Poly(trimethylene terephthalate‐block‐tetramethylene oxide) elastomer/single‐walled carbon nanotubes nanocomposites: Synthesis,structure, and properties

Nanocomposites based on poly(trimethylene terephthalate)‐block‐poly(tetramethylene oxide) (PTT‐PTMO)‐segmented copolymer and COOH‐functionalized single‐walled carbon nanotubes (SWCNTs) were prepared by in situ polymerization method. The obtained nanocomposites were characterized by thermogravimetric analysis, scanning electron microscopy, differential scanning calorimetry (DSC), DMTA, wide‐angle x‐ray scattering (WAXS), small‐angle X‐ray scattering, and tensile testing. The nanocomposites with low SWCNTs loading (<0.5 wt %) shows uniform dispersion of CNT in polymer matrix. As the SWCNTs loading in the nanocomposites increase, the significant improvement of thermo‐oxidative stability was observed. It was found that the nanocomposites have slightly higher degree of crystallinity (determined by DSC and WAXS) of poly(trimethylene terephthalate) (PTT) hard phase than neat PTT‐PTMO copolymer. The melting point of PTT hard phase and glass transition temperature of poly(tetramethylene oxide)‐rich phase were not affected by the presence of CNTs in polymer matrix. The SWCNTs played a role as nucleating agent in PTT‐PTMO matrix, which led to increase in the crystallization rate. Tensile tests showed that the tensile strength of the nanocomposites with 0.05–0.3 wt % loading of SWCNTs have improved tensile strength in comparison to the neat PTT‐PTMO copolymer without reduction elongation at break. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effects of preparation method on thermoelectric properties of poly(aniline-co-3,4-ethylenedioxythiophene)/SWCNT composites

Composites of conducting polymer and single-walled carbon nanotubes (SWCNTs) are attracting great attentions in harvesting low-grade waste heat. Prefabricated SWCNTs film used as the working electrode was placed at the liquid interface between the inorganic phase (dilute sulfuric acid solution) and the organic phase consisting of dichloromethane (DCM), aniline (ANI), and 3,4-ethylenedioxythiophene (EDOT), together with a platinum wire (the counter electrode) and a silver chloride (AgCl/Ag) electrode (the reference electrode), to perform electrochemical polymerization of ANI and EDOT at the liquid interface. Thermoelectric (TE) composites of poly(ANI-co-EDOT) and SWCNTs were produced. Compared with composites from ultrasonic mixing and coating methods, the 10 wt% SWCNTs-composites in situ formed in electrochemical polymerization have the highest power factor (PF) of 41.56 ± 3.58 μW m⁻¹ K⁻², higher than the PF values of the composites formed by other two methods. The work indicates that the TE properties of ANI-EDOT copolymer/SWCNT (poly[ANI-co-EDOT]/SWCNT) composites prepared by electrochemical polymerization were better than those of the composites obtained by physical mixing the electrochemically synthesized poly(ANI-co-EDOT) with SWCNTs. Moreover, SWCNTs treated with sodium dodecylbenzene sulfonate (SDBS) could further improve the TE properties of the composites.     

Temperature and pH‐response swelling behavior of poly(2‐ethyl‐2‐oxazoline)/chitosan interpenetrating polymer network hydrogels

Interpenetrating polymer network (IPN) hydrogels composed of poly(2‐ethyl‐2‐oxazoline) (PEtOz) and chitosan (CS) were prepared with radical polymerization and were characterized for their swelling properties. Sample OC11 (hydrogel weight ratio PEtOz/CS = 1/1) swelled more than samples OC21 (PEtOz/CS = 2/1) and OC31 (PEtOz/CS =3/1), exhibiting a swelling ratio of about 2000 wt % in deionized water; the swelling ratios of the other samples were about 1000 and 700 wt %. The swelling behavior of the IPN hydrogels was observed under various pH and temperature conditions. The swelling ratios of the samples ranged from about 2000 to 6500 wt % at lower pHs, with a maximum swelling ratio of about 6500 wt % in a pH 2 aqueous solution. They exhibited low critical solution temperature behavior, with sample OC31 more sensitive to temperature and sample OC11 more sensitive to pH. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1100–1103, 2006     

