Electrical and rheological properties of MWCNT/polycarbonate nanocomposites

The electrical and rheological percolation behaviors of polycarbonate/multiwall carbon nanotube nanocomposites were investigated. To determine the effects of surface functionalization on a carbon nanotube surface, poly(styrene-co-acrylonitrile) (SAN)-grafted multiwall carbon nanotubes were prepared using surface-initiated atom transfer radical polymerization. The amount of grafted SAN was controlled by changing the polymerization time and was characterized using TGA. FT-IR and TEM were used to characterize the surface of the functionalized carbon nanotubes. The rheological and electrical percolation behaviors of the SAN-grafted multiwall carbon nanotube/polycarbonate nanocomposites were compared to those of pristine multiwall carbon nanotubes, where the effects were shown to increase with increasing SAN content. The results are attributed to the compatibility of SAN with polycarbonates, which induced uniform dispersion of the functionalized carbon nanotubes. Uniform dispersion was also confirmed by evaluating a tensile-fractured nanocomposite specimen.     

Morphology and properties of highly filled iPP/TiO2 nanocomposites

Nanocomposites based on isotactic polypropylene (iPP) and titanium dioxide (TiO₂) nanoparticle containing 1–15 vol% (4.6–45.5 wt%) of the nanoparticle were prepared by the melt blending process. The effect of an anhydride‐modified polypropylene as a compatibilizer on dispersion of TiO₂ nanoparticles was assessed using SEM. TGA and DSC analysis were performed to study the thermal properties of the nanocomposites. Crystalline structures of iPP in the presence of TiO₂ were analyzed by XRD. Mechanical properties of the nanoparticles were measured and a micromechanical analysis was applied to quantify interface interaction between the polymer and particle. SEM results revealed improvement of TiO₂ particle dispersion by adding the compatibilizer. It was shown that the thermal stability and crystalline structure of the nanocomposite are significantly affected by the state of particle dispersion. TiO₂ nanoparticles were shown to be strong β‐nucleating agents for iPP, especially at concentrations less than 5 vol%. Presence of the β‐structure crystals reduced the elastic modulus and yield strength of the nanocomposites. Micromechanical analysis showed enhanced interaction between organic and inorganic phases of the compatibilized nanocomposites. POLYM. ENG. SCI., 54:874–886, 2014. © 2013 Society of Plastics Engineers     

Preferential distribution of clay layers in iPP/OMMT/PEOc ternary nanocomposites

Isotactic polypropylene (iPP)/organo-montmorillonite (OMMT) nanocomposite was modified by poly(ethylene-co-octene) (PEOc). PEOc-rich domains were well dispersed in the iPP matrix, with narrowly distributed size. OMMT layers were well dispersed, mainly intercalated and partially exfoliated. Compared with the case in the binary composites, many OMMT layers were preferential distributed inside and around the PEOc-rich domains in the ternary composite samples, which formed an enhanced OMMT filler network. The reason for the OMMT preferential distribution was considered to be dragged or wrapped by PEOc-rich domains during sample preparation and phase separation.     

Dynamic cure kinetics of epoxy/TiO2/MWCNT hybrid nanocomposites

The effect of multi-walled carbon nanotubes (MWCNTs) on cure kinetic parameters of the epoxy/amine/TiO₂ (1 wt%) resin system was studied dynamically at four heating rates using DTA. The presence of MWCNT in various amounts (0.1, 0.2, 0.4 and 0.6 wt%) neither retarded nor accelerated the cure reaction of the epoxy/amine/TiO₂ system in a considerable extent. Addition of MWCNTs increased the extent of cure of the corresponding nanocomposites, especially at higher contents up to 0.4 wt% MWCNT filled composite. However, increasing the MWCNT content to 0.6 wt% adversely affected the extent of cure due to nanoparticle agglomeration. The fracture surface morphology of the nanocomposites revealed that the cracks deviated on reaching the MWCNTs, while propagating in the polymer matrix. Fractional extent of conversion (α) was calculated using genetic algorithm. Flynn–Wall–Ozawa and Kissinger methods were used to analyze the kinetic parameters. The presence of MWCNTs did not affect the autocatalytic cure mechanism of epoxy/amine/TiO₂ resin system and also did not cause any considerable barrier effect on the curing process. Activation energy data fitted well in the cubic polynomial regression equations and the changes of E _a with respect to α proved the autocatalytic cure mechanism, being followed by all the MWCNT-containing epoxy-based hybrid nanocomposites.     

