Effect of multiwall carbon nanotubes on thermomechanical and electrical properties of poly(trimethylene terephthalate)

Multiwalled carbon nanotubes (MWCNTs) were synthesized using chemical vapor deposition and poly(trimethylene terephthalate) (PTT)/MWCNT composites with varying amounts of MWCNTs were prepared by melt compounding using DSM micro‐compounder. Morphological characterization by SEM and TEM showed uniform dispersion of MWCNTs in PTT matrix upto 2% (w/w) MWCNT loading. Incorporation of MWCNTs showed no effect on percent crystallinity but affected the crystallite dimensions and increased the crystallization temperature. Dynamic mechanical characterization of composites showed an increase in storage modulus of PTT upon incorporation of MWCNTs above glass transition temperature. The electrical conductivity of PTT/MWCNT composites increased upon incorporation of MWCNTs and percolation threshold concentration was obtained at a loading of MWCNTs in the range of 1–1.5% (w/w). © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

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

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

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     

Property reinforcement of acrylonitrile‐butadiene‐styrene by simultaneous incorporation of carbon nanotubes and self‐prepared copper particles

In this article, copper (Cu) crystallites were successfully prepared via low temperature molten salt method, and the possible formation mechanisms were proposed. The conductive fillers of multiwalled carbon nanotubes (MWCNTs) and as‐prepared Cu particles were designed and introduced into acrylonitrile‐butadiene‐styrene (ABS) blend to prepare different conductive composites. The dispersion states of conductive fillers and the morphologies of the composites were characterized using a field emission scanning electron microscope. The electrical resistivity of different composites was measured. The results showed that Cu and MWCNTs exhibited a synergistic effect in decreasing the electrical resistivity of the Cu/MWCNTs/ABS composites, because Cu that could locate between MWCNTs chain segments provides a better charge transport in the conductive pathways. Compared with pure ABS, the tensile strength, elastic modulus and thermal stability of the Cu/MWCNTs/ABS composites were significantly improved with the incorporation of Cu and MWCNTs. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41738.     

Study on interfacial properties of unidirectional flax/vinyl ester composites: Resin manipulation on vinyl ester system

Flax fibers are widely used as reinforcements in bio‐based polymer matrix composites. This study investigated the hydrophilic nature and surface purity of flax fiber that affects fiber/matrix adhesion in combination with hydrophobic structural polymers via matrix modification and the utilization of fiber treatment, specifically in a flax/vinyl ester (VE) composite. A new method to manipulate the vinyl ester system with acrylic resin (AR) was developed to produce flax reinforced. On the other hand, different types of chemical and physical treatments were applied on the flax fiber. FTIR was applied to evaluate the effects of surface treatments. Dynamic mechanical analysis (DMA) was used to analyze the unmodified and modified VE resin system. The surface of untreated and treated flax fibers and their composites were analyzed by scanning electronic microscopy (SEM). Sodium ethoxide‐treated flax/VE with 1% (wt) AR caused the best mechanical performance among all the flax/VE composites evaluated. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Synthesis and characterization of multiwalled carbon nanotube/polyurethane composites via surface modification multiwalled carbon nanotubes using silane coupling agent

Well‐dispersed multiwalled carbon nanotubes/polyurethane (MWCNTs/PU) composites were synthesized in situ polymerization based on treating MWCNTs with nitric acid and silane coupling agent. The morphology and degree of dispersion of the MWCNTs were studied using a high resolution transmission electron microscopy (HR‐TEM) and X‐ray powder diffraction (XRD). The result showed that MWCNTs could be dispersed still in the PU matrix well with the addition of 2 wt% MWCNTs. The thermal and mechanical properties of the composites were characterized by dynamic mechanical thermal analysis, thermogravimetric analysis, tensile, and impact testing. The result suggested that the glass transition temperature (T_g) of composites increased greatly with increasing MWCNTs content slightly, and the MWCNTs is also helpful to improve mechanical properties of composites. Furthermore, the composites have an excellent mechanical property with the addition of 0.5 wt% MWCNTs. The electrical property testing indicates that the MWCNTs can improve evidently the electrical properties of composites when adding 1 wt% MWCNTs to the PU matrix. The volume resistivity of composites reaches to an equilibrium value. POLYM. COMPOS., 33:1866–1873, 2012. © 2012 Society of Plastics Engineers     

