Development of conducting polychloroprene rubber using imidazolium based ionic liquid modified multi-walled carbon nanotubes

A simplified and an eco-friendly approach to develop polychloroprene rubber composites with high electrical conductivity is reported. The usage of room temperature ionic liquid, 1-butyl 3-methyl imidazolium bis(trifluoromethylsulphonyl)imide and a low concentration (5 phr) of commercial grade multi-walled carbon nanotubes (MWCNTs) in polychloroprene rubber exhibited an electrical conductivity of 0.1 S/cm with a stretchability >500%. The physical (cation-pi/pi-pi) interaction between the ionic liquid and the MWCNTs is evidenced by Raman spectroscopy. Transmission electron microscopy images exhibit an improved dispersion of the BMI modified tubes in matrix at various magnification scales. The dependency of dynamic properties on the concentration of ionic liquid at constant loading of nanotubes supports the fact that ionic liquid assists in the formation of filler-filler networks. The tensile modulus of 3 phr loaded modified MWCNT/CR composite is increased by 50% with regard to that of the unmodified MWCNT/CR composite. Mooney-Rivlin plot displays the existence of rubber-filler interactions.     

Influence of different carbon nanotubes on the electrical and mechanical properties of melt mixed poly(ether sulfone)-multi walled carbon nanotube composites

Commercial Udel® poly(ether sulfone) (PSU) was filled with three different commercially available multiwalled carbon nanotubes (MWCNTs) by small scale melt mixing. The MWCNTs were as grown NC 7000 and two of its derivatives prepared by ball milling treatment. One of them was unmodified (NC 3150); the other was amino modified (NC 3152). The main difference beside the reactivity was the reduced aspect ratio of NC 3150 and NC 3152 caused by ball milling process. All PSU/MWCNT composites with similar filler content were prepared under fixed processing conditions and comparative analysis of their electrical and mechanical properties were performed and were correlated with their microstructure, characterized by optical microscopy, scanning electron microscopy (SEM), and transmission electron microscopy (TEM). A non-uniform MWCNT dispersion was observed in all composites. The MWCNTs were present in form of agglomerates in the size of 10–60 μm whereas the deagglomerated part was homogeneously distributed in the PSU matrix. The differences in the agglomeration states correlate with the variations of properties between different PSU/MWCNT composites. The lowest electrical percolation threshold of 0.25–0.5 wt.% was observed for the shortened non-functionalized MWCNT composites and the highest for amine-modified MWCNT composites (ca. 1.5 wt.%). The tensile behavior of the three composites was only slightly altered with CNT loading as compared to the pure PSU. However, the elongation at break showed a reduction with MWCNT loading and the reduction was least for composite with best MWCNT dispersion.     

Study of the mechanical,electrical and morphological properties of PU/MWCNT composites obtained by two different processing routes

A comparative study of the influence of processing route on polyurethanes (PUs)/multiwalled carbon nanotube (MWCNT) composites mechanical and electrical properties and also morphology was undergone employing two differentiated processing methods, solvent casting and buckypaper infiltration, for producing PU composites with low, medium and high mass fractions of acid treated MWCNT, and with no covalent linkages between the matrix and the nanotubes. As for example, with a MWCNT mass fraction of ∼18 wt.% the second method produced stiffer (270 MPa), lighter (948 kg m⁻³) and more electrically conductive (1.8 S cm⁻¹) composite while the first one gave softer (111 MPa) and more ductile (141%) materials. These properties differences are related to the different PU/MWCNT dispositions obtained through each synthesis route. Nanotubes percolating concentration is found to be crucial on composite properties evolution and a preferential interaction of MWCNT with PU hard segments is observed for solvent cast composites.     

Enhanced conductivity behavior of polydimethylsiloxane (PDMS) hybrid composites containing exfoliated graphite nanoplatelets and carbon nanotubes

Polydimethylsiloxane (PDMS) hybrid composites consisting of exfoliated graphite nanoplatelets (xGnPs) and multiwalled carbon nanotubes functionalized with hydroxyl groups (MWCNTs-OH) were fabricated, and the effects of the xGnP/MWCNT-OH ratio on the thermal, electrical, and mechanical properties of polydimethylsiloxane (PDMS) hybrid composites were investigated. With the total filler content fixed at 4 wt%, a hybrid composite consisting of 75% × GnP/25% MWCNT-OH showed the highest thermal conductivity (0.392 W/m K) and electrical conductivity (1.24 × 10⁻³ S/m), which significantly exceeded the values shown by either of the respective single filler composites. The increased thermal and electrical conductivity found when both fillers are used in combination is attributed to the synergistic effect between the fillers that forms an interconnected hybrid network. In contrast, the various different combinations of the fillers only showed a modest effect on the mechanical behavior, thermal stability, and thermal expansion of the PDMS composite.     

