A polymeric solid electrolyte based on a binary blend of poly(ethylene oxide), poly(methyl vinyl ether-maleic acid) and LiClO4

A new polymeric solid electrolyte based on a PEO/PMVE-MAc blend, complexed with LiClO₄, was obtained and characterized by differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), polarized light optical microscopy, electrochemical impedance and cyclic voltammetry. DSC traces indicated miscibility for all the PSE samples. Crystallinity was suppressed for samples with LiClO₄ concentrations higher than 2.5 wt%. FTIR associated with DSC studies indicated that there is a preferential formation of complexes PEO/Li⁺/PMVE-MAc in all PSE samples studied here. The ionic conductivity of PSE reaches a maximum of about 10⁻⁵ S/cm at ambient temperature and 7.5 wt% LiClO₄. The electrochemical stability window is 4.5 V and associated with the other characteristics, make the PSE studied here suitable for applications in ‘smart-windows’, batteries, sensors, etc.     

Influence of 2,6 (N-pyrazolyl)isonicotinic acid on the photovoltaic properties of a dye-sensitized solar cell fabricated using poly(vinylidene fluoride) blended with poly(ethylene oxide) polymer electrolyte

A novel method of introducing a synthesized organic nitrogenous compound 2,6 (N-pyrazolyl)isonicotinic acid (BNIN) and its effect on the conduction behavior of poly(vinylidene fluoride) (PVdF)–poly(ethylene oxide) (PEO) polymer-blend electrolyte with potassium iodide (KI) and iodine (I₂) and the corresponding performance of the dye-sensitized solar cells (DSSCs) were studied. A systematic investigation of the blends using FTIR provides evidence of interaction of BNIN with the polymer. Differential scanning calorimetry (DSC) study proves the miscibility of these polymers. Due to the coordinating and plasticizing effects of BNIN, the ionic conductivity of polymer blend electrolytes is enhanced. The efficiency of DSSC using BNIN doped polymer blend electrolyte was 7.3% under an illumination of 60 mW cm⁻² were observed for the best performance of a solar cell in this work.     

Blending poly(methyl methacrylate) and poly(styrene‐co‐acrylonitrile) as composite polymer electrolyte

A blend of poly(methyl methacrylate) (PMMA) and poly(styrene‐co‐acrylonitrile) (PSAN) has been evaluated as a composite polymer electrolyte by means of differential scanning calorimetry (DSC), Fourier transform infrared (FTIR) spectroscopy, ac impedance measurements, and linear sweep voltammetry (LSV). The blends show an interaction with the Li⁺ ions when complexed with lithium perchlorate (LiClO₄), which results in an increase in the glass‐transition temperature (T_g) of the blends. The purpose of using PSAN as another component of the blend is to improve the poor mechanical properties of PMMA‐based plasticized electrolytes. The mechanical property is further improved by introducing fumed silica as inert filler, and hence the liquid electrolyte uptake and ionic conductivity of the composite systems are increased. Room‐temperature conductivity of the order of 10^?4 S/cm has been achieved for one of the composite electrolytes made from a 1/1 blend of PSAN and PMMA containing 120% liquid electrolyte [1M LiClO₄/propylene carbonate (PC)] and 10% fumed silica. These systems also showed good compatibility with Li electrodes and sufficient electrochemical stability for safe operation in Li batteries. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1319–1328, 2001     

Crystallization behavior of poly(l-lactic acid) affected by the addition of a small amount of poly(3-hydroxybutyrate)

The miscibility, crystallization and subsequent melting behavior in binary biodegradable polymer blends of poly(l-lactic acid) (PLLA) and low molecular weight poly(3-hydroxybutyrate) (PHB) have been investigated by differential scanning calorimetry (DSC), Fourier-transform infrared (FTIR) spectroscopy, and wide-angle X-ray diffraction (WAXD). DSC analysis results indicted that PLLA showed no miscibility with high molecular weight PHB (M_w = 650,000 g mol⁻¹) in the 80/20, 60/40, 40/60, 20/80 composition range of the PHB/PLLA blends. On the other hand, it showed some limited miscibility with low molecular weight PHB (M_w = 5000 g mol⁻¹) when the PHB content was below 25%, as evidenced by small changes in the glass transition temperature of PLLA. The partial miscibility was further supported by changes of cold-crystallization behavior of PLLA in the blends. During the nonisothermal crystallization, it was found that the addition of a small amount of PHB up to 30% made the cold-crystallization of PLLA occur in the lower temperature. Meanwhile, the crystallization of PHB and PLLA was observed in the heating process by monitoring characteristic IR bands of each component for the low molecular weight PHB/PLLA 20/80 and 30/70 blends. The temperature-dependent IR and WAXD results also revealed that for PLLA component crystallization, the disorder (α′) phase of PLLA was produced, and that the α′ phase changed to the order (α) phase just prior to the melting point.     

