Preparation and Characterization of Polyvinylpyrrolidone-functionalized Multiwalled Carbon Nanotube (PVP/f-MWNT) Nanocomposites

Polyvinylpyrrolidone/hydroxyl-functionalized multiwalled carbon nanotube and sulfonyl-functionalized multiwalled carbon nanotube nanocomposites were prepared in aqueous media. The structure, morphology, and thermal characterization of the prepared nanocomposites were done by Fourier transform infrared, scanning electron microscopy, thermogravimetric analysis, and differential scanning calorimetry techniques. The polyvinylpyrrolidone/hydroxyl-functionalized multiwalled carbon nanotube and polyvinylpyrrolidone/sulfonyl-functionalized multiwalled carbon nanotube nanocomposites improved the thermal properties of polyvinylpyrrolidone. According to the differential scanning calorimetry analysis, the glass transition temperature of 101.6 and 84.6°C is observed for the polyvinylpyrrolidone/hydroxyl-functionalized multiwalled carbon nanotube (5% w/w) and polyvinylpyrrolidone/sulfonyl-functionalized multiwalled carbon nanotube (5% w/w) nanocomposites, respectively. The energy-dispersive X-ray spectroscopy image of polyvinylpyrrolidone/sulfonyl-functionalized multiwalled carbon nanotube (5% w/w) nanocomposite showed a homogenous distribution of sulfonyl-functionalized multiwalled carbon nanotube in the polyvinylpyrrolidone matrix.     

A new modified multiwalled carbon nanotube paste electrode for quantification of tin in fruit juice and bottled water samples

In this paper, a new modified multiwalled carbon nanotube electrode is reported for anodic stripping voltammetry quantification of tin. The electrode is based on the use of N-Nitrozo-N-Phenylhydroxylamine (cupferron) and multiwalled carbon nanotube. The influence of supporting electrolytes, deposition time, and applied potential on the sensitivity of electrode were investigated. The detection limit was 0.12 ng/ml and the RSD at a concentration level of 50 ng/ml, was 1.5%. The electrode has been applied for the determination of tin in fruit juice and bottled water with the satisfactory results.     

Master batch approach for developing PVDF/EVA/CNT nanocomposites with co-continuous morphology and improved electrical conductivity

Conducting polymer composites constituted by co-continuous poly (vinylidene fluoride) (PVDF)/ ethylene- vinyl acetate copolymer (EVA) blends with multiwalled carbon nanotube (CNT) were prepared by melt mixing using different procedures. The effect of the master batch approach on the conductivity, morphology, mechanical, thermal and rheological properties of PVDF/EVA/CNT nanocomposites was compared with that based on one step mixing strategy. The selective extraction experiments revealed that CNT was preferentially localized in the EVA phase in all situations, even when PVDF@CNT master batch was employed. Nanocomposites prepared with EVA@CNT master batch displayed higher conductivity, whose value reached around 10⁻¹ S m⁻¹ with the addition of 0.56 vol% of CNT. The better electrical performance was attributed to the better distribution of the filler, as indicated by transmission electron microscopy and rheological behavior. The electrical and rheological behavior were also investigated as a function of the CNT content.     

Sidewall modification of multiwalled carbon nanotubes by Allivum sativum (garlic) and its effect on the deposition of gold nanoparticles

Sidewall modification of multiwalled carbon nanotubes (abbreviated as MWCNTs) was achieved using Allivum sativum (garlic) extract by an acid-free green process. These organosulfur modified-MWCNTs were then decorated with gold nanoparticles and examined by transmission electron microscopy. The presence of organosulfurs over the modified nanotube surface was confirmed. Nanotube surface modification and subsequent presence of thiols as an active linker was confirmed by Raman spectroscopy, Fourier transform infrared spectroscopy, energy dispersive X-ray and X-ray photoelectron spectroscopy. In the absence of these organosulfurs (thiols), no gold nanoparticle attachment was observed. Both small (1–8 nm) and large (12–20 nm) gold nanoparticles were found to decorate the modified nanotube surface suggesting coalescence among nanoparticles.     

