Sodium-alginate-based proton-exchange membranes as electrolytes for DMFCs

Novel mixed-matrix membranes prepared by blending sodium alginate (NaAlg) with polyvinyl alcohol (PVA) and certain heteropolyacids (HPAs), such as phosphomolybdic acid (PMoA), phosphotungstic acid (PWA) and silicotungstic acid (SWA), followed by ex-situ cross-linking with glutaraldehyde (GA) to achieve the desired mechanical and chemical stability, are reported for use as electrolytes in direct methanol fuel cells (DMFCs). NaAlg-PVA-HPA mixed matrices possess a polymeric network with micro-domains that restrict methanol cross-over. The mixed-matrix membranes are characterised for their mechanical and thermal properties. Methanol cross-over rates across NaAlg-PVA and NaAlg-PVA-HPA mixed-matrix membranes are studied by measuring the mass balance of methanol using a density meter. The DMFC using NaAlg-PVA-SWA exhibits a peak power-density of 68 mW cm(-2) at a load current-density of 225 mA cm(-2), while operating at 343 K. The rheological properties of NaAlg and NaAlg-PVA-SWA viscous solutions are studied and their behaviour validated by a non-Newtonian power-law.

Differential Scanning Calorimetry Of Si-As-Te Glasses

Differential scanning calorimetry (DSC) can be used for obtaining various non-isothermal properties of glassy materials. The thermal properties of the Si-As-Te glass system are discussed in relation to the interesting information obtained on the local ordering in these glasses.

Electron-beam irradiation effects on poly(ethylene-co-vinyl acetate) polymer

Poly(ethylene-co-vinyl acetate) (EVA) films were irradiated with a 1.2MeV electron beam at varied doses over the range 0-270kGy in order to investigate the modifications induced in its optical, electrical and thermal properties. It was observed that optical band gap and activation energy of EVA films decreased upon electron irradiation, whereas the transition dipole moment, oscillator strength and number of carbon atoms per cluster were found to increase upon irradiation. Further, the dielectric constant, the dielectric loss, and the ac conductivity of EVA films were found to increase with an increase in the dose of electron radiation. The result further showed that the thermal stability of EVA film samples increased upon electron irradiation.

Structural variants of hyperbranched polyesters

Hyperbranched polyesters based on 3,5-dihydroxybenzoic acid and its derivatives were prepared by self-condensation of the corresponding ester under standard trans-esterification conditions. The spacer segment length that connects the branching points was systematically varied by starting from the appropriate ethyl 3,5-bis(omega-hydroxyoligo(ethyleneoxy))benzoate. The thermal properties of the hyperbranched polyesters were studied using DSC, and they have been compared with those of the linear analogues prepared from the corresponding p-hydroxybenzoic acid derivatives and also with the molecularly ''kinked'' analogues prepared from the meta isomers. These hyperbranched polyesters were also terminally functionalized by using a potentially mesogenic 4-butoxybiphenylcarboxylic acid derivative in an attempt to prepare novel hyperbranched liquid crystalline polyesters. This was achieved by copolymerization of the AB(2) monomer with the mesogenic A-type capping unit. These polymers were found to be amorphous and did not exhibit any liquid crystalline phases, probably due to the random distribution of the mesogenic segments on the polymer framework, making it difficult to both crystallize and form mesophases.

Electron-Beam-Induced Modifications in High-Density Polyethylene

Post-irradiation studies have been carried out to elucidate the effects of electron beam irradiation on the structural, optical, dielectric, and thermal properties of high-density polyethylene (HDPE) films. The experimental results showed that both the optical band gap and activation energy of HDPE films decreases with an increase in the doses of electron radiation. The electrical measurements showed that dielectric constant and the ac conductivity of HDPE increases with an increase in the dose of electron radiation. The thermal analysis carried out using DSC and TGA revealed that the melting temperature, degree of crystallinity, and thermal stability of the HDPE films increased, obviously, due to the predominant cross-linking reaction following high doses of electron irradiation.

