In both materials there is a change in the deformation process at a critical filler content, ?_cr. Below ?_cr, deformation involves the growth of debonded regions; above ?_cr, deformation is confined to narrow damaged zones. There is a reduction in the strain at failure when this change in the deformation process occurs. Although the PHEE surface coating affects the debonding stress and the tensile strength, it does not affect the strain at failure or the tensile modulus. For both composite materials, the increase in modulus with ?_f can be adequately described using a simplified form of the Kerner equation. Polym. Eng. Sci. 44:1839–1847, 2004. © 2004 Society of Plastics Engineers.     

Preparation and characterization of polyethylene–clay nanocomposites by using chlorosilane‐modified clay

Clay was modified by trimethylchlorosilane; after modification, hydroxyl groups at the edge of layers were reacted and CEC value was drastically decreased. Polyethylene–clay composites were prepared by melt compounding. Wide angle X‐ray diffraction (WAXD) and transmission electron microscopy (TEM) showed that intercalated nanocomposites were formed using organoclay ion‐exchanged from chlorosilane‐modified clay, but conventional composites formed using organoclay directly ion‐exchanged from crude clay. Dynamic mechanical analysis (DMA) of PE and PE–clay composites was conducted; the results demonstrated that nanocomposites were more effective than conventional composites in reinforcement and addition of organoclay resulted in the increase of glass transition temperature (T_g), but crude clay had no effect on T_g of PE–clay composites. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 676–680, 2004     

The effect of matrix composition on the properties of cellulosic fibers–polyethylene composites

The solution/precipitation method was used for the preparation of polyethylene (PE)/cellulosic fibers composites. Blends of modified linear low density PE [linear low density PE‐grafted maleic anhydride (LLDPE‐g‐MAH)] with low density PE (LDPE) were used as matrices for the aforementioned composites. Blends of LDPE with a copolymer of LDPE and acrylic acid (AA)/n‐butyl acrylate (n‐BA) [(AA/n‐BA)–LDPE] were also studied for the same purpose. The reinforcing effect of cellulosic fibers in terms of tensile strength is more enhanced when mixtures of the modified polar polymer with pure PE were used as matrices, as compared with that corresponding to matrices consisting of modified PE alone. Regarding the Izod impact strength, composites of LLDPE‐g‐MAH presented the best performance with an improvement of 135% in comparison with specimens consisting of LDPE matrix, whereas composites of (AA/n‐BA)‐LDPE matrix showed a modest improvement of their impact resistance. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Single‐walled carbon nanotube/poly(methyl methacrylate) composites for electromagnetic interference shielding

Single‐walled carbon nanotube (SWNT)/poly(methyl methacrylate) (PMMA) composites were prepared using coagulation method. The electrical conductivity and the electromagnetic interference (EMI) shielding of SWNT/PMMA composites over the X‐band (8–12 GHz) and the microwave (200–2000 MHz) frequency range have been investigated. The electrical conductivity of composites increases with SWNT loading by 13 orders of magnitude, from 10^?15 to 10^?2 Ω^?1 cm^?1 with a percolation threshold of about 3 wt% SWNTs. The effect of the sample thickness on the shielding effectiveness has been studied, and correlated to the electrical conductivity of composites. The data suggest that SWNT/PMMA composites containing higher SWNT loading (above 10 wt%) be useful for EMI shielding and those with lower SWNT loading be useful for electrostatic charge dissipation. The dominant shielding mechanism of SWNT/PMMA composites was also discussed. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Preparation and properties of the single‐walled carbon nanotube/cellulose nanocomposites using N‐methylmorpholine‐N‐oxide monohydrate

Single‐walled carbon nanotube (SWNT)/cellulose nanocomposite films were prepared using N‐methylmorpholine‐N‐oxide (NMMO) monohydrate as a dispersing agent for the acid‐treated SWNTs (A‐SWNTs) as well as a cellulose solvent. The A‐SWNTs were dispersed in both NMMO monohydrate and the nanocomposite film (as confirmed by scanning electron microscopy) because of the strong hydrogen bonds of the A‐SWNTs with NMMO and cellulose. The mechanical properties, thermal properties, and electric conductivity of the nanocomposite films were improved by adding a small amount of the A‐SWNTs to the cellulose. For example, by adding 1 wt % of the A‐SWNTs to the cellulose, tensile strain at break point, Young's modulus, and toughness increased ～ 5.4, ～ 2.2, and ～ 6 times, respectively, the degradation temperature increased to 9°C as compared with those of the pure cellulose film, and the electric conductivities at ? (the wt % of A‐SWNTs in the composite) = 1 and 9 were 4.97 × 10^?4 and 3.74 × 10^?2 S/cm, respectively. Thus, the A‐SWNT/cellulose nanocomposites are a promising material and can be used for many applications, such as toughened Lyocell fibers, transparent electrodes, and soforth. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Oxidative stabilization of PAN/SWNT composite fiber

