Mechanical reinforcement of poly(1‐butene) using polypropylene‐grafted multiwalled carbon nanotubes

The mechanical properties of poly(1‐butene) reinforced by pristine multiwalled carbon nanotubes (MWNTs) and polypropylene‐grafted MWNTs (PP‐g‐MWNTs) were evaluated. The incorporation of pristine MWNTs to PB led to an improvement in stiffness, but not in strength, ductility, and toughness. In comparison, PP‐g‐MWNTs were able to improve the stiffness, strength, and toughness of PB significantly, without compromising the ductility. The mechanical properties of PB improved with increasing amount of PP‐g‐MWNTs up to an effective MWNT content of 1.5 wt%. Further increase in the effective MWNT content led to a downturn in mechanical properties due to the existence of MWNTs bundles as observed by microscopy. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Microstructure and water vapor transport properties of functionalized carbon nanotube‐reinforced dense‐segmented polyurethane composite membranes

This work investigates the influence of functionalized multiwall carbon nanotube (MWNT) on microstructure and water vapor transport properties of segmented polyurethane (SPU) membranes. SPUs were reinforced with four different concentration of MWNT viz. 0.25, 0.50, 1.0, and 2.5 wt%. Presence of the microcrystals in all SPU‐MWNT composite membranes was detected by wide angle X‐ray diffraction (WAXD). The percent crystallinity of SPU‐MWNT at 0.25 wt% content of MWNT was increased slightly when compared with the pristine SPU sample. However, further increase of MWNT decreases the order structure. Glass transition temperature was increases with increasing MWNT content in the SPUs, which signifies that MWNT could also affect the amorphous region of SPU. WAXD and transmission electron microscopy (TEM) results evidenced the interaction between SPUs and MWNT. In comparing the water vapor transport properties of MWNT‐SPU composite membranes, it was observed that at 0.25 wt% of MWNT in SPU, water vapor transport property increases slightly at soft segment crystal melting temperature. Further increase of MWNT content has no significant influence on the water vapor transport properties. However, at 2.5 wt% of MWNT in SPU matrix, water vapor transport was decreases due to the increase of stiffness in the polymer chains. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Isothermal and nonisothermal crystallization kinetics of poly(ε‐caprolactone)/multi‐walled carbon nanotube composites

Differential scanning calorimeter (DSC) and polarized optical microscopy (POM) have been used to investigate the isothermal and nonisothermal crystallization behavior of poly(ε‐caprolactone) (PCL)/multi‐walled carbon nanotube (MWNT) composites. PCL/MWNT composites have been prepared by mixing the PCL polymer with carboxylic groups containing multi‐walled carbon nanotubes (c‐MWNTs) in tetrahydrofuran solution. Raman spectrum of c‐MWNT indicated the possible presence of carboxylic acid groups at both ends and on the sidewalls of the MWNTs. The TEM micrograph showed that the c‐MWNT is well separated and uniformly dispersed in the PCL matrix. DSC isothermal results showed that the introduction of c‐MWNT into the PCL initiates strongly heterogeneous nucleation, which induced a change of the crystal growth process. The activation energy of PCL significantly decreases by adding 0.25 wt% c‐MWNT into PCL/c‐MWNT composites and then increases as c‐MWNT content increases. The result demonstrates that the addition of c‐MWNT into PCL induces the heterogeneous nucleation at lower c‐MWNT content and then inhibits the polymer chain transportation ability during crystallization at higher c‐MWNT content. In this study, we have also studied the nonisothermal crystallization kinetics and melting behavior of PCL/c‐MWNT composites at various cooling rates. The correlation among isothermal and nonisothermal crystallization kinetics and melting behavior of PCL/c‐MWNT composites can be also discussed. POLYM. ENG. SCI., 46:1309–1317, 2006. © 2006 Society of Plastics Engineers     

Synthesis and characterization of polyimide/multi‐walled carbon nanotube nanocomposites

Polyimide/multi‐walled carbon nanotube (PI‐MWNT) nanocomposites were fabricated by an in situ polymerization process. Chemical compatibility between the PI matrix and MWNTs is achieved by pretreatment of the carbon nanotubes in a mixture of sulfuric acid and nitric acid. The dispersion of MWNTs in the PI matrix was found to be enhanced significantly after acid modification. The glass transition (T_g) and decomposition (T_d) temperature of PI‐MWNT nanocomposites were improved as the MWNT content increased from 0.5 to 15 wt%. The storage modulus of the PI/MWNT nanocomposites is nine times higher than that of pristine PI at room temperature. The tensile strength of PI doubles when 7 wt% MWNTs is added. The dielectric constant of the PI‐MWNT nanocomposites increased from 3.5 to 80 (1 kHz) as the MWNT content increased to 15 wt%. The present study demonstrates that enhanced mechanical properties can be obtained through a simple in‐situ polymerization process. POLYM. COMPOS., 2008. © 2008 Society of Plastics Engineers     

