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.

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.

Characterisation of cellulose- and lignin-based materials using x-ray scattering methods

Wood is an important material for the construction and pulping industries. Using x-ray diffraction the microfibril angle of Sitka spruce wood was studied in the first part of this thesis. Sitka spruce (Picea sitchensis [Bong.] Carr.) is native to the west coast of North America, but due to its fast growth rate, it has also been imported to Europe. So far, its nanometre scale properties have not been systematically characterised. In this thesis the microfibril angle of Sitka spruce was shown to depend significantly on the origin of the tree in the first annual rings near the pith. Wood can be further processed to separate lignin from cellulose and hemicelluloses. Solid cellulose can act as a reducer for metal ions and it is also a porous support for nanoparticles. By chemically reducing nickel or copper in the solid cellulose support it is possible to get small nanoparticles on the surfaces of the cellulose fibres. Cellulose supported metal nanoparticles can potentially be used as environmentally friendly catalysts in organic chemistry reactions. In this thesis the size of the nickel and copper containing nanoparticles were studied using anomalous small-angle x-ray scattering and wide-angle x-ray scattering. The anomalous small-angle x-ray scattering experiments showed that the crystallite size of the copper oxide nanoparticles was the same as the size of the nanoparticles, so the nanoparticles were single crystals. The nickel containing nanoparticles were amorphous, but crystallised upon heating. The size of the nanoparticles was observed to be smaller when the reduction of nickel was done in aqueous ammonium hydrate medium compared to reduction made in aqueous solution. Lignin is typically seen as the side-product of wood industries. Lignin is the second most abundant natural polymer on Earth, and it possesses potential to be a useful material for many purposes in addition to being an energy source for the pulp mills. In this thesis, the morphology of several lignins, which were produced by different separation methods from wood, was studied using small-angle and ultra small-angle x-ray scattering. It was shown that the fractal model previously proposed for the lignin structure does not apply to most of the extracted lignin types. The only lignin to which the fractal model could be applied was kraft lignin. In aqueous solutions the average shape of the low molar mass kraft lignin particles was observed to be elongated and flat. The average shape does not necessarily correspond to the shape of the individual particles because of the polydispersity of the fraction and due to selfassociation of the particles. Lignins, and especially lignosulfonate, have many uses as dispersants, binders and emulsion stabilisers. In this thesis work the selfassociation of low molar mass lignosulfonate macromolecules was observed using small-angle x-ray scattering. By taking into account the polydispersity of the studied lignosulfonate fraction, the shape of the lignosulfonate particles was determined to be flat by fitting an oblate ellipsoidal model to the scattering intensity.

Ion Transport in a Polymer-Plastic Solid Soft Matter Electrolyte in the Light of Solvent Dynamics and Ion Association

Ion transport in a recently demonstrated promising soft matter solid plastic-polymer electrolyte is discussed here in the context of solvent dynamics and ion association. The plastic-polymer composite electrolytes display liquid-like ionic conductivity in the solid state,compliable mechanical strength (similar to 1 MPa), and wide electrochemical voltage stability (>= 5 V). Polyacrylonitrile (PAN) dispersed in lithium perchlorate (LiClO4)-succinonitrile (SN) was chosen as the model system for the study (abbreviated LiClO4-SN:PAN). Systematic observation of various mid-infrared isomer and ion association bands as a function of temperature and polyme concentration shows an effective increase in trans conformer concentration along with free Li+ ion concentration. This strongly supports the view that enhancement in LiClO4-SN:PAN ionic conductivity over the neat plastic electrolyte (LiClO4-SN) is due to both increase in charge mobility and concentration. The ionic conductivity and infrared spectroscopy studies are supported by Brillouin light scattering. For the LiClO4-SN:PAN composites, a peak at 17 GHz was observed in addition to the normal trans-gauche isomerism (as in neat SN) at 12 GHz. The fast process is attributed to increased dynamics of those SN molecules whose energy barrier of transition from gauche to trans has reduced under influences induced by the changes in temperature and polymer concentration. The observations from ionic conductivity, spectroscopy, and light scattering studies were further supplemented by temperature dependent nuclear magnetic resonance H-1 and Li-7 line width measurements.