Control over the surface plasmon band of block copolymer/Ag/Au nanoparticles composites by the addition of single walled carbon nanotubes

In this study, we demonstrate control over the localized surface plasmon band (SPB) of a micellar poly(styrene-block-4vinylpyridine) (PS-b-P4VP) copolymer thin film composite that includes Ag and Au nanoparticles (NPs) in the presence of single walled carbon nanotubes (SWCNTs). Ag and Au NPs are preferentially located in the P4VP core and the PS corona of ordered spherical PS-b-P4VP copolymer micelles, respectively. This structure gave rise to a single SPB due to the coupling of Ag and Au SPBs. The non-covalent addition of SWCNTs in the block copolymer micelles shifts the coupled SPB to a lower wavelength. The maximum shift in the coupled SPB of approximately 30 nm was achieved in the PS-b-P4VP/Ag/Au NPs composite. The carbon nanotube induced modulation of the coupled SPB stems from the charge accumulation effect of the SWCNTs placed between the two types of nanoparticles.     

Stability of surfactant-free high internal phase emulsions and its tailoring morphology of porous polymers based on the emulsions

Stable water-in-oil (w/o) high internal phase emulsions (HIPEs) having an internal phase of up to 95 vol% were prepared. The poly(styrene-methyl methacrylate-acrylic acid) (P(St-MMA-AA)) copolymer particles were used as stabilizer. The HIPEs prepared with addition of copolymer particles to the aqueous phase were stabilized by copolymer particles initially, followed by the mixture of copolymer particles and copolymer as the particles eventually dissolves in the organic phase, and finally by only copolymer. Stable w/o HIPEs having an internal phase of up to 92 vol% were also formed with P(St-MMA-AA) copolymer dissolved in the organic phase as the sole stabilizer. Porous polymers (polyHIPEs) were prepared based on these two types of surfactant-free HIPEs. The morphology of the polyHIPEs, such as the surface roughness of the voids and average void diameter, were tailored by tuning the internal phase volume fraction, NaCl, copolymer, and crosslinker concentrations.     

Modifying the electronic properties of single-walled carbon nanotubes using designed surfactant peptides

The electronic properties of carbon nanotubes can be altered significantly by modifying the nanotube surface. In this study, single-walled carbon nanotubes (SWCNTs) were functionalized noncovalently using designed surfactant peptides, and the resultant SWCNT electronic properties were investigated. These peptides have a common amino acid sequence of X(Valine)(5)(Lysine)(2), where X indicates an aromatic amino acid containing either an electron-donating or electron-withdrawing functional group (i.e. p-amino-phenylalanine or p-cyano-phenylalanine). Circular dichroism spectra showed that the surfactant peptides primarily have random coil structures in an aqueous medium, both alone and in the presence of SWCNTs, simplifying analysis of the peptide/SWCNT interaction. The ability of the surfactant peptides to disperse individual SWCNTs in solution was verified using atomic force microscopy and ultraviolet-visible-near-infrared spectroscopy. The electronic properties of the surfactant peptide/SWCNT composites were examined using the observed nanotube Raman tangential band shifts and the observed additional features near the Fermi level in the scanning tunneling spectroscopy dI/dV spectra. The results revealed that SWCNTs functionalized with surfactant peptides containing electron-donor or electron-acceptor functional groups showed n-doped or p-doped altered electronic properties, respectively. This work unveils a facile and versatile approach to modify the intrinsic electronic properties of SWCNTs using a simple peptide structure, which is easily adaptable to obtain peptide/SWCNT composites for the design of tunable nanoscale electronic devices.     