PAN/SWNT composite fibers have been spun with 0, 5, and 10 wt% single wall carbon nanotubes (SWNTs). Tensile fracture surfaces of polyacrylonitrile (PAN) fibers exhibited extensive fibrillation, while for PAN/SWNT composite fibers, tendency to fibrillate decreased with increasing SWNT content. The reinforcing effect of SWNTs on the oxidized polyacrylonitrile (PAN) fiber has been studied. At 10 wt% SWNTs, breaking strength, modulus, and strain to failure of the oxidized composite fiber increased by 100%, 160%, and 115%, respectively. Tensile fracture surfaces of thermally stabilized PAN and the PAN/SWNT fibers exhibited brittle behavior and well distributed SWNT ropes covered with the oxidized matrix can be observed in the tensile fracture surfaces of the fibers. No de-bonding has been observed between unoxidized or the oxidized PAN matrix and the nanotube ropes. Higher strain to failure of the oxidized composite fiber as compared to that of the oxidized control PAN fiber also suggests good adhesion/interaction between SWNT and the oxidized matrix. Thermal stresses generated on the composite fiber during the oxidation process were lower than those for the control fiber. The potential of PAN/SWNT composite fiber as the precursor material for the carbon fiber has been discussed.     

Processing and properties of carbon nanotube/poly(methyl methacrylate) composite films

A systematic study of the reinforcement of single‐walled carbon nanotubes (SWNTs), multiwalled carbon nanotubes, and vapor‐grown carbon nanofibers (VGCNFs) in poly(methyl methacrylate) (PMMA) is reported. SWNT/PMMA composite films with various SWNT concentrations (from 0.5 to 50 wt % with respect to the weight of PMMA) were processed from nitromethane. Two types of SWNTs were used: SWNT‐A, which contained 35 wt % metal catalyst, and SWNT‐B, which contained about 2.4 wt % metal catalyst. Properties of different nanotubes containing composites were compared with 15 wt % carbon nanotubes (CNTs). Property enhancement included electrical conductivity, mechanical properties, and solvent resistance. The thermal degradation of PMMA in the presence of CNTs in air and nitrogen environments was studied. No variation in the thermal degradation behavior of PMMA/CNT was observed in nitrogen. The peak degradation temperature increased for the composites in air at low CNT loadings. Dynamic and thermomechanical properties were also studied. At a 35 wt % SWNT loading, a composite film exhibited good mechanical and electrical properties, good chemical resistance, and a very low coefficient of thermal expansion. Property improvements were rationalized in terms of the nanotube surface area. Composite films were also characterized with Raman spectroscopy. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Synthesis and tensile properties of a novel composite of Chlorella and polyethylene

A novel composite of the green microalga Chlorella sp. with polyethylene (PE) was synthesized through chemical modification of PE with maleic anhydride (MA), with respect to the biological fixation of CO₂ with Chlorella sp. The interaction of Chlorella grains with a PE matrix is strikingly enhanced by the chemical modification of PE with MA. The tensile strength of a Chlorella–MA‐modified PE composite (Ch–MPE) with a Chlorella content of 40 wt % is more than 2 times greater than that of a composite derived from unmodified PE. The marked increase in tensile strength is attributed to the formation of chemical bonds between Chlorella grains and the PE matrix, from IR and SEM studies. Because of the satisfactory thermal plasticity of Ch–MPE, it can be easily shaped into plate and dishlike moldings by a heat‐pressurizing method. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 812–816, 2004     

Improvement of interfacial adhesion of poly(m‐phenylene isophthalamide) short fiber–thermoplastic elastomer (SEBS) composites by N‐alkylation on fiber surface

A composite of short‐fiber, poly(m‐phenylene isophthalamide), and thermoplastic elastomer styrene (ethylene–butylene) styrene (SEBS), was investigated. The fiber surface was modified by N‐alkylation (heptylation and dodecylation) to improve their compatibility with a less polar SEBS matrix. Observation of fiber‐surface morphology by SEM revealed surface roughness after N‐alkylation. Nearly complete coating of the polymer matrix on the fiber was observed on a fractured surface of the composite, which is evidence for the improvement of fiber–matrix adhesion. It was found that the modulus of the composites grew with increasing fiber loading to approximately the same extent for both unmodified and modified fiber composites. Tensile strength of the modified fiber composites was found to improve significantly over that of the unmodified fiber composite. This suggests that the presence of the alkyl group on the fiber surface is responsible for an improvement of interfacial adhesion. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2414–2422, 1999     

Influence of initial mixing methods on melt‐extruded single‐walled carbon nanotube–polypropylene nanocomposites

We report the first direct comparison of melt‐extruded polypropylene–single‐walled carbon nanotube (PP/SWNT) nanocomposites prepared by three different initial mixing methods. The standard deviation of the G‐band intensity obtained using Raman mapping was found to be the best measure of dispersion uniformity in the extruded composites, and dispersion uniformity was found to generally correlate with rheological and thermal properties. For all three initial mixing methods, both unmodified and sidewall‐functionalized purified SWNTs were evaluated. Surprisingly, in all cases, dodecylated SWNTs prepared using the reductive alkylation method were less uniformly dispersed in the final composite than the unmodified SWNTs. The simplest process, dry blending, resulted in poor nanotube dispersion and only polymer crystallization was significantly affected by the presence of the nanotubes. A slightly more complex rotary evaporation process resulted in significantly more uniform dispersion and significant changes in rheological properties, polymer crystallization, and thermal stability. The most elaborate process tested, hot coagulation, enabled the most uniform dispersion and the greatest change in properties but also resulted in some polymer degradation. POLYM. ENG. SCI., 50:1831–1842, 2010. © 2010 Society of Plastics Engineers