DSC and conductivity studies on PVA based proton conducting gel electrolytes

An attempt has been made in the present work to prepare polyvinyl alcohol (PVA) based proton conducting gel electrolytes in ammonium thiocyanate (NH₄SCN) solution and characterize them. DSC studies affirm the formation of gels along with the presence of partial complexes. The cole-cole plots exhibit maximum ionic conductivity (2.58 × 10⁻³ S cm⁻¹) for gel samples containing 6 wt% of PVA. The conductivity of gel electrolytes exhibit liquid like nature at low polymer concentrations while the behaviour is seen to be affected by the formation of PVA-NH₄SCN complexes upon increase in polymer content beyond 5 wt%. Temperature dependence of ionic conductivity exhibits VTF behaviour.     

Correlation between ionic conductivity and fluidity of polymer gel electrolytes containing NH4CF3SO3

Nonaqueous polymer gel electrolytes containing ammonium triflate (NH₄CF₃SO₃) and dimethylacetamide (DMA) with polymethylmethacrylate (PMMA) as the gelling polymer have been synthesized which show high value of conductivity (~ 10^-2 S/cm) at 25°C. The conductivity of polymer gel electrolytes containing different concentrations of NH₄CF₃SO₃ shows a small decrease with the addition of PMMA and this has been correlated with the variation of fluidity of these gel electrolytes. The small decrease in conductivity with PMMA addition shows that polymer plays the role of stiffener and this is supported by FTIR results which also indicates the absence of any active interaction between polymer and NH₄CF₃SO₃ in these gel electrolytes.     

星形网状聚合物电解质的制备及其离子导电性研究

聚乙二醇(PEG,Mn=400,600),季戊四醇与CH2Cl2在碱性条件下,通过williamson反应合成以季戊四醇为核、以聚氧化乙烯的嵌段物为臂的星形网状聚合物.FTIR和1H-NMR分析表明,聚合物分子为C[CH2-OCH2O-(CH2CH2O)n-CH2O-]4的重复单元结构.季戊四醇的加入明显地改善了聚合物电解质的成膜性、力学性能和热稳定性.对聚合物电解质进行交流阻抗导电性研究表明:在25℃,离子电导率随着锂盐浓度的变化相继出现两个峰值,当w(Li-ClO4/聚合物)=8%时,离子电导率达1.03× 10-4S/cm;离子电导率随着温度的升高而迅速增加,且呈非Arrhenius变化.     

Morphology and ionic conductivity of solid polymer electrolytes based on polyurethanes with various topological structures

Polyurethanes with linear, hyperbranched and comb-crosslinked structures were synthesized and were used to prepare solid polymer electrolytes. The polymer electrolytes were characterized by means of Fourier transform Raman spectroscopy, impedance spectroscopy (IS) and atomic force microscopy (AFM). The results showed that salt concentration significantly influences the morphology and conductivity of the three kinds of polyurethane/LiClO₄ system. When the mole ratios of the ether oxygen atom to lithium ion were controlled to be 12, 4 and 4 respectively for linear, hyperbranched and comb cross-linking polyurethane, the electrolytes typically displayed micro-phase separated morphology and the ionic conductivity also reached maxima respectively at 2.2 × 10^–7 S/cm, 2.8 × 10^–6 S/cm and 2.8 × 10^–5 S/cm at room temperature.     

Effect of ZrO2 on conductivity of PVC-PMMA-LiBF4-DBP polymer electrolytes

The preparation and characterization of composite polymer electrolytes of PVC-PMMA-LiBF₄-DBP for different concentrations of ZrO₂ have been investigated. FTIR studies indicate complex formation between the polymers, salt and plasticizer. The electrical conductivity values measured by a.c. impedance spectroscopy is found to depend upon the ZrO₂ concentration. The temperature dependence of the conductivity of the polymer films seems to obey the VTF relation. The conductivity values are presented and results discussed.     