Raman spectroscopic evidence for interfacial interactions in poly(bithiophene)/single-walled carbon nanotube composites

Electrochemical polymerization of 2,2′-bithiophene (BTh) on single-walled carbon nanotube (SWCNT) films has been studied by Raman scattering and infrared absorption spectroscopy. Covalent functionalization of SWCNTs with poly(bithiophene) (PBTh) in its un-doped and doped states is demonstrated. The occurrence of a charge transfer process at the interface of PBTh and SWCNTs, is shown by: (i) an up-shift of the Raman lines associated with the radial breathing modes of SWCNTs that reveals both a doping process and an additional twisting together as a rope with the conducting polymer as binding agent; (ii) a new Raman band in the range 1430-1450 cm⁻¹ indicating the functionalization of SWCNTs with PBTh in doped and un-doped states; (iii) strong absorption bands situated in the interval 600-800 cm⁻¹ resulting from steric hindrance produced by the nanotube binding to the polymeric chain. Treatment of the PBTh/SWCNT composite with aqueous NH₄OH solution forms un-doped PBTh covalently functionalized SWCNTs. At the resonant excitation of the metallic tubes, an additionally enhanced Raman process is generated by plasmon excitation in the metallic nanotubes. It is evidenced by a particular behavior in the Stokes and anti-Stokes branch of the PBTh Raman line at 1450 cm⁻¹.     

The purification of HiPco SWCNTs with liquid bromine at room temperature

A new procedure to purify HiPco single-walled carbon nanotubes (SWCNTs) from iron catalyst impurity is introduced. The protocol, which uses liquid bromine at room temperature (RT) as an oxidant, improves nanotube purity from iron by a factor of approximately 10, while maintaining good nanotube integrity as demonstrated by near infrared (NIR) luminescence and absorbance measurements. When HiPco SWCNTs are dissolved in RT Br₂(l) (free of O₂ and H₂O), the metallic iron impurity is quickly oxidized to its bromide salt and easily removed by aqueous washing or by washing with dilute acid. The iron content (by ICP-AE) for the purified SWCNT material was 2.8-3.6% by weight (for three different samples) for a single purification step, but could be lowered to 1.6-1.8% with an additional purification cycle. Characterization of the resulting purified SWCNT material has been achieved by TEM imaging, XPS, ICP-AE analysis, Raman spectroscopy, electronic absorption spectroscopy, and by NIR photoluminescence measurements. Finally, the new Br₂(l) purification procedure has been compared to and contrasted with other established purification procedures for HiPco SWCNTs and found to be a highly desirable alternative.     

Investigation of the rheological,dynamic mechanical,and tensile properties of single‐walled carbon nanotubes reinforced poly(vinyl chloride)

Polymer nanocomposites consisting of single‐walled carbon nanotubes (SWCNTs) and poly(vinyl chloride) were prepared by casting technique. The complex viscosity increased with increasing SWCNTs content, and it had a percolation concentration threshold equal to 0.45 wt % of SWCNTs. The storage modulus, G′, increased with increasing either SWCNTs content or frequency. A gradual decrease in the terminal zone slope of G′ for the nanocomposites with increasing SWCNTs content may be explained by the fact that the nanotube–nanotube interactions will be dominant at higher CNTs content, and lead to the formation of the interconnected or network‐like structures of SWCNTs in the polymer nanocomposites. The rheological loss factor indicates two relaxation peaks at frequencies of 0.11 and 12.8 Hz due to the interaction between SWCNTs and polymer chains and glass transition, respectively. Dynamic mechanical properties were measured for the prepared composites. The results indicate that the storage modulus changes steadily, and the tanδ peaks are less intense for high SWCNTs content. Tensile tests were measured and depicted by an increase in the elastic modulus with increasing SWCNTs content, but it decreases for all composites as the testing temperature increased. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Towards optimization of functionalized single-walled carbon nanotubes adhering with poly(3-hexylthiophene) for highly efficient polymer solar cells