Electromagnetic characteristic and microwave absorbing performance of different carbon-based hydrogenated acrylonitrile–butadiene rubber composites

Hydrogenated acrylonitrile–butadiene rubber (HNBR) was mixed with carbon fiber (CF), conductive carbon black (CCB) and multi-walled carbon nanotubes (MWCNT) to prepare microwave absorbing composites, their complex permittivity was measured in microwave frequencies (2–18 GHz), and their electromagnetic characteristics and microwave absorbing performance were studied. The real part and imaginary part of permittivity of the composites increased with increasing carbon filler loading, showing dependency on filler type. The microwave reflection loss of the composites also depended on the loading and type of fillers. The matching thickness of the absorber layer decreased with increasing permittivity, while the matching frequency decreased with increasing layer thickness. The minimum reflection loss was −49.3 dB for HNBR/MWCNT (100/10) composite, while −13.1 dB for HNBR/CCB (100/15) composite and −7.1 dB for HNBR/CF (100/30) composite. The efficient microwave absorption of HNBR/MWCNT composites is accounted from high conduction loss and dielectric relaxation of MWCNT, and strong interface scattering.     

In situ polymerized nanocomposites: Polystyrene/CNT and Poly(methyl methacrylate)/CNT composites

Carbon nanotubes (CNTs) were incorporated into polystyrene (PS) and poly(methyl methacrylate) (PMMA) matrices via in situ emulsion and emulsion/suspension polymerization methods. The polymerizations were carried out using various initiators, surfactants, and carbon nanotubes to determine their influence on polymerization and on the properties of the composites. The loading of CNTs in the composites varied from 0 to 15 wt.%, depending on the CNTs used. Morphology and dispersion of the CNTs were analyzed by transmission and scanning electron microscopy techniques. The dispersion of multi-walled carbon nanotubes (MWCNT) in the composites was excellent, even at high CNT loading. The mechanical properties, and electrical and thermal conductivities, of the composites were also analyzed. Both electrical and thermal conductivities were improved.     

TiO2-nanorod decorated carbon nanotubes for high-permittivity and low-dielectric-loss polystyrene composites

Polymer composites with high permittivity and low dielectric loss are highly desirable in electronic and electrical industry. Adding conductive fillers could significantly increase the permittivity of a polymer. However, polymer composites containing conductive fillers often exhibit very high dielectric loss due to their large electrical conduction or leakage currents. In this work, by engineering TiO₂-nanorod-decorated multi-walled carbon nanotubes (TD-CNTs), polystyrene (PS) composite with high permittivity and low dielectric loss have been successfully prepared. The composite containing of 17.2 vol.% TD-CNTs has a permittivity of 37 at 1 kHz, which is 13.7 times higher than that of the pure PS (2.7), while the dielectric loss still remains at a low value below 0.11. The dielectric properties of the composites are closely related to the length of CNTs and the loading level of TiO₂-nanorods on the CNT surfaces.     

Nanocomposites based on MWCNT and styrene–butadiene–styrene block copolymers: Effect of the preparation method on dispersion and polymer–filler interactions

Composites of Kraton-D® 1102 BT (a styrene–butadiene–styrene block copolymer) and multi-walled carbon nanotubes (MWCNTs) were prepared by melt mixing. The composites were characterized by electrical conductivity measurements (Coleman’s method), mechanical properties (DMA and stress–strain tests), thermal stability (thermogravimetry) and morphology of dispersion (SEM). Finally, the resulting composites were compared with those made by the solution casting method. The results showed a strong influence of the preparation methodology on the final properties of the composites due to changes in morphology. Composites prepared by casting showed a higher electrical conductivity than extruded ones; the composites with 6 wt.% of MWCNT prepared by extrusion presented conductivity of the same order of magnitude as the composite with 1 wt.% of MWCNT prepared by casting – 10⁻³ to 10⁻⁴ S cm⁻¹. However, the extruded samples presented better mechanical properties than the casting ones.     

