Comblike polymer electrolyte with main chain glass transition near room temperature

A new amorphous comblike polymer (CBP) based on methylvinyl ether/maleic anhydride altering copolymer backbone and on oligooxyethylene side chain was synthesized. The dynamic mechanical properties of CBP and its Li salt complexes were investigated by means of DDV-11-EA type viscoelastic spectrometry. Results showed that there were two glass transitions (alpha-transition and beta-transition) in the temperature range from -100 to 100 degrees C. The beta-transition was assigned to oligo-PEO side chains and the temperature of beta-transition increases with increasing Li salt content. The alpha-transition was assigned to the main chain of CBP. The temperature of the alpha-transition (T-alpha) is also dependent upon the Li-salt content, but not monotonic. The value of T-alpha lies between 30-45 degrees C in the Li salt concentration range studied, near room temperature. It was found that the CBP-Li salt complexes showed an unusual dependence of ionic conductivity on Li salt content. There are two peaks in the plot of the ionic conductivity vs. Li salt concentration, which has been ascribed to the movability of the CBP main chain at ambient temperature. The temperature dependence bf the ionic conductivity indicated that the Arrhenius relationship was not obeyed, and the plot of log sigma against 1/(T - T-0) showed the unusual dual VTF behavior when using side chain glass transition temperature (T-beta) as T-0.

Study of ion solvation and ion association in polymer gel electrolyte with polyethylene oxide-co-polypropylene oxide as a plasticizer

Using a molal conductance method, ion solvation and ion association in polytriethylene glycol dimethacrylate (PTREGD)-LiClO4 gel electrolytes with amorphous ethylene oxide-co-propylene oxide (EO-co-PO, <(M)over bar (n)>, = 1750) as the plasticizer were investigated. It was found that the fraction of solute existing as single ions (alpha(i)) and ion pairs (alpha(p)) decreases, while that of triple ions (alpha(t)) increases linearly with increasing salt concentration. The dependence of these fractions on molecular weight of plasticizer was also examined. It was shown that alpha(i) and alpha(t) increase and alpha(p) decreases with increasing molecular weight. The result of temperature dependence of these fractions was very interesting: when the temperature is lower than 55 degrees C, alpha(i) increases while alpha(p) and alpha(t) decrease with increasing temperature; however, when the temperature is higher than 55 degrees C, the reverse is true.

Comb polymer electrolytes - Ionic conductivity and cation-polymer interaction

Three comb polymers(CP) with oligo-oxyethylene side chains of the type -O(CH2CH2O)(n)CH3 were prepared from methyl vinyl ether/maleic anhydride alternating copolymer. Homogeneous amorphous polymer electrolytes were made from CP and LiCF3SO3 or LiClO4 by solvent-casting method, and their conductivities were measured as a function of temperature and salt concentration. The conductivity which displayed non-Arrhenius behaviour was analyzed using the Vogel-Tammann-Fulcher equation. The conductivity maximum appears at lower salt concentration when CP has longer side chains. XPS was used to study the cation-polymer interaction.

Compatibilization effect of graft copolymer on immiscible polymer blends .2. LLDPE/PS/LLDPE-g-PS systems

The compatibilizing effect of graft copolymer, linear low density polyethylene-g-polystyrene (LLDPE-g-PS), on immiscible LLDPE/PS blends has been studied by means of C-13 CP-MAS NMR and DSC techniques. The results indicate that LLDPE-g-PS is an effective compatibilizer for LLDPE/PS blends, and the compatibilizing effect of LLDPE-g-PS on LLDPE/PS blends depends on the PS grafting yield and molecular structure of the compatibilizers and also on the composition of the blends. It was found that LLDPE-g-PS chains connect two immiscible components, LLDPE and PS, through solubilization of chemically identical segments of LLDPE-g-PS into the noncrystalline region of the LLDPE and PS domain, respectively. Meanwhile, LLDPE-g-PS chains connect the crystalline region of LLDPE by isomorphism, resulting in an obvious change in the crystallization behavior of LLDPE. (C) 1996 John Wiley & Sons, Inc.