In this paper, we present the optimization of single-walled carbon nanotubes (SWCNTs) by acid-treatment, solution ultrasonication time and dispersion in photoactive layer for efficient organic solar cells. After non-covalently adhering with poly(3-hexylthiophene) (P3HT), pre-functionalized SWCNTs were blended into the composites of P3HT and [6,6]-phenyl-C₆₁-butyric acid methyl ester (PCBM) as photoactive layer, and a maximum power conversion efficiency (PCE) of 3.02% with a short-circuit current density of 11.46 mA/cm² was obtained from photovoltaic cell indium-tin oxide (ITO)/poly(ethylene-dioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS)/P3HT:PCBM:SWCNTs/Al with an optimum 0.3 wt% SWCNTs in P3HT:PCBM:SWCNTs nanocomposite, the PCE can be enhanced by more than 10% as compared to the control device ITO/PEDOT:PSS/P3HT:PCBM/Al. The performance improvement by incorporating with functionalized SWCNTs is mainly attributed to the extension of excitons dissociation area and fastening charge carriers transfer across the active layer.     

An easy method for direct metal coordination reaction on unoxidized single-walled carbon nanotubes

The transition metal copper (II) ion (Cu²⁺) was effectively coordinated with a single-walled carbon nanotube (SWCNT) to produce a SWCNT–Cu²⁺ complex by a metal coordination reaction. Since the complex was very reactive towards the carboxylic acid group, the chemical functionalization of SWCNTs was easy to accomplish. This approach was used to functionalize the surface of the SWCNTs with stearic acid or ethylenediaminetetraacetic acid for tuning of the relative hydrophobicity and hydrophilicity of the surface, respectively. The mild reaction conditions used for metal coordination of the SWCNTs minimized the defects that result from chemical modification of SWCNT. Thus, the electrical properties of unmodified SWCNTs were preserved. Various analytical techniques, including Fourier transform infrared spectroscopy, thermal gravimetric analysis, ultraviolet–visible spectroscopy, and water sorption isotherm measurements, were used to characterize the surface properties of the functionalized SWCNTs. Functionalization of SWCNTs by metal coordination reaction effectively modified the SWCNT surface, while conserving the excellent physical properties of the SWCNTs. The surface properties of the SWCNTs were easily tuned by introduction of the functional groups required for specific applications.     

Complex formation of methylcellulose with poly(acrylic acid)

Complex formation between poly(acrylic acid) and methylcellulose in aqueous solutions has been studied by viscometric and turbidimetric methods. The critical pH values in their dependence of polymer concentration were determined. The influence of the nature of a nonionic polymer on the composition and stability of interpolymer complexes is shown. The phase behaviour of acrylic acid‐graft‐methylcellulose copolymer in aqueous solutions is analysed from their complexation point of view. © 2000 Society of Chemical Industry     

Facile way to disperse single‐walled carbon nanotubes using a noncovalent method and their reinforcing effect in poly(methyl methacrylate) composites

In this work, a noncovalent method was used to functionalize and thereby disperse single‐walled carbon nanotubes (SWCNTs) in dimethylformamide with poly[methyl methacrylate‐co‐(fluorescein O‐acrylate)] as a surfactant, and then the resultant poly(methyl methacrylate) (PMMA)‐based nanocomposites were fabricated via solution casting. The dispersion level of carbon nanotubes in the solvent was investigated by means of scanning electron microscopy and atomic force microscopy. The results showed that carbon nanotubes were well wrapped by the surfactant, and small carbon nanotube bundles several nanometers or less in diameter and several micrometers in length were obtained. Both scanning electron microscopy and transmission electron microscopy confirmed the uniform dispersion of SWCNTs in the PMMA matrix. The mechanical properties of the composites were determined with a universal tension tester. The PMMA composite containing 2 wt % SWCNTs showed improved tensile properties versus neat PMMA, showing 56 and 30% enhancements of the tensile modulus and tensile stress, respectively. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Impact,Thermal, and Morphological Properties of Poly(Lactic Acid)/Poly(Methyl Methacrylate)/Halloysite Nanotube Nanocomposites

