Low percolation threshold in polycarbonate/multiwalled carbon nanotubes nanocomposites through melt blending with poly(butylene terephthalate)

Here, we demonstrate an easy method for the preparation of highly electrically conductive polycarbonate (PC)/multiwalled carbon nanotubes (MWCNTs) nanocomposites in the presence of poly(butylene terephthalate) (PBT). In the presence of MWCNTs, PC and PBT formed a miscible blend, and the MWCNTs in the PC matrix were uniformly and homogeneously dispersed after the melt mixing of the PC and PBT–MWCNT mixture. Finally, when the proportion of the PC and PBT–MWCNT mixture in the blend/MWCNT nanocomposites was changed, an electrical conductivity of 6.87 × 10^?7 S/cm was obtained in the PC/PBT–MWCNT nanocomposites at an MWCNT loading as low as about 0.35 wt %. Transmission electron microscopy revealed a regular and homogeneous dispersion and distribution of the MWCNTs and formed a continuous conductive network pathway of MWCNTs throughout the matrix phase. The storage modulus and thermal stability of the PC were also enhanced by the presence of a small amount of MWCNTs in the nanocomposites. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Reduction of percolation threshold through double percolation in melt‐blended polycarbonate/acrylonitrile butadiene styrene/multiwall carbon nanotubes elastomer nanocomposites

We demonstrate a method that involves melt blending of polycarbonate (PC) and melt‐blended acrylonitrile butadiene styrene (ABS) with multiwall carbon nanotubes (MWCNTs) to prepare electrically conducting PC/MWCNT nanocomposites at significantly low MWCNT loading. The partial solubility of ABS in PC led to a selective dispersion of the MWCNTs in the ABS phase after melt‐blending PC and ABS. Thus, a sudden rise in electrical conductivity (∼10⁸ orders of magnitude) of the nanocomposites was found at 0.328 vol% of MWCNT, which was explained in terms of double percolation phenomena. By optimizing the ratio of PC and the ABS–MWCNT mixture, an electrical conductivity of 5.58 × 10⁻⁵ and 7.23 × 10⁻³ S cm⁻¹ was achieved in the nanocomposites with MWCNT loading as low as 0.458 and 1.188 vol%, respectively. Transmission electron microscopy revealed a good dispersion and distribution of the MWCNTs in the ABS phase, leading to the formation of continuous MWCNT network structure throughout the matrix even at very low MWCNT loading. Storage modulus and thermal stability of the PC were also increased by the presence of a small amount of MWCNTs in the nanocomposites.POLYM. COMPOS., 2013. © 2013 Society of Plastics Engineers     

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     

Low percolation threshold and high electrical conductivity in melt‐blended polycarbonate/multiwall carbon nanotube nanocomposites in the presence of poly(ε‐caprolactone)

This study focuses on the electrical properties of polycarbonate (PC)/poly(ε‐caprolactone) (PCL)‐multiwall carbon nanotube (MWCNT) nanocomposites. MWCNTs were incorporated into thermoplastic PC matrix by simple melt blending using biodegradable PCL based concentrates with MWCNT loadings (3.5 wt%). Because of the lower interfacial energy between MWCNT and PCL, the nanotubes remain in their excellent dispersion state into matrix polymer. Thus, electrical percolation in PC/PCL‐MWCNT nanocomposites was obtained at lower MWCNT loading rather than direct incorporation of MWCNT into PC matrix. AC and DC electrical conductivity of miscible PC/PCL‐MWCNT nanocomposites were studied in a broad frequency range, 10¹?10⁶ Hz and resulted in low percolation threshold (p_c) of 0.14 wt%, and the critical exponent (t) of 2.09 from the scaling law equation. The plot of logσ_DC versus p^?1/3 showed linear variation and indicated the existence of tunneling conduction among MWCNTs. At low MWCNT loading, the influence of large polymeric gaps between conducting clusters is the reason for the frequency dependent electrical conductivity. Transmission electron microscopy and field emission scanning electron microscopy showed that MWCNTs were homogeneously dispersed and developed a continuous interconnected network path throughout the matrix phase and miscibility behavior of the polymer blend. POLYM. ENG. SCI., 54:646–659, 2014. © 2013 Society of Plastics Engineers     

Thermal and electrical conductivity of melt mixed polycarbonate hybrid composites co‐filled with multi‐walled carbon nanotubes and graphene nanoplatelets

In this work, we present thermoplastic nanocomposites of polycarbonate (PC) matrix with hybrid nanofillers system formed by a melt‐mixing approach. Various concentrations of multi‐walled carbon nanotubes (MWCNT) and graphene nanoplatelets (GnP) were mixed in to PC and the melt was homogenized. The nanocomposites were compression molded and characterized by different techniques. Torque dependence on the nanofiller composition increased with the presence of carbon nanotubes. The synergy of carbon nanotubes and GnP showed exponential increase of thermal conductivity, which was compared to logarithmic increase for nanocomposite with no MWCNT. Decrease of Shore A hardness at elevated loads present for all investigated nanocomposites was correlated with the expected low homogeneity caused by a low shear during melt‐mixing. Mathematical model was used to calculate elastic modulus from Shore A tests results. Vicat softening temperature (VST) showed opposite pattern for hybrid nanocomposites and for PC‐MWCNT increasing in the latter case. Electrical conductivity boost was explained by the collective effect of high nanofiller loads and synergy of MWCNT and GnP. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42536.     

