Modelling the DC electrical conductivity of polymer/carbon black composites

Several DC electrical conductivity models have been proposed to explain the properties of composite materials. In particular, generalized effective medium model was used, but, in many cases, the obtained parameters do not fit accurately the data. In this paper, we extended the study to Mamunya model, with adjustable parameters. Using different carbon black nanocomposites, we obtained a good agreement with the experimental results, but only for concentrations above the percolation critical concentration. Below this point, the fit is not accurate.     

Effect of polymer-filler interface interactions on percolation conductivity of thermoplastics filled with carbon black

Conductive composites based on PE, PP, PS, PMMA and PA filled with carbon black have been studied. It was found that percolation behavior of the conductivity depended on the degree of polymer-filler interaction. Equations taking into account the polymer-filler interactions were proposed to describe the conductivity of composite above and below the percolation threshold.     

Percolation of electrical conductivity in solution-cast blends containing polyaniline

The potential offered by intrinsically conductive polymers is limited by their poor mechanical properties. Blending with common thermoplastics can improve processability and mechanical properties and still preserve the electrical conductivity. In such blends, the morphology determines the mechanical and electrical properties. In this research, blends of polyaniline (PANI)-dodecyl benzene sulfonic acid (DBSA) with either polystyrene (PS) in xylene or polyvinylchloride (PVC) in bromobenzene were solution cast. The morphologies of the blends were characterized by optical microscopy (OM), electron microscopy, and small-angle X-ray scattering (SAXS). Electrical conductivity was measured for various compositions. The formation of a continuous network was strongly associated with percolation and conductivity. The morphologies of the two blends are significantly different. This difference arises from the different solvents used and their ability to swell the PAN1 aggregates and to promote their disintegration into small particles. Molecular calculations show that, indeed, bromobenzene, used in the PVC system, is able to penetrate the PANI-DBSA aggregates, while xylene, used in the PS system, cannot. Nevertheless, the small PANI-DBSA particles in the PVC matrix form a conductive network only at a relatively high content, while the coarse aggregates in the PS matrix form conductive paths at a relatively low content. These results are discussed in terms of the formation and stability of the PANI-DBSA dispersion.     

Scaling behavior of permeability and conductivity anisotropy near the percolation threshold

We use the finite-size scaling method to estimate the critical exponent that characterizes the scaling behavior of conductivity and permeability anisotropy near the percolation thresholdp _c . Here is defined by the scaling lawk _l /k _t –1(p–p _c ), wherek _t andk _t are the conductivity or permeability of the system in the direction of the macroscopic potential gradient and perpendicular to this direction, respectively. The results are (d=2)0.819±0.011 and (d=3)0.518±0.001. We interpret these results in terms of the structure of percolation clusters and their chemical distance. We also compare our results with the predictions of a scaling theory for due to Straley, and propose that (d=2)=t- _B , wheret is the critical exponent of the conductivity or permeability of the system, and _B is the critical exponent of the backbone of percolation clusters.     

SSIMS analysis of organics, polymer blends and interfaces

This paper gives a critical review on the applications of ToF SIMS in the areas of polymer additive characterization and in the study of polymer blends and interfaces. Polymer additives can readily be identified by ToF SIMS using their parent molecular ions or characteristic fragments. This analytical capability has been successfully applied to monitor the migration or segregation of additives during polymer processing. ToF SIMS is an ideal analytical tool for the study of polymer blends and interfaces because it is able to provide information on both surface composition and morphology. In combination with other analytical techniques such as AFM and XPS, ToF SIMS chemical imaging capability has opened up new horizons in the investigation of complex polymer blend systems. Finally the main advantages and limitations of ToF SIMS in these application areas are also discussed.     