Role of Carboxylic Acid-Functionalized MWCNTs in Potentially Biodegradable Poly(Amide–Imide) Nanocomposites Based on N,N′-(Pyromellitoyl)-bis-S-valine: Preparation,Thermal and Morphological Properties

A simple solution-blending process was used to efficiently disperse of carboxyl-modified multiwalled carbon nanotubes into a potentially biodegradable poly(amide–imide) to obtain poly(amide–imide)/carboxyl-modified multiwalled carbon nanotubes bionanocomposites. Carboxyl-modified multiwalled carbon nanotubes were utilized to better dispersion of multiwalled carbon nanotubes into the polymer matrix. The poly(amide–imide)/carboxyl-modified multiwalled carbon nanotube bionanocomposites were prepared with different carboxyl-modified multiwalled carbon nanotube contents (5–15 wt%). The resulting bionanocomposites are characterized by several techniques, powder X-ray diffraction, scanning electron microscopy, transmission electron microscopy analysis, Fourier transform infrared spectroscopy, and thermogravimetric analysis. Adding carboxyl-modified multiwalled carbon nanotube into polymer matrix significantly increased the thermal stability of bionanocomposites due to the increased interfacial interaction between the poly(amide–imide) matrix and carboxyl-modified multiwalled carbon nanotube.     

Preparation and characterization of novel polyethylene/carbon nanotubes nanocomposites with core–shell structure

Preparation of novel polyethylene/carbon nanotubes (CNTs) nanocomposites with core–shell structure was presented. The method involved in situ ethylene polymerization in which nanotube surface was treated with Grignard Agent, followed by reacting with active transition metal compound, TiCl₄. The multiwalled carbon nanotubes (MWCNTs) supported catalysts polymerize ethylene to form polymer nanocomposite. MWCNTs were homogeneously dispersed within polymer matrix, and as expected, the resultant nanocomposites featured core–shell structure which was confirmed by HRTEM. For the nanocomposite, the microscopic examination of the cryogenically fractured surface not only ensured a good distribution of carbon nano-particles in the PE matrix but also revealed the ductile-like fracture. The Raman spectroscopy and X-ray photoelectron spectroscopy (XPS) were employed for the study of covalent sidewall functionalization and chemical bonding environment of MWCNTs, also indicated effective immobilization of titanium catalyst on the MWCNTs surface. The crystalline properties, dielectric property and thermal stability of the nanocomposites were determined by WAXD, impedance analyzer and TGA. The dielectric result showed a slight decline of the dielectric constant of the nanocomposites with increase of the polymerization time, and lower dielectric loss was also observed.     

Transport and solvent sensing characteristics of styrene butadiene rubber nanocomposites containing imidazolium ionic liquid modified carbon nanotubes

Obtaining strong interfacial interaction between filler and polymer matrix is very crucial for the fabrication of polymer nanocomposites with superior performance. Present study is aimed to fabricate high performance styrene butadiene rubber (SBR) nanocomposites with imidazolium type ionic liquid modified multiwalled carbon nanotube (MWCNT). Ionic liquid facilitates the dispersion of MWCNT in rubber matrix and it is obvious from transmission electron microscopy images. Diffusion of toluene through SBR nanocomposite membranes has been investigated as a function of surface modified MWCNT (f-MWCNT) content to analyze the chain dynamics and filler-polymer interactions. O₂ gas barrier effect of nanocomposites with special reference to the filler loading is explored. The substantial improvement in the barrier effect in presence of filler interpreted on the grounds of a theoretical model describing permeability of heterogeneous systems. Finally solvent sensing characteristics of prepared nanocomposites are also analyzed and it is observed that prepared nanocomposites can be used as a flexible solvent sensor.     

Properties of microinjection molding of polymer multiwalled carbon nanotube conducting composites

The effects of processing conditions on the microstructure and properties of polypropylene/multiwalled carbon nanotube (PP/MWCNT) and polycarbonate/multiwalled carbon nanotube (PC/MWCNT) composites were studied. Samples of various MWCNT loadings were prepared by diluting commercial masterbatches. Different processing conditions were then used to systematically change the degree of nanotube alignment, from random to highly aligned. The crystallinity of the PP/MWCNT nanocomposites was found to go through a maximum as a function of nanotube content while the overall rate of crystallization increased. For the highly sheared microinjected PP/MWCNT samples well oriented crystals were formed. Electrical conductivity of the nanocomposites was improved by the presence of the crystalline structure; however, the high degree of nanotube alignment in the microparts resulted in a significant increase in the electrical percolation threshold. The PP nanocomposites exhibited mechanical properties significantly enhanced by nanotube loading; this effect was small in the case of the PC nanocomposites. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Scrutinization of Polystyrene Microsphere-grafted Multiwalled Carbon Nanotube and Silver Nanoparticle-based Hybrids: Morphology,Thermal Properties,and Antibacterial Activity

