Impact of ethylene carbonate on ion transport characteristics of PVdF-AgCF3SO3 polymer electrolyte system

The ionic transport in thin film plasticized polymer electrolytes based on polyvinylidene fluoride (PVdF) as the polymer host, silver triflate (AgCF₃SO₃) as salt and ethylene carbonate (EC) as plasticizer prepared by solution casting technique has been reported. Addition of silver triflate has resulted in an increase in the room temperature (298 K) electrical conductivity of the polymer from 10⁻⁶ to 10⁻⁵ S cm⁻¹ whereas incorporation of EC as the plasticizer has further enhanced the conductivity value by an order of magnitude to 10⁻⁴ S cm⁻¹ owing to the possible decrease in crystallinity of the polymer matrix as revealed by the detailed temperature-dependent complex impedance, silver ionic transference number, Fourier transform infrared and X-ray diffraction measurements.     

Highly strong and conductive carbon nanotube/cellulose composite paper

Carbon nanotube (CNT)/cellulose composite materials were fabricated in a paper making process optimized for a CNT network to form on the cellulose fibers. The measured electric conductivity was from 0.05 to 671 S/m for 0.5–16.7 wt.% CNT content, higher than that for other polymer composites. The real permittivities were the highest in the microwave region. The unique CNT network structure is thought to be the reason for these high conductivity and permittivity values. Compared to other carbon materials, our carbon CNT/cellulose composite material had improved parameters without decreased mechanical strength. The near-field electromagnetic shielding effectiveness (EMI SE) measured by a microstrip line method depended on the sheet conductivity and qualitatively matched the results of electromagnetic field simulations using a finite-difference time-domain simulator. A high near-field EMI SE of 50-dB was achieved in the 5–10 GHz frequency region with 4.8 wt.% composite paper. The far-field EMI SE was measured by a free space method. Fairly good agreement was obtained between the measured and calculated results. Approximately 10 wt.% CNT is required to achieve composite paper with 20-dB far-field EMI SE.     

Conductivity enhancement in carbon nanocone adhesive by electric field induced formation of aligned assemblies

We show how an alternating electric field can be used to assemble carbon nanocones (CNCs) and align these assemblies into microscopic wires in a commercial two-component adhesive. The wires form continuous pathways that may electrically connect the alignment electrodes, which leads to directional conductivity (～10(-3) S/m) on a macroscopic scale. This procedure leads to conductivity enhancement of at least 2-3 orders of magnitude in the case where the CNC fraction (～0.2 vol %) is 1 order of magnitude below the percolation threshold (～2 vol %). The alignment and conductivity are maintained on curing that joins the alignment electrodes permanently together. If the aligned CNC wires are damaged before curing, they can be realigned by an extended alignment period. This concept has implications in areas such as electronic packaging technology.     

Electrical conductivity of ion-doped graphite/polyethersulphone composites

The electrical conductivity of polyethersulphone (PES) insulating polymer was improved by incorporation of electrically conductive graphite and ions. An initial conducting pathway of the PES/graphite composites was formed at lower than 3 wt.% of the filler content. LiCl was found to be an effective dopant for the improvement of the electrical conductivities of the PES/graphite composites. By doping with 0.06 wt.% of LiCl the electrical conductivity was enhanced by two orders of magnitude. The enhancement resulted from intercalation of Li⁺ ions into interlayer spaces of the graphite. Upon intercalation, an acceptor GIC, Li-GIC, was consequently formed. The stability of the improved electrical conductivities of the composites contributed with doped-ions was assessed. The electrical conductivity of both un-doped and doped graphite/PES composites slightly increased with increasing temperature and slightly decreased by physical ageing. The enhancement of the electrical conductivities by doping ions was stable at the high temperatures.     

