l-Phenylalanine amino acid functionalized multi walled carbon nanotube (MWCNT) as a reinforced filler for improving mechanical and morphological properties of poly(vinyl alcohol)/MWCNT composite

Carbon nanotube dispersion in polymer matrix is one of the most crucially important aspects in carbon nanotube/polymer composites. This paper is aimed to discuss the considerable improvement in dispersion of multi walled carbon nanotubes (MWNTs) in poly(vinyl alcohol) (PVA) matrix that was attained through bio-functionalization of MWCNTs. Initially, for getting better dispersion in water, pure MWCNTs have been functionalized by l-phenylalanine amino acid. The functionalized MWCNTs (f-MWCNTs) show much enhanced solubility in water. So, effects of modified MWCNT on dispersion in PVA matrix and certain properties of the resulting composites, like; mechanical, thermal and morphological properties were studied. The prepared composites were examined by Fourier transform infrared spectroscopy, X-ray diffraction and transmission electron microscopy. Also, the mechanical and thermal properties of composite films have been investigated and revealed that incorporation of just a few percent of f-MWCNTs can improve the PVA mechanical and thermal properties significantly.     

A general and efficient route to covalently surface modification of MWCNTs by dopamine and their synergistic reinforcing effects in chitosan films

Multiwalled carbon nanotubes (MWCNTs) were considered as ideal filler in a polymer matrix due to their outstanding mechanical, electrical and thermal properties. This article describes a simple route to preparation of nanocomposite (NC) of chitosan and modified MWCNT by solution casting method. The process involves modification of MWCNT with dopamine and effects of modified MWCNT on dispersion, mechanical, thermal and morphological properties. Atomic force microscopy, Fourier transform infrared spectroscopy, X-ray diffraction (XRD), field emission scanning electron microscopy, transmission electron microscopy, have been used to characterize the NCs. Scanning electron micrographs showed that in all of the NC films, except chitosan/MWCNT-Dop NC 7 wt%, MWCNT were dispersed homogeneously throughout the chitosan matrix. The XRD studies showed that the crystallinity of composite films decreases through hydrogen bonding between chitosan and MWCNT-Dop. The determination of mechanical and thermal properties demonstrated that the NC films exhibited significant enhancement in strength, modulus, and thermal stability compared with the pure chitosan.     

Field emission properties of Cu/multiwalled carbon nanotube composite films fabricated by an electrodeposition technique

Composite films of Cu and multiwalled carbon nanotubes (MWCNTs) were fabricated by an electrodeposition technique, and their field emission properties were examined. Commercially available MWCNTs with various diameters (60–150 nm) were used. The microstructure of the composite films was analyzed by scanning electron microscopy and the field emission properties were measured using a diode-type system. Cu/MWCNT composite films with homogeneous dispersion of MWCNTs were fabricated using each type of MWCNT. Bare MWCNTs were present on the surface of the composite films and the ends of the protruding tips were fixed by the deposited copper matrix. The composite films produced clear emission currents and the corresponding Fowler–Nordheim (F–N) plots showed that these were field emission currents. The turn-on electric field tended to decrease with decreasing MWCNT diameter. A light-emitting device incorporating the Cu/MWCNT composite film as a field emitter was fabricated, and its light-emitting properties were investigated. Light emission with a brightness of around 100 cd m^?2 was observed for approximately 100 h.     

Preparation, crystallization, electrical conductivity and thermal stability of syndiotactic polystyrene/carbon nanotube composites

A homogeneous dispersion of multi-walled carbon nanotubes (MWCNTs) in syndiotactic polystyrene (sPS) is obtained by a simple solution dispersion procedure. MWCNTs were dispersed in N-methyl-2-pyrrolidinone (NMP), and sPS/MWCNT composites are prepared by mixing sPS/NMP solution with MWCNT/NMP dispersion. The composite structure is characterized by scanning electron microscopy and transmission electron microscopy. The effect of MWCNTs on sPS crystallization and the composite properties are studied. The presence of MWCNTs increases the sPS crystallization temperature, broadens the crystallite size distribution and favors the formation of the thermodynamically stable β phase, whereas it has little effect on the sPS γ to α phase transition during heating. By adding only 1.0 wt.% pristine MWCNTs, the increase in the onset degradation temperature of the composite can reach 20 °C. The electrical conductivity is increased from 10^{−10∼−16} (neat sPS) to 0.135 S m⁻¹ (sPS/MWCNT composite with 3.0 wt.% MWCNT content). Our findings provide a simple and effective method for carbon nanotube dispersion in polymer matrix with dramatically increased electrical conductivity and thermal stability.     

