Surfactant‐assisted processing of polyimide/multiwall carbon nanotube nanocomposites for microelectronics applications

The dispersion and stability of carbon nanotubes (CNTs) inside a polymer matrix, especially with a high CNT content, are still big challenges. Moreover, the interaction between CNTs and the polymer matrix should be strong enough to improve the mechanical properties. The efficient dispersion of CNTs is essential for the formation of a uniform distribution of a CNT network in a polymer composite. Polyimide/multiwall CNT nanocomposites were synthesized by in situ polymerization with the aid of a surfactant. A Fourier transform infrared spectroscopy study proved that the surfactant did not hamper the polymerization of the polyimide. The microstructure, storage modulus and electrical conductivity of the nanocomposites were improved using a particular amount of the surfactant. Environmental stability test results showed that the polyimide with 1 wt% of CNTs produced with the aid of the surfactant possessed excellent reliability in high‐temperature and high‐humidity environments. Surfactants were successfully used to obtain fine‐structure polyimide/CNT nanocomposites by in situ polymerization. The enhancement of the mechanical properties was attributed to the incorporation of the surfactant. A percolation of electrical conductivity could be achieved with 1 wt% of CNTs. Copyright © 2010 Society of Chemical Industry     

Electrical and mechanical properties of carbon nanotube‐epoxy nanocomposites

In this work, electrical conductivity and thermo‐mechanical properties have been measured for carbon nanotube reinforced epoxy matrix composites. These nanocomposites consisted of two types of nanofillers, single walled carbon nanotubes (SW‐CNT) and electrical grade carbon nanotubes (XD‐CNT). The influence of the type of nanotubes and their corresponding loading weight fraction on the microstructure and the resulting electrical and mechanical properties of the nanocomposites have been investigated. The electrical conductivity of the nanocomposites showed a significantly high, about seven orders of magnitude, improvement at very low loading weight fractions of nanotubes in both types of nanocomposites. The percolation threshold in nanocomposites with SW‐CNT fillers was found to be around 0.015 wt % and that with XD‐CNT fillers around 0.0225 wt %. Transmission optical microscopy of the nanocomposites revealed some differences in the microstructure of the two types of nanocomposites which can be related to the variation in the percolation thresholds of these nanocomposites. The mechanical properties (storage modulus and loss modulus) and the glass transition temperature have not been compromised with the addition of fillers compared with significant enhancement of electrical properties. The main significance of these results is that XD‐CNTs can be used as a cost effective nanofiller for electrical applications of epoxy based nanocomposites at a fraction of SW‐CNT cost. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Improvement of the mechanical and electrical properties of waste rubber with carbon nanotubes

The effect of carbon nanotubes (CNTs) on the stability of the mechanical and electrical properties of recycled waste rubber was experimentally investigated. The stress–strain curves of the composites were studied. The results show that the toughness, the area under the stress–strain curve, of the recycled rubber increased monotonically as a result of the addition of CNTs. The modulus of the nanocomposites increased by 28 times when only 5 wt % CNTs was added to the recycled rubber matrix. The effects of the cyclic fatigue and hysteresis for the composites were also examined. The strain energy density, dissipation energy, and linear damage accumulation versus the number of cycles are discussed for all of the samples. The analysis of the results showed that the strain energy density increased by 15 times at a CNT concentration of 5 wt %. The electrical properties were measured for all of the samples. The results indicate that the addition of CNTs to the recycled rubber improved its electrical conductivity by more than two orders. © 2011 Wiley Periodicals, Inc. J Polym Sci, 2011     

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     

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     

Effect of multiwall carbon nanotubes on thermomechanical and electrical properties of poly(trimethylene terephthalate)

Multiwalled carbon nanotubes (MWCNTs) were synthesized using chemical vapor deposition and poly(trimethylene terephthalate) (PTT)/MWCNT composites with varying amounts of MWCNTs were prepared by melt compounding using DSM micro‐compounder. Morphological characterization by SEM and TEM showed uniform dispersion of MWCNTs in PTT matrix upto 2% (w/w) MWCNT loading. Incorporation of MWCNTs showed no effect on percent crystallinity but affected the crystallite dimensions and increased the crystallization temperature. Dynamic mechanical characterization of composites showed an increase in storage modulus of PTT upon incorporation of MWCNTs above glass transition temperature. The electrical conductivity of PTT/MWCNT composites increased upon incorporation of MWCNTs and percolation threshold concentration was obtained at a loading of MWCNTs in the range of 1–1.5% (w/w). © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of carbon nanotubes decorated with silver nanoparticles as hybrid filler on properties of natural rubber nanocomposites