Preparation and properties of MWCNTs/poly(acrylonitrile‐ styrene‐butadiene)/epoxy hybrid composites

Poly(acrylonitrile‐styrene‐butadiene) (ABS) was used to modify diglycidyl ether of bisphenol‐A (DGEBA) type epoxy resin, and the modified epoxy resin was used as the matrix for making multiwaled carbon tubes (MWCNTs) reinforced composites and were cured with diamino diphenyl sulfone (DDS) for better mechanical and thermal properties. The samples were characterized by using infrared spectroscopy, pressure volume temperature analyzer (PVT), thermogravimetric analyzer (TGA), dynamic mechanical analyzer (DMA), thermo mechanical analyzer (TMA), universal testing machine (UTM), and scanning electron microscopy (SEM). Infrared spectroscopy was employed to follow the curing progress in epoxy blend and hybrid composites by determining the decrease of the band intensity due to the epoxide groups. Thermal and dimensional stability was not much affected by the addition of MWCNTs. The hybrid composite induces a significant increase in both impact strength (45%) and fracture toughness (56%) of the epoxy matrix. Field emission scanning electron micrographs (FESEM) of fractured surfaces were examined to understand the toughening mechanism. FESEM micrographs reveal a synergetic effect of both ABS and MWCNTs on the toughness of brittle epoxy matrix. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Novel method of dispersion of multiwalled carbon nanotubes in a flexible epoxy matrix

We describe a simple and novel method for dispersing multiwalled carbon nanotubes (MWCNTs) in a flexible epoxy matrix. The MWCNTs were modified with half‐neutralized dicarboxylic acids having different numbers of carbon atoms. The modified MWCNTs were prereacted with epoxy in the presence of triphenylphosphine. The dispersion of the MWCNTs and the enhancement in the tensile properties were found to be better for composites prepared with a solvent. Among the half‐neutralized dicarboxylic acids used, half‐neutralized adipic acid (HNAA) exhibited the best performance. Scanning electron microscopy and transmission electron microscopy studies clearly indicated an improvement in the level of dispersion of the MWCNTs with the addition of the modifier. The good dispersion of the MWCNTs and the resulting improvement in their properties were attributed to the cation–π interactions (the cation of HNAA and the π‐electron clouds of the MWCNTs) between the HNAA and MWCNTs and the chemical bonding of ? COOH groups of HNAA and the epoxy resin. The cation–π interaction and chemical bonding was assessed with Fourier transform infrared spectroscopy and Raman spectroscopy. This approach did not destroy the π–electron clouds of the MWCNTs in contrast to a chemical functionalization strategy. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2610–2618, 2013     

Improvement in properties of multiwalled carbon nanotube/polypropylene nanocomposites through homogeneous dispersion with the aid of surfactants

The effects of different surfactants on the properties of multiwalled carbon nanotubes/polypropylene (MWCNT/PP) nanocomposites prepared by a melt mixing method have been investigated. Sodium dodecyl sulfate (SDS) and sodium dodecylbenzene sulfonate (NaDDBS) were used as a means of noncovalent functionalization of MWCNTs to help them to be dispersed uniformly into the PP matrix. The effects of these surfactant‐treated MWCNTs on morphological, rheological, thermal, crystalline, mechanical, and electrical properties of MWCNT/PP composites were studied using field emission scanning electron microscopy, optical microscopy, rheometry, tensile, and electrical conductivity tests. It was found that the surfactant‐treatment and micromixing resulted in a great improvement in the state of dispersion of MWCNTs in the polymer matrix, leading to a significant enhancement of Young's modulus and tensile strength of the composites. For example, with the addition of only 2 wt % of SDS‐treated and NaDDBS‐treated MWCNTs, the Young's modulus of PP increased by 61.1 and 86.1%, respectively. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Influence of the epoxy functionalization of multiwall carbon nanotubes on the nonisothermal cure kinetics and thermal properties of epoxy/multiwall carbon nanotube nanocomposites