Miscibility of chitosan/poly(ethylene oxide) blends and effect of doping alkali and alkali earth metal ions on chitosan/PEO interaction

The miscibility of Chitosan (CS) and poly(ethylene oxide) (PEO) in their blends and the effect of K⁺ and Ca²⁺ doping on the CS/PEO interaction have been investigated in this work. CS and PEO appeared to be miscible and the DSC analysis suggested the Flory-Huggins interaction parameter χ_AB to be −0.21. Doping of K⁺ and Ca²⁺ into the CS/PEO blend matrix enhanced the cooperative interaction between CS and PEO and this enhancement was larger for Ca²⁺ than for K⁺. The difference between Ca²⁺ and K⁺ possibly reflects a stronger multi-valence interaction of Ca²⁺ with the amino and hydroxyl groups of CS as well as the ether groups of PEO to form a stable CS/Ca²⁺/PEO complex and a less significant interaction of K⁺, as suggested by DSC, WAXD and FTIR results. MD simulations clearly indicated the correlation between the dynamic behavior and the interaction of K⁺ and Ca²⁺ in the CS/PEO blend matrix.     

High-pressure solution blending of poly(?-caprolactone) with poly(methyl methacrylate) in acetone + carbon dioxide

The miscibility of blends of poly(?-caprolactone) (PCL, M_w = 14,300) with poly(methyl methacrylate) (PMMA, M_w = 15K or 540K) in acetone + CO₂ mixed solvent has been explored. The liquid-liquid phase boundaries at different temperatures have been determined for mixtures containing 10 wt% total polymer blend, 50 wt% acetone and 40 wt% CO₂. The PCL and PMMA contents of the blends were varied while holding the total polymer concentration at 10 wt%. The polymer blend solutions all displayed LCST-type behavior and required higher pressures than individual polymer components for complete miscibility. Complete miscibilities were achieved at pressures within 40 MPa. The DSC scans show that the blends are microphase-separated. The blends display the melting transition of PCL and the glass transition temperature of the PMMA phases. The presence of PMMA is found to influence the crystallization and melting behavior of PCL in the blends. The DSC results on heat of melting and the FTIR spectra, specifically the changes at 1295 cm⁻¹ band show the changes (decrease) in overall crystallinity of the blend upon addition of PMMA.     

Miscibility of C60-end-capped poly(ethylene oxide) with poly(vinyl chloride)

The miscibility of blends of single [60]fullerene (C₆₀)-end-capped poly(ethylene oxide) (FPEO) or double C₆₀-end-capped poly(ethylene oxide) (FPEOF) with poly(vinyl chloride) (PVC) has been studied. Similar to poly(ethylene oxide) (PEO), both FPEO and FPEOF are also miscible with PVC over the entire composition range. X-ray photoelectron spectroscopy showed the development of a new low-binding-energy Cl2p doublet and a new high-binding-energy O1s peak in FPEO/PVC blends. The results show that the miscibility between FPEO and PVC arises from hydrogen bonding interaction between the α-hydrogen of PVC and the ether oxygen of FPEO. From the melting point depression of PEO, FPEO or FPEOF in the blends, the Flory-Huggins interaction parameters were found to be −0.169, −0.142, −0.093 for PVC/PEO, PVC/FPEO and PVC/FPEOF, respectively, demonstrating that all the three blend systems are miscible in the melt. However, the incorporation of C₆₀ slightly impairs the interaction between PEO and PVC.     

Blends of poly(ethylene oxide) and poly(4-vinylphenol-co-2-hydroxyethyl methacrylate): thermal analysis, morphological behaviour and specific interactions

DSC and optical microscopy were used to determine the miscibility and crystallinity of blends of poly(ethylene oxide) (PEO) with poly(4-vinylphenol-co-2-hydroxyethyl methacrylate) (PVPh-HEM). A single glass transition temperature was observed for all blends, indicating miscibility. A progressive decrease in the degree of crystallinity and in the size of the PEO spherullites is observed, as PVPh-HEM is added. FTIR was used to probe the intermolecular specific interactions of the blends and the miscibility of the blend is mainly attributed to PVPh-HEM/PEO intermolecular interactions via hydrogen bonding.     