Effect of molecular weight on conductivity of polymer electrolytes

The ionic conductivity, σ, of mixtures of poly(ethylene oxide) (PEO) and lithium bis(trifluoromethanesulfone)imide (LiTFSI) was measured as a function of molecular weight of the PEO chains, M, over the range 0.2-5000 kg/mol. Our data are consistent with an expression σ = σ₀ + K/M proposed by Shi and Vincent [Solid State Ionics 60 (1993)] where σ₀ and K are exponential and linear functions of inverse temperature respectively. Explicit expressions for σ₀ and K are provided.     

Effects of plasticizer and nanofiller on the dielectric dispersion and relaxation behaviour of polymer blend based solid polymer electrolytes

Solid polymer electrolytes consisted of poly(ethylene oxide) (PEO) and poly(methyl methacrylate) (PMMA) blend (50:50 wt/wt%) with lithium triflate (LiCF₃SO₃) as a dopant ionic salt at stoichiometric ratio [EO + (CO)]:Li⁺ = 9:1, poly(ethylene glycol) (PEG) as plasticizer (10 wt%) and montmorillonite (MMT) clay as nanofiller (3 wt%) have been prepared by solution cast followed by melt–pressing method. The X–ray diffraction study infers that the (PEO–PMMA)–LiCF₃SO₃ electrolyte is predominantly amorphous, but (PEO–PMMA)–LiCF₃SO₃–10 wt% PEG electrolyte has some PEO crystalline cluster, whereas (PEO–PMMA)–LiCF₃SO₃–10 wt% PEG–3 wt% MMT electrolyte is an amorphous with intercalated and exfoliated MMT structures. The complex dielectric function, ac electrical conductivity, electric modulus and impedance spectra of these electrolytes have been investigated over the frequency range 20 Hz to 1 MHz. These spectra have been analysed in terms of the contribution of electrode polarization phenomenon in the low frequency region and the dynamics of cations coordinated polymer chain segments in the high frequency region, and also their variation on the addition of PEG and MMT in the electrolytes. The temperature dependent dc ionic conductivity, dielectric relaxation time and dielectric strength of the plasticized nanocomposite electrolyte obey the Arrhenius behaviour. The mechanism of ions transportation and the dependence of ionic conductivity on the segmental motion of polymer chain, dielectric strength, and amorphicity of these electrolytes have been explored. The room temperature ionic conductivity values of the electrolytes are found ∼10⁻⁵ S cm⁻¹, confirming their use in preparation of all-solid-state ion conducting devices.     

Investigations on the effect of complexation of NaF salt with polymer blend (PEO/PVP) electrolytes on ionic conductivity and optical energy band gaps

Sodium ion conducting polymer blend electrolyte films, based on polyethylene oxide (PEO) and polyvinyl pyrrolidone (PVP) complexed with NaF salt, were prepared using solution casting technique. The complexation of the salt with the polymer blend was confirmed by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and UV-vis spectroscopy. Electrical conductivity of the films was measured with impedance analyzer in the frequency range of 1 Hz to 1 MHz and in the temperature range of 303-348 K. It was observed that the magnitude of conductivity increased with the increase in the salt concentration as well as the temperature. UV-vis absorption spectra in wavelength region of 200-800 nm were used to evaluate the optical properties like direct and indirect optical energy band gaps, optical absorption edge. The optical band gaps decreased with the increase in Na⁺ ion concentration. This suggests that NaF, as a dopant, is a good choice to improve the electrical properties of PEO/PVP polymer blend electrolytes.     

Effect of Pt and Fe catalysts in the transformation of carbon black into carbon nanotubes

In this research carbon nanotubes and carbon nano onion-like structures were synthesized from carbon black using metal catalysts at 400 °C and 700 °C. Platinum and iron-group metals were used as catalysts for the transformation of CB into graphitized nanocarbon and the effect of both metals was compared. The synthesized products were characterized using X-ray diffraction (XRD), transmission electron microscope (TEM), high resolution transmission electron microscope (HRTEM) and Raman spectroscopy. The characterization shows that this process is very efficient in the synthesis of high quality graphitized products from amorphous carbon black, even though the process temperature was relatively low in comparison with previous studies. Distinguished graphitic walls of the newly formed carbon nanostructures were clearly visible in the HRTEM images. Possible growth difference related to the type of catalyst used is briefly explained with the basis of electron vacancies in d-orbitals of metals.     

