The effect of composition, electron irradiation and quenching on ionic conductivity in a new solid polymer electrolyte: (PEG) (x) NH4I

We have prepared, characterized and investigated a new PEG-2000 based solid polymer electrolyte (PEG) x NH4I. Ionic conductivity measurements have been made as a function of salt concentration as well as temperature in the range 265–330 K. Selected compositions of the electrolyte were exposed to a beam of 8 MeV electrons to an accumulated dose of 10 kGy to study the effect on ionic conductivity. The electrolyte samples were also quenched at liquid nitrogen temperature and conductivity measurements were made. The ionic conductivity at room temperature exhibits a characteristic double peak for the composition x = 20 and 70. Both electron beam irradiation and quenching at low temperature have resulted in an increase in conductivity by 1–2 orders of magnitude. The enhancement of conductivity upon irradiation and quenching is interpreted as due to an increase in amorphous region and decrease in crystallinity of the electrolyte. DSC and proton NMR measurements also support this conclusion.

Buckling in polymer monolayers: Molecular-weight dependence

We present systematic investigations of buckling in Langmuir monolayers of polyvinyl acetate formed at the air-water interface. On compression the polymer monolayers are converted to a continuous membrane with a thickness of ~2–3 nm of well-defined periodicity, lambdab. Above a certain surface concentration the membrane undergoes a morphological transition buckling, leading to the formation of striped patterns. The periodicity seems to depend on molecular weight as per the predictions of the gravity-bending buckling formalism of Milner et al. for fluidlike films on water. However anomalously low values of bending rigidity and Young's modulus are obtained using this formalism. Hence we have considered an alternative model of buckling-based solidlike films on viscoelastic substrates. The values of bending rigidity and Young's modulus obtained by this method, although lower than expected, are closer to the bulk values. Remarkably, no buckling is found to occur above a certain molecular weight. We have tried to explain the observed molecular-weight dependence in terms of the variation in isothermal compressive modulus of the monolayers with surface concentration as well as provided possible explanations for the obtained low values of mechanical properties similar to that observed for ultrathin polymer films.

Reduction of Permittivity in Epoxy Nanocomposites at Low Nano-filler Loadings

Experimental studies reveal a reduction in the values of permittivity for epoxy nanocomposites; at low filler loadings as compared to neat epoxy over a wide frequency range. This permittivity reduction is attributed to the interaction dynamics between nanoparticles: and epoxy chains at the interface region and interestingly, this interaction has also been found to influence the glass transition temperatures (T-g) of the examined nanocomposite systems. Accordingly, a dual nanolayer interface model for an epoxy based nanocomposite system is analyzed to explain the obtained permittivity characteristics.

Electrical Discharge Resistant Characteristics of Epoxy Nanocomposites

This paper reports the electrical discharge resistant characteristics of epoxy nanocomposite systems with SiO2 and Al2O3 nano-fillers. A comparative study is performed between unfilled epoxy systems, nanoparticle filled epoxy systems and a bimodal system containing both micrometer and nanometer sized fillers of the same material. The samples are exposed to surface discharges and the levels of surface degradation are analyzed through SEM and surface roughness measurements. Significant variations were observed in the electrical discharge resistant characteristics between the different composite systems and it is seen that the introduction of nano-fillers to epoxy is advantageous in improving the electrical discharge resistance of epoxy.

Effect of polymer coating on the thermal decomposition of composite propellant oxidizers

Ammonium perchlorate (AP) has been coated with polystyrene (PS), cellulose acetate (CA), Novolak resin and polymethylmethacrylate (PMMA) by a solvent/nonsolvent method which makes use of the coacervation principle. The effect of polymer coating on AP decomposition has been studied using thermogravimetry (TG) and differential thermal analysis (DTA). Polymer coating results in the desensitization of AP decomposition. The observed effect has been attributed to the thermophysical and thermochemical properties of the polymer used for coating. The effect of polystyrene coating on thermal decomposition of aluminium perchlorate trihydrazinate and ammonium nitrate as well as on the combustion of AP-CTPB composite propellants has been studied.