Electrical and thermal property enhancement of fiber-reinforced polymer laminate composites through controlled implementation of multi-walled carbon nanotubes

Aligned carbon nanotubes (CNTs) are implemented into alumina-fiber reinforced laminates, and enhanced mass-specific thermal and electrical conductivities are observed. Electrical conductivity enhancement is useful for electrostatic discharge and sensing applications, and is used here for both electromagnetic interference (EMI) shielding and deicing. CNTs were grown directly on individual fibers in woven cloth plies, and maintained their alignment during the polymer (epoxy) infiltration used to create laminates. Using multiple complementary methods, non-isotropic electrical and thermal conductivities of these hybrid composites were thoroughly characterized as a function of CNT volume/mass fraction. DC and AC electrical conductivity measurements demonstrate high electrical conductivity of >100 S/m (at 3% volume fraction, ∼1.5% weight fraction, of CNTs) that can be used for multifunctional applications such as de-icing and electromagnetic shielding. The thermal conductivity enhancement (∼1 W/m K) suggests that carbon-fiber based laminates can significantly benefit from aligned CNTs. Application of such new nano-engineered, multi-scale, multi-functional CNT composites can be extended to system health monitoring with electrical or thermal resistance change induced by damage, fire-resistant structures among other multifunctional attributes.     

A simple, low-cost approach to prepare flexible highly conductive polymer composites by in situ reduction of silver carboxylate for flexible electronic applications

In recent years, efforts to prepare flexible highly conductive polymer composites at low temperatures for flexible electronic applications have increased significantly. Here, we describe a novel approach for the preparation of flexible highly conductive polymer composites (resistivity: 2.5 × 10⁻⁵ Ω cm) at a low temperature (150 °C), enabling the wide use of low cost, flexible substrates such as paper and polyethylene terephthalate (PET). The approach involves (i) in situ reduction of silver carboxylate on the surface of silver flakes by a flexible epoxy (diglycidyl ether of polypropylene glycol) to form highly surface reactive nano/submicron-sized particles; (ii) the in situ formed nano/submicron-sized particles facilitate the sintering between silver flakes during curing. Morphology and Raman studies indicated that the improved electrical conductivity was the result of sintering and direct metal-metal contacts between silver flakes. This approach developed for the preparation of flexible highly conductive polymer composites offers significant advantages, including simple low temperature processing, low cost, low viscosity, suitability for low-cost jet dispensing technologies, flexibility while maintaining high conductivity, and tunable mechanical properties. The developed flexible highly conductive materials with these advantages are attractive for current and emerging flexible electronic applications.     

Novel silicon carbide/polypyrrole composites; preparation and physicochemical properties

Novel silicon carbide/polypyrrole (SiC/PPy) conducting composites were prepared using silicon carbide as inorganic substrate. The surface modification of SiC was performed in aqueous solution by oxidative polymerization of pyrrole using ferric chloride as oxidant. Elemental analysis was used to determine the mass loading of polypyrrole in the SiC/PPy composites. Scanning electron microscopy showed the surface modification of SiC by PPy. PPy in composites was confirmed by the presence of PPy bands in the infrared spectra of SiC/PPy containing various amounts of conducting polymer. The conductivity of SiC/PPy composites depends on PPy content on the surface. The composite containing 35 wt.% PPy showed conductivity about 2 S cm⁻¹, which is in the same range as the conductivity of pure polypyrrole powder prepared under the same conditions using the same oxidant. PPy in the composites was clearly detected by X-ray photoelectron spectroscopy (XPS) measurements by its N1s and Cl2p peaks. High resolution scans of the C1s regions distinguished between silicon carbide and polypyrrole carbons. The fraction of polypyrrole at the composite surface was estimated from the silicon and nitrogen levels. The combination of XPS and conductivity measurements suggests that the surface of the SiC/PPy composites is polypyrrole-rich for a conducting polymer mass loading of at least 12.6 wt.%.     

Electrical conductivity and Raman imaging of double wall carbon nanotubes in a polymer matrix

Raman spectroscopy is used to access the dispersion state of DWNTs in a PEEK polymer matrix. The interaction of the outer tube with the matrix can be determined from the line shape of the Raman G band. This allows us to distinguish regions where the nanotubes are well dispersed and regions where the nanotubes are agglomerated. The percolation threshold of the electrical conductivity of the double wall carbon nanotubes (DWNTs)/PEEK nanocomposites is found to be at 0.2-0.3 wt%. We find a maximum electrical conductivity of 3 × 10⁻² S cm⁻¹ at 2 wt% loading. We detect nanotube weight concentrations as low as 0.16 wt% by Raman spectroscopy using a yellow excitation wavelength. We compare the Raman images with transmission electron microscopy images and electrical conductivity measurements. A statistical method is used to find a quantitative measure of the DWNTs dispersion in the polymer matrix from the Raman images.     