Effect of plasticizers on magnesium-poly(ethyleneoxide) polymer electrolyte

Solid polymer electrolytes (SPEs) of poly(ethyleneoxide) and magnesium triflate, which are plasticized with propylene carbonate (PC), ethylene carbonate (EC) and a mixture of PC and EC, are studied for their conductivity, ac impedance of the Mg I SPE interface, cyclic voltammetry, infrared spectroscopy and differential scanning calorimetry. in the presence of plasticizers, the ionic conductivity (a) increases from a value of 1 x 10(-8) S cm(-1) to about 1 x 10(-4) S cm(-1) at ambient temperature. The a is found to follow a VTF relationship with temperature. The values of the activation energy, pre-exponential factor and equilibrium glass transition temperature are shown to depend on the concentration of plasticizer. Ac impedance studies indicate lower interfacial impedance of Mg/plasticized SPE than stainless steel/plasticized SPE. The impedance spectra are analyzed using a non-linear least square curve fitting technique and the interfacial resistance of Mg/plasticized SPE is evaluated. The cyclic voltammetric results suggest a quasireversible type of Mg/Mg2+ couple in plasticized SPE. (C) 2000 Elsevier Science B.V. All rights reserved.

Studies on a nanocomposite solid polymer electrolyte with hydrotalcite as a filler

We have prepared a new nanocomposite polymer electrolyte using nanoparticles of hydrotalcite, an anionic clay, as the filler. Hydrotalcite has the chemical composition [M-1-x(2+) M-x(3+) (OH)(2)](x+) [A(x/n)(n-)center dot mH(2)O] where M2+ is a divalent cation (e.g. Mg2+, Ni2+, Co2+,etc.) and M3+ is a trivalent cation (e.g. Al3+, Fe3+, Cr3+, etc.). A(n-) is an anion intercalated between the positively charged double hydroxide layers. The nanoparticles of [Mg0.67Al0.33 (OH)(2)] [(CO3)(0.17)center dot mH(2)O] were prepared by the co-precipitation method (average particle size as observed by TEM similar to 50 nm) and were doped into poly(ethylene glycol) PEG (m.w.2000) complexed with LiCIO4. Samples with different wt.% of hydrotalcite were prepared and characterized using XRD, DSC, TGA, impedance spectroscopy and NMR. Ionic conductivity for the pristine sample, similar to 7.3 x 10(-7) S cm(-1), was enhanced to a maximum of = 1.1 x 10(-5) S cm(-1) for 3.6 wt.% nanoparticle doped sample. We propose that the enhancement of ionic conductivity is caused by percolation effects of the high conductivity paths provided by interfaces between the nanoparticles and the polymer electrolyte. (C) 2010 Elsevier B.V. All rights reserved.

Studies on LDPE-cyanoethylated lignocellulosics blends using epoxy functionalized LDPE as compatibilizer

Rubberwood flour and cellulose have been plasticized by cyanoethylation and then blended with low-density polyethylene (LDPE). A small quantity of epoxy functionalized polyethylene i.e., polyethylene-co-glycidyl methacrylate (PEGMA) has been added to further enhance the mechanical properties. The mechanical properties were measured according to the standard ASTM methods. SEM analysis was performed for both fractured and unfractured blend specimens. The mechanical properties were improved by the addition of PEGMA compatibilizer. LDPE blends with cyanoethylated wood flour (CYWF) showed higher tensile strength and modulus than cyanoethylated cellulose CYC-LDPE blends. However CYC-LDPE blends exhibited higher relative elongation at break values as compared with the former. The TGA analysis showed lowering of thermal stability as the filler content is increased and degradation temperature of LDPE is shifted slightly to lower temperature. DSC analysis showed loss of crystallinity for the LDPE phase as the filler content is increased for both types of blends. Dielectric properties of the blends were similar to LDPE, but were lowered on adding PEGMA. (c) 2006 Wiley Periodicals, Inc.