Electrical, structural and magnetic properties of polyaniline/pTSA-TiO2 nanocomposites

Polyaniline (PANI)/para-toluene sulfonic acid (pTSA) and PANI/pTSA-TiO2 composites were prepared using chemical method and characterized by infrared spectroscopy (IR), powder X-ray diffraction (XRD), scanning electron microscopy (SEM). The electrical conductivity and magnetic properties were also measured. In corroboration with XRD, the micrographs of SEM indicated the homogeneous dispersion of TiO nanoparticles in bulk PANI/pTSA matrix. Conductivity of the PANI/pTSA-TiO2 was higher than the PAN[/pTSA, and the maximum conductivity obtained was 9.48 (S/cm) at 5 wt% of TiO2. Using SQUID magnetometer, it was found that PANI/pTSA was either paramagnetic or weakly ferromagnetic from 300 K down to 5 K with H-C approximate to 30 Oe and M-r approximate to 0.015 emu/g. On the other hand,PANI/pTSA-TiO2 was diamagnetic from 300 K down to about 50 K and below which it was weakly ferromagnetic. Furthermore, a nearly temperature-independent magnetization was observed in both the cases down to 50 K and below which the magnetization increased rapidly (a Curie like susceptibility was observed). The Pauli susceptibility (chi(pauli)) was calculated to be about 4.8 X 10(-5) and 1.6 x 10(-5)emug(-1) Oe(-1) K for PANI/pTSA and PANI/pTSA-TiO2, respectively.

Morphological transitions in polymer monolayers under compression

We present a systematic investigation of morphological transitions in poly vinylacetate Langmuir monolayers. On compression, the polymer monolayer is converted to a continuous membrane with a thickness of similar to 2-3 nm. Above a certain surface concentration the monolayer, on water, undergoes a morphological transition-buckling, leading to formation of striped patterns of period of lambda(b)similar to 160 nm, as determined from in situ grazing incidence small angle x-ray scattering measurements. The obtained value is much smaller than what has been typically observed for Langmuir monolayers on water or thin films on soft substrates. Using existing theories for buckling of fluidlike films on fluid substrates, we obtain very low values of bending rigidity and Young's modulus of the polymer monolayer compared to that observed earlier for lipid or polymeric monolayers. Since buckling in these monolayers occurs only above a certain surface concentration, we have looked at the possibility that the buckling in these films occurs due to changes in their mechanical properties under compression. Using the model of Huang and Suo of buckling of solidlike films on viscoelastic substrates, we find values of the mechanical properties, which are much closer to the bulk values but still significantly lower. Although the reduction could be along the lines of what has been observed earlier for ultrathin polymer film or surface layers of polymers, the possibility of micromechanical effects also determining the buckling in such polymer monolayers cannot be ruled out. We have provided possible explanation of the buckling of the poly vinylacetate monolayers in terms of the change in isothermal compression modulus with surface concentration.

Novel Self-Supported Natural and Synthetic Polymer Membranes for Air Humidification

Novel self-supported natural and synthetic polymer membranes of chitosan-hydroxy ethyl Cellulose-montmorillonite (CS-HEC-MMT) and polyvinyl alcohol (PVA)-polystyrene sulfonic acid (PSSA) are prepared by solution casting method followed by crosslinking. These membranes are employed for air humidification at varying temperatures between 30 degrees C and 70 degrees C and their performances are compared with commercial Nafion membranes. High hater fluxes with desired humidified-air output have been achieved for CS-HEC-MMT and PVA-PSSA hybrid membranes at air-flow rates of 1-10 slpm. Variation in the air/water mixing ratio, dew point, and relative humidity that ultimately results in desired water flux With respect to air-flow rates are also quantified for all the membranes. Water flux values for CS-HEC-MMT are less than those for Nafion (R) and PVA-PSSA membranes, but the operational Stability of CS-HEC-MMT membrane is higher than PVA-PSSA and comparable with Nafion (R) both of which can operate up to 70 degrees C at repetitive cycles of humidification.

Effect of Pressure on Polymer Ignition

Auto-ignition temperature of polystyrene, poly(vinyl chloride) and carboxy terminated polybutadiene has been measured at various oxygen pressures (1-28 atm) in a high pressure differential thermal analysis assembly at a heating rate of 10°C/min. The exothermic peak appears between 250-350°C in polystyrene and poly(vinyl chloride) and between 150-200°C for carboxy terminated polybutadiene. Ignition appears to be controlled by in situ forma tion and degradation of polymeric peroxides. Inverse dependence of ignition temperature on oxygen pressure is explained by the rate equation which con siders that ignition of a particular sample, of a fixed geometry, occurs when gasification rate reaches a unique critical value.