Decoration of carbon nanotube (CNT) surfaces with silver nanoparticles (AgNPs) was performed using N,N-dimethylformamide reducing agent. The CNT-decorated with AgNP (CNT-AgNP) was then used to prepare natural rubber (NR) nanocomposites via latex mixing method. Cure characteristics, mechano-thermal relaxation, electrical conductivity, and thermal properties of the composites were investigated. It was found that the CNT-AgNP gave cure properties improved over plain NR compounds in terms of scorch time, degree of vulcanization, and activation energy. In addition, temperature scanning stress relaxation measurement revealed stronger network formation after incorporation of AgNP into the NR matrix due to the interaction among CNT and AgNP particles. This also provided high conductivity and low percolation threshold concentration for the CNT-AgNP filled NR, relative to plain CNT filled NR composites. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47281.     

Isotactic polypropylene composites reinforced with multiwall carbon nanotubes,part 2: Thermal and mechanical properties related to the structure

Polypropylene nanocomposites containing multiwall carbon nanotubes (MWCNT), from 0.1 to 3 wt %, are prepared by dilution of a polypropylene based masterbatch (20% MWCNT) with isotactic polypropylene (iPP) using extrusion processing. CNT are found to enhance significantly the thermal stability of iPP in nitrogen and air atmosphere. Dynamic mechanical analysis and tensile tests confirm the reinforcement effect of small amount of nanotubes in iPP. Rheology, structure, and properties are correlated determine the optimal limits of nanofiller content required for improving the performance of nanocomposites. The rheological flocculation threshold of φ* = 0.5% is found as a critical concentration for the formation of a flocculated type of structure in the dispersions. It is proposed, that the flocculated structure is responsible for the maximal improvement of nanocomposite mechanical and thermal properties. The MWCNT additive slightly enhances the local dynamics of iPP molecules in the glass transition region and suppresses the global relaxation of the chain segments in the amorphous regions, resulting in a reinforcement effect. The fracture mechanism is discussed and associated with the hierarchy of the flocculated nanocomposite morphology and the bridging of matrix cracks by CNT. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effects of mineral fillers addition and preparation method on the morphology and electrical conductivity of epoxy/multiwalled carbon nanotube nanocomposites

This study investigated the correlation between the electrical conductivity and the micro and nanomorphology of multiwalled carbon nanotubes (MWCNTs)/epoxy nanocomposites with and without the inorganic fillers montmorillonite (MMT), sepiolite and calcium carbonate (CaCO₃). The nanocomposites were prepared by dispersing the MWCNT and fillers through ultrasonication directly in the resin or solvent. For nanocomposites without fillers, the compositions prepared with solvent demonstrated higher electrical conductivities, which correlate with a microscale morphology formed by networks of highly interconnected MWCNT agglomerates. The addition of MMT induced a deleterious effect on the electrical conductivity of the nanocomposites since this filler hinders the formation of MWCNT agglomerate networks. The effect of sepiolite on electrical conductivity is also negative, but in this case, nonmorphological effects are likely of greater importance. The addition of CaCO₃ improved the electrical conductivity of the binary nanocomposites under specific conditions. For this filler, a synergic effect was achieved for the composition prepared with solvent, which resulted in an approximately sixfold increase in electrical conductivity relative to the nanocomposite without filler.     

Preparation,structure and properties of thermoplastic olefin nanocomposites containing functionalized carbon nanotubes

The morphology and properties of multiwalled carbon nanotube modified polypropylene (PP)/ethylene–octene copolymer blends were studied. Polypropylene chains are covalently grafted onto the surface of carbon nanotubes (CNTs) in order to improve their interaction with the polymer matrix. It is observed that functionalization of CNTs improves their dispersion and increases the interfacial bonding between CNTs and polymer matrix. The functionalized CNTs are selectively distributed in the continuous polypropylene phase. The size of the dispersed elastomer phase decreases after the addition of CNTs. Functionalized CNTs act as a nucleating agent and increase the crystallinity of the polypropylene. More importantly, an important increase in impact strength, stiffness and toughness can be achieved through introducing functionalized CNTs. Copyright © 2011 Society of Chemical Industry     

Effect of annealing treatment on the structure and properties of polyurethane/multiwalled carbon nanotube nanocomposites