Improved stability of volume resistivity in carbon black/ethylene-vinyl acetate copolymer composites by employing multi-walled carbon nanotubes as second filler

Semiconductive polymer shielding layers of power cable require stable volume resistivity to protect the insulation layer from stress enhancements when carbon black (CB)/polymer composite undergoes thermal cycles. For the CB-filled polymer composites, CB would often re-aggregate when temperature is close to the melting point of polymer matrix, so that the conductive network would be destroyed. Re-distribution of CB and re-formation of conductive CB network under thermal cycles might be the main reason for the instability of volume resistivity. In this work, the re-aggregation of CB in the CB/polymer composites was disclosed. Besides, a small amount of multi-walled carbon nanotubes (MWNTs) was employed as cofiller with CB to improve the stability of volume resistivity of the polymer composites under thermal cycles. The total weight fraction of conductive fillers (CB or CB cofilled with MWNTs) was set as 35 wt%. Compared with the polymer composites loaded with CB solely, the volume resistivity of the composites filled with CB-MWNTs was much more stable with changing temperature. This can be attributed to the enhancement of conductive networks when the MWNTs are employed as second conductive filler.     

Poly (N‐methylaniline)/multi‐walled carbon nanotube composites—Synthesis,characterization, and electrical properties

This study described the synthesis of hydrochloric acid (HCl)‐doped poly (N‐methylaniline) (PNMA) with carboxylic groups containing multi‐walled carbon nanotubes (c‐MWNTs) via in situ polymerization. Based on the π–π electron interaction between c‐MWNTs and the N‐methylaniline monomer and the hydrogen bond interaction between the carboxyl groups of c‐MWNTs and imine groups of N‐methylaniline monomers, N‐methylaniline molecules were adsorbed on the surface of c‐MWNTs and polymerized to form PNMA/c‐MWNT composites. Scanning electron microscopy images showed that both the thinner fibrous phase and the larger block phase could be observed. The individual fibrous phases had diameters from several tens to hundreds of nanometers, depending on the PNMA content. Transmission electron microscopy proved that PNMA/c‐MWNTs composite fibrous phases were core (c‐MWNT)‐shell (PNMA) tubular structures. The structure of PNMA/c‐MWNT composites was characterized by FTIR, UV–vis spectra, and X‐ray diffraction patterns. The electrical conductivities of PNMA/c‐MWNT composites were much higher than that of PNMA without c‐MWNTs. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2356–2361, 2006     

Electrical properties and electromagnetic interference shielding effectiveness of multiwalled carbon nanotubes‐reinforced EMA nanocomposites

Electrical and electromagnetic interference shielding effectiveness (EMI SE) properties of the ethylene methyl acrylate (EMA)/multiwalled carbon nanotube (MWNT) nanocomposites have been studied. High resolution transmission electron microscope (HRTEM) was used to validate the MWNTs dispersion state and network connections of its microstructure. The electrical resistance of the nanocomposites decreases significantly with MWNTs content. DC resistivity and AC conductivity measurement on the nanocomposite samples showed that the insulator to conductor transition took place within 10 wt% MWNTs concentration. It has been found that as MWNT concentration increased network connections improved. The EMI SE of the nanocomposites has also been investigated. The highest SE (∼20 dB) of these nanocomposites is realistic for an industrial application. EMA/MWNT nanocomposites provide sufficient intrinsic EMI shielding capability which may be hopeful for electrical and electronic applications. The morphology correlates well with the electrical and electromagnetic behavior of these nanocomposites. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Effect of the carbon black structure on the stability and efficiency of the conductive network in polyethylene composites

Composites of high‐density polyethylene (HDPE) with different kinds of carbon black (CB) were prepared through melt blending. The influence of the CB structure on the stability and efficiency of the conductive network in HDPE/CB composites were mainly investigated. Scanning electron microscopy was used to observe the morphology of the CB primary aggregates. The relationship between the temperature‐resistivity behaviors of the composites and the crystallization behaviors of the matrix were also investigated. High‐structure CB built an effective conductive network at a low filler content compared to the low‐structure one because of its branched morphology. Therefore, the composite containing high‐structure CB revealed a lower percolation threshold. The composite containing low‐structure CB obtained a stronger positive temperature coefficient (PTC) intensity because the cluster network was fragile and easily damaged during matrix melting. The reproducibility of the results of PTC effect of the composite containing high‐structure CB was better than that of the composite containing a low‐structure one. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Effect of nanoclay on positive temperature coefficient to resistivity characteristics of high density polyethylene/silver‐coated glass bead composites