Highly Efficient and Thermally Stable Second-Order Nonlinear Optical Chromophores and Electrooptic Polymers

Organic polymeric electro-optic (E-O) materials have attracted significant attention because of their potential use as fast and efficient components of integrated photonic devices (1,2). However, the practical application of these materials in optical devices is somewhat limited by the stringent material requirements imposed by the device design, fabrication processes and operating environments. Among the various material requirements, the most notable ones are large electro-optic coefficients (r(33)) and high thermal stability (3). The design of poled polymeric materials with high electro-optic activity (r(33)) involves the optimization of the percent incorporation of efficient (large beta mu) second order nonlinear optical (NLO) chromophores into the polymer matrices and the effective creation of poling-induced non-centrosymmetric structures. The factors that affect the material stability are a) the inherent thermal stability of the NLO chromophores, b) the chemical stability of the NLO chromophores during the polymer processing conditions, and c) the long-term dipolar alignment stability at high temperatures. Although considerable progress has been made in achieving these properties (4), organic polymeric materials suitable for practical E-O device applications are yet to be developed. This chapter highlights some of our approaches in the optimization of molecular and material nonlinear optical and thermal properties.

Moving boundaries due to distributed sources in a slab

Analytical and numerical solutions have been obtained for some moving boundary problems associated with Joule heating and distributed absorption of oxygen in tissues. Several questions have been examined which are concerned with the solutions of classical formulation of sharp melting front model and the classical enthalpy formulation in which solid, liquid and mushy regions are present. Thermal properties and heat sources in the solid and liquid regions have been taken as unequal. The short-time analytical solutions presented here provide useful information. An effective numerical scheme has been proposed which is accurate and simple.

On the formation of poly(ethyleneoxide)-poly(vinylalcohol) blends

Poly(ethyleneoxide)-poly(vinylalcohol) blends were prepared and characterized using thermal, spectroscopic and structural methods, By all indications the blends appear to be microscopically inhomogeneous with no strong interpolymer bonding. The high degree of crystallinity in PEO regions induces a significant degree of ordering in neighbouring PVA regions, as evident from thermal properties. PVA obtained from solvent evaporation exhibits an irreversible endothermic transition which could be order-disorder type. Both IR and NMR spectroscopies also suggest the presence of subtle structural ordering influence of PEO on PVA. It is found to be possible to prepare self supporting films of the blends which consists of fine dispersion of PEO and PVA in each other. (C) 1999 Elsevier Science Ltd. All rights reserved.

Enhanced lithium-ion transport in PEG-based composite polymer electrolyte with Mn0.03Zn0.97Al2O4 nanoparticles

The ion conduction and thermal properties of composite solid polymer electrolyte (SPE) comprising Poly(ethylene) Glycol (PEG, mol wt. 2000), lithium perchlorate (LiClO4) and insulating Mn0.03Zn0.97Al2O4 nanoparticle fillers were studied by complex impedance analysis and DSC techniques. The average size of the nanoparticles was determined by powder X-ray diffraction (XRD) using Scherrer's equation and was found to be similar to 8 nm. The same was also determined by TEM imaging and found to be similar to 12 nm. The glass transition temperature T, as measured by differential scanning calorimeter (DSC), showed a minimum at 5 mol% of narroparticles. Fractional crystallinity was determined using DSC. NMR was used to deter-mine crystallinity of a pure PEG sample, which was then used as the standard. Fractional crystallinity X. was the lowest for 5 mol% and beyond. The ionic conductivity of the composite polymer electrolyte containing 5 mol% Mn0.03Zn0.97Al2O4 nanoparticles was found to be 1.82 x 10(-5) S/cm, while for the pristine one, it was 7.27 x 10(-7) S/cm at room temperature. As a function of nanoparticle content, conductivity was observed to go through two maxima, one at around 5 mol% and another shallower one at around 12 mol%. The temperature dependence of conductivity could be divided into two regions, one consistent with Arrhenius behaviour and the other with VTF. We conclude that the enhancement of ionic conductivity on the addition of Mn0.03Zn0.97Al2O4 nanoparticles is a result of reduction in both the T, and the crystallinity. (C) 2002 Elsevier Science B.V. All rights reserved.