Photodegradation of EPDM/MWCNT nanocomposites: Effect of singlet oxygen

The photo-oxidation of ethylene propylene diene monomer (EPDM)/multiwall carbon nanotubes (MWCNT) nanocomposites has been studied under accelerated UV-irradiation (λ ≥ 290 nm) in the presence of singlet oxygen. The rate of photodegradation of EPDM/MWCNT is found to be higher when compared to the pristine polymer in presence of singlet oxygen. The enhancement of the rate of degradation of composite has been described through [2 + 2] photocycloaddition reaction between singlet oxygen and double bonds on composite which is followed by cleavage. The rate of degradation and the formation of new functional groups on the composite has been monitored by FTIR spectroscopy and found to be increased with irradiation time. The changes in surface morphology have been studied by scanning electron microscope. Differential scanning calorimetry measurements revealed an increase in the glass transition temperature of photodegraded EPDM and EPDM/MWCNT nanocomposites. POLYM. COMPOS., 2009. © 2008 Society of Plastics Engineers     

Electrospun PVDF/MWCNT/OMMT hybrid nanocomposites: preparation and characterization

Electrospinning technique was employed to prepare neat PVDF, nanoclay-PVDF and carbon nanotube (MWCNT)-PVDF nanocomposites, and nanoclay-carbon nanotube-PVDF hybrid nanocomposites. A mixture of dimethyl formamide/acetone (60/40) was used to fluidize the polymer and nanofillers. Electrospinning process was conducted under optimized conditions. Maximum modification was achieved at 0.15 wt% nanofiller. Rheological measurements on the prepared solutions revealed decreased material functions in the presence of nanoclay, whereas the rheological properties of MWCNT-PVDF solution did not show any significant reduction compared with those of neat PVDF solution. The behaviors of the hybrid nanocomposite solutions, though dependent on their composition and their material functions, increased with MWCNT concentration. These differences, together with variations in electrical properties of nanoclay and MWCNT, led to changes in morphology of the fiber during electrospinning process. Under electrospinning conditions designed for neat PVDF solution, mats with beads and with the highest fiber diameter were produced. Meanwhile, incorporation of both nanoclay and MWCNT into the solutions resulted in bead-free fibers with thinner diameter. Fourier transformed infrared spectrophotometry (FTIR) and X-ray diffractometry (XRD) were used to measure the β-phase crystalline content in electrospun mats. Complete agreement was found between the FTIR and XRD results. The lowest and highest β-phase contents were obtained for neat PVDF mat and hybrid nanocomposite mat containing 0.1 wt% clay, respectively. The mixing procedure of nanofillers and the PVDF solution was also found to be important. In case of hybrid nanocomposites, more β-crystals were formed when the nanoclay was first mixed in the absence of MWCNT.     

Surface modification of MWCNT and its influence on properties of paraffin/MWCNT nanocomposites as phase change material