Positive temperature coefficient to resistivity characteristics of high density polyethylene (HDPE)/silver (Ag)‐coated glass bead (45 wt%) composites, without and with nanoclay, has been investigated with reference to HDPE/carbon black (CB) (10 wt%) composites. Plot of resistivity versus temperature of HDPE/CB (10 wt%) composites showed a sudden rise in resistivity (PTC trip) at ≈128°C, close to the melting temperature (T_m) of HDPE. However, for HDPE/Ag coated glass bead (45 wt%) composites, the PTC trip temperature (≈88°C) appeared well below the T_m of HDPE. Addition of 1 phr clay in the composites resulted in an increase in PTC trip temperature of HDPE/Ag‐coated glass bead (45 wt%) composites, whereas no significant effect of clay on PTC trip temperature was evident in HDPE/CB/clay composites. We proposed that the PTC trip temperature in HDPE/Ag‐coated glass bead composites was governed by the difference in coefficient of thermal expansion of HDPE and Ag‐coated glass beads. The room temperature resistivity and PTC trip temperature of HDPE/Ag‐coated glass bead (45 wt%) composites were found to be very stable on thermal cycling. Dynamic mechanical analyzer results showed higher storage modulus of HDPE/Ag‐coated glass bead (45 wt%) composites compared with the HDPE/CB (10 wt%) composites. Thermal stability of HDPE/Ag‐coated glass bead (45 wt%) composites was also improved compared with that of HDPE/CB (10 wt%) composites. POLYM. COMPOS., 2012. © 2012 Society of Plastics Engineers     

Free‐standing aniline oligomer functionalized multiwalled carbon nanotube films from a filtration method

High electrochemical active free‐standing multiwalled carbon nanotube (MWNT) films have been synthesized from aniline oligomer functionalized MWNTs (MWNT‐AO), by using filtration of the acidic phosphate ester (APE) doped MWNT‐AO dispersions. The homogeneously distributed MWNTs endowed APE/MWNT films automatically releasing from the filter membrane. The sheet resistivity of MWNT‐AO (850 Ω sq^?1) showed a lower value than that of carboxyl MWNTs (1273 Ω sq^?1), due to the doping effect of MWNT on aniline oligomer, confirmed by the N1s X‐ray photoelectron spectrum. However, it showed a higher sheet resistivity value of 1526 Ω sq^?1 after further doped by APE, because of the presence of unreacted dopant. After removing the residual insulating dopant by the vacuum filtration, the resultant APE/MWNT films showed the sheet resistivity value as low as 131 Ω sq^?1. Thermogravimetric analysis showed that the MWNT loading in the film can be over than 77%, which showed the specific capacitance as high as 249 F g^?1. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40259.     

Resistivity–volume expansion characteristics of carbon black‐loaded polyethylene

The resistivity and volume expansion of carbon black (CB)/high‐density polyethylene (HDPE) composite with different CB volume fractions at different temperatures were measured simultaneously. A model based on Meyer's theory is proposed to explain the positive temperature coefficient resistance (PTCR) effect. The relationship between resistivity and volume expansion was determined. It was found that the phase change is the main cause of the PTC effect in the crystalline polymer PTC materials. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 53–58, 2000     

Shape‐memory polyurethane/multiwalled carbon nanotube fibers

Shape‐memory polyurethane/multiwalled carbon nanotube (SMP–MWNT) composites with various multiwalled carbon nanotube (MWNT) contents were synthesized, and the corresponding SMP–MWNT fibers were prepared by melt spinning. The influence of the MWNT content on the spinnability, fracture morphology, thermal and mechanical properties, and shape‐memory behavior of the shape‐memory polymer was studied. The spinning ability of SMP–MWNTs decreased significantly with increasing MWNT content. When the MWNT content reached 8.0 wt %, the fibers could not be produced because of the poor rheological properties of the composites. The melt‐blending, extrusion, and melt‐spinning processes for the shape‐memory fiber (SMF), particularly at low MWNT contents, caused the nanotubes to distribute homogeneously and preferentially align along the drawing direction of the SMF. The crystallization in the SMF was promoted at low MWNT contents because it acted as a nucleation agent. At high MWNT contents, however, the crystallization was hindered because the movement of the polyurethane chains was restricted. The homogeneously distributed and aligned MWNTs preserved the SMF with high tenacity and initial modulus. The recovery ratio and recovery force were also improved because the MWNTs helped to store the internal elastic energy during stretching and fixing. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