A computer simulation study of ionic conductivity in polymer electrolytes

In this paper we present a computer simulation study of ionic conductivity in solid polymeric electrolytes. The multiphase nature of the material is taken into account. The polymer is represented by a regular lattice whose sites represent either crystalline or amorphous regions with the charge carrier performing a random walk. Different waiting times are assigned to sites corresponding to the different phases. A random walk (RW) is used to calculate the conductivity through the Nernst-Einstein relation. Our walk algorithm takes into account the reorganization of the different phases over time scales comparable to time scales for the conduction process. This is a characteristic feature of the polymer network. The qualitative nature of the variation of conductivity with salt concentration agrees with the experimental values for PEO-NH₄I and PEO-NH₄SCN. The average jump distance estimated from our work is consistent with the reported bond lengths for such polymers.     

Effect of branching in base polymer on ionic conductivity in hyperbranched polymer electrolytes

Novel hyperbranched polymer, poly[bis(diethylene glycol)benzoate] capped with a 3,5-bis[(3′,6′,9′-trioxodecyl)oxy]benzoyl group (poly-Bz1a), was prepared, and its polymer electrolyte with LiN(CF₃SO₂)₂, poly-Bz1a/LiN(CF₃SO₂)₂ electrolyte, was all evaluated in thermal properties, ionic conductivity, and electrochemical stability window. The poly-Bz1a/LiN(CF₃SO₂)₂ electrolyte exhibited higher ionic conductivity compared with a polymer electrolyte based on poly[bis(diethylene glycol)benzoate] capped with an acetyl group (poly-Ac1a), and the ionic conductivity of poly-Bz1a/LiN(CF₃SO₂)₂ electrolyte was to be 7×10⁻⁴ S cm⁻¹ at 80 °C and 1×10⁻⁶ S cm⁻¹ at 30 °C, respectively. The existence of a 3,5-bis[(3′,6′,9′-trioxodecyl)oxy]benzoyl group as a branching unit present at ends in the base polymer improved significantly ionic conductivity of the hyperbranched polymer electrolytes. The polymer electrolyte exhibited the electrochemical stability window of 4.2 V at 70 °C and was stable until 300 °C.     

Structure evolution of carbon black under ionic-liquid-assisted microwave irradiation

The interactions between the carbon black (CB) and the ionic liquid (IL), 1-butyl-3-methyl-imiazolium hexafluorophosphate ([BMIM⁺][PF₆⁻]), are firstly examined. The CB, mixed with the IL via simple blending, is then subjected to microwave (MW) irradiation to prepare the modified CB. The structure evolutions of the modified CB such as the microcrystalline structure and surface chemistry are revealed by Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and pore analysis. After mixing but before MW irradiation, the microcrystalline arrangement of CB turns to be more ordering and microcrystalline size (La) to be a little bigger but with a limited degree. Under MW irradiation, the IL undergoes severe decomposition. The combination of localized high temperature (proposed to be higher than 425 °C) and the decomposition of the IL leads to substantial structure changes of the CB. The graphitization of the CB surface, the disordering of the microcrystalline and the decrease in La are disclosed. In addition, compared with the untreated CB, the CB treated with IL-assisted MW irradiation is found to have much higher volume of the smaller mesopore.     

Physical properties of carbon composite materials with low percolation threshold

Electrical and thermal properties of binary systems consisted of stearine and expanded graphite (EG) of different bulk densities (0.003 and 0.4 g/cm³), stearine and fine-crystalline graphite (CG) were examined. Heat capacity measurements display that phonon spectrum of graphite does not change after chemical and heat treatment in the temperature range from 300 to 700 K. It was shown that the value of samples’ percolation threshold depends on aspect ratio of using the electroconducting filler: EG as electroconducting filler is 20 times more effective than common crystal graphite.     