The thermoplastic polyurethane/multiwalled carbon nanotube (TPU/CNT) nanocomposites with high conductivity and low percolation threshold value were prepared by melting blending and annealing treatment. The effect of annealing process on the microphase structure and the properties of TPU/CNT nanocomposites was studied. It has been shown that CNT flocculation can occur in TPU/CNT nanocomposites during the annealing process. At a critical CNT content, which defined the percolation threshold, CNTs could form conductivity network. The conductive percolation threshold value of TPU/CNT nanocomposites was decreased from 10 to 4% after annealing process, and the conductivity of TPU/CNT nanocomposites with 10 vol % of CNT could reach 1.1 S/m after an annealing time of 1 h. The significant enhancement of electrical conductivity was influenced by the annealing time and the content of CNTs. The formation of CNT networks was also verified by dynamic viscoelastic characterization. The results of X‐ray diffraction and differential scanning calorimetry indicated that annealing process reinforced the microphase separation of the nanocomposites. Mechanical properties test showed that the annealing treatment was in favor of improving the mechanical properties; however, further increase in the annealing time has negative effect on the mechanical properties. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Dispersion and mechanical properties of polypropylene/multiwall carbon nanotubes composites obtained via dynamic packing injection molding

In this article, polypropylene (PP)/multiwall carbon nanotubes (MWNTs) composites were prepared through dynamic packing injection molding, in which the oscillatory shear was exerted on the molten composite during packing and solidification stage of injection‐molding. A simultaneous increase of tensile strength and impact strength has been achieved for PP/MWNTs composites containing only 0.6 wt % MWNTs. Particularly, the impact strength was found increased by almost 50% at such low MWNTs content. These improvements in properties were attributed to uniform dispersion and possible orientation of nanotube induced by shear stress. It was suggested that the dynamic packing injection molding could provide much strong shear force for better dispersion of MWNTs in PP matrix, on one hand, but breakdown the aspect ratio of MWNTs, on the other. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1880–1886, 2007     

Copolyester nanocomposites based on carbon nanotubes: reinforcement effect of carbon nanotubes on viscoelastic and dielectric properties of nanocomposites

Nanocomposites based on an amorphous copolyester, poly(ethylene glycol‐co‐cyclohexane‐1,4‐dimethanol terephthalate) and carbon nanotubes were fabricated using a simple melt processing technique. The reinforcement effect of carbon nanotubes in the copolyester was investigated experimentally using different approaches based on dynamic mechanical analysis, rheology and dielectric analysis. The nanocomposites show a mechanical reinforcement effect with significant increase in the stiffness especially in the rubbery regime with increasing nanotube content. An increase in T_g and a decrease in damping are seen, which are derived from the presence of a percolating superstructure of the filler. Rheological experiments show an increase in storage modulus up to four orders of magnitude. Viscolelastic characterization shows that the percolation threshold is at 3 wt% of nanotubes. Dielectric relaxation spectroscopy confirms the presence of this percolating structure. We conclude that the responses of both rheological and electrical properties are different, although both are related to the formation of a percolating network superstructure of the filler. Copyright © 2007 Society of Chemical Industry     

Electrical, mechanical, and glass transition behavior of polycarbonate-based nanocomposites with different multi-walled carbon nanotubes

Five commercially available multi-walled carbon nanotubes (MWNTs), with different characteristics, were melt mixed with polycarbonate (PC) in a twin-screw micro compounder to obtain nanocomposites containing 0.25-3.0 wt.% MWNT. The electrical properties of the composites were assessed using bulk electrical conductivity measurements, the mechanical properties of the composites were evaluated using tensile tests and dynamic mechanical analysis (DMA), and the thermal properties of the composites were investigated using differential scanning calorimetry (DSC). Electrical percolation thresholds (p_cs) were observed between 0.28 wt.% and 0.60 wt.%, which are comparable with other well-dispersed melt mixed materials. Based on measurements of diameter and length distributions of unprocessed tubes it was found that nanotubes with high aspect ratios exhibited lower p_cs, although one sample did show higher p_c than expected (based on aspect ratio) which was attributed to poorer dispersion achieved during mixing. The stress-strain behavior of the composites is only slightly altered with CNT addition; however, the strain at break is decreased even at low loadings. DMA tests suggest the formation of a combined polymer-CNT continuous network evidenced by measurable storage moduli at temperatures above the glass transition temperature (T_g), consistent with a mild reinforcement effect. The composites showed lower glass transition temperatures than that of pure PC. Lowering of the height of the tanδ peak from DMA and reductions in the heat capacity change at the glass transition from DSC indicate that MWNTs reduced the amount of polymer material that participates in the glass transition of the composites, consistent with immobilization of polymer at the nanotube interface.     