High electrical conductivity of nylon 6 composites obtained with hybrid multiwalled carbon nanotube/carbon fiber fillers

The synergetic effect of multiwalled carbon nanotubes (MWNTs) and carbon fibers (CFs) in enhancing the electrical conductivity of nylon 6 (PA6) composites was investigated. To improve the compatibility between the fillers and the PA6 resin, we grafted γ‐aminopropyltriethoxy silane (KH‐550) onto the MWNTs and CFs after carboxyl groups were generated on their surface by chemical oxidation with nitric acid. Fourier transform infrared spectroscopy and thermogravimetric analysis proved that the KH‐550 molecules were successfully grafted onto the surface of the MWNTs and CFs. Scanning electron microscopy and optical microscopy showed that the obtained modified fillers reduced the aggregation of fillers and resulted in better dispersion and interfacial compatibility. We found that the electrical percolation threshold of the MWNT/PA6 and CF/PA6 composites occurred when the volume fraction of the fillers were 4 and 5%, respectively. The MWNT/CF hybrid‐filler system exhibited a remarkable synergetic effect on the electrically conductive networks. The MWNT/7% CF hybrid‐filler system appeared to show a second percolation when the MWNT volume fraction was above 4% and a volume resistivity reduction of two orders of magnitude compared with the MWNT/PA6 system. The mechanical properties of different types of PA6 composites with variation in the filler volume content were also studied. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40923.     

Influence of radiation structures on positive‐temperature‐coefficient and negative‐temperature‐coefficient effects of irradiated low‐density polyethylene/carbon black composites

The electrical‐resistivity/temperature behaviors of low‐density polyethylene (LDPE)/carbon black (CB) composites irradiated with ⁶⁰Co γ rays were studied. The experimental results showed that the irradiated composites could be separated into insoluble crosslinking networks with CB (gel) and soluble components (sol) by solvent‐extraction techniques. When the sol of an irradiated LDPE/CB composite was extracted, the electrical conductivity of the system increased. The positive‐temperature‐coefficient (PTC) and negative‐temperature‐coefficient (NTC) intensities of the gels of the irradiated composites became extremely small and independent of the radiation dose. The sols and gels of the irradiated LDPE/CB composites, which had different thermal behaviors, played important roles in the appearances of the PTC and NTC effects. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 700–704, 2005     

Conductive network formation and electrical properties of poly(vinylidene fluoride)/multiwalled carbon nanotube composites: Percolation and dynamic percolation

Conductive network formation and its dynamic process for multiwalled carbon nanotubes (MWNTs) and carboxyl‐tethered MWNT (MWNT‐COOH) filled poly(vinylidene fluoride)(PVDF) systems were investigated. Based on real‐time tracing the variation of electrical resistivity of systems with isothermal treatment time, the conductive network formation was evaluated. It was found that the conductive network formation was temperature and time dependent. The percolation time, characterized at a certain annealing time where the electrical resistivity started to decrease drastically, decreased with the increase of the filler concentration or the annealing temperature. However, the values of the percolation time and the activation energy of conductive network formation for the PVDF/MWNT‐COOH system were higher than those of the PVDF/MWNT system, indicating that the interaction between MWNTs and PVDF molecules played an important role in the conductive network formation of the composites. Furthermore, a modified thermodynamic percolation model was proposed to predict the percolation time of PVDF/MWNT composites. It was found that the calculated results fit the experimental data very well. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Electrical properties and morphology of carbon black‐filled HDPE/EVA composites

The sensitive effect of weight ratio of the high‐density polyethylene (HDPE)/ethylene‐vinylacetate copolymer (EVA) on the electrical properties of HDPE/EVA/carbon black (CB) composites was investigated. With the EVA content increasing from 0 wt % to 100 wt %, an obvious change of positive temperature coefficient (PTC) curve was observed, and a U‐shaped insulator‐conductor‐insulator transition in HDPE/EVA/CB composites with a CB concentration nearby the percolation threshold was found. The selective location of CB particles in HDPE/EVA blend was analyzed by means of theoretical method and scanning electron micrograph (SEM) in order to explain the U‐shaped insulator‐conductor‐insulator transition, a phenomenon different from double percolation in this composite. The first significant change of the resistivity, an insulator‐conductor transition, occurred when the conductive networks diffused into the whole matrix due to the forming of the conductive networks and the continuous EVA phase. The second time significant change of the resistivity, a conductor‐insulator transition, appeared when the amorphous phase is too large for CB particles to form the conductive networks throughout the whole matrix. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Morphology,Resistivity, and PTC behavior of EVOH/CB composites prepared by solvent‐casting saponification and precipitation saponification