Electromagnetic interference shielding behavior of poly(trimethylene terephthalate)/multi-walled carbon nanotube composites

Poly(trimethylene terephthalate) [PTT]/multiwalled carbon nanotube [MWCNT] composites having varying amounts of MWCNTs were fabricated with an aim to investigate the potential of such composites as an effective light weight electromagnetic interference (EMI) shielding material in the frequency range of 12.4-18 GHz (Ku-band). PTT/MWCNT composite with shielding effectiveness (SE) of 36-42 dB was obtained at 10% (w/w) MWCNT loading. Shielding mechanism was studied by resolving the total SE into absorption (SE_A) and reflection loss (SE_R). PTT/MWCNT composite showed absorption dominated shielding; thus it can be used as microwave, radar absorbing and stealth material. The effect of MWCNT loadings on electrical conductivity (σ) and dielectric properties of PTT and the correlation among conductivity, tan δ, absorption loss and reflection loss were also studied.     

The mechanical and viscoelastic properties of SSBR vulcanizates filled with organically modified montmorillonite and silica

The mechanical and the dynamic rheological behavior of solution-polymerized styrene butadiene rubber (SSBR) filled with compounding fillers organic montmorillonite (OMMT)/silica (SiO₂) were studied. The mechanical properties of the vulcanizates could be improved by incorporation of low OMMT contents, and the best reinforcement effect appeared when 7 phr (parts per hundred rubber) OMMT was added. Moreover, due to the formation of the exfoliated silicate platelet in the matrix, a strong cooperative reinforcement effect to the vulcanizate could be gained for the vulcanizate containing 7 phr OMMT and 20 phr SiO₂. Incorporation of SiO₂ up to 50 phr to the vulcanizates with or without OMMT resulted in marked reinforcement effect, and the best mechanical properties were obtained for 7 phr OMMT filled composites. On the other hand, compounding fillers OMMT/SiO₂ significantly influences the dynamic mechanical behavior of the vulcanizates. It was found that the compounding filler with a certain composition facilitated preparing SSBR vulcanizates with optimized wet traction, rolling resistance, and strength properties.     

Enhanced microwave absorbing performance of hydrogenated acrylonitrile–butadiene rubber/multi-walled carbon nanotube composites by in situ prepared rare earth acrylates

Rare earth oxides (REO = Gd₂O₃, Dy₂O₃, Tm₂O₃) and acrylic acid (AA) were in situ reacted in hydrogenated acrylonitrile–butadiene rubber (HNBR) to prepare HNBR/multi-walled carbon nanotube (MWCNT)/REO/AA composites. The HNBR/MWCNT/REO/AA composites have higher permittivity and dielectric loss than HNBR/MWCNT composite, leading to significantly enhanced microwave absorbing performance of the HNBR/MWCNT/REO/AA composites. Dielectric permittivity analysis reveals that the HNBR/MWCNT/REO/AA composites have longer dielectric relaxation time and higher conductivity than the HNBR/MWCNT composite. The HNBR/MWCNT composite has the minimum reflection loss of −15.1 dB, while the HNBR/MWCNT/REO/AA composites have the minimum reflection loss of −48.8 dB. The improvement of microwave absorbing performance is attributed to the stronger interfacial polarization and higher conductivity after formation of in situ prepared rare earth acrylates.     

Effect of coupling agent and nanoclay on properties of HDPE,LDPE, PP,PVC blend and Phargamites karka nanocomposite

High density polyethylene (HDPE), low density polyethylene (LDPE), polypropylene (PP) and poly(vinyl chloride) (PVC) were solution blended by using a mixture of xylene and tetrahydrofuran as solvent and polyethylene-co-glycidyl methacrylate (PE-co-GMA) as compatibilizer. The minimum ratio of solvents to obtain a homogenous solution was optimised. Wood polymer composites (WPC) were prepared by using solution blended polymer, wood flour and nanoclay. X-ray diffraction studies of WPC treated with 1 and 3 phr nanoclay showed higher exfoliation compared to WPC treated with 5 phr nanoclay. TEM study also supported the above findings. FTIR studies indicated an interaction between wood, PE-co-GMA and clay. SEM study indicated an increase in miscibility among polymers due to addition of PE-co-GMA as compatibilizer. Thermal stability improved on addition of clay to the WPC. WPC treated with 3 phr clay showed highest mechanical properties. Hardness and water absorption were improved significantly with the addition of nanoclay to wood/polymer composite.     