Soft matter electrolytes based on polymethylmetacrylate dispersions in lithium bis(trifluoromethanesulfonyl)imide/1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ionic liquids

Ion transport in a polymer-ionic liquid (IL) soft matter composite electrolyte is discussed here in detail in the context of polymer-ionic liquid interaction and glass transition temperature The dispersion of polymethylmetacrylate (PMMA) in 1-butyl-3-methylimidazolium hexafluorophosphate (BMIPF6) and 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide (BMITFSI) resulted in transparent composite electrolytes with a jelly-like consistency The composite ionic conductivity measured over the range -30 C to 60 C was always lower than that of the neat BMITFSI/BMIPF6 and LiTFSI-BMITFSI/LiTFSI-BMIPF6 electrolytes but still very high (>1 mS/cm at 25 degrees C up to 50 wt% PMMA) While addition of LiTFSI to IL does not influence the glass T-g and T-m melting temperature significantly dispersion of PMMA (especially at higher contents) resulted in increase in T-g and disappearance of T-m In general the profile of temperature-dependent ionic conductivity could be fitted to Vogel-Tamman-Fulcher (VTF) suggesting a solvent assisted ion transport However for higher PMMA concentration sharp demarcation of temperature regimes between thermally activated and solvent assisted ion transport were observed with the glass transition temperature acting as the reference point for transformation from one form of transport mechanism to the other Because of the beneficial physico-chemical properties and interesting ion transport mechanism we envisage the present soft matter electrolytes to be promising for application in electrochromic devices (C) 2010 Elsevier Ltd All rights reserved

Protonation of polyaniline and its polyelectrolyte complexes at different ionic strength: contribution of Donnan effect

UV-visible spectra of polyaniline and its polyelectrolyte complexes show evidence for different degree of protonation when equilibrated with different ionic strength at a particular pH, due to the Donnan effect. For pure polyaniline, when the fixed charge on the film is positive, protonation is higher ionic strength whereas, when the polyaniline is doped with a polyelectrolyte resulting in a net negative fixed charge on the film, the protonation is less at higher ionic strength.

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.

Coupled electro-mechanical response of an electroactive polymer cantilever structure and its application in energy harvesting

Ionic polymer-metal composites (IPMC), piezoelectric polymer composites and nematic elastomer composites are materials, which exhibit characteristics of both sensors and actuators. Large deformation and curvature are observed in these systems when electric potential is applied. Effects of geometric non-linearity due to the chargeinduced motion in these materials are poorly understood. In this paper, a coupled model for understanding the behavior of an ionic polymer beam undergoing large deformation and large curvature is presented. Maxwell's equations and charge transport equations are considered which couple the distribution of the ion concentration and the pressure gradient along length of a cantilever beam with interdigital electrodes. A nonlinear constitutive model is derived accounting for the visco-elasto-plastic behavior of these polymers and based on the hypothesis that the presence of electrical charge stretches/contracts bonds, which give rise to electrical field dependent softening/hardening. Polymer chain orientation in statistical sense plays a role on such softening or hardening. Elementary beam kinematics with large curvature is considered. A model for understanding the deformation due to electrostatic repulsion between asymmetrical charge distributions across the cross-sections is presented. Experimental evidence that Silver(Ag) nanoparticle coated IPMCs can be used for energy harvesting is reported. An IPMC strip is vibrated in different environments and the electric power against a resistive load is measured. The electrical power generated was observed to vary with the environment with maximum power being generated when the strip is in wet state. IPMC based energy harvesting systems have potential applications in tidal wave energy harvesting, residual environmental energy harvesting to power MEMS and NEMS devices.