Poly(ethylene‐co‐vinyl alcohol)/carbon black (EVOH/CB) composites were prepared by a solvent‐casting saponification (‐D) and precipitation saponification (‐P) methods with a poly(ethylene‐co‐vinyl acetate)/CB (EVA/CB) toluene suspension. The effects of the CB content and saponification time on the morphology, electrical resistivity, thermal, and mechanical properties of EVA/CB composites were examined. The volume resistivity (ρ _v) of the EVA/CB‐D and EVA/CB‐P samples decreased significantly with increasing CB content and the percolation threshold of such composites was determined about 10 wt%. At 10 wt% of CB content, the ρ _v of EVA/CB‐D composite decreased significantly with the saponification time, whereas ρ _v of EVA/CB‐P composites did not change. As the saponification time increased, EVA/CB25wt% composites form cavity structure which CB is usually located in oval cavities larger than the particles themselves. This oval cavity structure almost resembles extruded high‐density polyethylene (HDPE)/CB composites. The morphology and PTC behavior of prepared composites were compared with those of HDPE/CB and the mechanism of PTC and NTC effects was discussed. POLYM. COMPOS., 38:1462–1473, 2017. © 2015 Society of Plastics Engineers     

Electrical conductivity and thermal properties of acrylonitrile‐butadiene‐styrene filled with multiwall carbon nanotubes

Composites of Acrylonitrile‐butadiene‐styrene (ABS) and multiwall carbon nanotubes (MWNTs) have been prepared via solution‐blending. The electrical conductivity of these composites is analyzed. The MWNT‐filled ABS shows percolation point of the electrical conductivity at low filler loadings (1–2 wt%). The micro‐structure of the composites is also analyzed by scanning electron microscopy showing that the nanotubes are dispersed quite homogeneously in the polymer‐matrix. The thermogravimetric analysis is used to study the thermal degradation of ABS/MWNTs composites in nitrogen. MWNTs tend to destabilize the ABS matrix in the 220–450°C degradation regions but improve the thermal stability in the 425–850°C regions. With further addition of MWNTs, the features of the destabilization in the 220–450°C degradation region did not change much but in the 425–850°C degradation process, the MWNTs reinforced stabilization and the quality of the char residue of amorphous carbon deposition was improved. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Resistivity‐temperature behavior of carbon fiber filled semicrystalline composites

Carbon fiber (CF) filled low‐density polyethylene (LDPE) composites were prepared by the conventional melt‐mixing method. The distribution of CF in the composite was studied by wide‐angle X‐ray diffraction (WAXD) and scanning electron microscope (SEM) observations. A phenomenological model was proposed to illustrate the resistivity‐temperature behavior of CF‐filled semicrystalline composites. The effects of the content and aspect ratio of CF on the positive temperature coefficient (PTC) and the room temperature resistivity were elucidated. A balance between the PTC intensity and the room‐temperature resistivity can be achieved by using a mixture of CFs with low and high aspect ratios. The negative temperature coefficient (NTC) phenomenon can be effectively eliminated by crosslinking under γ‐ray radiation, and the crosslinked composite exhibits a higher PTC intensity and PTC transition temperature than the noncrosslinked counterpart. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1222–1228, 2004     

Resistivity–temperature characteristics of filler-dispersed polymer composites

Composites containing carbon nano tube (CNT) or carbon black (CB) conductive particle filler have the special characteristics of positive-temperature-coefficient (PTC) effects of resistivity. We quantitatively studied the relationship between poly(vinylidene fluoride) (PVDF) polymer's thermal volume expansion and the PTC effects of PVDF/CNT and PVDF/CB. The equation to revise filler content at each temperature due to the considerable thermal volume expansion rate of PVDF polymer indicates that filler content decreased with rising temperature. The graphs of filler content at room temperature plotted against apparent filler content with PTC effect were linear and their slopes were constant. From these graphs, we can determine the filler content necessary to occurring PTC effects. For example, the CNT content was 89% at room temperature, and the CB content was 93%. To our knowledge, this study is the first to report such phenomena.