Multiwalled carbon nanotubes (MWCNTs) were modified by an organo-silane in order to improve their dispersion state and stability in paraffin wax. A family of paraffin-based phase change material (PCM) composites filled with MWCNTs was prepared with different loadings (0, 0.1, 0.5, and 1 wt%) of pristine MWCNTs and organo-silane modified MWCNTs (Si-MWCNT). Structural analyses were performed by means of Fourier transform infrared (FTIR), scanning electron microscopy (SEM), and rheological studies using temperature sweeps. Moreover, phase change transition temperatures and heat of fusion as well as thermal and electrical conductivities of the developed PCM nanocomposites were determined. The SEM micrographs and FTIR absorption bands appearing at approximately 1038 and 1112 cm⁻¹ confirmed the silane modification. Differential scanning calorimetery (DSC) results indicate that the presence of Si-MWCNTs leads to slightly favorable enhancement in the energy storage capacity at the maximum loading. It was also shown that the thermal conductivity of the PCM nanocomposites, in both solid and liquid phases, increased with increasing the MWCNT content independent of the kind of MWCNTs by up to about 30% at the maximum loading of MWCNTs. In addition, the modification of MWCNTs made the samples completely electrically nonconductive, and the electrical surface resistivity of the PCMs containing pristine MWCNTs decreased with increasing MWCNTs loading. Furthermore, the rheological assessment under consecutive cyclic phase change demonstrated that the samples containing modified MWCNTs are more stable compared to the PCM containing pristine MWCNTs. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48428.     

Effect of processing techniques on the performance of Epoxy/MWCNT nanocomposites

The aim of this study is to investigate the optimum technique to disperse Multi‐Walled Carbon Nanotubes (MWCNTs) in SC‐1 epoxy uniformly and to evaluate the effect of processing technique on the performance of SC‐1 epoxy. To achieve better dispersion, MWCNT was mixed with SC‐1 resin directly or premixed with a solvent and then mixed with SC‐1 resin after evaporating the solvent using sonication, thinky mixing and three‐roll mill methods either in isolation or combination. Flexural tests were performed to evaluate mechanical performances and results exhibit up to 27.13, 13.51, and 21.99% improvement on flexural strength, flexural modulus, and maximum strain, respectively, over neat epoxy with only 0.2 wt % loading. Dynamic mechanical analysis (DMA), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) indicated improvement in storage modulus, T_g, inflection temperature, and residue content, respectively over neat SC‐1 epoxy. Thermal and mechanical properties at higher loading conditions were seen to either reduce or not significantly improve. This was attributed to high viscosity of nanocomposites as determined by rheological analysis which prevents good dispersion of MWNCTs into epoxy system at 0.4 wt % loading. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Improving rheological properties of covalently MWCNT/epoxy nanocomposites via surface re-modification

This article describes the application of the chemical surface re-modification of carboxylated multi-walled carbon nanotubes (MWCNTs) through in-situ esterification of oligomeric unsaturated aliphatic hydroxyl terminated polyesters. The Fourier transform infrared spectroscopy and the thermogravimetric analysis proved covalent treatment of MWCNTs. Consequently, the acid–base titration method was employed to determine the population of the re-modified sites within the polyester chains. The dispersion state of the re-modified MWCNTs was investigated by the transmission electron microscopy relevant to the cured nanocomposite sample along with the Ultraviolet–Visible spectroscopy while using various solvents. The degree of dispersion was correlated to the Hansen solubility parameters. In summary, our study shows an appropriate dispersion of the re-modified MWCNTs into the solvents with a high dispersive fashion. In addition, the rheological properties of the re-modified MWCNTs/epoxy resin having various nanoinclusions were considerably studied and discussed. Also, an improved rheological response was observed in the case of the re-modified MWCNT nanocomposite samples.     

Cure behavior of epoxy/MWCNT nanocomposites: The effect of nanotube surface modification