Polymer electrolytes based on poly(ethylene glycol) dimethyl ether and the ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate: Preparation, physico-chemical characterization, and theoretical study

Polymer electrolytes based on poly(ethylene glycol) dimethyl ether (PEGdME) and the ionic liquid (IL) 1-butyl-3-methylimidazolium hexafluorophosphate ([bmim]PF₆) have been prepared and characterized by different techniques. Coordination of the IL by the polymer occurs mainly in the amorphous phase. This finding was correlated with previous theoretical investigations of a similar model for polymer electrolytes based on poly(ethylene oxide), PEO, and IL. It has been obtained ionic conductivity σ ∼ 10⁻³ S cm⁻¹ for the polymer electrolyte with 35 wt% of IL at 100 °C. The same order of magnitude for σ was obtained by molecular dynamics simulation of PEO/IL. This work demonstrates consistency between experimental and theoretical results for polymer electrolytes containing ionic liquids.     

Miscibility and phase behavior in thermosetting blends of polybenzoxazine and poly(ethylene oxide)

Thermosetting polymer blends composed of polybenzoxazine (PBA-a) and poly(ethylene oxide) (PEO) were prepared via in situ curing reaction of benzoxazine (BA-a) in the presence of PEO, which started from the initially homogeneous mixtures of BA-a and PEO. Before curing, the BA-a/PEO blends displayed the single and composition-dependant glass transition temperatures (T_g's) in the entire blend composition, and the equilibrium melting point depression was also observed in the blends. It is judged that the BA-a/PEO blends are completely miscible. The miscibility was mainly ascribed to the contribution of entropy to mixing free energy since the molecular weight of BA-a is rather low. However, phase separation occurred after curing reaction at the elevated temperature, which was confirmed by differential scanning calorimetry (DSC) and scanning electronic microscopy (SEM). It was expected that the PBA-a/PEO blends would be miscible since PBA-a possesses a great number of phenolic hydroxyls in the molecular backbone, which are potential to form the intermolecular hydrogen bonding interactions with oxygen atoms of PEO and thus would fulfill the miscibility of the blends. To interpret the experimental results, we investigated the variable temperature Fourier transform infrared spectroscopy (FTIR) of the blends via model compound. The FTIR results indicate that the phenolic hydroxyl groups could not form the efficient intermolecular hydrogen bonding interactions at the elevated temperatures (e.g. the curing temperatures), i.e. the phenolic hydroxyl groups existed mainly in the non-associated form in the system. Therefore, the decrease of the mixing entropy still dominates the phase behavior of thermosetting blends at the elevated temperature.     

Miscibility and rheologically determined phase diagram of poly(ethylene oxide)/poly(<Emphasis Type="Italic">ε</Emphasis>-caprolactone) blends

Poly(ethylene oxide)/poly(ε-caprolactone) (PEO/PCL) blends can be widely used in lithium rechargeable battery area or as medical materials, while the miscibility and phase diagram of the blends are still unclear. The present work attempted to establish the blends’ phase diagram using rheometry and investigated the miscibility. The results showed that a miscibility window of upper critical solution temperature character of the blends is revealed. Meanwhile, the abnormal rheological behavior of PEO at temperatures higher than 130 °C has little influence on the phase diagram determination. Different rheological properties of PEO/PCL blends from those of PEO revealed the existence of interactions between PEO and PCL molecular chains. Whereas shear-induced mixing or shear-induced phase separation might occur in phase diagram determination of PEO/PCL blends using rheometry.     

Poly(hydroxyether sulfone) and its blends with poly(ethylene oxide): miscibility, phase behavior and hydrogen bonding interactions

Poly(hydroxyether sulfone) (PHES) was synthesized through polycondensation of bisphenol S with epichlorohydrin. It was characterized by Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy and differential scanning calorimetry (DSC). The miscibility in the blends of PHES with poly(ethylene oxide) (PEO) was established on the basis of the thermal analysis results. DSC showed that the PHES/PEO blends prepared by casting from N,N-dimethylformamide (DMF) possessed single, composition-dependent glass transition temperatures (T_gs), indicating that the blends are miscible in amorphous state. At elevated temperatures, the PHES/PEO blends underwent phase separation. The phase behavior was investigated by optical microscope and the cloud point curve was determined. A typical lower critical solution temperature behavior was observed in the moderate temperature range for this blend system. FTIR studies indicate that there are the competitive hydrogen bonding interactions upon adding PEO to the system, which was involved with the intramolecular and intermolecular hydrogen bonding interactions, i.e. -OH?OS, -OH?-OH and -OH versus ether oxygen atoms of PEO between PHES and PEO. In terms of the infrared spectroscopic investigation, it is judged that from weak to strong the strength of the hydrogen bonding interactions is in the following order: -OH?OS, -OH?-OH and -OH versus ether oxygen atoms of PEO.     