Poly(lactic acid)/poly(methyl methacrylate) blends containing halloysite nanotube (2 and 5 phr) and epoxidized natural rubber (5–15 phr) were prepared by melt mixing. The impact strength of poly(lactic acid)/poly(methyl methacrylate) blend was slightly improved by the addition of halloysite nanotube. Adding epoxidized natural rubber further increased the impact strength of poly(lactic acid)/poly(methyl methacrylate)/halloysite nanotube nanocomposite. Single T_g of poly(lactic acid)/poly(methyl methacrylate) is observed and this indicates that poly(lactic acid)/poly(methyl methacrylate) blend is miscible. The addition of halloysite nanotube into poly(lactic acid)/poly(methyl methacrylate) slightly increased the T_g of the blends. The epoxidized natural rubber could encapsulate some of the halloysite nanotube and prevent the halloysite nanotube from breaking into shorter length tube during the melt shearing process.     

The study of thermodynamics and kinetics methyl orange and malachite green by SWCNTs,SWCNT-COOH and SWCNT-NH2 as adsorbents from aqueous solution

The effective removal of dyes from aqueous wastes is among the most important issues for many industrialized countries. Removal of methyl orange (MO) and malachite green (MG) from aqueous solutions were studied using single-walled carbon nanotubes (SWCNTs), carboxylate functionalized single-walled carbon nanotubes (SWCNT-COOH) and amide functionalized single-walled carbon nanotubes (SWCNT-NH₂). The adsorption process was found to be controlled by temperature, ionic strength, initial concentration, adsorbent dosage and contact time. The microstructure of carbon nanotubes was characterized using SEM and FTIR. The adsorbents studied exhibits high efficiency for MO and MG adsorption and the equilibrium states could be achieved in 20, 20, 15 (min) for SWCNTs, SWCNT-COOH, SWCNT-NH₂, respectively. Adsorption capacity of each adsorbent increased with increasing active groups on the surface of carbon nanotube, where SWCNT-NH₂ was the most effectively adsorbent.     

Thermoresponsive behaviour in aqueous solution of poly(maleic acid‐alt‐vinyl acetate) grafted with poly(N‐isopropylacrylamide)

The synthesis of a thermoresponsive graft copolymer consisting of a maleic acid/vinyl acetate alternating copolymer backbone (MAc‐alt‐VA) and poly(N‐isopropylacrylamide) (PNIPAM) side chains is reported. Turbidimetric measurements in dilute aqueous solutions showed that no macroscopic phase separation takes place when the temperature is raised above the lower critical solution temperature (LCST) of PNIPAM, even at pH = 2. Moreover, in semi‐dilute aqueous solutions, a pronounced thermally induced viscosity increase (thermothickening) was observed. This thermoresponsive behaviour has been attributed to the interconnection of the hydrophilic MAc‐alt‐VA graft copolymer backbones by means of the hydrophobic PNIPAM side chain aggregates formed as the temperature increases above the LCST of this polymer. Copyright © 2004 Society of Chemical Industry     

Influence of electrochemically prepared poly(pyrrole-co-N-methyl pyrrole) and poly(pyrrole)/poly(N-methyl pyrrole) composites on corrosion behavior of copper in acidic medium

Poly(pyrrole-co-N-methyl pyrrole) copolymer and poly(pyrrole)/poly(N-methyl pyrrole) bilayer composites were electrochemically synthesized on copper by cyclic voltammetry from aqueous solution of 0.3 M oxalic acid and 0.1 M monomer. Synthesis of copolymers were performed with different monomer feed ratios (pyrrole:N-methyl pyrrole, 8:2, 6:4, 5:5, 4:6 and 2:8) and in order to determine the copolymer, which has the best corrosion performance, anodic polarization was applied to copolymer coated samples. It was found that the performance of coatings was strongly dependent to the monomer feed ratio and the copolymer synthesized with 8:2 concentration ratio showed the most protective property compared to others. Bilayer of poly(pyrrole)/poly(N-methyl pyrrole) was also synthesized to compare the anticorrosive properties. Polymer films were characterized by ATR-FTIR spectroscopy and SEM techniques. Corrosion behavior of polymer composites was investigated in 0.1 M H₂SO₄ solution by anodic polarization and electrochemical impedance spectroscopy. Different approaches such as phase angle at high frequency and areas under Bode plots were used to evaluate corrosion performances of the coatings. Copolymer and bilayer coatings were found to have higher protection effect than single polypyrrole coatings. Moreover, bilayer coating exhibited better protection efficiency than copolymer coating against corrosion of copper when the obtained results were compared.     