Studies on water-swellable elastomer .1. Synthesis and characterization of amphiphilic polymer

A new amphiphilic polymer i.e., polyethylene glycol (PEG) grafted crystalline neoprene, which was used as compatibilizer to improve the compatibility of elastomer and water-absorbent resin, has been investigated. The synthesis was based on the reaction between chlorine in neoprene and sodium salts of PEG. PEGs with molecular weights of 600 and 2000 were used. The grafting percent and the PEG content were calculated through elemental analysis of chlorine in the resulted copolymers. The maximum grafting percent of copolymers was ca. 24.80%. The molecular parameters such as number-average molecular weight and the average number of grafting chains on one CR backbone were also calculated and discussed. (C) 1996 John Wiley & Sons, Inc.

An investigation on ion solvation and ion association in a gel-type solid state polymer electrolyte

Ion salvation and ion association in polytriethylene glycol dimethacrylate (PTREGD)-LiClO4 gel-type polymer electrolytes were investigated. It was found that the fraction of solute existing as single ions (alpha(i)) decreases and that of triple ions (alpha(i)) increases linearly with increasing LiClO4 concentration, while for ion pairs, as the salt concentration increases, its fraction (alpha(p)) increases first and then falls down. The findings can be rationalized by the fact that the ionic conductance of the polymer electrolyte may be mainly contributed by triple ions and higher ionic aggregates with unequal numbers of positive and negative charges in the salt concentration range of practical significance, i.e. in the range of 0.5-1.5 mol/l. The temperature dependence of these fractions was also examined. In the case of tetraethylene glycol as the solvent, alpha(i) and alpha(p) increase as the temperature is raised, but alpha(t) decreases as the temperature increases from 25 degrees C to 85 degrees C. It seems that the increase of alpha(i) and alpha(p) results from the redissociation of triple ions at higher temperature, The same changing trend of those fractions is also observed when PEG(400) is used as the solvent.

Study on new comb polymer electrolyte(III)

A new solid polymer electrolyte has been prepared using NaClO4 and a comb-branch polymer with oligo(ethylene oxide) side chains. The thermal and ionic conductive properties of the electrolytes were investigated. The profile of conductivity at various temperatures follows the VTF plots.

Study on a new comb polymer electrolyte(II)

A comb polymer(CP350) with oligo-oxyethlene side chains was prepared from methyl vinyl ether/maleic anhydride copolymer. Homogeneous amorphous polymer electrolyte were made from the comb polymer and LiCF3SO3 by solvent casting from acetone, and their conductivities were measured as a function of temperature and salt concentration. Maximum conductivity close I to 5.08 x 10(-5)S/cm was achieved at room temperature at [Li]/[EO] ratio of about 0.12.

STUDY ON MASS-TRANSPORT IN EASTMAN-AQ POLYMER FILM BY USING NON-STEADY-STATE CHRONOAMPEROMETRY AT AN ULTRAMICRODISK ELECTRODE

Non-steady-state chronoamperometry of ultramicroelectrodes is a powerful method for the study of mass transport in polymer films. This method has many advantages over the conventional methods at a macroelectrode and the steady state method at an ultramicroelectrode, which yield the most information. The apparent diffusion coefficient, D(app), and the concentration of reactant in the film, c(f), can be determined from a single experiment without knowing the thickness of the film. We studied the transport of several species such as Ru(NH3)63+, Ru(bpy)3(2+), NR and MV2+ in Eastman-AQ polymer film coated ultramicroelectrodes by using this method.

MUTUAL ENTANGLEMENTS IN POLY(VINYL ACETATE) POLY(METHYL ACRYLATE) INTERPENETRATING POLYMER NETWORKS

An equation has been derived for the equilibrium swelling of sequential interpenetrating polymer networks (IPNs), which exhibit a single glass transition temperature and the two components are considered to be compatible. The properties of the equilibrium swelling and elastic modulus of sequential poly(vinyl acetate)/poly(methyl acrylate) IPNs have been discussed according to the derived equation and the Siegfried-Thomas-Sperling formula of the elastic modulus for homo IPNs. In both fully swollen and bulk states, there was favourable evidence for added physical crosslinks in poly(vinyl acetate)/poly(methyl acrylate) IPNs. The Binder-Frisch theory is also discussed.