Polystyrene microsphere (emulsion polymerization) was grafted on pure multiwalled carbon nanotube and amine-modified multiwalled carbon nanotube. Silver nanoparticle was also decorated on nanotube using chemical reduction (dimethylformamide). Amine-modified multiwalled carbon nanotube secures better silver attachment on nanotube wall. Polystyrene/Ag–amine-modified multiwalled carbon nanotube depicted fine dispersion in polymer latex due to modification. The 10% decomposition temperature and maximum degradation temperature of polystyrene/Ag–amine-modified multiwalled carbon nanotube was increased to 352 and 424°C. Antibacterial properties of nanocomposite were studied against respiratory track demolishing Gram-positive Staphylococcus aureus bacteria and two Gram-negative bacteria (Escherichia coli and Pseudomonas aeruginosa). Ag nanoparticle was found responsible to potential death rate of microbes.     

Functionalization of multiwalled carbon nanotubes with polystyrene under atom transfer radical polymerization conditions

Linear Polystyrene (PS) was grafted onto the convex surfaces of multiwalled carbon nanotubes (MWCNTs). Bromine-terminated polystyrene synthesized by atom transfer radical polymerization (ATRP) was directly reacted with MWCNTs under ATRP conditions using CuBr/2,2′-bipyridine as catalyst. The PS-grafted MWCNT samples were characterized by scanning electron microscopy, transmission electron microscopy, FT-IR spectra, Raman spectra, ¹H NMR, UV-vis spectra, thermal gravimetric analyses, and X-ray diffraction. The products can dissolve in organic solvents such as 1,2-dichlorobenzene, tetrahydrofuran and chloroform to form well-dispersed solutions. Optical limiting property measurements in chloroform were carried out at 532 nm using the open-aperture z-scan technique. The results demonstrate that the samples preserve good optical limiting properties when the polymer is covalently attached to the carbon nanotube.     

Structure and conductivity of multi-walled carbon nanotube/poly(3-hexylthiophene) composite films

This work reports a structure-property investigation of a conjugated polymer nanocomposite with enhanced conductivity. Regioregular poly(3-hexylthiophene) (rrP3HT) was used to prepare composites with thin, short, multi-walled carbon nanotube (MWNT) addition over a wide range of concentrations. Scanning and transmission electron microscopies demonstrated an excellent dispersion and good wetting properties within the carbon nanotube composites. Coated MWNTs showed superstructures of P3HT self-organized on nanotube surfaces. Changes in the long range order and on the self-ordered mesophase of the bulk material were investigated by infrared and Raman spectroscopies, differential scanning calorimetry and X-ray diffraction. Interplay between charge transport through the semiconducting polymer and carbon nanotube network increased the composite's conductivity after percolation to values close to 10⁻² S cm⁻¹.     

Synthesis of Bio-Based Polyamide/Acid-Functionalized Multiwalled Carbon Nanotube Nanocomposites Using Vanillin

Synthesis of bio-based polyamide/acid-functionalized multiwalled carbon nanotube nanocomposites (PA/FCNT NCs) is reported in this investigation. New aliphatic–aromatic bio-based polyamide (PA) was synthesized through direct polycondensation reaction between bio-based diacid derived from a renewable resource; vanillin and diamine containing ether linkages. To obtain a homogeneous dispersion of multiwalled carbon nanotubes (MWCNTs) in the PA matrix, acid-functionalized MWCNTs (FCNTs) were used and PA nanocomposites with three different FCNT contents (1, 5 and 7?wt%) were prepared. The resulting NCs were characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), and thermogravimetric analysis (TGA).     

Modification of pristine multiwalled carbon nanotube by grafting with poly(methyl methacrylate) using benzoyl peroxide initiator

Multiwalled carbon nanotube was successfully grafted with poly(methyl methacrylate) by free radical mechanism using benzoyl peroxide initiator. The reaction was carried out in situ, where the initiator and methyl methacrylate monomer generated the polymer‐free radical that was subsequently grafted to the surface of the pristine multiwalled carbon nanotube. The multiwalled carbon nanotube grafted poly(methyl methacrylate) (MWCNT‐g‐PMMA) were characterized using Fourier transform infrared, differential scanning calorimetry, thermogravimetric analysis, ¹³ C‐solid NMR spectroscopy, X‐ray photoelectron spectroscopy, and scan electron microscopy. From the result of the characterizations, the grafting of poly(methyl methacrylate) on to multiwalled carbon nanotube was confirmed, and a percentage grafting of 41.51% weight was achieved under optimized conditions with respect to the temperature and the amount of the initiator. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43270.     