Effect of complexing salt on conductivity of PVC/PEO polymer blend electrolytes

Solid polymer electrolyte membrane comprising poly(vinyl chloride) (PVC), poly(ehylene oxide) (PEO) and different lithium salts (LiClO₄, LiBF₄ and LiCF₃SO₃) were prepared by the solution casting technique. The effect of complexing salt on the ionic conductivity of the PVC/PEO host polymer is discussed. Solid polymer electrolyte films were characterized by X-ray diffraction, FTIR spectroscopy, TG/DTA and ac impedance spectroscopic studies. The conductivity studies of these solid polymer electrolyte (SPE) films are carried out as a function of frequency at various temperatures ranging from 302 K to 353 K. The maximum room temperature ionic conductivity is found to be 0·079 × 10^?4 S cm^?1 for the film containing LiBF₄ as the complexing salt. The temperature dependence of the conductivity of polymer electrolyte films seems to obey the Vogel-Tamman-Fulcher (VTF) relation.     

气相二氧化硅聚集体的网络结构对硅橡胶性能的影响

采用RPA橡胶加工分析仪,在一定的温度和频率下,分析不同性质结构的气相二氧化硅在高温硅橡胶中的聚集体网络结构差异及聚集体网络对填充胶Payne效应的影响。研究发现,高分支结构聚集体的填充胶具有明显的Payne效应,补强效果好。原子力显微镜（AFM）表明,高分支结构的聚集体在高温胶基体中分散均匀,呈三维链网结构,聚集体橡胶约为100-200nm。示差扫描量热（DSC）分析表明,在-42℃左右,填充胶结晶而失去弹性。     

Effect of ionic liquid dispersion on performance of a conducting polymer based Schottky diode

The effect of ionic liquid (IL) dispersion on the performance of Schottky diode fabricated with poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) has been investigated. Two kinds of ILs including 1-butyl-3-methylimidazolium hexafluorophosphate (BMIPF6, hydrophobic IL) and 1-butyl-3-methylimidazolium chloride (BMICL, hydrophilic IL) were dispersed to the PEDOT:PSS by mechanical stirring and sonication processes. Schottky diodes were fabricated with these mixtures. The forward current of Schottky diodes fabricated with PEDOT:PSS dispersed BMI PF6 (SD-BMIPF6)/BMICL (SD-BMICL) by mechanical stirring is slightly reduced compared with that of Schottky diodes fabricated with pristine PEDOT:PSS (SD-PEDOT). However, SD-BMIPF6 and SD-BMICL by sonication technique show higher forward current with respect to SD-PEDOT. Compared with SD-BMIPF6 and SD-BMICL, the forward current of SD-BMICL is much higher than that of SD-BMIPF6. Since the BMICL has hydrophilic nature, the enhancement of forward current might be due to the uniform dispersion of the BMICL on the PEDOT:PSS matrix.     

聚离子液体型聚合物电解质的制备及表征

以N-乙烯基咪唑、溴乙酸甲酯和二（三氟甲基磺酰亚胺）锂（LiTFSI）为原料,采用溶液聚合法制备了聚（1-乙烯基-3-乙酸甲酯基咪唑二（三氟甲基磺酰亚胺））（PMVIm-TFSI）。将其与LiTFSI和聚（甲基丙烯酸甲酯-醋酸乙烯酯）（P（MMA-VAc））共混制得了不同质量比的聚合物电解质。核磁共振（1 HNMR）、红外光谱（FT-IR）、示差扫描量热计（DSC）、热重分析（TGA）、X射线衍射（XRD）、扫描电镜（SEM）、交流阻抗（AC impedance）等对电解质的测试结果表明,PMVIm-TFSI掺杂到P（MMA-VAc）和LiTFSI组成的电解质中后其电导率得到了极大的改善,30℃下最高可达4.71×10-4S/cm,同时热稳定性也得到了极大的提高。此外,该共混电解质（透过率≥90%）还可以运用到电致变色器件（ECD）导电离子材料中,也显示出了优良的电化学性能。     

Influence of thermal expansion on the conductivity of polymer conducting composites

The temperature dependence of conductivity in systems that undergo a metal-dielectric phase transition is investigated. A quantitative theory is developed that makes it possible to calculate electrical conductivity as a function of temperature for these systems with allowance made for thermal expansion of a polymer and a filler.Deceased.Tashkent State University. Translated from Inzhenerno-Fizicheskii Zhurnal, Vol. 66, No. 3, pp. 335–337, March, 1994.     