Effects of glucose‐functionalized multiwalled carbon nanotubes on the structural,mechanical, and thermal properties of chitosan nanocomposite films

A series of multiwalled carbon nanotubes (MWCNTs) grafted by chitosan nanocomposite (NC) films were prepared by a direct blending process and solution casting method. In this study, we modified multiwalled carbon nanotubes with glucose (MWCNT–Gl) for this purpose, and the effects of MWCNT–Gl on the structural, mechanical, and thermal properties of chitosan films with different contents of MWCNT–Gl were investigated. The structure, thermal stability, and mechanical properties of the composite were examined by X‐ray diffraction, Fourier transform infrared spectroscopy, field emission scanning electron microscopy, transmission electron microscopy, thermogravimetric analysis, and mechanical testing. The results indicate that the MWCNTs treated by glucose were dispersed well in the chitosan matrix, and the tensile properties of the NC films were improved greatly compared with neat chitosan. Also, with increasing MWCNT–Gl content, the crystalline nature of chitosan decreased. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42022.     

The preparation of cation-functionalized multi-wall carbon nanotube/sulfonated polyurethane composites

Covalent functionalization of multi-wall carbon nanotubes (MWCNTs) with minimal alteration to the MWCNT surface is important to achieve homogenously dispersed carbon nanotubes while maintaining their unique mechanical and electrical properties. Carboxylic acid derivatized MWCNTs (MWCNT-COOH) were covalently functionalized with 3,3′-iminobis(N,N-dimethylpropylamine) (DMPA). Upon subsequent quaternization of DMPA, dendritic ammonium cation-functionalized MWCNTs (MWCNT-DMPA⁺) were formed, where two ammonium cations were incorporated per amide site. Thermogravimetric analysis and X-ray photoelectron spectroscopy demonstrated successful covalent functionalization and formation of the surface-bound ammonium salt. Raman spectroscopy and atomic force microscopy indicated the absence of an appreciable decrease in the MWCNT aspect ratio. Compared with pristine MWCNTs and MWCNT-COOH, MWCNT-DMPA⁺ exhibited enhanced dispersibility in N,N-dimethylformamide (DMF) as observed with UV–Visible spectroscopy and transmission electron microscopy (TEM). In addition, blending the cation-bound MWCNT-DMPA⁺ with anion-bound sulfonated polyurethane in DMF generated novel composites with a nanotube content ranging from 0.5 to 5 wt.%. Characterization of the composite films using both field emission scanning electron microscopy and TEM revealed that MWCNT-DMPA⁺ exhibited uniform dispersion in sulfonated polyurethane matrices even at 5 wt.%. Tensile analysis showed that the modulus of the sulfonated polyurethane matrix linearly increased with MWCNT-DMPA⁺ content.     

Rapid and green functionalization of multi-walled carbon nanotubes by glucose: structural investigation and the preparation of dopamine-based poly(amide-imide) composites

Functionalization of multi-walled carbon nanotubes (MWCNTs) by glucose was performed through esterification reaction. The reaction was carried out in water, in the presence of N,N′-carbonyldiimidazole as a catalyst. Glucose-functionalized MWCNTs (MWCNTs-Gl) were characterized by a set of methods including Fourier-transform infrared spectroscopy, X-ray diffraction, field emission scanning, and transmission electron microscopy. Thermogravimetric analysis (TGA) results also demonstrated the presence of organic portions of the functionalized MWCNTs. MWCNT-Gl/poly(amide-imide) (PAI) composite films with different MWCNTs-Gl content (5, 10, and 15 wt%) were prepared by ultrasonication-assisted solution blending method. Microscopic observations showed that the dispersion of the MWCNTs-Gl was improved by the organic groups on the MWCNT surface and functional groups on the PAI. TGA results showed that the hybrid films exhibited a good thermal stability. According to mechanical tensile tests, the tensile strength and the Young’s modulus of the MWCNT-Gl/PAI composites were increased with increasing MWCNTs-Gl content.     