Electric field effects on CNTs/vinyl ester suspensions and the resulting electrical and thermal composite properties

In this study, electrical conductivity of a vinyl ester based composite containing low content (0.05, 0.1 and 0.3 wt.%) of double and multi-walled carbon nanotubes with and without amine functional groups (DWCNTs, MWCNTs, DWCNT-NH₂ and MWCNT-NH₂) was investigated. The composite with pristine MWCNTs was found to exhibit the highest electrical conductivity. Experiments aimed to induce an aligned conductive network with application of an alternating current (AC) electric field during cure were carried out on the resin suspensions with MWCNTs. Formation of electric anisotropy within the composite was verified. Light microscopy (LM), scanning electron (SEM) and transmission electron microscopy (TEM) were conducted to visualize dispersion state and the extent of alignment of MWCNTs within the polymer cured with and without application of the electric field. To gain a better understanding of electric field induced effects, glass transition temperature (T_g) of the composites was measured via Differential Scanning Calorimetry (DSC). It was determined that at 0.05 wt.% loading rate of MWCNTs, the composites, cured with application of the AC electric field, possessed a higher T_g than the composites cured without application of the AC electric field.     

The effect of molecular chain polarity on electric field-induced aligned conductive carbon nanotube network formation in polymer melt

Two ethylene–vinyl acetate (EVA) copolymers containing 10 and 25 wt.% vinyl acetate (EVA10 and EVA25) were utilized to explore the effect of molecular polarity on the formation of conductive carbon nanotube (CNT) network in EVA melt under an electric field. Because of the different interfacial energy, it was supposed to be stronger molecular chain-CNT interaction in CNT/EVA25 than that in CNT/EVA10. The critical time for conductive CNT network formation decreased with annealing temperature, filler loading and EVA polarity. The activation energy of conductive CNT network formation (93.9 kJ/mol) in CNT/EVA10 is lower than that (104.7 kJ/mol) in CNT/EVA25. By a thermodynamic percolation model, the percolation threshold at the equilibrium state was about 0.19 vol.% for CNT/EVA10, while it rose to 0.27 vol.% for CNT/EVA25. Morphological observation showed a high degree of CNT alignment in CNT/EVA10 compared to CNT/EVA25 after application of an electric field. The results suggested the strong CNT–EVA chain interaction and higher viscosity of polymer matrix limited the CNT alignment and the conductive network tended to form easily in EVA melt with a low chain polarity.     

Conductive polymer composites based on metallic nanofiller as smart materials for current limiting devices

The influence of the structure and the temperature on the Conductive Polymer Composites (CPC) properties has been studied. The investigated CPC are based on homo- and heterogeneous polymer blends of high density polyethylene, polybutylene terephthalate and poly(m-xylene adipamide), filled with dispersed silver nanoparticles (Ag). It is shown that by the appropriate use of the immiscible polymers blends the percolation threshold can be decreased twice, what significantly reduces costs and keeps better mechanical properties. Additionally, it was found that depending on the choice of CPC structure the commutation temperature from a conducting state to an insulating state can be observed between 45 and 180 °C. The observed high intensity of Positive Temperature Coefficient (PTC) effect, i.e. a sharp (narrow temperature range) and strong (10 orders of magnitude) resistivity increase, makes such composites promising for current limiting devices and temperature sensors.     

Yttria-stabilized zirconia-based composites with adaptive thermal conductivity

Thermal conductivity trends in a “chameleon coating” thin film were characterized with a time-domain thermoreflectance (TDTR) technique. A yttria-stabilized zirconia (YSZ)-based nanocomposite material containing ∼21 vol.% silver (Ag) was employed for this study. The thermal conductivity (k) of the as-deposited composite film was measured with TDTR and found to have a value of 7.4 ± 1.4 W m⁻¹ K⁻¹. The film was then annealed at 500 °C for 1 h to stimulate Ag flow from within the composite to the surface via diffusion. The Ag that coalesced on the surface during annealing was removed to expose the underlying porous YSZ matrix, and the sample was reexamined with the TDTR technique. The thermal conductivity of the porous nanocomposite YSZ material was then measured to be 1.6 ± 0.2 W m⁻¹ K⁻¹, which is significantly lower than a fully dense control sample of pure nanocrystalline YSZ (2.0 ± 0.1 W m⁻¹ K⁻¹). The annealed film displayed a 20% reduction in thermal conductivity as compared to the control sample and a 4–5-fold reduction in thermal conductivity as compared to the as-deposited material. The experiments demonstrate temperature triggering of a composite material, resulting in self-modifying thermal conductivity and diffusion-controlled porosity. These aspects can be used to enhance or restrict thermal transport (i.e., a thermal switch). The applicability of the TDTR technique to measurements of thin, nanoporous film materials is also demonstrated.     