Multiwall carbon nanotubes were functionalized with epoxy groups by chemical modification in four stages. At each stage, the compound was characterized by Fourier transform infrared spectroscopy and scanning electron microscopy (SEM). Epoxy composite samples were prepared by mixing diglycidyl ether of bisphenol A‐based epoxy resin and synthetic epoxy‐functionalized multiwall carbon nanotube (E‐MWCNT) with different percentages (1, 3, 6, 9, 12, and 15%) in acetone. Ultrasonic dispersion was used to produce homogenous blends. The optimum ratio of the reacting components (9%) was investigated by total enthalpy of the curing reaction from differential scanning calorimetry (DSC) thermograms. The kinetics of the curing reaction for epoxy composites with 4,4′‐diaminodiphenylsolfon as a curing agent was studied by means of a DSC nonisothermal technique. The kinetic parameters such as activation energy, pre‐exponential factor, and rate constant were obtained from DSC data. The structure ofthe nanocomposites and dispersion of the E‐MWCNTs in the nanocomposites were observed using SEM, and the thermal properties were studied by thermogravimetric analysis. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Poly(propylene) composite with hybrid nanofiller: Dynamic properties

Mechanical, impact, and relaxation properties of in situ synthesized carbon nanotubes‐polyaniline (CNT‐PANi) hybrid nanoparticle‐filled poly(propylene) (PP) composites with or without an amphiphilic dispersing agent were investigated using tensile testing, notched Charpy impact testing, and dynamical mechanical testing methods. The reference material was MWCNT filled PP composite. Ethyl gallate (EG) was the dispersing agent which realizes high conductivity in PP composites with hybrid filler. Measured properties showed quite similar behavior of CNT‐PANi hybrid and neat CNT filled composites. Addition of 20% EG in PP did not cause essential differences compared to the neat PP. When the dispersing agent was added in filler containing PP composites, remarkable effects were observed, especially in PP‐hybrid composites. Mechanically, these materials had improved tensile properties, but they were brittle compared to the materials without dispersing agent. Dynamic mechanical analysis showed improvement in storage modulus, and in loss modulus the α transition was well observable. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Tribological behaviors of hybrid PTFE/nomex fabric/phenolic composite reinforced with multiwalled carbon nanotubes

Modification of composites was a general method to improve their tribological behaviors. On the way to explore composites with enhanced tribological behaviors, we have successfully prepared hybrid PTFE/Nomex fabric/phenolic composite filled with multiwalled carbon nanotubes (MWCNTs) or MWCNTs modified by polystyrene (PS) with a grafting to method. The results of pin‐on‐disc type wear tests indicated tribological behaviors were improved both for hybrid PTFE/Nomex fabric/phenolic composite filled with MWCNTs and MWCNTs‐PS, especially for that of filled with MWCNTs‐PS. And the probable reason was also discussed based on the characterization results. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation and properties of multiwalled carbon nanotube/epoxy‐amine composites

Different amounts of multiwalled carbon tubes (MWCNTs) were incorporated into an epoxy resin based on diglycidyl ether of bisphenol A and both epoxy precursor and composite were cured with 4,4′‐diamino diphenyl sulfone. Transmission and scanning electron microscopy demonstrated that the carbon nanotubes are dispersed well in the epoxy matrix. Differential scanning calorimetry measurements confirmed the decrease in overall cure by the addition of MWCNTs. A decrease in volume shrinkage of the epoxy matrix caused by the addition of MWCNTs was observed by pressure–volume–temperature measurements. Thermomechanical and dynamic mechanical analysis were performed for the MWCNT/epoxy composites, showing that the T_g was slightly affected, whereas the dimensional stability and stiffness are improved by the addition of MWCNTs. Electrical conductivity measurements of the composite samples showed that an insulator to conductor transition takes place between 0.019 and 0.037 wt % MWCNTs. The addition of MWCNTs induces an increase in both impact strength (18%) and fracture toughness (38%) of the epoxy matrix with very low filler content. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Rice hull biocomposites,part 2: Effect of the resin composition on the properties of the composite