Ionic conductivity of bis(2-cyanoethyl) ether-lithium salt and poly(propylether imine)-lithium salt liquid electrolytes

We report here a multiple-nitrile based lithium-salt liquid electrolyte. The ionic conductivity of poly (propyl ether imine) (abbreviated as PETIM) lithium salt dendrimer liquid electrolyte was observed to be a function of dendrimer generation number, n=0 (monomer)-3. While the highest room temperature ionic conductivity value (similar to 10(-1) Sm-1) was recorded for the bis-2cyanoethyl ether monomer (i.e. zeroth generation; G(0)-CN), conductivity decreased progressively to lower values (similar to 10(-3) Sm-1) with increase in generation number (G(1)-CN -> G(3)-CN). The G(0)-CN and higher dendrimer generations showed high thermal stability (approximate to 150 to 200 degrees C), low moisture sensitivity and tunable viscosity (similar to 10(-2) (G(0)-CN) to 3 (G(3)-CN) Pa s). The linker ether group was found to be crucial for ion transport and also eliminated a large number of detrimental features, chiefly moisture sensitivity, chemical instability associated typically with prevalent molecular liquid solvents. Based on the combination of several beneficial physicochemical properties, we presently envisage that the PETIM dendrimers especially the G(0)-CN electrolytes hold promise as electrolytes in electrochemical devices such as lithium-ion batteries.

Role of silica nanoparticles in conductivity enhancement of nanocomposite solid polymer electrolytes: (PEG(x) NaBr): ySiO(2)

Nanocomposite solid polymer electrolytes (NCSPEs) with conducting species other than Li ions are being investigated for solid-state battery applications. Pristine solid polymer electrolytes (SPEs) do not show ionic conductivity suitable for batteries. Addition of inert fillers to SPEs is known to enhance the ionic conductivity. In this paper, we present the role of silica nanoparticles in enhancing the ionic conductivity in NCSPEs with sodium as conducting species. Sodium bromide is complexed with the host polyethylene glycol polymer by solution cast method and silica nanoparticles (SiO2, average particle size 7 nm) are incorporated into the complex in small amounts. The composites are characterized by powder XRD and IR spectroscopy. Conductivity measurements are undertaken as a function of concentration of salt and also as a function of temperature using impedance spectroscopy. Addition of silica nanoparticles shows an enhancement in conductivity by 1-2 orders of magnitude. The results are discussed in terms of interaction of nanoparticles with the nonconducting anions.

Polymer solar cells: design of materials by donor-acceptor approach

A brief overview of our group research activities is given and the concept of donor acceptor is described for the development of conjugated polymers for optoelectronic devices. In particular, a new family of conjugated polymers based on dithienopyrrole has been synthesized to demonstrate the concept of donor-acceptor. The dithienopyrrole was coupled to benzodithiophene via Stille coupling to obtain two low band gap polymers P5a and P5b having -C18H37 and -2-ethylhexyl alkyl chain respectively. Both the polymers exhibit absorption within the solar spectrum with an optical band gap below 2 eV. Atomic force microscopy revealed that both the polymers form smooth film with roughness of 2.4 nm and photoluminescence measurement of polymer/fullerene derivative blend film suggests effective dissociation of exciton.

Efficiency limitations in a low band-gap diketopyrrolopyrrole-based polymer solar cell

We report the performance and photophysics of a low band-gap diketopyrrolopyrrole-based copolymer used in bulk heterojunction devices in combination with PC71BM. We show that the short lifetime of photogenerated excitons in the polymer constitutes an obstacle towards device efficiency by limiting the diffusion range of the exciton to the donor-acceptor heterojunction. We employ ultrafast transient-probe and fluorescence spectroscopy techniques to examine the excited state loss channels inside the devices. We use the high boiling point solvent additive 1,8-diiodooctane (DIO) to study the photoexcited state losses in different blend morphologies. The solvent additive acts as a compatibiliser between the donor and the acceptor material and leads to smaller domain sizes, higher charge formation yields and increased device efficiency.