Morphology,thermal expansion,and electrical conductivity of multiwalled carbon nanotube/epoxy composites

Multiwalled carbon nanotube/epoxy composites loaded with up to 0.5 wt % multiwalled carbon nanotubes were prepared and characterized. Infrared microscopy, scanning electron microscopy, thermogravimetry, differential scanning calorimetry, thermomechanical analysis, and electrical conductivity measurements of the composites were performed. Infrared microscopy and scanning electron microscopy images showed that the debundled nanotubes were well dispersed. The thermal expansion coefficients, before and after the glass transition, remained approximately constant with the addition of nanotubes, whereas the electrical conductivity at room temperature increased approximately 5 orders of magnitude. This result was attributed to the thermal expansion coefficients of the intertube gap on the carbon nanotube bundles, which were in the same range as that of the epoxy resin. Therefore, nanocomposites capable of electrostatic dissipation can be processed as neat epoxy materials with respect to the volume changes with temperature. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Investigation on flame retardancy and rheological and thermomechanical characterisation of multiwall carbon nanotube reinforced nanocomposites

Abstract

In the present work, the influence of multiwalled carbon nanotubes (MWCNTs) on the flame retardancy and rheological, thermal and mechanical properties of polybutilen terephthalate (PBT) and polypropylene (PP) matrixes has been investigated. The carbon nanotube content in the thermoplastic materials was 2 and 5?wt‐%. The nanocomposites were obtained by diluting a masterbatch containing 20?wt‐% nanotubes using a twin‐screw extruder and the thermal properties were analysed by differential scanning calorimetry and thermogravimetric analysis; thermomechanical properties were determined by dynamic mechanical thermal analysis and the rheological behaviour was studied by a Thermo Haake Microcompounder. The results concerning the flame retardancy show that the MWCNTs are not equally effective as flame retardants in PP and PBT. The ignition time is increased only for PBT whereas the extinguishing time is decreased for PP and PBT. The reinforcement of the thermoplastics with multiwall carbon nanotubes is improved regarding the mechanical and thermal properties of the nanocomposites compared to pristine materials and the behaviour of thermoplastic nanocomposites regarding fire retardancy depends on the nature of the polymeric matrix.     

Preparation and properties of cyclic olefin copolymers multiwalled carbon nanotube nanocomposites

Nanocomposites of cyclic olefin copolymer (COC) and two types of multiwalled carbon nanotubes (MWCNTs) with different aspect ratios were prepared. The morphology, thermal behavior, and electrical conductivity of the nanocomposites were investigated by scanning electron microscopy, differential scanning calorimetry, thermal gravimetric analysis, and the DC conductivity measurement. It was found that the developed nanocomposite preparation method resulted in good nanotubes dispersion in the polymer matrix for both types of MWCNTs. No appreciable differences in glass transition temperatures were observed between the pure COC and nanocomposites. On the other hand, CNTs significantly improved the thermo‐oxidative stability of the COC. The nanocomposites showed significant delay in onset of degradation and the degradation temperature was ～ 40°C higher than that of the pure COC. The nanocomposites also showed substantially higher DC conductivity, which increased with the nanotube concentration and aspect ratio. An increase of DC electrical conductivity over 10⁹ times can be achieved by the addition of 2 wt % CNTs. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synergistic effect of carbon nanotubes and clay platelets in reinforcing properties of silicone rubber nanocomposites

Fine powders of montmorillonite (MMT)/multiwalled carbon nanotube (MWCNT) hybrids have been prepared by simple grinding of MWCNT with MMT in different weight ratios of MMT to MWCNT (10 : 1, 6 : 1, 3 : 1, 1 : 1, and 1 : 3) and characterized by wide‐angle X‐ray diffraction, field emission scanning electron microscopy, and transmission electron microscopy. These studies have established the formation of the exfoliated structures of MMT/MWCNT (1 : 1) hybrid, in which MWCNTs exist in the state of single nanotubes that are adsorbed and intercalated on the surface and in between the MMT nanoplatelets. The hybrid has subsequently been used as reinforcing nanofiller in the development of high‐performance silicone rubber (SR) nanocomposites, and a remarkably synergistic effect of MMT and MWCNT on SR properties has been observed. The tensile strength of SR containing 1% w/w of the MMT/MWCNT (1 : 1) hybrid is improved by 215%, whereas the SR filled with MMT or MWCNT alone showed an improvement of 46 and 25%, respectively, over that of unfilled SR. In addition, SR/1 wt % MMT/MWCNT (1 : 1) nanocomposites also exhibit the maximum improvement in thermal stability corresponding to 10% weight loss by 70°C, crystallization and melting temperatures increased by 8 and 6°C as inferred from thermogravimetric analysis and differential scanning calorimetry, respectively. This approach is promising for the preparation of high‐performance SR nanocomposites by using different dimension nanofillers together. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41818.     

