The effect of zirconium oxide coating on the lithium nickel cobalt oxide for lithium secondary batteries

The electrochemical properties of LiNi_0.8Co_0.2O₂ coated with ZrO₂ by three different coating processes (ball-milling, sol-gel method, simple grinding) were investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), and electrochemical impedance spectroscopy (EIS). Results showed that the ZrO₂ coating significantly improved the capacity retention of the cathode by suppressing the impedance growth at the interface between electrodes and electrolyte and the best cyclability was obtained in the case of employing the simple grinding for the ZrO₂ coating. On the other hand, the initial capacities of the ZrO₂-coated LiNi_0.8Co_0.2O₂ cathode were slightly decreased.     

Li NMR, ionic conductivity and self-diffusion coefficients of lithium ion and solvent of plasticized organic-inorganic hybrid electrolyte based on PPG-PEG-PPG diamine and alkoxysilanes

Organic-inorganic hybrid electrolytes based on poly(propylene glycol)-block-poly(ethylene glycol)-block-poly(propylene glycol) bis(2-aminopropyl ether) (D2000) complexed with LiClO₄ via the co-condensation of an epoxy trialkoxysilane and tetraethoxysilane have been prepared and plasticized by a solution of ethylene carbonate (EC)/propylene carbonate (PC) mixture (1:1 by weight). The cross-linked hybrid network shows no solvent exudation and retains a large amount of plasticizer over 70 wt.% in stable state. The in situ built in silica network provides the hybrid electrolytes with good mechanical properties. The ionic conductivity of the dry hybrid electrolyte films was enhanced by two orders of magnitude via plasticization, reaching a maximum conductivity value of 4.0 × 10⁻³ S/cm at 30 °C. Variable temperature ⁷Li-{¹H} magic angle spinning (MAS) NMR demonstrated that the Li⁺ cations can be complexed by the polymer network as well as by the plasticizing solvents, but not with the incorporated silica network. Furthermore, the ⁷Li chemical shift change indicated a progressive change in the lithium coordination from lithium-polymer to lithium-solvent with increasing temperatures. The role of the solvents and the mobility of the lithium ions were investigated by pulsed gradient spin echo (PGSE) NMR measurements to elucidate the behavior of the ionic conductivity.     

Rheological and electrical properties of polycarbonate/multi-walled carbon nanotube composites

Rheological and electrical properties of the polycarbonate (PC)/multi-walled carbon nanotube (MWNT) were studied. The MWNT was funtoinalized by treating with the hydrogen peroxide (H₂O₂). The H₂O₂ treated MWNT was dried by thermal and freeze drying methods. From the morphological studies, the degree of entanglement of the MWNT was decreased after treating with the H₂O₂. For the H₂O₂ treated MWNT (thermal drying), the length of the MWNT was shortened compared that of the H₂O₂ treated MWNT (freeze drying). The rheological and electrical properties of the PC/MWNT (H₂O₂ treated) composites increased compared that of the PC/MWNT (untreated) composites. Also, the electrical conductivity showed higher value for the PC/MWNT (H₂O₂ treated, freeze drying) composites compared that of the PC/MWNT (H₂O₂ treated, thermal drying) composites. From the results of the morphological, rheological, and electrical properties of the PC/MWNT composites, it is suggested that the electrical and rheological properties of the PC/MWNT composites are affected by the MWNT-MWNT network structure, which is related with the MWNT morphologies such as the degree of aggregation and aspect ratio of the MWNT.     

A study of global vs. local properties for maleic anhydride modified polypropylene nanocomposites

Nanoindentation of organomodified clay filled maleated polypropylene (MAPP) was investigated. The study aims to identify the relative increase in local stiffness in comparison to the increase in mechanical properties of the bulk in polypropylene-based nanocomposites. Such a study allows one to assess confined material property in addition to increased filler volume at the local scale. A mixture of highly intercalated and well exfoliated clay structures, when dispersed in MAPP matrix, was observed under transmission electron microscopy. The degree of exfoliation was found to increase with clay loading, which was attributed to the higher viscosity and mechanical shear forces during melt compounding. Instrumented indentation was performed on (1) clay aggregate supported by MAPP matrix, (2) clay-matrix boundary, and (3) the MAPP matrix. The clay aggregated region generally showed higher stiffness as compared to the matrix. And, the relative increase in indentation stiffness is substantially higher than the relative increase in tensile and compressive stiffnesses for clay reinforced systems. Polymer chain confinement and topological constraint appeared to be operative to enhance local stiffness in the clay aggregated region. Good correlation was, however, obtained between the change in macroscopic stiffness and the change in highly local indentation stiffness as a result of clay reinforcement.     