Enhanced mechanical and electrical properties of carbon fiber/poly(ether ether ketone) laminates via inserting carbon nanotubes interleaves

The carbon fiber/(carbon nanotubes/polyetherimide)/poly ether ether ketone (CF/(CNTs/PEI)/PEEK) laminates are prepared by inserting carbon nanotubes/polyetherimide (CNTs/PEI) interleaves into interlaminar region. The mechanical properties and electrical conductivities of the developed laminates are evaluated. The results indicate that the interlaminar shear strength and flexural strength of CF/(CNTs/PEI)/PEEK laminates are increased by 42.9% and 24.7%, after inserting CNTs2.91/PEI interleaves, respectively. The cross-sectional images of laminates after mechanical tests verify strong fiber-resin adhesion by scanning electron microscope observation. The pertinent mechanism responsible for the improvement of mechanical properties is mechanical interlocking effect of CNTs. After incorporating CNTs/PEI interleaves, the electrical conductivity of laminates is markedly improved due to the formation of conductive pathway. This work suggests that this method is compatible with the preparation process of thermoplastic composites. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 137, 48658.     

Preparation and properties of polyurethane/multiwalled carbon nanotube nanocomposites by a spray drying process

A spray drying approach has been used to prepare polyurethane/multiwalled carbon nanotube (PU/MWCNT) composites. By using this method, the MWCNTs can be dispersed homogeneously in the PU matrix in an attempt to improve the mechanical properties of the nanocomposites. The morphology of the resulting PU/MWCNT composites was investigated by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). SEM and TEM observations illustrate that the MWCNTs are dispersed finely and uniformly in the PU matrix. X‐ray diffraction results indicate that the microphase separation structure of the PU is slightly affected by the presence of the MWCNTs. The mechanical properties such as tensile strength, tensile modulus, elongation at break, and hardness of the nanocomposites were studied. The electrical and the thermal conductivity of the nanocomposites were also evaluated. The results show that both the electrical and the thermal conductivity increase with the increase of MWCNT loading. In addition, the percolation threshold value of the PU composites is significantly reduced to about 5 wt % because of the high aspect ratio of carbon nanotubes and exclusive effect of latex particles of PU emulsion in dispersion. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Thermal conductivity of carbon nanotubes and graphene in epoxy nanofluids and nanocomposites

We employed an easy and direct method to measure the thermal conductivity of epoxy in the liquid (nanofluid) and solid (nanocomposite) states using both rodlike and platelet-like carbon-based nanostructures. Comparing the experimental results with the theoretical model, an anomalous enhancement was obtained with multiwall carbon nanotubes, probably due to their layered structure and lowest surface resistance. Puzzling results for functionalized graphene sheet nanocomposites suggest that phonon coupling of the vibrational modes of the graphene and of the polymeric matrix plays a dominant role on the thermal conductivities of the liquid and solid states.PACS: 74.25.fc; 81.05.Qk; 81.07.Pr.     

Effect of strain on the properties of a styrene–butadiene rubber filled with multiwall carbon nanotubes

Multiwall carbon nanotubes were dispersed in a styrene–butadiene copolymer. The effect of nanotube concentration on the tensile characteristics of the composites was examined. Electrical properties carried out under uniaxial extension show an increase in resistivity upon gradual stretching. A second stretch performed after total release of the stress was shown to lead to a flat response in resistivity. Atomic force microscopy was used to examine orientational effects and changes in filler structure occurring upon application of an uniaxial deformation. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Influence of aminosilane‐functionalized carbon nanotubes on the rheometric,mechanical, electrical and thermal degradation properties of epoxidized natural rubber nanocomposites

We describe the preparation, characterization and physical properties of multiwalled carbon nanotube (MWCNT)‐filled epoxidized natural rubber (ENR) composites. To ensure better dispersion in the elastomer matrix, the MWCNTs were initially subjected to aminopropyltriethoxysilane (APS) treatment to bind amine functional groups (?NH₂) on the nanotube surface. Successful grafting of APS on the MWCNT surface through Si–O–C linkages was confirmed using Fourier transform infrared spectroscopy. Grafting of APS on the MWCNT surface was further corroborated using elemental analysis. ENR nanocomposites with various filler loadings were prepared by melt compounding to generate pristine and APS‐modified MWCNT‐filled elastomeric systems. Furthermore, we determined the effects of various filler loadings on the rheometric, mechanical, electrical and thermal degradation properties of the resultant composite materials. Rheometric cure characterization revealed that the torque difference increased with pristine MWCNT loading compared to the gum system, and this effect was more pronounced when silane‐functionalized MWCNTs were loaded, indicating that this effect was due to an increase in polymer–carbon nanotube interactions in the MWCNT‐loaded materials. Loading of silane‐functionalized MWCNTs in the ENR matrix resulted in a significant improvement in the mechanical, electrical and thermal degradation properties of the composite materials, when compared to gum or pristine MWCNT‐loaded materials.© 2013 Society of Chemical Industry