Universal microstructure and conductivity relaxation of polymer-conductor composites across the percolation threshold

Micro-structural and impedance analysis of series of insulating polymer/conductor composites (PCC) as a function of frequency and volume fractions of the conductor (f_con) have been studied. Evidences of conductivity relaxation have been noticed with a correlation with the sample micro-structure. This has been understood and explained in terms of equivalent electrical circuit model of the material established through complex impedance spectroscopy (CIS) across the percolation threshold (f_c) for all the PCC. CIS analysis confirmed that PCC with f_con ≥ f_c, exhibit conductivity/interfacial relaxation due to polarization of Maxwell–Wagner–Sillars (MWS) type at f_c and the relaxation frequency increases with increase of f_con. The modulus spectroscopy analysis suggests the presence of two types of relaxations in different frequency ranges; (i) dipolar relaxation associated with the flipping of dipoles present in the pure polymer for f_con < f_c and (ii) the conductivity/interfacial relaxation due to the formation of artificial MWS dipoles at the interface of the two components. A long range dc conductivity appears at f_con ≥ f_c and Jonschers universal fractional power law is satisfied for both the regions of f_con < f_c and f_con ≥ f_c in all PCC.     

Role of salt concentration on conductivity optimization and structural phase separation in a solid polymer electrolyte based on PMMA-LiClO4

Although a large number of ionic conductors based on poly(methyl-methacrylate) (PMMA) are reported in literature, an optimization of salt concentration with respect to conductivity and stability properties remains by and large neglected. We report, perhaps for the first time, such an optimization of salt (LiClO₄) concentration on structural, morphological, electrical, and ion–polymer interaction in PMMA-based solid polymer films. The active coordination site for the cation (Li⁺), out of the two possible electron donating functional groups (i.e. C=Ö and Ö–CH₃) in PMMA, has been ascertained on the basis of evidences recorded in Fourier transform infrared spectrum. The results suggested C=Ö as the only possible site in PMMA matrix for coordination with Li⁺ cation. The X-ray diffraction results have clearly indicated an optimum limit of salt dissolution in PMMA matrix corresponding to O/Li = 4 (i.e., ~21wt.%) above which “phase-separation” occurs distinctly. The effect of salt concentration on amorphous → crystalline phase changes in PMMA and its correlation to morphology have been clearly observed in terms of their impact on electrical properties. An optimum electrical conductivity of ~7.2 × 10^?5S cm^?1 has been recorded at 100°C (~PMMA glass transition). The temperature dependence of conductivity follows typical Vogel–Tamman–Fulcher behavior.     

Electrical,optical, and structural characterization of polymer blend (PVC/PMMA) electrolyte films

Ion-conducting solid polymer blend electrolytes based on polyvinyl chloride (PVC)/poly methyl methacrylate (PMMA) complexed with sodium perchlorate (NaClO₄) were prepared in various concentrations by solution cast technique. The features of complexation of the electrolytes were studied by X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy. DC conductivity of the films was measured in the temperature range 303–398 K. Transference number measurements were carried out to investigate the nature of charge transport in the polymer blend electrolyte system. The electrical conductivity increased with increasing dopant concentration, which is attributed to the formation of charge transfer complexes. The polymer complexes exhibited Arrhenius type dependence of conductivity with temperature. In the temperature range studied, two regions with different activation energies were observed. Transference number data showed that the charge transport in this system is predominantly due to ions. Optical properties like absorption edge, direct band gap, and indirect band gap were estimated for pure and doped films from their optical absorption spectra in the wavelength region 200–600 nm. It was found that the energy gap and band edge values shifted to lower energies on doping with NaClO₄ salt. Paper presented at the Third International Conference on Ionic Devices (ICID 2006), Chennai, Tamil Nadu, India, Dec. 7–9, 2006.     