Combination of Plasma Functionalization and Phase Inversion Process Techniques for Efficient Dispersion of MWCNTs in Polyamide 6: Assessment through Morphological,Electrical, Rheological and Thermal Properties

Different contents of multiwalled carbon nanotube (MWCNTs) functionalized by He-dielectric barrier discharge (DBD) plasma followed by an exposure to NH₃ were incorporated into PA6 matrix via a phase inversion based solution method. Optical and electron microscopic results were indicative of the excellent dispersion state of the MWCNTs. The differential scanning calorimetry and thermogravimetric analysis measurements revealed that even addition of a slight amount of the MWCNTs significantly increased the thermal stability and crystallization temperature. Moreover, the low electrical percolation threshold of the PA 6/functionalized MWCNTs nanocomposites was another confirmation for achieving a good dispersion state of MWCNTs using this approach.     

Isothermal crystallization behavior of polyamide 6,6/multiwalled carbon nanotube nanocomposites

The good dispersion of functionalized multiwalled carbon nanotube (f‐MWCNT) in polyamide 6,6 (PA 6,6) matrix was prepared by solution mixing techniques. The crystalline structure and crystallization behaviors of PA 6,6 and PA 6,6/f‐MWCNT nanocomposites were studied by X‐ray diffraction (XRD), differential scanning calorimetry (DSC), and polarized optical microscopy (POM) analysis. DSC isothermal results revealed that the overall isothermal crystallization rates of PA 6,6 increased as well as the activation energy of PA 6,6 extensively decreased by adding f‐MWCNT into PA 6,6, suggesting that the addition of f‐MWCNT probably induces the heterogeneous nucleation. The effect of f‐MWCNT on the chain arrangement for the crystallization of PA 6,6/f‐MWCNT nanocomposites was also discussed. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

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     

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.     

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).     

On the dispersion of CNTs in polyamide 6 matrix via solution methods: assessment through electrical, rheological, thermal and morphological analyses

In this study, polyamide 6 (PA 6)/multi-walled carbon nanotube (MWCNT) nanocomposites were prepared by different solution methods based on phase inversion, drop-casting and simple evaporation processes. Optical microscopy and field emission scanning electron microscopy techniques were used to investigate the dispersion states of the nanotubes in PA 6 matrix. The results indicated that the dispersion state of MWCNTs in the nanocomposites prepared by the phase inversion-based method was better than those in the nanocomposites prepared by the other two methods. Electrical, rheological, differential scanning calorimetry and thermo-gravimetric analysis measurements showed that the PA 6/MWCNTs nanocomposites prepared by the phase inversion-based method had higher electrical conductivity, storage modulus, crystallization temperature and thermal stability in comparison with those prepared by the other two methods, attributed to the better dispersion state of MWCNTs. These results confirmed achievement of a good dispersion state of MWCNTs within PA 6 matrix by the phase inversion-based efficient approach.     

The Improvement of Electrical Property of Multiwalled Carbon Nanotubes with Plasma Modification and Chemical Oxidation in the Polymer Matrix

We prepared a series of multiwalled carbon nanotube/polymer nanocomposites with two types of tube. One was plasma-modified with maleic anhydride and the other was modified with acid and the same plasma treatment. The morphology of the modified multiwalled carbon nanotube was observed by transmission and scanning electron microscopy. The surface structure was characterized by X-ray diffraction and X-ray photoelectron spectroscopy. The optimum conductivity of multiwalled carbon nanotube/polymer nanocomposites with specific ratios was of the order of 10⁻³ S/cm for a total MWCNT content of 2.0 and 2.5 wt%.     