Manipulation of the Hydration Levels in Minerals of Sodium Cadmium Bisulfate toward the Design of Functional Materials

Several variants of hydrated sodium cadmium bisulfate, Na(2)Cd(2)(SO(4))(3) center dot 3H(2)O, Na(2)Cd(SO(4))(2) center dot 2H(2)O, and Na(2)Cd(SO(4))(2) center dot 4H(2)O have been synthesized, and their thermal properties followed by phase transitions have been invesigated. The formation of these phases depends on the stochiometry and the time taken for crystallization from water. Na(2)Cd(2)(SO(4))(3)center dot 3H(2)O, which crystallizes in the trigonal system, space group P3c, is grown from the aqueous solution in about four weeks. The krohnkite type mineral Na(2)Cd(SO(4))(2) center dot 2H(2)O and the mineral astrakhanite, also known as blodite, Na(2)Cd (SO(4))(2)center dot 4H(2)O, crystallize concomittantly in about 24 weeks. Both these minerals belong to the monoclinic system(space group P2(1)/c). Na(2)Cd(2)(SO(4))(3)center dot 3H(2)O loses water completely when heated to 250 degrees C and transforms to a dehydrated phase (cubic system, space group I (4) over bar 3d) whose structure has been established using ab initio powder diffration techniques. Na(2)Cd(SO(4))(2)center dot 2H(2)O transforms to alpha-Na(2)Cd(SO(4))(2) (space group C2/c) on heating to 150 degrees C which is a known high ionic conductor and remains intact over prolonged periods of exposure to moisture (over six months). However, when alpha-Na(2)Cd(SO(4))(2) is heated to 570 degrees C followed by sudden quenching in liquid nitrogen beta-Na(2)Cd(SO(4))(2) (P2(1)/c) is formed. beta-Na(2)Cd(SO(4))(2) takes up water from the atmosphere and gets converted completely to the krohnkite type mineral in about four weeks. Further, beta-Na(2)Cd(SO(4))(2) has a conductivity behavior comparable to the a-form up to 280 degrees C, the temperature required for the transformation of the beta- to alpha-form. These experiments demonstrate the possibility of utilizing the abundantly available mineral sources as precursors to design materials with special properties.

A new beam finite element for the analysis of functionally graded materials

A new beam element is developed to study the thermoelastic behavior of functionally graded beam structures. The element is based on the first-order shear deformation theory and it accounts for varying elastic and thermal properties along its thickness. The exact solution of static part of the governing differential equations is used to construct interpolating polynomials for the element formulation. Consequently, the stiffness matrix has super-convergent property and the element is free of shear locking. Both exponential and power-law variations of material property distribution are used to examine different stress variations. Static, free vibration and wave propagation problems are considered to highlight the behavioral difference of functionally graded material beam with pure metal or pure ceramic beams. (C) 2003 Elsevier Science Ltd. All rights reserved.

Effect of Nature of the Precursor on Crystallinity and Microstructure of MOCVD-Grown ZrO2 Thin Films