Microwave absorption properties of a wave-absorbing coating employing carbonyl-iron powder and carbon black

To prevent serious electromagnetic interference, a single-layer wave-absorbing coating employing complex absorbents composed of carbonyl-iron powder (CIP) and carbon black (CB) with epoxy resin as matrix was prepared. The morphologies of CIP and CB were characterized by scanning electron microscope (SEM) and transmission electron microscope (TEM), respectively. The electromagnetic parameters of CIP and CB were measured in the frequency range of 2-18 GHz by transmission/reflection technology, and the electromagnetic loss mechanisms of the two particles were discussed, respectively. The microwave absorption properties of the coatings were investigated by measuring reflection loss (RL) using arch method. The effects of CIP ratio, CB content and thickness on the microwave absorption properties were discussed, respectively. The results showed that the higher thickness, CIP or CB content could make the absorption band shift towards the lower frequency range. Significantly, the wave-absorbing coating could be applied in different frequency ranges according to actual demand by controlling the content of CIP or CB in composites.     

Absorption properties of carbonyl-iron/carbon black double-layer microwave absorbers

Double-layer materials were devised in order to improve the absorbing properties of electromagnetic wave absorbing plates. The double-layer wave absorbing materials are composed of a matching layer and an absorption layer. The matching layer is the surface layer through which most of the incident waves can enter, and the absorption layer beneath it plays an important role in incident wave attenuation. The total thickness of the double layer is the sum of the thicknesses of these two layers. Carbonyl iron (CI) and carbon black (CB) were used as absorbents in the matching and absorption layers, respectively. The structures of the CI and CB particles were analyzed using scanning electron microscopy and transmission electron microscopy; the dielectric properties and absorption mechanisms were also studied. In the testing frequency range 2-18 GHz, the results show that the double-layer absorbers have two absorption peaks, and the positions and values of these peaks change with the content level of the absorbents. When the mass fraction of CI in the matching layer is 50% and the total thickness of the absorber is 4 mm, the effective absorption band (below −8 dB) reaches 5.5, 5.8, and 6.5 GHz. Where the mass fraction of CB is 50% or 60% and the mass fraction of CI is 70%, the bandwidth with reflection loss below −4 dB is larger than 10 GHz.     

New nanocomposites containing metal nanoparticles, carbon nanotube and polymer

Metal-carbon nanotube-graft-polymer (MCNT-g-P) nanocomposites were synthesized and characterized successfully. In this work, multiwall carbon nanotubes (MWCNT) were opened using HNO₃/H₂SO₄ mixture and filled by metal nanoparticles such as silver nanoparticles through wet chemistry method. Then MWCNT containing metal nanoparticles were used as macroinitiator for ring opening polymerization of ε-caprolactone and MCNT-g-P nanocomposites were obtained. Length of grafted polymer arms onto the MWCNT was controlled using MWCNT/ε-caprolactone ratio. Structure and properties of nanocomposites were evaluated by TEM, DSC, TGA, and spectroscopy methods.     

Electronic thermal conductivity of armchair graphene nanoribbons and zigzag carbon nanotubes

Through the Green's function formalism and tight-binding Hamiltonian model calculations, the temperature dependent electronic thermal conductivity (TC) for different diameters of zigzag carbon nanotubes and their corresponding unzipped armchair graphene nanoribbons is calculated. All functional temperature dependencies bear crossovers, for which, at higher temperatures, nanotubes have a slightly higher TC than their derived nanoribbons, while below that crossover, both systems exhibit a significant coincidence over a moderate range of lower temperatures. Noticeably, TC decreases with increasing the width or diameter of the corresponding systems. Also, at low temperatures TC is proportional to the density of states around the Fermi level, and thus increasing for metal or semiconductors of narrower gap cases.