The effect of carboxyl and fluorine modified multi-wall carbon nanotubes (MWCNTs) on the curing behavior of diglycidyl ether of bisphenol A (DGEBA) epoxy resin was studied using differential scanning calorimetry (DSC), rheology and infrared spectroscopy (IR). Activation energy (E_a) and rate constants (k) obtained from isothermal DSC were the same for the neat resin and fluorinated MWCNT system (47.7 and 47.5 kJ/mol, respectively) whereas samples containing carboxylated MWCNTs exhibited a higher activation energy (61.7 kJ/mol) and lower rate constant. Comparison of the activation energies, rate constants, gelation behavior and vitrification times for all of the samples suggests that the cure mechanisms of the neat resin and fluorinated sample are similar but different from the carboxylated sample. This can be explained by the difference in how the fluorinated nanotubes react with the epoxy resin compared to the carboxylated nanotubes. Although the two systems have different reaction mechanisms, both systems have similar degrees of conversion as calculated from the infrared spectroscopic data, glass transition temperature (T_g), and predictions based on DSC data. This difference in reaction mechanism may be attributed to differences in nanotube dispersion; the fluorinated MWCNT system is more uniformly dispersed in the matrix whereas the more heterogeneously dispersed carboxylated MWCNTs can hinder mobility of the reactive species and disrupt the reaction stoichiometry on the local scale.     

Material removal mechanisms by EDM of zirconia reinforced MWCNT nanocomposites

Several composites of tetragonal zirconia polycrystals doped with 3 mol% yttria (3Y-TZP) and multiwalled carbon nanotubes (MWCNT) with concentrations from 0.5 to 4 wt% CNT were processed, spark plasma sintered, and characterised for a wide range of mechanical, electrical and thermal properties. In particular, a strong increase in electrical conductivity at room temperature was found with only 0.5 wt% CNT. However, the thermal conductivity was decreasing with increasing CNT content. Electrical discharge machining (EDM) using die sinking was carried out using the composites of 1 and 2 wt% CNT as workpieces. It was shown that both compositions could be successfully machined by EDM. The surface integrity and the subsurface were studied by SEM/FIB in order to determine the material removal mechanisms, which were found to be associated to spalling and melting/evaporation. Raman Spectroscopy was used to evaluate the damage of CNTs after EDM.     

MWCNT/Hectorite hybrid filled acrylonitrile butadiene rubber/ ethylene-co-vinyl acetate blend nanocomposites: preparation and properties

Multiwalled carbon nanotube/hectorite hybrid filler (HMH) was prepared by simple dry grinding method. It was subsequently used for the reinforcement of technologically compatible acrylonitrile butadiene rubber (NBR)/ ethylene-co-vinyl acetate (EVA) blend through solution intercalation method. Analysis of the prepared blend nanocomposites confirms homogeneous dispersion of the constituent fillers in the polymer matrix and significant interaction between two types of constituent fillers. Mechanical properties of NBR/EVA blend are significantly improved with HMH content up to 4 wt.% followed by reversion. Maximum improvement observed in tensile strength, elongation at break and toughness are 106%, 37% and 171% respectively without significant rise in Young’s modulus. Results also show best dynamic mechanical and dielectric response at 4 wt.% and 3 wt.% HMH content respectively. Enhanced mechanical, dynamic mechanical and dielectric properties of the blend nanocomposites attained may be attributed to fair degree of compatibility between the two polymer matrices, homogeneous dispersion of fillers and improved polymer-filler interaction.     

Synthesis and photocatalytic performance of PVA/TiO2/graphene‐MWCNT nanocomposites for dye removal

TiO₂/graphene‐MWCNT nanocomposite was prepared using solvothermal reaction for the effective distribution of TiO₂ nanoparticles on carbonaceous materials. TiO₂/graphene‐MWCNT nanocomposite was immobilized in poly(vinyl alcohol) (PVA) matrix for a convenient recovery after wastewater purification. MWCNT was incorporated in a nanocomposite not only to prevent the restacking of graphene but also to increase the electron transfer from TiO₂. The detailed characterization of the nanocomposite was performed using SEM, EDX, XRD, XPS, and FTIR. The photocatalytic performance of PVA/TiO₂/graphene‐MWCNT nanocomposite was investigated by UV spectroscopy on the basis of degradation of organic pollutants. PVA/TiO₂/graphene‐MWCNT nanocomposite showed improved photocatalytic decomposition of more than 70% of residual dye left in case of using PVA/TiO₂/graphene nanocomposite due to the improved electron transfer and the higher adsorption of organic pollutants. PVA/TiO₂/graphene‐MWCNT nanocomposite was suitable as a promising material for the recyclable photocatalytic wastewater purification system. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40715.     