Electrostatic polymer processing of isotactic poly(4-methyl-1-pentene) fibrous membrane

Isotactic poly(4-methyl-1-pentene) (P4M1P) is a widely used polymer in industrial applications and specifically, in medical products. Producing micro- or nanofibers would expand the usefulness of P4M1P to a broad range of medical applications. The choice and quality of solvent for the solution used for electrospinning can have a dramatic effect on the spinnability of fibers and on their morphological appearance. In this study, four solvent systems: cyclohexane, cyclohexane/acetone mixture, cyclohexane/dimethyl formamide (DMF) mixture and cyclohexane/acetone/DMF mixture have been investigated. As demonstrated by FE-SEM, electrospun fibers with different morphologies including round, twisted with a roughened texture, curled and twisted-ribbon shapes were formed. The fiber shape and morphology depended strongly on the type and amount of non-solvent used.     

Fabrication of SiO2-ZrO2 composite fiber mats via electrospinning

(1 ? x)SiO₂-(x)ZrO₂ (x = 0.1, 0.2) composite fiber mats were prepared by electrospinning their sol-gel precursors of zirconium acetate and tetraethyl orthosilicate (TEOS) without using a polymer binder. The electrospun composite fibers were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), fourier transform infrared spectroscopy (FT-IR) and mercury porosimetry. The composite fibers having a tetragonal crystalline ZrO₂ were obtained by calcining the electrospun composite fibers at high temperatures. The results show that the structure and crystallization of ZrO₂ in the composite fibers can be controlled by sintering temperature, while the porosity and morphology of the fiber mats did not depend on the sintering temperature.     

Preliminary investigation of poly(ether sulfone)/poly(aryl ether ketone) containing 1,4‐naphthalene blends

The blends of poly(ether sulfone) and poly(aryl ether ketone) containing 1,4‐naphthalene were prepared by melt mixing in a Brabender‐like apparatus. The specimens for measurements were made by compression molding under pressure and then were water‐quenched at room temperature. The tensile strength, tensile modulus, elongation at break, thermal analysis, and scanning electron microscopy were each measured. The dependence of tensile strength, tensile modulus, and elongation at break on blend systems was obtained. The effects of composition and miscibility on the mechanical properties are discussed. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 472–476, 2006     

Characterization and comparison of diblock and triblock amphiphilic copolymers of poly(δ‐valerolactone)

Three types of pegylated amphiphilic copolymers of poly(δ‐valerolactone) (PVL) were copolymerized with methoxy poly(ethylene glycol) (MePEG) and poly(ethylene glycol) (PEG₄₀₀₀ and PEG_10,000), respectively. Pegylation of PVL allowed copolymers possessing amphiphilic property and efficiently self‐assembled to form micelles with a low critical micelle concentration (CMC) in the range of 10^?7–10^?8M. The average molecular weight of copolymers was in the range of 10,000–20,000 Da, and the polydispersity of copolymers was about 1.7–1.8. Higher mobility of low molecular weight PEG (i.e., MePEG and PEG₄₀₀₀) than high molecular weight PEG_10,000 allowed valerolactone ring opening more efficient in terms of PVL/MePEG and PVL/PEG₄₀₀₀ copolymers possessing longer chain length in hydrophobic domain. Pegylated PVL with low CMC and triblock structure was preferred to encapsulate drug during micelle formation. Although all of these amphiphilic copolymers exhibited controlled release character, the micelles formed by triblock copolymer possessed a more stable core‐shell conformation than that by diblock copolymer, and resulted in the release of drug from triblock micelles slower than that from diblock micelles. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1836–1841, 2006     

Rheological properties of polypropylene modified by high‐intensity ultrasonic waves

A new method using high‐intensity ultrasonic waves, instead of peroxide‐aided reactive extrusion, was applied to modify a linear polypropylene into a branched structure. The ultrasonic waves induced chain scission and created reactive macromolecules of polypropylene successfully in the melt state without any peroxide. To enhance and control the recombination reaction during sonication, a multifunctional agent and an antioxidant were used. The rheological property measurements clearly confirmed that the modified polypropylene had a nonlinear branched structure. It showed shear‐thinning behaviors in its viscosities at low frequencies, high elastic behaviors in Cole–Cole plots, and a high rheological polydispersity index in comparison with a linear polypropylene. The degradation or recombination of polypropylene was adequately controlled by an antioxidant, which stabilized the structure during sonication. Also, the use of an antioxidant was quite effective in improving the extrusion processability by delaying the instability of the extrudate to a higher shear rate. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Dielectric behavior of three phase polyimide percolative nanocomposites

Three phase ceramic–metal–plastic (cermetplas) percolative nanocomposite films were prepared using polyimide, as the matrix to prepare the composite films. Silver nanoparticles with a mean particle size of about 41 nm were prepared and used as the metal phase. Nanocomposites of barium titanate (BaTiO₃) particles in polyimide matrix, with silver as metallic inclusion, were formulated using effective medium theory and percolation theory. The concentration and frequency dependence of dielectric permittivity (ε) and loss tangent (tan δ) measurements were reported and discussed for cermetplas below the percolation threshold. Experimental results for cermetplas show that a ε of above 500 can be achieved below the percolation. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci, 2006