Reducing resistivity of polyamide-6/multi-walled carbon nanotube composites by adding ultra-fine rubber particles on account of non-volume exclusion effect

The volume resistivity of polyamide-6(PA6)/multi-walled carbon nanotube (MWCNT) composites was found to be further reduced by adding a kind of ultra-fine rubber particle (URP) with average diameter of 150 nm due to non-volume exclusion effect. With the addition of 16 phr URP, the percolation threshold of PA6/MWCNT composites was reduced from 6 phr MWCNTs to 3 phr. Besides, at a constant loading of 4 phr MWCNTs, increase of URP loading led to two changes and a plateau for the volume resistivity of composites. The morphological observations of composites revealed that the decrease of volume resistivity was attributed to both homogenous dispersion and stretching of MWCNTs in PA6. The mechanism on better dispersion and stretching of MWCNTs with the help of URP was also given.     

A comparative study on the electrical,thermal and mechanical properties of ethylene–octene copolymer based composites with carbon fillers

Conducting polymer composites (CPC) were prepared with an ethylene–octene copolymer (EOC) matrix and with either carbon fibers (CFs) or multiwall carbon nanotubes (MWCNTs) as fillers. Their electrical and thermal conductivities, mechanical properties and thermal stabilities were evaluated and compared. CF/EOC composites showed percolation behavior at a lower filler level (5 wt.%) than the MWCNT/EOC composites (10 wt.%) did. Alternating current (AC) conductivity and real part of permittivity (dielectric constant) of these composites were found to be frequency-dependent. Dimensions and electrical conductivities of individual fillers have a great influence on the conductivities of the composites. CF/EOC composites possessed higher conductivity than the MWCNT-composites at all concentrations, due to the higher length and diameter of the CF filler. Both electrical and thermal conductivities were observed to increase with increasing filler level. Tensile moduli and thermal stabilities of both (CF/EOC and MWCNT/EOC) composites increase with rising filler content. Improvements in conductivities and mechanical properties were achieved without any significant increase in the hardness of the composites; therefore, they can be potentially used in pressure/strain sensors. Thermoelectric behavior of the composites was also studied. Accordingly, CF and MWCNT fillers are versatile and playing also other roles in their composites than just being conducting fillers.     

Structure–property relationships in isotactic polypropylene/multi-walled carbon nanotubes nanocomposites

In this work, the influence of multi-walled carbon nanotubes (MWCNT) on electrical, thermal and mechanical properties of CNT reinforced isotactic polypropylene (iPP) nanocomposites is studied. The composites were obtained by diluting a masterbatch of 20 wt.% MWCNT with a low viscous iPP, using melt mixing. The morphology of the prepared samples was examined through SEM, Raman and XRD measurements. The effect of MWCNT addition on the thermal transitions of the iPP was investigated by differential scanning calorimetry (DSC) measurements. Significant changes are reported in the crystallization behavior of the matrix on addition of carbon nanotubes: increase of the degree of crystallinity, as well as appearance of a new crystallization peak (owing to trans-crystallinity). Dynamic mechanical analysis (DMA) studies revealed an enhancement of the storage modulus, in the glassy state, up to 86%. Furthermore, broadband dielectric relaxation spectroscopy (DRS) was employed to study the electrical and dielectric properties of the nanocomposites. The electrical percolation threshold was calculated 0.6–0.7 vol.% MWCNT from both dc conductivity and dielectric constant values. This value is lower than previous mentioned ones in literature in similar systems. In conclusion, this works provides a simple and quick way for the preparation of PP/MWCNT nanocomposites with low electrical percolation threshold and significantly enhanced mechanical properties.     

Effects of hybrid carbon fillers of polymer composite bipolar plates on the performance of direct methanol fuel cells

The effects of carbon filler type on the properties and performance of composite bipolar plates fabricated by compression molding of carbon fillers such as graphite, carbon black (CB), multi-walled carbon nanotube (MWNT), carbon fiber (CF) and powder type epoxy have been investigated. The electrical conductivity and flexural properties of the composites are increased by increasing the content of fibrous conducting fillers, e.g. MWNT and CF. On the contrary, incorporation of particulate fillers such as CB and graphite plays a significant role in enhancing the electrical conductivity but has a negative effect on the flexural properties of the composites. The current–voltage curve of the fuel cell indicates that the performance of the fuel cell is improved upon selection of an optimum amount of carbon filler in the composite bipolar plates.     