The effect of EPIDA units on the conductivity of poly(ethylene glycol)-4,4′-diphenylmethane diisocyanate-EPIDA polyurethane electrolytes

Novel thermoplastic polyurethanes with chelating groups were synthesized from 4,4′-diphenylmethane diisocyanate (MDI), poly(ethylene glycol) (PEG), and EP-IDA. Differential scanning calorimetry (DSC), fourier transform infrared spectroscopy (FT-IR), and impedance spectroscopy (IS) were used to monitor changes in the morphology of these polyurethanes with the concentration of lithium perchlorate (LiClO₄) dopants. Adding the salt significantly changes the FTIR spectrum of the polyurethane, indicating an interaction between the lithium cation within the urethane group and the chelating group. The soft segment T_g increases with LiClO₄ concentration, as determined by DSC, indicating that solubility of the lithium cation in the host polyurethane increases with the chelating groups. IS shows that the bulk conductivity reaches a maximum as the salt concentration is increased. One of the investigated polyurethane electrolytes has an ionic conductivity as high as ∼10⁻⁶ S cm⁻¹ at room temperature.     

Photocurrent in and miscibility of poly(N-vinylcarbazole)/poly(methyl methacrylate) blends

Summary Steady-state photocurrent in poly(N-vinylcarbazole)(PVCz) (26,48 wt%)/poly(methyl methacrylate)(PMMA) blends is for the first time measured. The PVCz(26,48 wt%)/PMMA blends showed almost the same carrier-generation efficiencies at electric fields higher than 1 × 10⁵ V · cm⁻¹. The results are explained by high miscibility of the PVCz(26,48 wt%)/PMMA blends, suggesting the existence of PVCz chains in continous PMMA-rich phase in the phase-separated structure. The miscibility is also evaluated by means of excimer fluorescence of PVCz in these blends and fluorescence microscopy. Received: 26 December 2000/Revised version: 16 January 2001/Accepted: 19 January 2001     

The phase behavior and the Flory-Huggins interaction parameter of blends containing amorphous poly(resorcinol phthalate-block-carbonate), poly(bisphenol-A carbonate) and poly(ethylene terephthalate)

The phase behavior of the blends of poly(ethylene terephthalate) (PET) and poly(Resorcinol Phthalate-block-Carbonate) (RPC) and the blends of PET and poly(Bisphenol-A Carbonate) (PC) was investigated by dynamic mechanical analysis (DMA), differential scanning calorimetry (DSC), and transmission electron microscopy (TEM). Blends of high molecular weight PET and RPC copolymer with 20 mol% resorcinol phthalate (RPC20) showed two glass transition temperatures in DMA and DSC but the cold crystallization rate of PET phase was substantially lowered as compared to neat PET, indicating partial miscibility at all compositions. The RPC20 with M_w = 31,500 g/mol formed miscible blends with PET when PET has weight-average molecular weight <9500 g/mol. The Flory-Huggins interaction parameter between PET and RPC20 was calculated to be 0.029 ± 0.003 by using the Flory-Huggins equation at critical composition and molecular weight. PC with M_w = 30,000 g/mol formed miscible blends with PET only when PET had molecular weight <2800 g/mol, indicating PC/PET blends were much less miscible than RPC20/PET blends. Group contribution methods agreed well with the experimental results obtained both in the present study and a previous study [1], predicting that the addition of a resorcinol phthalate block to a PC backbone should increase the miscibility of PC and PET.     

Ionomeric blends of poly(ethylene oxide) with poly(styrene‐co‐maleic anhydride) ionomer: Miscibility,crystallization, and melting behavior

The miscibility and crystallization behavior of poly(ethylene oxide) (PEO) and poly(styrene‐co‐maleic anhydride) ionomer (SMAI) blends were studied by the dynamic mechanical analysis (DMA) and differential scanning calorimetry (DSC). This study has demonstrated that the presence of ion–dipole interactions enhances the miscibility of otherwise immiscible polymers in the PEO and high molecular weight poly(styrene‐co‐maleic anhydride) (SMA). The effect of ion–dipole interactions on enhancing miscibility is confirmed by the presence of a single glass transition temperature (T_g) and a depression of the equilibrium melting temperature of the PEO component. The equilibrium melting temperature of PEO in the blends are obtained using Hoffman‐Weeks plots. The interaction energy density, β, is calculated from these data using the Nishi‐Wang equation. The results suggest that PEO and SMAI blends are thermodynamically miscible in the melt. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1–7, 2000     