Effect of core–shell rubber toughening on mechanical,thermal, and morphological properties of poly(lactic acid)/multiwalled carbon nanotubes nanocomposites

The effect of core–shell rubber (CSR) toughening on mechanical and thermal properties of poly(lactic acid)/multiwalled carbon nanotubes (PLA/CNT) nanocomposites were investigated. The nanocomposites were prepared by direct melt blending method in a counter-rotating twin-screw extruder. The contents of CSR were varied between 5 and 20 wt % while the content of CNT was kept at 5 phr. The extruded samples were injection molded into the desired test specimens for mechanical and thermal properties analysis. The impact strength of PLA/CNT increased with increasing CSR content with concomitant decrease in tensile strength and modulus. Interestingly, the flexural strength increased at low CSR content before decreasing at 15 and 20% content. Differential scanning calorimetry analysis on the second heating cycle shows no crystallinity content for PLA/CNT and all CSR toughened PLA/CNT nanocomposites, while thermogravimetric analysis shows lower thermal degradation of all CSR toughened PLA/CNT as compared to PLA/CNT nanocomposite. This study reveals significant correlation between CSR loading with the mechanical and thermal properties of the nanocomposites. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47756.     

Electrical and mechanical properties of acrylonitrile‐butadiene‐styrene/multiwall carbon nanotube nanocomposites prepared by melt‐blending

The electrical properties in polymer/carbon nanotube (CNT) nanocomposites are governed not only by the degree of dispersion but also to a greater extent on the aspect ratio of the CNTs in the final composites. Melt‐mixing of polymer and CNTs at high shear rate usually breaks the CNTS that lowers the aspect ratio of the nanotubes. Thus, homogeneous dispersion of CNTs while retaining the aspect ratio is a major challenge in melt‐mixing. Here, we demonstrate a novel method that involves melt‐blending of acrylonitrile‐butadiene‐styrene (ABS) and in situ polymerized polystyrene (PS)/multiwalled CNT (MWCNT) nanocomposites, to prepare electrically conducting ABS/MWCNT nanocomposites with very low CNT loading than reported. The rationale behind choosing PS/MWCNT as blending component was that ABS is reported to form miscible blend with the PS. Thus, (80/20 w/w) ABS/(PS/MWCNT) nanocomposites obtained by melt‐blending showed electrical conductivity value ≈1.27 × 10^?6 S cm^?1 at MWCNT loading close to 0.64 wt %, which is quite lower than previously reported value for ABS/MWCNT system prepared via solution blending. Scanning electron microscopy and differential scanning calorimetry analysis indicated the formation of homogenous and miscible blend of ABS and PS. The high temperature (100°C) storage modulus of ABS (1298 MPa) in the nanocomposites was increased to 1696 MPa in presence of 0.64 wt % of the MWCNT. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Thermal and mechanical properties of phosphorylated multiwalled carbon nanotube/polyvinyl chloride composites

The fabrication of carbon nanotube/polyvinyl chloride (PVC) composites and a study of their thermal and mechanical properties are reported. Phosphorylated multiwalled carbon nanotube (p-MWCNT) and pristine MWCNT were used. The MWCNT were embedded in the polymer matrix through melt mixing. The phosphorylation of the MWCNT and their dispersion in the PVC matrix were characterized by scanning and transmission electron microscopy and Raman spectroscopy. Thermal analysis by thermal gravimetric analysis and differential scanning calorimetry, showed an increase in glass transition temperature and melting temperature for the composites with respect to pure PVC. The modulus of the MWCNT/PVC composites increased while there was a reduction in their tensile strength, indicating a decrease in polymer toughness.     

The characteristics of carbon nanotube‐reinforced poly(phenylene sulfide) nanocomposites

Multiwall carbon nanotube reinforced poly (phenylene sulfide) (PPS) nanocomposites were successfully fabricated through melt compounding. Structural, electrical, thermal, rheological, and mechanical properties of the nanocomposites were systematically studied as a function of carbon nanotube (CNT) fraction. Electrical conductivity of the polymer was dramatically enhanced at low loading level of the nanotubes; the electrical percolation threshold lay between 1 and 2 wt % of the CNTs. Rheological properties of the PPS nanocomposites also showed a sudden change with the CNT fraction; the percolation threshold was in the range of 0–0.5 wt % of CNTs. The difference in electrical and rheological percolation threshold was mainly due to the different requirements needed in the carbon nanotube network in different stages. The crystallization and melting behavior of CNT‐filled PPS nanocomposites were studied with differential scanning calorimetry; no new crystalline form of PPS was observed in the nanocomposites, but the crystallization rate was reduced. The thermal and mechanical properties of the nanocomposites were also investigated, and both of them showed significant increase with CNT fraction. For 5 wt % of CNT‐filled PPS composite, the onset of degradation temperature increased by about 13.5°C, the modulus increased by about 33%, and tensile strength increased by about 172%. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Montmorillonite–multiwalled carbon nanotube nanoarchitecture reinforced thermoplastic polyurethane