Compatibilizing effects of poly(styrene-graft-ethylene oxide) in blends of polystyrene and butyl acrylate polymers

The compatibilizing effect of poly(styrene-graft-ethylene oxide) in polystyrene (PS) blends with poly(n-butyl acrylate) (PBA) and poly(n-butyl acrylate-co-acrylic acid) (PBAAA) was investigated. No significant effects of the graft copolymer on the domain size were found in the PBA blends. By functionalizing PBA with acrylic acid, the average size of the polyacrylate domains was reduced considerably by the graft copolymer. Thermal and dynamic mechanical analysis of the PS/PBAAA blends revealed that the PBAAA glass transition temperature (T_g) decreased with increasing graft copolymer content. The effect of the graft copolymer in the PS/PBAAA blends can be explained by interactions across the interface due to the formation of hydrogen bonds between the poly(ethylene oxide) (PEO) side chains in the graft copolymer and the acrylic acid segments in the PBAAA phase. Hydrogen bonding was confirmed by IR analysis of binary blends of PEO and PBAAA. Partial miscibility in the PEO/PBAAA blends was indicated by a PEO melting point depression and by a T_g reduction of the PBAAA phase. The thermal properties of the PEO/PBA blends indicated only very limited miscibility. © 1996 John Wiley & Sons, Inc.     

Synthesis and elastomer behavior of a novel polymer electrolyte of acrylic ester–salt copolymer

This paper studied the synthesis of a novel elastomeric copolymer electrolyte in an aqueous phase. The monomer, sodium allyl sulfonate (SAS), was dissolved in continuous aqueous phase and the second monomer, methyl acrylate (MA), was supplied from MA micelles as dispersed phase. The copolymerization of the two monomers took place in continuous aqueous phase. Confirmed by FTIR and ¹H‐NMR, a binary copolymer electrolyte of MA and SAS, poly(MA‐co‐SAS), was obtained. The glass transition temperature of the copolymer was indicated as 20.4°C by DSC thermogram, thus, it behaves an elastomer in normal ambient temperature. The mechanical properties of the composite films consisting of both poly(MA‐co‐SAS) and Cu²⁺ ions or reduced copper were affected by the content of ions and reduced copper. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2796–2802, 2006     

Carbon nanotubes and silver nanoparticles for multifunctional conductive biopolymer composites

This article fabricates and characterizes the combination of single walled carbon nanotubes (SWCNTs) and silver nanoparticles (Ag) with a biodegradable polymer matrix. Different SWCNT amount were mixed with Ag nanoparticles and introduced in the poly(ε-caprolactone) (PCL) polymer matrix by solvent cast process. Nanostructure synergistic effects were evaluated in terms of morphological, electrical, dielectrical, mechanical and biological properties of binary PCL/Ag, PCL/SWCNTs and ternary PCL/Ag/SWCNTs composites. Results showed a good dispersion of nanostructures in the PCL and an increase of Young modulus with silver content in the binary systems. The PCL/Ag composites exhibited poor electrical properties, while in PCL/Ag/SWCNTs ternary films higher values of conductivity were measured compared to both binary composites. Results obtained in this research indicate that Ag particles facilitate the formation of conductive pathways in the presence of SWCNTs, they act as conductive bridges among nanotube bundles and facilitate the electron transfer. The addition of a small percentage of SWCNTs promoted significantly the electrical properties of PCL/Ag nanohybrid films. Biocompatibility of binary and ternary composites, evaluated by human mesenchymal stem cells-bone marrow derived (hBM-MSCs), suggests that the combination of Ag nanoparticles and SWCNTs with a biodegradable polymer opens new perspectives for biomedical applications.