Some properties of organosoluble poly(2,5-didodecyloxy-p-phenylenevinylene) and its blends with poly(oxyethylene)

An organosoluble precursor of poly(2,5-didodecyloxy-p-phenylenevinylene) (PDDOPV) with high molecular weight was synthesized via the chlorine precursor route and characterized by IR and UV-Vis spectra, GPC, DSC, and elemental analysis. Factors effecting the thermal elimination reaction were studied. The solubility, absorption spectra and photoluminescence spectra of PDDOPV were also investigated. The conductivity of PDDOPV doped with different dopants (I₂, Br₂, FeCl₃ and H₂SO₄) and the I₂-doped conductivity of PDDOPV/PEO (polyoxyethylene) blends and PDDOPV/PEO/LiClO₄ blends were compared. The results showed that a synergistic mixed conductivity existed in the I₂-doped PDDOPV/PEO/LiClO₄ blend.     

Compatibilizing effects of poly(styrene-graft-ethylene oxide) in blends of polystyrene and butyl acrylate polymers

The compatibilizing effect of poly(styrene-graft-ethylene oxide) in polystyrene (PS) blends with poly(n-butyl acrylate) (PBA) and poly(n-butyl acrylate-co-acrylic acid) (PBAAA) was investigated. No significant effects of the graft copolymer on the domain size were found in the PBA blends. By functionalizing PBA with acrylic acid, the average size of the polyacrylate domains was reduced considerably by the graft copolymer. Thermal and dynamic mechanical analysis of the PS/PBAAA blends revealed that the PBAAA glass transition temperature (T_g) decreased with increasing graft copolymer content. The effect of the graft copolymer in the PS/PBAAA blends can be explained by interactions across the interface due to the formation of hydrogen bonds between the poly(ethylene oxide) (PEO) side chains in the graft copolymer and the acrylic acid segments in the PBAAA phase. Hydrogen bonding was confirmed by IR analysis of binary blends of PEO and PBAAA. Partial miscibility in the PEO/PBAAA blends was indicated by a PEO melting point depression and by a T_g reduction of the PBAAA phase. The thermal properties of the PEO/PBA blends indicated only very limited miscibility. © 1996 John Wiley & Sons, Inc.     

Correlation between interactions, miscibility, and spherulite growth in crystalline/crystalline blends of poly(ethylene oxide) and polyesters

Crystalline/crystalline blend systems of poly(ethylene oxide) (PEO) and a homologous series of polyesters, from poly(ethylene adipate) to poly(hexamethylene sebacate), of different CH₂/CO ratios (from 3.0 to 7.0) were examined. Correlation between interactions, miscibility, and spherulite growth rate was discussed. Owing to proximity of blend constituents' T_g's, the miscibility in the crystalline/crystalline blends was mainly justified by thermodynamic and kinetic evidence extracted from characterization of the PEO crystals grown from mixtures of PEO and polyesters at melt state. By overcoming experimental difficulty in assessing the phase behavior of two crystalline polymers with closely spaced T_g's, this work has further extended the range of polyesters that can be miscible with PEO. The interaction parameters (χ₁₂) for miscible blends of PEO with polyesters [poly(ethylene adipate), poly(propylene adipate), poly(butylene adipate), and poly(ethylene azelate) with CH₂/CO = 3.0-4.5] are all negative but the values vary with the polyester structures, with a maximum for the blend of PEO/poly(propylene adipate) (CH₂/CO = 3.5). The values of interactions are apparently dependent on the structures of the polyester constituent in the blends; interaction strength for the miscible PEO/polyester systems correlate in the same trend with the PEO crystal growth rates in the blends.     

Effects of lithium perchlorate on poly(ethylene oxide) spherulite morphology and spherulite growth kinetics

Effects of lithium perchlorate (LiClO₄) on the crystallization behaviors of poly(ethylene oxide) (PEO) were investigated by differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), and polarized optical microscopy (POM) in PEO/LiClO₄ system. DSC results indicate that there are nucleation effects of LiClO₄ on the crystallization of PEO. But, on the other hand, the coordination of lithium ion with the oxygen ether atoms of PEO can obviously reduce the crystallinity and spherulite growth rate of PEO. This contrary effect of LiClO₄ on the crystallization of PEO in PEO/LiClO₄ complexes system was analyzed and discussed in detail. The Laurizen–Hoffman theory was used to describe the Li‐coordinated crystallization kinetics of PEO spherulite. It showed that the nucleation constant (K_g) and folding surface free energy (σ_e) decreased with increasing LiClO₄ contents, and the energy necessary for the transport of segments across the liquid–solid interface (ΔE) increased on increasing the contents of LiClO₄. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012