Spray deposited fluoropolymer/multi-walled carbon nanotube composite films with high dielectric permittivity at low percolation threshold

High performance perfluoro alkoxy (PFA) and chemical vapor deposition-grown multi-walled carbon nanotube (MWCNT) composite films with thicknesses of 30 μm were prepared using a scalable spray deposition technique. A homogeneous distribution of MWCNTs within the PFA matrix was confirmed by electron and optical microscopy. Dielectric and AC conductivity measurements showed a significant enhancement of dielectric permittivity for PFA/MWCNT films at low frequencies, and a very weak dependence of dielectric permittivity on temperature in the range 25-230 °C. Very low percolation threshold volume fractions of ca. 0.0043 and 0.0017 were attained for MWCNTs with two different aspect ratios, which have been explained by an inherent feature of spray route, a microcapacitor model and percolation theory. The combination of PFA/MWCNT composites and the spray deposition route provides a promising approach for the fabrication of industrial scale composite films with well-controlled dielectric properties for micro-electronic and high temperature applications.     

Preparation and application of a multiwalled carbon nanotube composite monolithic column

A multiwalled carbon nanotube (MWCNT) composite monolithic column was prepared by the redox initiation method, and MWCNTs were embedded into the monolithic material. In this experiment, 1‐octene was used as monomer, triethylene glycol dimethacrylate was used as the crosslinking agent, propanol and 1‐dodecanol were used as porogens, hydroxyl‐functionalized MWCNTs were used as the inorganic material, and dibenzoyl peroxide and N,N‐dimethyl aniline were used as initiators. The MWCNT composite monolithic column was characterized by scanning electron microscopy, mercury intrusion porosimetry, and nitrogen adsorption–desorption isotherm measurements. The MWCNT composite monolith showed a uniform structure and a high permeability. The MWCNT composite monolithic column uses the high‐performance liquid chromatography to analyze the sample. Compared with the monolithic column without MWCNTs, the MWCNT composite monolith not only improved the column efficiency but also shortened the separation time. Six small molecules were successfully separated by the MWCNT composite monolith in 3 min, with the highest column efficiency reaching 36,000 plates/m In addition, the monolith was also used to separate complex protein samples, including snailase, plasma, and egg white. Therefore, the monolithic column was suitable both for the separation of macromolecules and small molecules. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45070.     

Highly stable polyimide composite films based on 1,2,4-triazole ring reinforced with multi-walled carbon nanotubes: Study on thermal,mechanical, and morphological properties

A novel diamine bearing aromatic pendant triazole ring, namely, 3,5-diamino-N-(1H-[1,2,4]triazol-3-yl)-benzamide, was successfully synthesized. The prepared diamine and a commercial dianhydride were reacted in situ in the presence of carboxylated multi-walled carbon nanotubes (MWCNTs) with stirring to give a homogeneous MWCNT/poly(amic acid) mixture which was then heated under a heating program to give a series of MWCNT/polyimide (PI) composites with different proportions of MWCNT (5, 10, and 15 wt%). The composite films were tested for different properties including spectral, morphological, thermal, and mechanical properties. Scanning and transmission electron microscopy revealed the modified MWCNTs were well dispersed in the PI matrix while the structure of the polymer and the MWCNTs structure were stable in the preparation process. The thermal stability of the films containing MWCNTs was improved as the MWCNT content increased from 5 to 15 wt% due to the improved interfacial interaction between the PI matrix and surface-modified MWCNTs. Tensile tests on the composites showed an increase in the elastic modulus and the yield strength, and decrease in the failure strain.     