Effect of carbon nanotubes on the curing and thermomechanical behavior of epoxy/carbon nanotubes composites

The processing of carbon nanotube based nanocomposites is one of the fastest growing areas in materials research due to the potential of significantly changing material properties even at low carbon nanotube concentrations. The aim of our work is to study the curing and thermomechanical behavior of carbon nanotube/epoxy nanocomposites that are critical from an application standpoint. Multiwall carbon nanotubes–epoxy composites are prepared by solvent evaporation based on a commercially available epoxy system and functionalized multiwalled carbon nanotubes. Three weight ratio configurations are considered (0.1, 0.5, and 1.0 wt%) and compared to both the neat epoxy to investigate the nano‐enrichment effect. We focus here on the modification of the curing behavior of the epoxy polymer in the presence of carbon nanotubes. It has been observed that introducing the multiwall carbon nanotubes delays the polymerization process as revealed by the modification of the activation energy obtained by differential scanning calorimetry. The viscoelastic response of the nanocomposites was studied from the measurements of storage modulus and the loss factor using dynamic mechanical analysis to evaluate the effect of the interface in each matrix/carbon nanotube system with changing matrix mobility. These measurements provide indications about the increase in the storage modulus of the composites, shift in the glass transition temperature due to the restriction of polymer chain movement by carbon nanotubes. POLYM. COMPOS., 35:441–449, 2014. © 2013 Society of Plastics Engineers     

Effect of in situ fibrillation on polyethylene/poly(ethylene terephthalate)/multiwalled carbon nanotube electromagnetic shielding foams

In this study, polyethylene (PP)/polyethylene terephthalate (PET)/multiwalled carbon nanotube (MWCNT) nanocomposites with nanofibrillary structure were processed by hot drawing-assisted extrusion technology, and nonfoaming and microfoaming samples were processed by injection molding machine. Scanning electron microscope micrographs showed that when PET content was 2.5 wt%, PET fibers had a larger aspect ratio, which brought an outstanding promotion on microfoaming of PP matrix, and further details were provided by DSC and rheology analysis. When foaming sample loaded with 2.5 wt% PET and 3 wt% MWCNT, the best shielding effectiveness achieved 29.91 dB·cm³·g⁻¹ in the test frequency range about 8.2–12.4 GHz. The results proved that the introduction of PET fibers optimized the microfoaming effect, and the uniform cell structure promoted the MWCNT dispersion and internal reflection of electromagnetic wave. Therefore, the shielding property is absorption-dominated type and meets the requirements of lightweight and ultraefficient shielding demand of industry.     

Polyethylene multiwalled carbon nanotube composites

Polyethylene (PE) multiwalled carbon nanotubes (MWCNTs) with weight fractions ranging from 0.1 to 10 wt% were prepared by melt blending using a mini-twin screw extruder. The morphology and degree of dispersion of the MWCNTs in the PE matrix at different length scales was investigated using scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscopy (AFM) and wide-angle X-ray diffraction (WAXD). Both individual and agglomerations of MWCNTs were evident. An up-shift of 17 cm⁻¹ for the G band and the evolution of a shoulder to this peak were obtained in the Raman spectra of the nanocomposites, probably due to compressive forces exerted on the MWCNTs by PE chains and indicating intercalation of PE into the MWCNT bundles. The electrical conductivity and linear viscoelastic behaviour of these nanocomposites were investigated. A percolation threshold of about 7.5 wt% was obtained and the electrical conductivity of PE was increased significantly, by 16 orders of magnitude, from 10⁻²⁰ to 10⁻⁴ S/cm. The storage modulus (G′) versus frequency curves approached a plateau above the percolation threshold with the formation of an interconnected nanotube structure, indicative of ‘pseudo-solid-like’ behaviour. The ultimate tensile strength and elongation at break of the nanocomposites decreased with addition of MWCNTs. The diminution of mechanical properties of the nanocomposites, though concomitant with a significant increase in electrical conductivity, implies the mechanism for mechanical reinforcement for PE/MWCNT composites is filler-matrix interfacial interactions and not filler percolation. The temperature of crystallisation (T_c) and fraction of PE that was crystalline (F_c) were modified by incorporating MWCNTs. The thermal decomposition temperature of PE was enhanced by 20 K on addition of 10 wt% MWCNT.     

in situ synthesis of biopolyurethane nanocomposites reinforced with modified multiwalled carbon nanotubes