Montmorillonite (MMT)–multiwalled carbon nanotube (MWCNT) hybrids were prepared in different weight ratios by simple dry grinding method and characterized. Subsequently, MMT–MWCNT (1:1) hybrid was used as reinforcing filler in developing thermoplastic polyurethane (TPU) nanocomposites by solution blending method. Thermogravimetric analysis showed that 0.25 wt% hybrid‐loaded TPU nanocomposite exhibited maximum enhancement of 31°C corresponding to 50 wt% loss in thermal stability when compared with neat TPU. Differential scanning calorimetry of this composite also indicated that its crystallization and melting temperatures are enhanced by 37 and 13°C, respectively. Mechanical data showed that tensile strength and Young's modulus of 0.50 wt% filled TPU were maximum improved by 57 and 87.5%, respectively. Dynamic mechanical analysis (DMA) measurements indicated 174% (50°C) improvement in storage modulus of 0.50 wt% hybrid‐loaded TPU. Such improvements in thermal and mechanical properties have been attributed to homogeneous dispersion, strong interfacial interaction, and synergistic effect. POLYM. COMPOS., 37:1775–1785, 2016. © 2014 Society of Plastics Engineers     

Time–Temperature-Transformation Cure Diagram of Multiwall Carbon Nanotube/Epoxy Composites

This work describes the effects of multiwall carbon nanotube on the isothermal time–temperature-transformation cure diagram to obtain a comprehensive cure map for a 2 wt% multiwall carbon nanotube/epoxy composite. The viscoelastic and thermal properties of the nanocomposites for a wide range of isothermal cure temperatures were obtained using a strain-controlled rheometer ARES TA and a differential scanning calorimetry. The thermal and rheological analyses were used to investigate the vitrification and the gelation of the nanocomposite, and to draw the time–temperature-transformation diagram. This diagram is completed by adding the iso-viscosity curves.     

The thermal properties of a carbon nanotube‐enriched epoxy: Thermal conductivity,curing, and degradation kinetics

Multiwalled carbon nanotube‐enriched epoxy polymers were prepared by solvent evaporation based on a commercially available epoxy system and functionalized multiwalled carbon nanotubes (COOH–MWCNTs). Three weight ratio configurations (0.05, 0.5, and 1.0 wt %) of COOH–MWCNTs were considered and compared with neat epoxy and ethanol‐treated epoxy to investigate the effects of nano enrichment and processing. Here, the thermal properties of the epoxy polymers, including curing kinetics, thermal conductivity, and degradation kinetics were studied. Introducing the MWCNTs increased the curing activation energy as revealed by differential scanning calorimetry. The final thermal conductivity of the 0.5 and 1.0 wt % MWCNT‐enriched epoxy samples measured by laser flash technique increased by up to 15% compared with the neat material. The activation energy of the degradation process, investigated by thermogravimetric analysis, was found to increase with increasing CNT content, suggesting that the addition of MWCNTs improved the thermal stability of the epoxy polymers. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2722–2733, 2013     

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 bone ash fillers on mechanical and thermal properties of biobased epoxy nanocomposites

In this study, the fabrication and characterization of bone ash filled biobased epoxy resin (Super SAP 100/1000, contains 37% biobased carbon content) nanocomposites are presented. Biosource bone ash was modified by size reduction and surface modification processes using a combination of ball milling and sonochemical techniques and characterized using X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. The modified bone ash particles were incorporated into biobased epoxy with noncontact mixing process. The as-fabricated nanocomposites were characterized using various thermal and mechanical analyses. The nanocomposites showed significant improvement in flexural strength (41.25%) and modulus (34.56%) for 2 wt% filler loading. Dynamic mechanical analysis (DMA) results showed improvement in both storage modulus and loss modulus. Additionally, DMA results showed a slight reduction in glass transition temperature which also complies with differential scanning calorimetry results. Thermomechanical analysis results showed a reduction in the coefficient of thermal expansion. Thermogravimetric analysis results showed improved thermal stability at both onset of degradation and the major degradation. These enhanced thermal and mechanical performances of the epoxy nanocomposites allows them to be suitable for lightweight aerospace, automotive, and biomedical applications.