In the present work, we report the deposition of zirconia thin films on Si(100) at various substrate temperatures by low-pressure metalorganic chemical vapor deposition (MOCVD). Three different zirconium complexes, viz., tetrakis(2,4-pentadionato)zirconium(IV), [Zr(pd)4], tetrakis(2,2,6,6-tetramethyl-3,5-heptadionato)zirconium(IV), [Zr(thd)4], and tetrakis(t-butyl-3-oxo-butanoato)zirconium(IV), [Zr(tbob)4] are used as precursors. The relationship between the molecular structures of the precursors and their thermal properties, as examined by TG/DTA is presented. The films deposited using these precursors have distinctly different morphology, though all of them are of the cubic phase. The films grown from Zr(thd)4 are well crystallized, showing faceted growth at 575°C, whereas the films grown from Zr(pd)4 and Zr(tbob)4 are not well crystallized, and display cracks. These differences in the observed microstructure may be attributed to the different chemical decomposition pathways of the precursors during the film growth, which influence the nucleation and the growth processes. This is also evidenced by the different kinetics of growth from these three precursors under otherwise identical CVD conditions. The details of thin film deposition, and film microstructure analysis by XRD and SEM is presented. The dielectric behavior of the films deposited from different precursors, as studied by C-V measurements, are compared.

Synthesis, characterization, degradation of biodegradable castor oil based polyesters

A new family of castor oil based biodegradable polyesters was synthesized by catalyst free melt condensation reaction between two different diacids and castor oil with D-mannitol. The polymers synthesized were characterized by NMR spectroscopy, FF-IR and the thermal properties were analysed by DSC. The results of DSC show that the polymer is rubbery in physiological conditions. The contact angle measurement and hydration test results indicate that the surface of the polymer is hydrophilic. The mechanical properties, evaluated in the tensile mode, shows that the polymer has characteristics of a soft material. In vitro degradation of polymer in PBS solution carried out at physiological conditions indicates that the degradation goes to completion within 21 days and it was also found that the rate of degradation can be tuned by varying the curing conditions. (C) 2011 Elsevier Ltd. All rights reserved.

Thermodynamic, Raman and electrical switching studies on Si15Te85-xAgx (4 <= x <= 20) glasses

We have investigated thermal properties of bulk Si15Te85-xAgx (4 <= x <= 20) glasses in detail, through alternating differential scanning calorimetry experiments. The composition dependence of thermal parameters reveal the signatures of rigidity percolation and chemical threshold at compositions x = 12 and x = 19, respectively. The stability and glass forming ability of these glasses have also been determined using the data obtained from different thermodynamic quantities and it is found that the Si15Te85-xAgx glasses in the region 12 <= x <= 17 are more stable when compared to other glasses of the same series. Further, the blueshift observed in Raman spectroscopy investigations, in the composition range 12 <= x <= 13, support the occurrence of stiffness threshold in this composition range. All Si15Te85-xAgx (4 <= x <= 20) glasses are found to exhibit memory type switching (for sample thickness 0.25 mm) in the input current range 3-9 mA. The effect of rigidity percolation and chemical thresholds on switching voltages are observed at x = 12 and 19, respectively. (C) 2012 American Institute of Physics. [doi:10.1063/1.3682759]

Chitosan-polyvinyl alcohol-sulfonated polyethersulfone mixed-matrix membranes as methanol-barrier electrolytes for DMFCs

Chitosan (CS)-polyvinyl alcohol (PVA) cross-linked with sulfosuccinic acid (SSA) and modified with sulfonated polyethersulfone (SPES) mixed-matrix membranes are reported for their application in direct methanol fuel cells (DMFCs). Polyethersulfone (PES) is sulfonated by chlorosulfonic acid and factors affecting the sulfonation reaction, such as time and temperature, are studied. The ion-exchange capacity, degree of sulfonation, sorption, and proton conductivity for the mixed-matrix membranes are investigated. The mixed-matrix membranes are also characterised for their mechanical and thermal properties. The methanol-crossover flux across the mixed-matrix membranes is studied by measuring the mass balance of methanol using the density meter. The methanol cross-over for these membranes is found to be about 33% lower in relation to Nafion-117 membrane. The DMFC employing CS-PVA-SPES mixed-matrix membrane with an optimum content of 25 wt % SPES delivers a peak power-density of 5.5 mW cm-2 at a load current-density of 25 mA cm-2 while operating at 70 degrees C. (C) 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012