Curing enhancement and network effects in multi‐walled carbon nanotube‐filled vulcanized natural rubber: evidence for solvent sensing

Electrically and thermally conductive polymer composites offer great possibilities in various electronic fields because of their low weight and ease of processing. This paper addresses the curing behaviour and network properties of conducting multi‐walled carbon nanotube (MWCNT)‐reinforced natural rubber (NR) nanocomposites, emphasizing the sensing and diffusion performances. NR/MWCNT composites were prepared following a special master batch technique which allows the appropriate distribution of nanotubes within the elastomer. The sensing responses of the composites towards solvents were observed as variations in electrical resistance. Thermal resistance and glass transition behaviour were examined and correlated with the swelling measurements as evidence for solvent sensing. An optimum level of 3 phr of MWCNTs is understood to lead to the best properties for the NR/MWCNT composites. Finally, the structural morphology and interfacial interactions were found to have correlations with cure reactions, glass transition temperatures and sensing responses of all compositions. © 2017 Society of Chemical Industry     

Crystallization behavior and mechanical strength of poly(butylene succinate‐co‐ethylene glycol)‐based nanocomposites using functionalized multiwalled carbon nanotubes

Biodegradable poly(butylene succinate‐co‐ethylene glycol) (PBSG)/multiwalled carbon nanotube (MWCNT) nanocomposites were successfully prepared through physical blending and silication between PBSG and acyl aminopropyltriethoxysilane functionalized multiwalled carbon nanotube (MWCNT‐APTES). Nuclear magnetic resonance (NMR) spectra observations revealed that the PBSG chains were covalently attached to the MWCNT‐APTES by hydrolysis. PBSG/MWCNT‐APTES nanocomposites after hydrolysis showed excellent interfacial compatibility between PBSG and MWCNT‐APTES, which was helpful for the dispersion of MWCNT in the PBSG matrix. The incorporation of MWCNT‐APTES accelerated the crystallization of PBSG in the nanocomposites for both approaches of physical blending and hydrolysis due to the heterogeneous nucleation effect of MWCNT while the crystal structure of PBSG was remained. Furthermore, the crystallization rate of PBSG in PBSG/MWCNT‐APTES nanocomposites after hydrolysis was slower than that in the nanocomposite by physical blend. The tensile strength and modulus of the nanocomposites increased about 6% and 11% with the addition of only 1 wt% MWCNT‐APTES compared with that of neat PBSG, and was larger for the PBSG/MWCNT‐APTES nanocomposites after hydrolysis. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

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     

Preparation and characterization of extruded nanocomposite based on polycarbonate/butadiene‐acrylonitrile‐styrene blend filled with multiwalled carbon nanotubes

Nanocomposites of polycarbonate/acrylonitrile‐butadiene‐styrene (PC/ABS) with multiwall carbon nanotubes (MWCNT) prepared by masterbatch dilution are investigated in this work. Melt compounding with twin screw extruder is followed by complete characterization of morphology, rheological‐, mechanical‐, and thermal‐properties of the nanocomposites. Light‐transmission‐ and scanning electron microscopy shows the preferential location of MWCNT in the PC. Nevertheless, relatively good dispersion in the whole matrix is achieved, what is corroborated with the specific mechanical energy. The study of viscoelastic properties of PC/ABS‐MWCNT shows the fluid–solid transition below 0.5 wt % MWCNT. Beyond this point the continuous nanofiller network is formed in the matrix promoting the reinforcement. Addition of 0.5 wt % MWCNT reduces ductility of PC/ABS and enhances Young's modulus by about 30% and yield stress by about 20%. Moreover, theoretical values of stiffness calculated within this work agree with the experimental data. Electrical conductivity, showing percolation at 2.0 wt % MWCNT, are influenced by processing temperature. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40271.     