Trimming studies on polymer thick-film resistors

PVC-graphite polymer thick-film resistors were trimmed by a conventional air abrasive technique and the post-trim drift in resistance with time was found to be negative. The net decrease in resistance of trimmed resistors in a given time was found to be a function of resistor composition, cutting speed and temperature. Detailed studies showed this decrease to be due to a decrease in cut width with time. Two new methods, namely bombardment trimming and radiation trimming, were also tried for adjusting the resistance of these resistors and the results were compared with those obtained from abrasive trimming studies.

Styrene Oxidation to Benzaldehyde by Polymer Anchored Wilkinson Complex

Wilkinson complex, insolubilized by anchoring to polymeric Amberlite beads, had been used for the liquid-phase catalytic oxidation of styrene to benzaldehyde and formaldehyde in toluene medium. Styrene conversion was followed by measuring the oxygen volume in contact with the reaction mixture in a specially designed closed batch apparatus. Styrene conversion depended upon catalyst loading and distribution inside the porous beads, while temperature had little effect on it. The internal diffusional effects on the conversion process have been taken into consideration by a mathematical model which allowed calculation of effectiveness factors for various catalyst loadings and corresponding catalyst distributions. The influence of external diffusion was separately determined by plotting initial rate versus catalyst loading. The proposed method can be readily extended to immobilized enzymes in porous matrices.

Nucleation parameters for polymer crystallization from non-isothermal thermal analysis

Differential scanning calorimetry (DSC) has been used to obtain kinetic and nucleation parameters for polymer crystallization under a non-isothermal mode of operation. The available isothermal nucleation growth-rate equation has been modified for non-isothermal kinetic analysis. The values of the nucleation constant (K g ) and surface free energies (sgr, sgr e ) have been obtained for i-polybutene-1, i-polypropylene, poly(L-lactic acid), and polyoxymethylene and are compared with those obtained from isothermal kinetic analysis; a good agreement in both is seen.

Styrene Oxidation to Benzaldehyde by Polymer Anchored Wilkinson Complex

Wilkinson complex, insolubilized by anchoring to polymeric Amberlite beads, had been used for the liquid-phase catalytic oxidation of styrene to benzaldehyde and formaldehyde in toluene medium. Styrene conversion was followed by measuring the oxygen volume in contact with the reaction mixture in a specially designed closed batch apparatus. Styrene conversion depended upon catalyst loading and distribution inside the porous beads, while temperature had little effect on it. The internal diffusional effects on the conversion process have been taken into onsideration by a mathematical model which allowed calculation of effectiveness factors for various catalyst loadings and corresponding catalyst distributions. The influence of external diffusion was separately determined by plotting initial rate versus catalyst loading. The proposed method can be readily extended to immobilized enzymes in porous matrices.

Thermo-chemical interpretation of polymer degradation

A correlation has been established between the heat of depolymerization (DeltaH) of vinyl polymers for going from solid polymer state to gaseous monomer state and the activation energy (E) of degradation. On this basis it has been shown that the rate controlling step in the degradation lies in the initiation step. Attempt has been made to correlate theE and DeltaH with glass transition temperature (Tg) and melting temperature (Tm) of the polymers.[/ p]

Extraordinary synergy in the mechanical properties of polymer matrix composites reinforced with 2 nanocarbons

One of the applications of nanomaterials is as reinforcements in composites, wherein small additions of nanomaterials lead to large enhancements in mechanical properties. There have been extensive studies in the literature on composites where a polymer matrix is reinforced by a single nanomaterial such as carbon nanotubes. In this article, we examine the significant synergistic effects observed when 2 different types of nanocarbons are incorporated in a polymer matrix. Thus, binary combinations of nanodiamond, few-layer graphene, and single-walled nanotubes have been used to reinforce polyvinyl alcohol. The mechanical properties of the resulting composites, evaluated by the nanoindentation technique, show extraordinary synergy, improving the stiffness and hardness by as much as 400% compared to those obtained with single nanocarbon reinforcements. These results suggest a way of designing advanced materials with extraordinary mechanical properties by incorporating small amounts of 2 nanomaterials such as graphene plus nanodiamond or nanodiamond plus carbon nanotube.