Antistatic packaging based on PTT/PTT-g-MA/ABS/MWCNT nanocomposites: Effect of the chemical functionalization of MWCNTs

Polymer/carbon nanotube nanocomposites have attracted high interest for a wide spectrum of applications, including antistatic packaging used to protect electronic devices against electrostatic discharge. Polytrimethylene terephthalate (PTT)/maleic-anhydride-grafted PTT (PTT-g-MA)/acrylonitrile butadiene styrene (ABS) blend-based multiwall carbon nanotubes (MWCNTs) nanocomposites were prepared through extrusion. It was conducted chemical functionalization on the MWCNTs by oxidation using nitric acid to introduce functional groups. The effect of the amount (0.5 or 1.0 wt%) and functionalization of MWCNTs on the nanocomposites was investigated. Despite the poor barrier properties of PTT/PTT-g-MA/ABS/MWCNT nanocomposites due to the presence of voids confirmed by scanning electron microscopy (SEM), the nanocomposites with functionalized MWCNT (MWCNTf) showed excellent barrier properties, indicating that the functionalization process improved the interaction between the MWCNTs and the matrix. The addition of MWCNTs into PTT/PTT-g-MA/ABS blend decreased the electrical resistivity by eight orders of magnitude. The use of MWCNTf may still disrupt the electrical network pathway and slightly decreasing the electrical resistivity, but the nanocomposites present the desired properties required for antistatic packaging.     

Microwave‐assisted synthesis and characterization of polyimide/functionalized MWCNT nanocomposites containing quinolyl moiety

Polyimide‐MWCNT nanocomposites were prepared by the reaction of a heterocyclic diamine monomer of bis(4‐amino‐3,5‐dimethylphenyl)‐2‐chloro‐3‐quinolylmethane (BACQM), pyromellitic dianhydride (PMDA) with unmodified MWCNT (MWCNT), acid‐functionalized MWCNT (acid‐MWCNT) or amine‐functionalized MWCNT (amine‐MWCNT) using microwave irradiation as well as by the conventional method. The structure of the monomer was confirmed by FTIR, ¹H‐NMR, and ¹³C‐NMR spectral techniques. The glass transition temperature (T_g) of the MWCNTs/polyimide nanocomposite was found to be higher than that of the unfilled polyimide system. The T_g's of both systems were higher when prepared with the microwave method than the conventional synthesis. The T_g's of the nanocomposites using acid and amine functionalized MWCNTs are greater than 300°C, in both methods. This is attributed to the presence of hydrogen bond and strong covalent bond in both the acid‐MWCNT/polyimide and amine‐MWCNT/polyimide systems. The morphological studies of the nanocomposites synthesized using microwave irradiation show that a distinct MWCNT nanofibrillar network is formed in the matrix when MWCNT or acid‐MWCNT is used. A homogeneous morphology, without distinct nanotube domains is seen when the amine‐MWCNT is covalently linked to the polymer. POLYM. COMPOS., 37:2417–2424, 2016. © 2015 Society of Plastics Engineers     

Polypropylene random copolymer/MWCNT nanocomposites: Isothermal crystallization kinetics,structural, and morphological interpretations

This article describes the crystallization process of polypropylene random copolymer (PPCP) under isothermal conditions in presence of varying amounts of multiwalled carbon nanotubes (MWCNT) ranging from 0.5 to 4.0% w/w. Increase in the crystallization temperature under dynamic conditions confirmed the nucleating behavior of MWCNTs, which was also corroborated by crystallization studies under isothermal conditions. The crystallization kinetics was analyzed using Avrami equation and the parameters such as Avrami exponent, the equilibrium melting temperature and fold surface energy for the crystallization of PPCP chains in nanocomposites were obtained from the calorimetric data in order to determine the effect of MWCNTs on these parameters. Spherulitic growth of PPCP crystals was also investigated as a function of time and MWCNT content using hot stage polarizing microscope. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41734.     