Conductive,mechanical, and chemical resistance properties of polyurushiol/multiwalled carbon nanotube composite coatings

The polyurushiol (PUS)/multiwalled carbon nanotube (MWCNT) composite coatings were prepared by in situ composite method. The fracture morphology of the composite films showed that MWCNTs had been well dispersed in PUS matrix, which significantly decreased the electrical resistivity and the gloss of the composite films. The nonconducting/conducting state transition took place at approximately 3.0 wt% of MWCNTs with the volume electrical resistivity of 10⁴ Ω cm. The results of the mechanical tests revealed that the impact of strength and the storage modulus of the coatings increased with the addition of MWCNTs. Furthermore, the PUS/MWCNTs composite films had good chemical resistance. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Structure characterization and DC conductivity of honeycomb patterned poly(N‐vinylcarbazole)/multiwalled carbon nanotube composite film via pretreatment at high temperature

Poly(N‐vinylcarbazole) (PVK) composites containing different concentrations of multiwalled carbon nanotube (MWCNT) were synthesized through the oxidative polymerization of N‐vinylcarbazole with ferric chloride. The synthesized composites were characterized using Fourier transform infrared spectroscopy, ultraviolet‐visible spectra, and thermogravimetric analysis. A honeycomb‐patterned film was fabricated by casting the PVK–MWCNT composite solution under humid conditions. The morphology of the honeycomb‐patterned films in the PVK–MWCNT polymer composites and the dependence of its pore diameter and pore height on MWCNT concentration were analyzed using scanning electron microscopy. The honeycomb‐patterned films were treated at 150, 250, 400, and 490°C to study the arrangement of MWCNTs in the patterned films and to measure the DC conductivity depending on the calcination temperature. DC conductivity of the patterned films was increased by increasing the concentration of MWCNT in the composites and in the increased pretreatment temperature. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Studies on effect of ethyl 4-amino cinnamate functionalized multiwall carbon nanotubes (f-MWCNTs) on properties of millable polyurethane rubber (MPU) nanocomposites

Multiwall carbon nanotubes (MWCNTs) were prepared using chemical vapor deposition (CVD) technique in presence of nano Co/Mo-MgO as an efficient catalyst. Further the as-synthesized MWCNTs were functionalized using ethyl 4-amino cinnamate (f-MWCNTs) to improve its wettability or compatibility with the chains of polymer. The as-synthesized MWCNTs and f-MWCNTs were subjected to various characterization techniques Raman spectroscopy, X-ray diffraction, FTIR, FESEM and TGA to investigate its size, presence of functional groups and stability. It was observed that diameter of f-MWCNTs were found to be ~ 45 nm with thermally more stable. Further, f-MWCNTs (0 to 1 %) were reinforced in MPU rubber using two roll mill and molded on compression molding machine. The dumbbell shape specimens were then subjected to mechanical and thermal study. It was observed that both the tensile strength and % elongation at break of MPU nanocomposites increases significantly up to 0.8 wt loading and decreases thereafter. This improvement in properties was due to uniform dispersion of f-MWCNTs into the chains of MPU rubber with homogeneity in bonding, while the decrement in properties at 1wt % loading was due to agglomeration of f-MWCNTs at some places. Also the functionalization using ethyl 4-amino cinnamate increases the compatibility of MWCNTs with MPU rubber chains. Besides this, functionalization makes the surface of MWCNTs smooth with enhancement in bonding between the two surfaces that is filler as well as matrix counterpart. Significant improvement in mechanical and thermal properties are achieved due to modification MPU with functionalized MWCNT.     

The production of functionalized multiwall carbon nanotube/amino acid-based poly(amide–imide) composites containing a pendant dopamine moiety