The fibre/matrix interface and its influence on mechanical and physical properties of Cu-MMC

Fibre or wire reinforced copper or copper alloys (Cu-MMCs) have been developed as a high temperature heat sink material in the scheme of the integrated European project “Extremat”. The Cu-MMC of interest for application e.g. in fusion reactors should be able to operate at 550 °C and posses a thermal conductivity of at least 200 W/m/K. Properties of the developed Cu-MMCs with the SCS-6 SiC-fibres and W-wires in a matrix of pure Cu or CuCrZr are discussed. W-wire reinforced CuCrZr is selected as a candidate material for application in the fusion reactor with the highest thermal loadings, i.e. in the divertor. A divertor mockup is produced which will be tested under a high heat flux of up to 20 MW/m².     

Fabrication and characterization of recyclable carbon nanotube/polyvinyl butyral composite fiber

A surface-draw method to fabricate recyclable carbon nanotube/polyvinyl butyral (CNT/PVB) composite fibers is reported. This method is effective for both single-walled carbon nanotube (SWCNT) and multi-walled carbon nanotube. The CNT mass content of CNT/PVB composite fibers can vary from 0 to 80 wt.%, which is higher than most CNT/polymer composites reported to date. The diameter of the composite fibers can be controlled in the range of 10-100 μm, with essentially unlimited draw length. The composite fibers with 7.4 wt.% SWCNTs showed optimal tensile properties. Compared with pure PVB fibers, the tensile strength, failure strain, and elastic modulus of the composite fiber have improved about 127%, 27%, and 73%, respectively. In addition, SWCNT/PVB composites with 66.7 wt.% SWCNTs have the highest conductivity of 42.9 S m⁻¹. More importantly, the major benefit is the “greenness” of the method, which involves environment friendly ethanol-water solvent with no functionalization of the nanotube required, and only simple apparatus are needed. The CNT/PVB composite fibers obtained can be dissolved in ethanol solution and reformed with the surface draw method without any additional treatment; and the material properties after recycle is comparable to those fabricated in the first round.     

Synthesis, characterization and electrical conductivity studies on A3Bi2P3O12 (A = Na, K) materials

Crystalline Na₃Bi₂P₃O₁₂, K₃Bi₂P₃O₁₂ and glassy K₃Bi₂P₃O₁₂ compounds were prepared by solid-state reaction method. The prepared samples are characterized by X-ray powder diffraction, Fourier transform infrared spectroscopy and differential scanning calorimetry. The crystalline materials are found to be orthorhombic. The electrical conductivity measurements on the crystalline and glassy samples show that at ∼373 K, the σ_DC for crystalline K₃Bi₂P₃O₁₂ (0.81 × 10⁻⁸ S/cm) is about two orders of magnitude higher than the corresponding glassy phase (1.25 × 10⁻¹⁰ S/cm). The scaling results show that the conductivity relaxation mechanism is independent of temperature.     

Chemical and thermal reduction of graphene oxide and its electrically conductive polylactic acid nanocomposites

Graphene oxide (GO) was reduced with biocompatible glucose and polyvinylpyrrolidone (PVP) and incorporated in polylactic acid (PLA). The thermal reduction of GO during the compression molding of PLA was also studied to delineate the reduction efficiencies from thermal and chemical processes. Results indicate that glucose is more effective in the reduction of GO (rGO-g) with a much higher electrical conductivity than PVP and thermally treated GO. Even rGO-g was also highly efficient in improving the electrical conductivity of PLA. The composite with ∼1.25 vol.% of rGO-g exhibited a high conductivity of ∼2.2 S/m due to the chemical reduction of GO with glucose and the thermal reduction of rGO-g during the compression molding process.     