Micromechanical deformations in PP/lignocellulosic filler composites: Effect of matrix properties

Polypropylene composites were prepared from three different PP matrices, a homopolymer, a random and a heterophase copolymer, and corn cob to study the effect of matrix characteristics on deformation and failure. The components were homogenized in an internal mixer and compression molded to 1 mm thick plates. Mechanical properties were characterized by tensile testing, while micromechanical deformations by acoustic emission measurements and fractography. The results proved that the dominating micromechanical deformation process may change with matrix properties. Yield stress determined from the stress vs. strain traces may cover widely differing processes. Debonding is the dominating process when the adhesion of the components is poor, while matrix yielding and/or filler fracture dominate when adhesion is improved by the introduction of a functionalized polymer. The dominating deformation mechanism is determined by component properties and adhesion. Interfacial adhesion, matrix yield stress and the inherent strength of the reinforcement can be limiting factors in the improvement of composite strength. The properties of polymer composites reinforced with lignocellulosic fillers are determined by micromechanical deformation processes, but they are independent of the mechanism of these processes.     

Electrical and mechanical characterization of stretchable multi-walled carbon nanotubes/polydimethylsiloxane elastomeric composite conductors

Stretchable, elastomeric composite conductor made of multi-walled carbon nanotubes (MWNTs) and polydimethylsiloxane (PDMS) has been fabricated by simple mixing. Electrical percolation threshold, amount of filler at which a sharp decrease of resistance occurs, has been determined to be ∼0.6 wt.% of MWNTs. The percolation threshold composition has also been confirmed from swelling experiments of the composite; the equilibrium swelling ratio slightly increases up to ∼0.6 wt.%, then decreases at higher amount of filler MWNTs. Upon cyclic stretching/release of the composite, a fully reversible electrical behavior has been observed for composites having filler content below the percolation threshold value. On the other hand, hysteretic behavior was observed for higher filler amount than the threshold value, due to rearrangement of percolative paths upon the first cycle of stretching/release. Finally, mechanical moduli of the composites have been measured and compared by buckling and microtensile test. The buckling-based measurement has led to systematically higher (∼20%) value of moduli than those from microtensile measurement, due to the internal microstructure of the composite. The elastic conductor may help the implementation of various stretchable electronic devices.     

Preparation of high k expanded graphite/CaCuTi4O12/cyanate ester composites with low dielectric loss through controlling the interfacial action between conductors and ceramics

New composites with high dielectric constant and low dielectric loss, based on expanded graphite (EG), CaCuTi₄O₁₂ (sCCTO) and cyanate ester (CE) resin, were developed by controlling the interaction between EG and sCCTO. Difference from EG, surface modified EG (mEG) has an additional strong chemical interaction with sCCTO, this not only improves the dispersion of fillers, but also enhances the filler-matrix interfacial adhesion, leading to different micro-structures and dielectric properties. Specifically, the percolation thresholds of mEG/sCCTO/CE and EG/sCCTO/CE composites are 3.45 vol% and 2.86 vol%, respectively. When the loading of conductors approaches the percolation threshold, mEG/sCCTO/CE composite has much higher dielectric constant and lower dielectric loss than EG/sCCTO/CE composite. The nature behind these attractive data was revealed by building an equivalent circuit.     

Synergy in hybrid polymer/nanocarbon composites. A review

The aim of this review article is to report the most recent developments in the understanding of and beliefs about the properties of polymer hybrid composites that are reinforced with various combinations of nanometer-sized carbon and mineral fillers. The discussions are primarily focused on an analysis and comparison of the electrical, thermal, and mechanical properties. It is shown that the introduction of a mixed (hybrid) system of filler nanoparticles into polymer matrices enhances the macro- and microproperties of the composites as a result of the synergistic interactions between the fillers and the simultaneous creation of a unique filler network in the polymer. The synergy of various types of carbon nanofillers and combinations of nanocarbon materials with inorganic fillers manifests itself as modifications of most of the properties of hybrid polymer composites relative to the properties of a polymer system containing a single filler. The reinforcing effect is related to the structure and particle geometry of the hybrid fillers, the interactions between the fillers, the concentrations and the processing methods.The existence of synergy between different types of carbon nanofillers, as well as with mineral fillers, shows great potential and could significantly increase applications of carbon-based nanomaterials.