The high compatibility of amino-acid based poly(amide–imide) (PAI) as a polymer matrix for acid-modified multi-walled carbon nanotubes (MWCNTs) is discussed. PAI was synthesized from the direct polycondensation reaction of N,N′-(pyromellitoyl)-bis-l-isoleucine with a dopamine-based diamine, 3,5-diamino-N-(3,4-dihydroxy-phenethyl)benzamide, in a medium consisting of a molten salt, tetrabutylammonium bromide, and triphenyl phosphite as the activator under microwave radiation. To obtain a homogeneous dispersion of MWCNTs in the PAI matrix, acid-functionalized MWCNTs were used. Composites containing 5, 10, and 15 wt.% MWCNT–COOH exhibited a relatively good dispersion on the macroscopic scale. MWCNT/PAI composite films have been prepared by casting a solution of precursor polymer containing MWCNTs into a thin film and its tensile properties examined. Incorporation of MWCNTs improved the mechanical properties significantly. Composites were also characterized by Fourier transform infrared spectroscopy, X-ray diffraction, scanning and transmission electron microscopy, and thermal gravimetric analysis. The thermal stability of the composites containing the CNTs was improved due to the increased interfacial interaction between the PAI matrix and the modified CNTs and their good dispersion.     

High dispersion and electrochemical capacitive performance of NiO on benzenesulfonic functionalized carbon nanotubes

This work describes an effective method to synthesize structurally uniform composite of nickel oxide/benzenesulfonic functionalized multiwalled carbon nanotubes composite (NiO/f-MWCNTs) using benzenesulfonic MWCNTs as the substrate. Benzenesulfonic group here is bifunctional both for solubilizing MWCNTs into aqueous solution and for tethering Ni²⁺ precursor onto MWCNTs surfaces to facilitate the follow-up chemical deposition of NiO by supplying surface binding and anchoring groups. The composite has a uniform surface dispersion and large coverage of NiO onto f-MWCNTs, which is characterized by X-ray diffraction, transmission electron microscopy, scanning electron microscope, cyclic voltammetry and galvanostatic charge/discharge measurements. The NiO/f-MWCNTs composite improved the utilization of electrochemical capacitive materials and delivered capacity of 384 F/g at the constant current of 0.20 A/g due to f-MWCNTs as substrate.     

The bulk polymerisation of N-vinylcarbazole in the presence of both multi- and single-walled carbon nanotubes: A comparative study

The bulk polymerisation of N-vinylcarbazole (NVC) at an elevated temperature in the presence of both multi- and single-walled carbon nanotubes (CNTs) leads to the formation of two different types of composite materials, the morphology and properties of which were characterised by a field emission scanning electron microscopy (FE-SEM), Fourier transform infrared (FTIR) spectroscopy, Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis, and electrical property measurements. The efficiency of CNTs to initiate the NVC polymerisation was investigated using both multi-walled CNTs (MWCNTs) and single-walled CNTs (SWCNTs). The focus was on three major aspects: the degree of polymerisation, the morphology and the properties of the resulting nanocomposite materials. Results showed that SWCNTs were more efficient in initiating NVC polymerisation than MWCNTs, and the morphology of resultant nanocomposites revealed wrapping and grafting of some poly(N-vinylcarbazole) (PNVC) chains on the SWCNT surfaces. The morphology of the PNVC/MWCNT nanocomposites showed only homogeneous wrapping of the outer surfaces of MWCNTs by PNVC chains. The direct current (dc) electrical conductivity of pure PNVC improved dramatically in the presence of both MWCNTs and SWCNTs, however, the extent of improvement is higher in the case of PNVC/MWCNT nanocomposites.     

Multi-walled carbon nanotube/polyimide composite film fabricated through electrophoretic deposition

Multi-walled carbon nanotube (MWCNT)/polyimide composite films were fabricated through electrophoretic deposition (EPD) of MWCNT-polyamic acid colloidal suspension which was derived from carboxylated-MWCNTs and poly(pyromellitic dianhydride-co-4,4′-oxydianiline) (PMDA-ODA). Under electric field, both negatively charged MWCNTs and PMDA-ODA colloid particles migrate onto a positively charged anode simultaneously, and are converted to a coherent MWCNT/polyimide composite film in the ensuing imidization reaction. Uniform dispersion of MWCNTs in the composite film was observed using transmission electron microscopy. The thickness of the prepared composite film can be tuned by varying processing conditions such as deposition time and anode conductivity. The electrical conductivity of the composite film increased with increasing the concentration of MWCNTs in EPD suspension. The mechanical reinforcement of polyimide using MWCNTs was evaluated by tensile testing and nanoindentation testing.     