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     

Electrical conductivity and oxygen permeability of polyacrylonitrile/multiwalled carbon nanotubes composites

Polyacrylonitrile (PAN)/Multiwalled carbon nanotube (MWCNT) nanocomposites were prepared by nonconventional ultrasonic‐assisted emulsifier free emulsion polymerization technique with variable percentage of functionalized carbon nanotube. PAN/MWCNT nanocomposites were characterized by ultraviolet‐visible (UV‐visible) spectroscopy and Fourier transform infrared (FTIR) spectroscopy. The result from UV‐visible suggested that the functionalized MWCNT had interfacial interaction with PAN matrices. The surface morphology of functionalized MWCNT and PAN/MWCNT nanocomposites were studied by scanning electron microscopy (SEM). Electrical properties of PAN/MWCNT nanocomposites were measured and the result indicated that the conductivity increased with increasing concentration of MWCNTs. The oxygen permeability of PAN/MWCNT nanocomposites gradually increased with increase of MWCNT concentration, the result which was in agreement with the vertical alignment ofMWCNT in SEM. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Synthesis of New PI/MWCNT Containing Sulfone Groups via In Situ Polymerization: Study on Thermal,Electrical, and Optical Properties

New series of polyimide (PI) nanocomposites reinforced with three different amounts of multiwalled carbon nanotubes (MWCNT; 0.5, 1, and 3 wt%) were prepared by casting, evaporation and thermal imidization. Homogeneous dispersion of MWCNT in PI matrix was investigated by transmission electron microscopy. The effects of MWCNT on the thermal properties of the PI were investigated by thermogravimetric analysis. The results showed that the thermal stability of the nanocomposites enhanced with the increasing MWCNTs content. The resultant PI/MWCNT nanocomposites were electrically conductive with significant conductivity enhancement at 3 wt% MWCNT, which is favorable for many practical uses.     

Morphology,mechanical performance,and nanoindentation behavior of injection molded PC/ABS‐MWCNT nanocomposites

In this work, nanocomposites of polycarbonate/acrylonitrile‐butadiene‐styrene (PC/ABS) with various loads of multiwall carbon nanotubes (MWCNT) are investigated. Material is previously formed by masterbatch dilution approach and further processed by injection molding at various velocities. Microscopic characterization of nanocomposites morphology reveals stronger dependence of MWCNT dispersion on processing parameters at higher nanofiller load. Dispersion of carbon nanotubes at various distances from the injection gate is studied by Raman spectroscopy showing lower deviation at elevated injection velocity. Nanoindentation results that are in agreement with uniaxial tensile testing show a slight decrease of nanocomposites' mechanical performance at 3.0 wt % MWCNT in samples injected at reduced velocity. This is explained by the increase of agglomeration behavior at these conditions. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42014.     

Graphene nanoplate and multiwall carbon nanotube–embedded polycarbonate hybrid composites: High electromagnetic interference shielding with low percolation threshold

This study has reported the preparation of polycarbonate (PC)/graphene nanoplate (GNP)/multiwall carbon nanotube (MWCNT) hybrid composite by simple melt mixing method of PC with GNP and MWCNT at 330°C above the processing temperature of the PC (processing temperature is 280°C) followed by compression molding. Through optimizing the ratio of (GNP/MWCNT) in the composites, high electromagnetic interference shielding effectiveness (EMI SE) value (∼21.6 dB) was achieved at low (4 wt%) loading of (GNP/MWCNT) and electrical conductivity of ≈6.84 × 10⁻⁵ S.cm⁻¹ was achieved at 0.3 wt% (GNP/MWCNT) loading with low percolation threshold (≈0.072 wt%). The high temperature melt mixing of PC with nanofillers lowers the melt viscosity of the PC that has helped for better dispersion of the GNPs and MWCNTs in the PC matrix and plays a key factor for achieving high EMI shielding value and high electrical conductivity with low percolation threshold than ever reported in PC/MWCNT or PC/graphene composites. With this method, the formation of continuous conducting interconnected GNP‐CNT‐GNP or CNT‐GNP‐CNT network structure in the matrix polymer and strong π–π interaction between the electron rich phenyl rings and oxygen atom of PC chain, GNP, and MWCNT could be possible throughout the composites. POLYM. COMPOS., 37:2058–2069, 2016. © 2015 Society of Plastics Engineers     

Unique nucleation of multi-walled carbon nanotube and poly(ethylene 2,6-naphthalate) nanocomposites during non-isothermal crystallization

Multi-walled carbon nanotube (MWCNT) and poly(ethylene 2,6-naphthalate) (PEN) nanocomposites are prepared by a melt blending process. There are significant dependence of non-isothermal crystallization behavior and kinetics of PEN/MWCNT nanocomposites on the MWCNT content and cooling rate. The incorporation of MWCNT accelerates the mechanism of nucleation and crystal growth of PEN, and this effect is more pronounced at lower MWCNT content. Combined Avrami and Ozawa analysis is found to be effective in describing the non-isothermal crystallization of the PEN/MWCNT nanocomposites. The MWCNT in the PEN/MWCNT nanocomposites exhibits much higher nucleation activity than any nano-scaled reinforcement. When a vary small quantity of MWCNT was added, the activation energy for crystallization is lower, then gradually increased, and becomes higher than that of pure PEN above 1.0 wt% MWCNT content. The incorporation of MWCNT improves the storage modulus and loss modulus of PEN/MWCNT nanocomposites.     