A free radical thermoset resin consisting of a copolymer of conjugated linseed oil (CLO) or conjugated soybean oil (CSO), n‐butyl methacrylate (BMA), divinylbenzene (DVB), and maleic anhydride (MA) has been reinforced with rice hulls. Composites containing 70 wt % of the filler were compression molded, the conjugated oil content in the resin was kept constant at 50 wt %, and the relative amounts of BMA, DVB, and MA were varied to afford composites with different resin compositions. Tensile tests, DMA, thermogravimetric analysis, and Soxhlet extraction of the different composites prepared have been used to establish the relationship between resin composition and the properties of the composites. Overall, the mechanical properties tend to improve when MA is introduced into the resin. Scanning electron microscopy of selected samples showed a better filler–resin interaction for MA‐containing composites and samples prepared from CLO exhibit better properties than those prepared from CSO. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Functionalized multi‐wall carbon nanotubes/silicone rubber composite as capacitive humidity sensor

Functionalized multi‐wall carbon nanotubes (MWCNTs) treated by mixed acids have been used to develop a capacitive humidity sensor based on MWCNTs/silicone rubber (SR) composite film. The MWCNTs/SR composites were prepared through conventional solution processed method. The micrographs of MWCNTs/SR composites were observed by transmission electron microscopy (TEM) and scanning electron microscope. The FT‐IR spectra demonstrated the successfully grafting of ? OH groups on the treated MWCNTs. The sensing properties of the composite at different relative humidity (RH) and frequency were characterized and linear sensing responses of the MWCNTs/SR composites to RH were observed. The treated MWCNTs/SR composite film (Tr‐film) had higher sensitivity than that of the untreated MWCNTs/SR composite film (Un‐film). Experimental data indicate that the Tr‐film exhibits an excellent long‐term stability, small hysteresis, and fine reproducibility. The response and recovery time of the Tr‐film were 30 and 27 s, respectively. Thereby, such Tr‐film had potential applications as humidity sensors. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40342.     

A comparative study on the properties of the different amino‐functionalized multiwall carbon nanotubes reinforced epoxy resin composites

Multiwall carbon nanotubes (MWCNTs) were amino‐functionalized by 1,2‐ethylenediamine (EDA)' triethylenetetramine (TETA), and dodecylamine (DDA), and investigated by fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, and thermogravimetric analysis (TGA). The dispersion of the DDA functionalized MWCNT in DMF is better than that of the MWCNT functionalized by the EDA and the TETA. Carbon nanotubes reinforced epoxy resin composites were prepared, and the effect of the amino‐functionalization on the properties of the composites was investigated by differential scanning calorimetry (DSC), dynamical mechanical analysis (DMA), and TGA. The composites reinforced by the MWCNTs demonstrate improvement in various mechanical properties. The increase of T_g of the composites with the addition of amino‐functionalized MWCNT compared to the T_g of the composites with the addition of unfunctionalized MWCNT was due to the chemical combination and the physical entanglements between amino group from modified MWNTs and epoxy group from the epoxy resin. The interfacial bonding between the epoxy and the amino group of the EDA and the TETA‐modified MWCNT is more important than the well dispersion of DDA‐modified MWCNT in the composites for the improvement of the mechanical properties. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Fabrication of bimetallic nanoparticles/multi-walled carbon nanotubes composites for microelectronic circuits

A method for the fabrication of electrically-conducting polymer composites has been developed by mixing modified multi-walled carbon nanotubes (MWCNTs) functionalized by bimetallic nanoparticles (Ag/Ni/MWCNTs) into a UV curable resin. MWCNTs were treated by a concentrated H₂SO₄/HNO₃ mixture followed by ultrasonication with AgNO₃ and NiSO₄ in an ethylene glycol solution, producing MWCNTs decorated with Ag and Ni nanoparticles. The microstructure and surface morphology of the Ag/Ni/MWCNTs were investigated by scanning electron microscopy, transmission electron microscopy, and energy dispersive X-ray spectrometry. It was found that the addition sequences of NiSO₄ and AgNO₃ influence the morphology of the Ag/Ni/MWCNTs. The electrically-conducting polymer composites were obtained by dispersing the prefabricated Ag/Ni/MWCNTs in UV curable resin, the curing process of which was tracked by Fourier transform infrared spectroscopy, and the electrical resistance was measured using the four-probe method. The fabrication of microelectronic patterns made by screen printing on different substrates was described.     