Synthesis and properties of new polyamide/multiwalled carbon nanotube nanocomposites containing a pyridine group

The effects of multiwalled carbon nanotubes (MWCNTs) on the thermal properties and flame retardancy of a new polyamide (PA) derived from glutaric acid and aromatic diamine were investigated in this work. The synthesized PA containing pyridine and trialkylamine groups was characterized by ¹H NMR and SEC. The PA unit structure was geometrically optimized at the B₃LYP/6‐311⁺⁺G(d, p) level of theory. PA showed a glass transition temperature of 151 ºC. PA nanocomposites containing two different amounts of MWCNTs were prepared via the solution intercalation technique with the solvent N,N‐dimethylacetamide. Transmission electron microscopy showed that MWCNTs were exfoliated in the polymer matrix, resulting in well‐dispersed morphologies at 3 wt% MWCNT content. The redox behaviors of PA and the nanocomposites were examined using cyclic voltammetry (CV). PA showed a reversible oxidation process in the CV scan. Thermal and flammability properties of the nanocomposites were studied by TGA in nitrogen and air, DSC and with a microscale combustion calorimeter. The TGA results showed that the addition of MWCNTs resulted in a substantial increase in the thermal stability and char yields of the nanocomposites compared with neat PA. The heat release rate and total heat release were significantly reduced in the presence of MWCNTs. © 2013 Society of Chemical Industry     

Influence of polymer swelling and dissolution into food simulants on the release of graphene nanoplates and carbon nanotubes from poly(lactic) acid and polypropylene composite films

The study compared the effects of swelling and dissolution of a matrix polymer by food simulants on the release of graphene nanoplates (GNPs) and multiwall carbon nanotubes (MWCNTs) from poly(lactic) acid (PLA) and polypropylene (PP) composite films. The total migration was determined gravimetrically in the ethanol and acetic acid food simulants at different time and temperature conditions, while migrants were detected by laser diffraction analysis and transmission electron microscopy. Swelling, thermal analysis, and scanning electron microscopy were applied to characterize the degradation of polymer films at the migration conditions. The release of nanoparticles was found in a high‐temperature migration test of 4 h at 90 °C. The hydrolytic dissolution of the PLA polymer in the food simulants caused a migration of GNPs (>100 nm) from the PLA/GNP/MWCNT films into the simulant solvents, while the entangled MWCNTs formed a network on the film surface, preventing their migration from the PLA composite films. In contrast, the PP polymer slightly swells in ethanol solvents, allowing some short carbon nanotubes to be released from the surface and cut edges of the PP/MWCNT film into food simulants. Mathematical modeling of diffusion was applied that accounts for type of polymer, time–temperature conditions, and solvent concentration; model parameters were validated with experimental results. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45469.     

Electrochemical behavior of glassy carbon electrodes modified by multi-walled carbon nanotube/surfactant films in a buffer solution and an ionic liquid

The electrochemical behavior of glassy carbon (GC) electrodes coated with multi-walled carbon nanotube (MWCNT)/surfactant films was studied in an ionic liquid and a phosphate buffer solution (pH = 6.86), using cyclic voltammetry. The dispersion of MWCNTs in different media was investigated by scanning and transmission electron microscopy. Cast films of MWCNT/zwitterionic dodecyldimethylamine oxide on a GC electrode show a typical redox couple in phosphate buffer solution, which is better than that of MWCNT/anionic sodium dodecyl sulfate and cationic alkyltrimethylammonium bromide. However in the ionic liquid, 1-n-butyl-3-methylimidazolium hexafluorophosphate ([bmim][PF₆]), the GC electrode modified by MWCNT/cationic surfactant films shows a well-defined irreversible reduction of MWCNTs. The cyclic voltammograms clearly show that the surfactant hydrophilic group plays an important role in the electrochemical behavior of the MWCNTs. The electrolytes also have an important effect. In an ionic liquid, the strong binding of the ionic liquid cations with the MWCNTs may change the structure of the modified films and lead to changes of electrochemical behavior.