Nonisothermal crystallization kinetics study of LDPE/MWCNT nanocomposites: Effect of aspect ratio and surface modification

In this article, the effect of aspect ratio and chemical modification of multiwall carbon nanotubes (MWCNT) on the nonisothermal crystallization kinetics of LDPE/MWCNT nanocomposites was studied. Nine different samples were prepared using different MWCNT to study both effects. The cooling rate (R) was varied in the range 2–10°C/min. In this article, the effect of CNT loading, surface modification, and aspect ratio were studied. For the same MWCNT concentration, aspect ratio and  COOH modification had weak influence on both the peak crystallization temperature and the crystallization onset temperature. However, the crystallization onset temperature was significantly affected by the amount of MWCNT. The rate parameters in the modified Avrami method and Mo method [F(T)] of analyses show a very good fit of data. The Vyazovkin and Sbirrazzuoli method of analysis, which is based on Hoffman–Lauritzen theory for secondary crystallization, was also used. Temperature dependency of activation energy was obtained for 30–75% relative crystallinity of the produced nanocomposites. Activation energy based on calculations of Hoffman‐Lauritzen theory showed a decrease with the increase in the concentration of MWCNT and crystallization temperature. A proposed model of the form E = a exp (‐bXT) which relates the activation energy, E, to relative crystallinity, X, and crystallization temperature, T, was able to fit the whole set of data. Incorporation of MWCNT in nanocomposites lowers the activation energy; hence enhances the initial crystallization process as suggested by the different methods of data analyses. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Binary [Cu2O/MWCNT] and ternary [Cu2O/ZnO/MWCNT] nanocomposites: formation, characterization and catalytic performance in partial ethanol oxidation

Cuprous oxide agglomerates composed of 4-10 nm Cu2O nanoparticles were deposited on multiwalled carbon nanotubes (MWCNTs) and on ZnO/MWCNTs to give binary [Cu2O/MWCNT] and ternary [Cu2O/ZnO/MWCNT] composites. Di-aqua-bis[2-(methoxyimino)propanoato]copper Cu[O2CCCH3NOMe](2)·2H2O 1 in DMF was used as single source precursor for the deposition of nanoscaled Cu2O. The precursor decomposes either in air or under argon to yield CuO2 by in situ redox reaction. Thermogravimetric coupled mass spectroscopic analysis (TG-MS) of 1 revealed that methanol formed during the decomposition of 1 acts as a potential in situ reducing agent. Scanning electron microscopy (SEM) of the binary [Cu2O/MWCNT] nano-composite shows an increase of cuprous oxide loading depending on the precursor amount, along the periphery of the MWCNTs as well as formation of larger particle agglomerates. Transmission electron microscopy (TEM) of the sample shows crystalline domains of size 4-10 nm surrounded by an amorphous region within the larger particles. SEM and TEM of ternary [Cu2O/ZnO/MWCNT] clearly reveal that Cu2O nanoparticles are primarily deposited on ZnO rather than on MWCNTs. The catalytic activities of the [Cu2O/MWCNT] and [Cu2O/ZnO/MWCNT] binary and ternary composites were studied for the selective partial oxidation of ethanol to acetaldehyde with molecular oxygen. While using binary [Cu2O/MWCNT] (13.8 wt% Cu) as catalyst, acetaldehyde was obtained with a yield of 87% at 355 °C (selectivity 96% and conversion 91%). When nanoscale ZnO is present, the resulting [Cu2O/ZnO/MWCNT] composite shows preferential hydrogen and CO2 formation due to the fact that the dehydrogenation and total oxidation pathway is more favoured compared to the binary composite. Significant morphological changes of the catalyst during the catalytic process were observed.