Effect of polymer,plasticizer and filler on orally disintegrating film

Context: Difficulty in swallowing tablets or capsules has been identified as one of the contributing factors to non-compliance of geriatric patients. Although orally disintegrating tablet was designed for fast disintegration in mouth, the fear of taking solid tablets and the risk of choking for certain patient populations still exist.

Objective: The objective of this study was to develop and characterize orally disintegrating film (ODF), which was prepared using different combinations of polymers, plasticizers and fillers.

Materials and methods: Effects of hydroxypropyl methylcellulose (HPMC), polyethylene glycol 400 (PEG 400), glycerin, polyvinyl pyrrolidone (PVP), mannitol and microcrystalline cellulose (MCC) on physical property of ODF formed were studied. The ODF was prepared using the solvent casting method.

Results: Increase in HPMC concentration formed ODF with greater tensile strength. Incorporation of plasticizer (PEG 400 and glycerin) reduced tensile strength but increased elasticity of the ODF formed. PVP increased both tensile strength and elasticity of the ODF. Increase in MCC:mannitol ratio reduced the tensile strength and elasticity of the ODF. Disintegration time of film decreased corresponding to decrease in tensile strength of the film. Formulation R with the optimum tensile strength (13.10?N/mm²), bending flexibility (40 times) and disintegration time (41.50?s) was chosen as final formulation. A total of 80% of the drug was released within five minutes and the ODF was stable at least for one year actual condition.

Conclusion: An ODF containing donepezil HCl was developed and characterized. The donepezil HCl ODF has the potential to improve the compliance of Alzheimer disease patients.     

Effects of preparation methods on structure,ionic conductivity and dielectric relaxation of solid polymeric electrolytes

The solid polymer electrolytes (SPEs) consisted of poly(ethylene oxide) (PEO) and lithium perchlorate (LiClO₄) (PEO₂₀–LiClO₄ and PEO₈–LiClO₄ electrolytes of composition stoichiometric ratios EO:Li⁺ = 20:1 and 8:1) have been prepared by various blending methods. The simple solution casting, solution–cast hot pressed, dry blended melt pressed, high intensity ultrasonic assisted, microwave irradiated, and both the ultrasonicated and microwave irradiated solution–cast followed by their remelt with hot pressed methods have been used for preparation of the SPEs films. The complex formation between etheric oxygen (EO) of PEO and cation (Li⁺) of LiClO₄ is confirmed by relative changes in amorphous phase of these electrolytes which is investigated by X-ray diffraction measurements. It is found that the amount of amorphous phase of these SPEs is strongly influenced by their preparation methods and the salt concentration. The complex dielectric function, ac electric conductivity, electric modulus and impedance spectra of the electrolytes are studied over the frequency range of 20 Hz to 1 MHz by dielectric relaxation spectroscopy at ambient temperature. The dc ionic conductivity of PEO₈–LiClO₄ electrolytes is found two to three orders of magnitude higher than that of the PEO₂₀–LiClO₄ electrolytes, which is significantly affected by their preparation methods. The cations coupled PEO chain segmental dynamics and its correlation with the ionic conductivity of these electrolytes has been explored by considering the values of relaxation times and dielectric relaxation strength. Results reveal that the ionic conductivity of PEO₈–LiClO₄ electrolytes can be tuned over two orders of magnitude by adopting different blending methods with a state-of-the-art engineering.     

Fabrication and characterization of nanostructured conducting polymer films containing magnetic nanoparticles

In this study, the layer-by-layer technique is used to deposit nanostructured films exhibiting electrical conductivity and magnetic behavior, from poly(o-ethoxyaniline) (POEA), sulfonated polystyrene (PSS) and positively-charged maghemite nanoparticles. In order to incorporate the nanoparticles into the films, maghemite nanoparticles, in the form of magnetic fluid, were added to POEA solutions, and the resulting suspensions were used for film deposition. UV-Vis spectroscopy and atomic force microscopy images reveal that POEA remains doped in the films, even in the presence of the maghemite nanoparticles, and its typical globular morphology is also present. Electrical measurements show that a POEA/PSS film prepared from POEA solution containing 800 µL of the magnetic fluid exhibits a similar conductivity to that of the control film and, additionally, magnetic measurements indicated that nanosized maghemite phase was incorporated within the polymeric film.     