MONOLAYER FORMATION OF A NOVEL AMPHIPHILIC POLYMER PAMC16S

Poly(2-acrylamido-hexadecylsulfonic acid) (PAMC16S) forms a stable monolayer on a pure water surface. More closely packed monolayers can be obtained when the subphase contains Cd2+ or Ca2+. Self-assembled monolayers have been formed on gold surfaces and characterized by contact angle measurement, XPS and electrochemical analysis. The results show that the monolayers are hydrophobic with the hydrophilic sulfonic acid groups adjacent to the metal surfaces and with the hydrocarbon chains extended from the surfaces. The monolayers exhibit great adsorption stability during the faradaic reactions, illustrating the advantage of polymeric LB films in potential applications.

A collision model for DNA separation by capillary electrophoresis in dilute polymer solution

A theoretical description. based on chemical kinetics and electrochemistry, is given of DNA separation in dilute polymer solution by capillary electrophoresis. A self-consistent model was developed leading to predictions of the DNA electrophoretic velocity as a function of the experimental conditions - polymer concentration, temperature, and electric field strength. The effect of selected experimental variables is discussed. The phenomena discussed are illustrated for the example of 100 bp DNA ladder separation in dilute HPMC solution by capillary electrophoresis. This model is the first single model that can fully explain the dependence of DNA electrophoretic velocity on electrophoretic conditions.

Polymer and metallodielectric based photonic crystals

The bottom-up colloidal synthesis of photonic crystals has attracted interest over top-down approaches due to their relatively simplicity, the potential to produce large areas, and the low-costs with this approach in fabricating complex 3-dimensional structures. This thesis focuses on the bottom-up approach in the fabrication of polymeric colloidal photonic crystals and their subsequent modification. Poly(methyl methacrylate) sub-micron spheres were used to produce opals, inverse opals and 3D metallodielectric photonic crystal (MDPC) structures. The fabrication of MDPCs with Au nanoparticles attached to the PMMA spheres core–shell particles is described. Various alternative procedures for the fabrication of photonic crystals and MDPCs are described and preliminary results on the use of an Au-based MDPC for surface-enhanced Raman scattering (SERS) are presented. These preliminary results suggest a threefold increase of the Raman signal with the MDPC as compared to PMMA photonic crystals. The fabrication of PMMA-gold and PMMA-nickel MDPC structures via an optimised electrodeposition process is described. This process results in the formation of a continuous dielectric-metal interface throughout a 3D inverted photonic crystal structure, which are shown to possess interesting optical properties. The fabrication of a robust 3D silica inverted structure with embedded Au nanoparticles is described by a novel co-crystallisation method which is capable of creating a SiO2/Au NP composite structure in a single step process. Although this work focuses on the creation of photonic crystals, this co-crystallisation approach has potential for the creation of other functional materials. A method for the fabrication of inverted opals containing silicon nanoparticles using aerosol assisted chemical vapour deposition is described. Silicon is a high dielectric material and nanoparticles of silicon can improve the band gap and absorption properties of the resulting structure, and therefore have the potential to be exploited in photovoltaics.

Multiple Dynamic Processes Contribute to the Complex Steady Shear Behavior of Cross-Linked Supramolecular Networks of Semidilute Entangled Polymer Solutions.

Molecular theories of shear thickening and shear thinning in associative polymer networks are typically united in that they involve a single kinetic parameter that describes the network -- a relaxation time that is related to the lifetime of the associative bonds. Here we report the steady-shear behavior of two structurally identical metallo-supramolecular polymer networks, for which single-relaxation parameter models break down in dramatic fashion. The networks are formed by the addition of reversible cross-linkers to semidilute entangled solutions of PVP in DMSO, and they differ only in the lifetime of the reversible cross-links. Shear thickening is observed for cross-linkers that have a slower dissociation rate (17 s(-1)), while shear thinning is observed for samples that have a faster dissociation rate (ca. 1400 s(-1)). The difference in the steady shear behavior of the unentangled vs. entangled regime reveals an unexpected, additional competing relaxation, ascribed to topological disentanglement in the semidilute entangled regime that contributes to the rheological properties.