Rheological and thermal properties of poly(ethylene oxide)/multiwall carbon nanotube composites

Poly(ethylene oxide) (PEO) based nanocomposites were prepared by the dispersion of multiwall carbon nanotubes (MWCNTs) in aqueous solution. MWCNTs were added up to 4 wt % of the PEO matrix. The dynamic viscoelastic behavior of the PEO/MWCNT nanocomposites was assessed with a strain‐controlled parallel‐plate rheometer. Prominent increases in the shear viscosity and storage modulus of the nanocomposites were found with increasing MWCNT content. Dynamic and isothermal differential scanning calorimetry studies indicated a significant decrease in the crystallization temperature as a result of the incorporation of MWCNTs; these composites can find applications as crystallizable switching components for shape‐memory polymer systems with adjustable switching temperatures. The solid‐state, direct‐current conductivity was also enhanced by the incorporation of MWCNTs. The dispersion level of the MWCNTs was investigated with scanning electron microscopy. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Cellulose acetate/multiwalled carbon nanotube nanocomposites with improved mechanical,thermal, and electrical properties

Cellulose acetate (CA)‐based nanocomposites with various contents of neat multiwalled carbon nanotube (MWCNT) or acid‐treated one (MWCNT‐COOH) are prepared via melt‐compounding method and investigated their morphology, thermal stability, mechanical, and electrical properties. SEM microphotographs reveal that MWCNT‐COOHs are dispersed uniformly in the CA matrix, compared with neat MWCNTs. FTIR spectra support that there exists a specific interaction between carboxyl groups of MWCNT‐COOHs and ester groups of CA, indicating good interfacial adhesion between MWCNT‐COOHs and CA matrix. Accordingly, thermal stability and dynamic mechanical properties of CA/MWCNT‐COOH nanocomposites were higher than those of CA/MWCNT composites. On the contrary, electrical volume resistivities of CA/MWCNT‐COOH nanocomposites are found to be somewhat higher than those of CA/MWCNT composites, which is because of the deterioration of graphene structures for MWCNT‐COOHs and the good dispersion of MWCNT‐COOHs in the CA matrix. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of processing parameters on the surface resistivity of ethylene propylene diene terpolymer/multiwalled carbon nanotube nanocomposites

In this study, ethylene propylene diene terpolymer (EPDM) is melt‐mixed with multiwalled carbon nanotube (MWCNT). To realize full‐scale application of MWCNT to the rubber industries, the effect of melt‐processing parameters on the surface resistivity in the rubber/MWCNT nanocomposites should be well understood. The effect of rotor speed, mixing temperature, and annealing time on the surface resistivity of the EPDM/MWCNT nanocomposites has been investigated. The surface resistivity of EPDM/MWCNT nanocomposites with 3 phr MWCNT increases with increasing the rotor speed and decreasing the mixing temperature. Tensile strength and tensile modulus of EPDM/MWCNT (3 phr) nanocomposites are higher than those of EPDM, respectively. For the nanocomposite with 3 phr MWCNT loadings, surface resistivity increases as the annealing time at room temperature increases. This is the first report that surface resistivity of rubber/MWCNT nanocomposites increases significantly on annealing at room temperature. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40129.     

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     

Polyurethane/clay nanocomposites with improved helium gas barrier and mechanical properties: Direct versus master‐batch melt mixing route

Thermoplastic polyurethane (TPU)/clay nanocomposite films were produced by incorporation of organo‐modified montmorillonite clay (Cloisite 30B) in TPU matrix by two different melt‐mixing routes (direct and master‐batch‐based mixing), followed by compression molding. In master‐batch mixing where the master‐batch was prepared by mixing of clay and TPU in a solvent, better dispersion of clay‐layers was observed in comparison to the nanocomposites produced by direct mixing. As a consequence, superior mechanical and gas barrier properties were obtained by master‐batch mixing route. The master‐batch processing resulted in 284 and 236% increase in tearing strength and tearing energy, respectively, with 5 wt % clay‐loading. Interestingly, in case of master‐batch mixing, the tensile strength, stiffness as well as breaking extension increased simultaneously up to 3 wt % clay‐loading. The helium gas permeability reduced by about 39 and 31% for the TPU/clay nanocomposites produced by mater‐batch and direct mixing routes, respectively, at 3 wt % loading of clay. Finally, the gas permeability results have been compared using three different gas permeability models and a good correlation was observed at lower volume fraction of clay. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46422.