The effects of salt concentration on ion state and conductivity in comb cross-linked polymer electrolytes

A new type of comb cross-linked polyurethane/acrylate polymer was designed. The polymer has sparse network structure with many long comb molecule chains. A new solid polymer electrolyte (SPE) was prepared based on the polymer. The salt in the solid polymer electrolytes has different existent states with different salt contents. With increase of salt concentration, the ion pairing gradually becomes important existent form of salt, and T _g value of the SPE increases. At the same time, ionic conductivity increases rapidly. It is possible to design novel solid polymer electrolytes with high ionic conductivity to meet practical application by comb cross-linked polymer with high salt content.     

Studies on polymer electrolyte poly(vinyl) pyrrolidone (PVP) complexed with ionic liquid: Effect of complexation on thermal stability,conductivity and relaxation behaviour

Polymer electrolyte films of PVP + x wt% ionic liquid (IL) (1-ethyl-3-methylimidazolium tetrafluoroborate [EMIM][BF₄]) for x = 0, 5, 10, 15, 20, 25 wt% have been prepared using solution cast technique. These films were characterized by TGA, DSC, FT-IR and ac impedance spectroscopy techniques. From XRD studies it is found that the inclusion of IL increases the amorphocity of polymeric membranes. DSC thermograms show that the glass transition (T_g) and melting temperatures (T_m) of PVP shift upon complexation with IL. FT-IR analysis shows the complexation of PVP with IL. Thermogravimetric studies show that PVP decomposes in a single step while PVP/IL membranes exhibit two step decomposition; lower value of decomposition temperature corresponds to the decomposition of PVP/IL complex while the higher decomposition temperature has been attributed to the decomposition of PVP. The decomposition temperature of PVP/IL complex decreases with the increasing amount of IL in the PVP membrane. Temperature dependence of conductivity and dielectric relaxation frequencies have also been studied for PVP and PVP/IL membranes. Both show thermally activated Arrhenius behaviour.     

Microstructure, mechanical properties and ionic conductivity of BICUVOX - ZrO2 composite solid electrolytes

The composites of Cu-partially substituted bismuth vanadate (BICUVOX.1) mixed with a small amount of partially stabilized zirconia (3Y-TZP) were prepared to investigate their microstructure, mechanical properties and ionic conductivity. It was found that the addition of 0.5 to 1 wt% 3Y-TZP reduces the grain size to lower than 1 m in diameter, leading to improvements in micro-hardness and toughness by more than 15%. Due to preferential distribution of 3Y-TZP particles along grain boundaries, grain boundary conductivity and total conductivity decreased with increasing 3Y-TZP content at low temperature, but the decrements remained rather modest and, in addition, became less significant at higher temperature to disappear at 700 K and above.     

Defect structure and ionic conductivity as a function of thermal history in BIMGVOX solid electrolytes

The defect structure of the oxide ion conducting solid electrolyte, Mg substituted Bi₄V₂O_11– (BIMGVOX), was examined by high-resolution powder neutron diffraction. A detailed explanation of interpretation of the defect structure is presented. The general formula for the BIMGVOX solid solutions Bi₂V_1–x Mg _x O_5.5–3x/2 assumes complete oxidation of vanadium to V^V. Analysis of the neutron diffraction data reveals the defect structure and indicates that there is, in fact, partial reduction of vanadium to V^IV. The extent of reduction is dependent on thermal history, with high temperature quenched samples showing a greater degree of reduction than exponentially slow cooled samples. This is correlated with differences in electrical behaviour at low and high temperatures. Differences in ionic conductivity and activation energies between samples with different thermal histories are explained in terms of the balance between charge carrier concentration and the extent of defect trapping effects.