Biopolyurethane nanocomposites reinforced with silane‐modified multiwalled carbon nanotubes (s‐MWCNT) were successfully prepared. The carbon nanotube surfaces were modified by means of functional amine groups via ozone oxidation followed by silanization. The surface structure of the s‐MWCNTs was characterized by Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy, and thermogravimetric analysis. The s‐MWCNTs were incorporated into a vegetable oil‐based polyurethane (PU) network via covalent bonding to prepare PU nanocomposites. The effect of s‐MWCNT loading on the morphology, thermomechanical, and tensile properties of the PU nanocomposites was studied. It was determined that the s‐MWCNTs were dispersed effectively in the polymer matrix and that they improved the interfacial strength between the reinforcing nanotubes and the polymer matrix. Storage modulus, glass transition temperature, Young's modulus, and tensile strength of the nanocomposites increased with increasing s‐MWCNT loading up to 0.8%. However, increasing the s‐MWCNT content to 1.2 wt % resulted in a decrease in thermomechanical properties of the PU nanocomposites. This effect was attributed to the fact that at high s‐MWCNT contents, the increased number of amine groups competed with the polyol's hydroxyl groups for isocyanate groups, causing a decrease in the integrity of the PU matrix. High s‐MWCNT contents also facilitated aggregation of the nanotubes, causing a decrease in thermomechanical properties. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42515.     

Synthesis of s‐triazine‐based hyperbranched polyurethane for novel carbon‐nanotube‐dispersed nanocomposites

s‐Triazine‐based hyperbranched polyurethanes (HBPUs) with different hard segments were synthesized by A₂ + B₃ approach. Various kinds of multiwalled carbon nanotube (MWNT) nanocomposites with HBPU were prepared to investigate an impact of hyperbranched polymer on dispersion of MWNTs in the polymer matrix and the resulting properties of nanocomposites. Synthesized HBPUs were characterized using FTIR and NMR measurements. The highly branched structures were found very effective in enhancing the pristine MWNT dispersion in the polymer matrix. As a result, the MWNT‐reinforced HBPU nanocomposites showed a steep increase in the yield stress and modulus and enhanced shape memory effect with an increase of hard segment and MWNT loading. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Electrochemical study of double-walled carbon nanotube electrode/block polyether-lithium bis(trifluorosulphonyl)imide salt polymer electrolyte interface

Electrodes of double-walled carbon nanotubes functionalized with ∼5 mass% of carboxyl groups (DWCNT-COOH) were prepared as an entangled and porous mat structure to facilitate the infiltration of polymer electrolytes. A system composed by a block copolymer of polyethylene-b-poly(ethylene oxide) or PE-b-PEO with lithium bis(trifluorosulphonyl)imide salt was optimized with respect to salt concentration. The 25 mass% of polymer electrolyte-DWCNT-COOH composite showed typical electronic conductivity of carbon nanotube-based composites (i.e., conductivities of 10⁻² S cm⁻¹ were obtained). The Nyquist plots for the nanocomposite led to the assignment of separate semi-circles to the electronic transfer through the nanotube and at the polymer electrolyte–nanotube interface. A complete cell with two electrode nanocomposites and a polymer electrolyte layer was tested in a wide range of cell potentials and temperatures. The operation of this configuration at 100 °C and a 4 V window was demonstrated.     

Flow induced orientation of multiwalled carbon nanotubes in polycarbonate nanocomposites: Rheology, conductivity and mechanical properties

We investigated the effect of flow field and deformation rate on the nanotube alignment and on the properties of PC/multiwalled carbon nanotube nanocomposites. Samples of various MWCNT loadings were prepared by diluting a commercial masterbatch containing 15 wt% nanotubes using optimized melt mixing conditions. Different processing conditions were then used to systematically change the degree of nanotube alignment, from random orientation to highly aligned. Morphological studies and Raman spectroscopy analysis revealed that the nanotubes are preferentially aligned in the flow direction, particularly at large injection or compression rates. Rheological measurements corresponding to high shear rate conditions showed drastic changes in the viscoelastic behavior. The complex viscosity significantly decreased and percolation threshold notably rose. High degrees of nanotube alignment also resulted in a significant increase in the electrical percolation threshold. The mechanical properties of the nanocomposites for different nanotube loadings were also shown to depend on the processing conditions, and somehow improved when the material was processed at higher rates. Finally, we used a power-law type equation to correlate the percolation behavior and the nanotube alignment. The estimated percolation threshold and the power index, q, significantly increase with the degree of nanotube alignment as determined by Raman analysis.