Effect of functionalized carbon nanotubes on the thermal conductivity of epoxy composites

Direct functionalized carbon nanotubes (CNTs) were utilized to form the heat flow network for epoxy composites through covalent integration. A method of preparing a fully heat flow network between benzenetricarboxylic acid grafted multi-walled carbon nanotubes (BTC-MWCNTs) and epoxy matrix is described. A Friedel-Crafts modification was used to functionalize MWCNTs effectively and without damaging the MWCNT surface. Raman spectra, X-ray photoelectron spectra and thermogravimetric analysis reveal the characteristics of functionalized MWCNTs. The scanning electron microscope images of the fracture surfaces of the epoxy matrix showed BTC-MWCNTs exhibited higher solubility and compatibility than pristine-MWCNTs. The MWCNTs/epoxy composites were prepared by mixing BTC-MWCNTs and epoxy resin in tetrahydrofuran, followed by a cross-linking reaction with a curing agent. The BTC was grafted onto the MWCNTs, creating a rigid covalent bond between MWCNTs and epoxy resin and forming an effective network for heat flow. The effect of functionalized MWCNTs on the formation of the heat flow network and thermal conductivity was also investigated. The thermal conductivity of composites exhibits a significant improvement from 0.13 to 0.96 W/m K (an increase of 684%) with the addition of a small quantity (1-5 vol%) of BTC-MWCNTs.     

Effect of convergent–divergent flow on thermal and crystallization properties of PP/MWCNTs nanocomposites

A melt‐mixing process based on convergent–divergent flow has been used to prepare PP/MWCNT composites with a self‐built convergent–divergent die (C‐D die) composed of different numbers of convergent plates. Dynamic extensional deformation was generated in the C‐D die, which improved the mixing effect and mixing efficiency of the composites during extrusion. The C‐D die acted as a mixer for composites when mounted onto a capillary rheometer. The residence time of PP/MWCNTs melt in the extensional flow field is adjusted by changing the numbers of convergent plates and the velocity of the ram. The intensity of extensional flow field is controlled by the structure of the convergent plate and the ram velocity. Influences of convergent–divergent flow on PP/MWCNTs composites were characterized in terms of transmission electron microscopy (TEM), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). TEM results showed that MWCNTs disperse more homogeneously with the increase of convergent plates. DSC showed that the crystallinity of PP/MWCNTs composites increased and the crystallization temperature shifted to higher temperature with the increase of the numbers of the convergent plates. TGA showed that the thermal stability of composites improved remarkably. The decomposition temperature increases from 381 to 408.2°C when the numbers of convergent plates increased from 2 to 8. In addition, the increase of ram velocity also has the same influences on the dispersion of MWCNTs in the resin and the properties of PP/MWCNTs nanocomposites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42330.     

Effect of amino‐functionalization of multi‐walled carbon nanotubes on the dispersion with epoxy resin matrix

Amino‐functionalization of multiwalled carbon nanotubes (MWCNTs) was carried out by grafting triethylenetetramine (TETA) on the surfaces of MWCNTs through the acid–thionyl chloride way. The amino‐functionalized MWCNTs show improved compatibility with epoxy resin and, as a result, more homogenous dispersion in the matrix. The mechanical, optical, and thermal properties of the amino‐functionalized MWCNT/epoxy composites were also investigated. It was found that introducing the amino‐functionalized MWCNTs into epoxy resin greatly increased the charpy impact strength, glass transition temperature, and initial decomposing temperature of cured epoxy resin. In addition, introducing unfunctionalized MWCNTs into epoxy resin was found greatly depressing the light transmission properties, which would affirmatively confine the application of the MWCNTs/epoxy composites in the future, while much higher light transmittance than that of unfunctionalized MWCNTs/epoxy composites was found for amino‐functionalized MWCNTs/epoxy composites. SEM of the impact cross section and TEM of ultrathin film of the amino‐functionalized MWCNTs/epoxy composites showed that the amino‐functionalized MWCNTs were wetted well by epoxy matrix. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 97–104, 2006