The low temperature thermoelectric properties of CuxTiSe2−ySy

The low temperature thermoelectric properties of TiSe₂, co-doped with Cu and S, are reported. Partial S substitution for Se changes the magnitude of the indirect bandgap, while the Cu-doping independently controls the n-type carrier concentration. The Seebeck coefficients are negative, in the range of −50 to −200 μV K⁻¹, and the resistivities are 0.1-10 mΩ cm. The thermal conductivity for the sample with the largest thermoelectric power factor was found to be relatively low, 3-4 W m⁻¹ K⁻¹, and decreases with decreasing temperature. The thermoelectric efficiencies for the best materials found in this system, typified by Cu_0.02TiSe_1.7S_0.3, were largest at 0.07 at 300 K and decreased to 0.01 at 75 K.     

Poly(vinyl alcohol) reinforced with large-diameter carbon nanotubes via spray winding

For practical application of carbon nanotube (CNT)/polymer composites, it is critical to produce the composites at high speed and large scale. In this study, multi-walled carbon nanotubes (MWNTs) with large diameter (∼45 nm) and polyvinyl alcohol (PVA) were used to increase the processing speed of a recently developed spraying winding technique. The effect of the different winding speed and sprayed solution concentration to the performance of the composite films were investigated. The CNT/PVA composites exhibit tensile strength of up to 1 GPa, and modulus of up to 70 GPa, with a CNT weight fraction of 53%. In addition, an electrical conductivity of 747 S/cm was obtained for the CNT/PVA composites. The good mechanical and electrical properties are attributed to the uniform CNTs and PVA matrix integration and the high degree of tube alignment.     

Synthesis and Li ion conductivity of Li2O-Nb2O5-P2O5 glasses and glass-ceramics

Glasses with the compositions of xLi₂O-(70 − x)Nb₂O₅-30P₂O₅, x = 30-60, and their glass-ceramics are synthesized using a conventional melt-quenching method and heat treatments in an electric furnace, and Li⁺ ion conductivities of glasses and glass-ceramics are examined to clarify whether the glasses and glass-ceramics prepared have a potential as Li⁺ conductive electrolytes or not. The electrical conductivity (σ) of the glasses increases monotonously with increasing Li₂O content, and the glass of 60Li₂O-10Nb₂O₅-30P₂O₅ shows the value of σ = 2.35 × 10⁻⁶ S/cm at room temperature and the activation energy (E_a) of 0.48 eV for Li⁺ ion mobility in the temperature range of 25-200 °C. It is found that two kinds of the crystalline phases of Li₃PO₄ and NbPO₅ are formed in the crystallization of the glasses and the crystallization results in the decrease in Li⁺ ion conductivity in all samples, indicating that any high Li⁺ ion conducting crystalline phases have not been formed in the present glasses. 60Li₂O-10Nb₂O₅-30P₂O₅ glass shows a bulk nanocrystallization (Li₃PO₄ nanocrystals with a diameter of ∼70 nm) and the glass-ceramic obtained by a heat treatment at 544 °C for 3 h in air exhibits the values of σ = 1.23 × 10⁻⁷ S/cm at room temperature and E_a = 0.49 eV.     

Highly conducting poly(methyl methacrylate)/carbon nanotubes composites: Investigation on their thermal, dynamic-mechanical, electrical and dielectric properties

Nanocomposites of poly(methyl methacrylate) (PMMA) containing various multi-walled carbon nanotubes (MWCNT) contents were prepared using melt mixing. Several techniques were employed to study the influence of the MWCNT addition on the thermal, mechanical, electrical and dielectric properties of the PMMA matrix. The electrical percolation threshold (p_c) was found to be 0.5 vol.% by performing AC and DC conductivity measurements. Significantly high conductivity levels (σ_dc) were achieved: σ_dc exceeds 10⁻² S/cm already at 1.1 vol.%, the criterion for EMI shielding (σ_dc > 10⁻¹ S/cm) is fulfilled at 2.9 vol.%, and the highest loaded sample (5.2 vol.%) gave a maximum value of 0.5 S/cm. Dielectric relaxation spectroscopy measurements in broad frequency (10⁻¹−10⁶ Hz) and temperature ranges (−150 to 170 °C) indicated weak polymer-filler interactions, in consistency with differential scanning calorimetry and dynamic-mechanical analysis findings. Weak polymer-filler interactions and absence of crystallinity facilitate the achievement of high conductivity levels in the nanocomposites.