PEO Blend Research Articles

Polymer Compositional Ratio-Dependent Morphology, Crystallinity, Dielectric Dispersion, Structural Dynamics, and Electrical Conductivity of PVDF/PEO Blend Films

The polymer blend (PB) films consisted of poly(vinylidene fluoride) (PVDF) and poly(ethylene oxide) (PEO) with different compositional ratios (i.e., PVDF/PEO =100/0, 75/25, 50/50, 25/75, and 0/100 wt%) have been prepared by solution casting method. These PB films were characterized by scanning electron microscopy (SEM), energy dispersive X-ray (EDX) spectroscopy, X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, and dielectric relaxation spectroscopy (DRS). The pristine films of PVDF and PEO have spherulite morphologies, which change enormously with the variation of their compositions in blend films. The EDX spectra confirm the linear variation of the amount of respective polymer elements, with the change of its compositional ratio in the PB films. The XRD and FTIR results confirm that the semicrystalline PVDF film has predominantly α- and β-phase crystals. The degree of crystallinity of these PB films exhibits non-linear increase, with increasing amount of PEO in the films. The relative fraction of the β-phase crystal of the PVDF in these complex PB films has been determined from the fractional relations based on the areas and intensities of crystalline peaks, observed in their XRD patterns which is found the maximum (~50%) for the 75 PVDF/25 PEO blend film. The dielectric dispersion of these PB films in the frequency window of 20 Hz-1MHz at 27 °C reveals that the real part of the complex permittivity is governed predominantly by the interfacial polarization effect at lower audio frequencies, whereas it mainly depends on the polymer compositional ratio at higher radio frequencies. The segmental relaxation process peak of the PEO chain observed in the loss part of the electric modulus spectra, shifts toward the lower frequency side with a significant suppression of intensity as the amount of PVDF enhances in the PB films. This result confirms that the PEO dynamics face considerable hindrance by the PVDF structures. The dc electrical conductivity of these PB films increases non-linearly with increasing amount of PEO in the films, and varies by more than an order of magnitude with the variation of the compositional ratio over the entire range. The temperature-dependent study of 50 PVDF/50 PEO blend film confirms its thermally activated dielectric properties and the structural dynamics with the relaxation activation energy of 0.23 eV. The compositional ratio-dependent dielectric properties of PVDF/PEO blend films offer a promising potential for their use as dielectric permittivity- and electrical conductivity-tunable insulating materials, with engineered functionality for flexible electronics and electrical devices.

Fabrication of doxycycline-loaded electrospun PCL/PEO membranes for a potential drug delivery system.

Potential usage of biodegradable and biocompatible polymeric nanofibers is the most attention grabbing topic for the drug delivery system. In order to fabricate ultrafine fibers, electrospinning, one of the well-known techniques, has been extensively studied in the literature. In the present study, the objective is to achieve the optimum blend of hydrophobic and hydrophilic polymers to be used as a drug delivery vehicle and also to obtain the optimum amount of doxycycline (DOXH) to reach the optimum release. In this case, the biodegradable and biocompatible synthetic polymers, poly(ε-caprolactone) (PCL) and poly(ethylene oxide) (PEO), were blended with different ratios for the production of DOXH-loaded electrospun PCL/PEO membranes using electrospinning technique, which is a novel attempt. The fabricated membranes were subsequently characterized to optimize the blending ratio of polymers by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction analysis (XRD) and water contact angle analysis. After the characterization studies, different amounts of DOXH were loaded to the optimized blend of PCL and PEO to investigate the release of DOXH from the membrane used as a drug delivery vehicle. In vitro drug release studies were performed, and in vitro drug release kinetics were assessed to confirm the usage of these nanofiber materials as efficient drug delivery vehicles. The results indicated that 3.5% DOXH-loaded (75:25 w/w) PCL/PEO is the most acceptable membrane to provide prolonged release rather than immediate release of DOXH.

Free volume defects and transport properties of mechanically stable polyhedral oligomeric silsesquioxane embedded poly(vinyl alcohol)‐poly(ethylene oxide) blend membranes

AbstractPolymer membrane based gas transport and pervaporation processes are fast growing areas in separation technology and have received wide attention as areas of ‘clean technology’. Mechanically stable novel polyhedral oligomeric silsesquioxane (POSS) embedded poly(vinyl alcohol) (PVA)/poly(ethylene oxide) (PEO) blend membranes were prepared by solution blending followed by casting. The addition of carboxymethyl cellulose enhanced the interfacial activities of the PVA and PEO blends. The peripheral organic substituent on POSS plays a key role in achieving compatibility with polymers whereas the rigid Si–O–Si core of POSS imparts high mechanical strength. Compared to PVA membrane, poly(ethylene glycol) and octa(tetramethylammonium) functionalized POSS embedded PVA/PEO membranes exhibit 680% and 580% enhancement in Young's modulus as well as 130% and 140% improvement in tensile strength respectively. The Einstein, Kerner and Frankel–Acrivos models were applied to compare the experimental and theoretical Young's modulus of PVA‐PEO/POSS membranes. The presence of an ethylene oxide tail on POSS as well as PEO in the blend membrane enhances the CO2 affinity of the membrane. The presence of a hydrophilic functional group on the POSS improves the hydrophilicity of the membrane and produces more binding sites for water molecules in the membrane during the pervaporation separation of a tetrahydrofuran–water azeotropic mixture. The transport properties of the membrane are further elucidated by means of free volume defect analysis carried out by positron annihilation lifetime spectroscopy and coincidence Doppler broadening spectroscopy. © 2019 Society of Chemical Industry

Effect of Silk Fibroin on Cell Viability in Electrospun Scaffolds of Polyethylene Oxide.

In this study, a coating from electrospun silk fibroin was performed with the aim to modify the surface of breast implants. We evaluated the effect of fibroin on polymeric matrices of poly (ethylene oxide) (PEO) to enhance cell viability, adhesion, and proliferation of HaCaT human keratinocytes to enhance the healing process on breast prosthesis implantation. We electrospun six blends of fibroin and PEO at different concentrations. These scaffolds were characterized by scanning electron microscopy, contact angle measurements, ATR-FTIR spectroscopy, and X-ray diffraction. We obtained diverse network conformations at different combinations to examine the regulation of cell adhesion and proliferation by modifying the microstructure of the matrix to be applied as a potential scaffold for coating breast implants. The key contribution of this work is the solution it provides to enhance the healing process on prosthesis implantation considering that the use of these PEO–fibroin scaffolds reduced (p < 0.05) the amount of pyknotic nuclei. Therefore, viability of HaCaT human keratinocytes on PEO–fibroin matrices was significantly improved (p < 0.001). These findings provide a rational strategy to coat breast implants improving biocompatibility.

Development of electrospun nanofibers containing chitosan/PEO blend and phenolic compounds with antibacterial activity

Electrospun nanofibers can be formed with chitosan as the polymers found in biological sources have antibacterial ability. The objective of this work was to evaluate whether chitosan/polyethylene oxide (PEO) blend nanofibers containing microalgal phenolic compounds exhibit antibacterial activity. Nanofibers produced with a 3% chitosan/2% PEO blend containing 1% phenolic compounds had an average diameter of 214 ± 37 nm, which resulted in a high temperature of maximum degradation, an important parameter for food packaging. The potential antibacterial activity of this nanofibers was confirmed by their inhibition of Staphylococcus aureus ATCC 25923 (6.4 ± 1.1 mm) and Escherichia coli ATCC 25972 (5.5 ± 0.4 mm). The polymeric nanofibers produced from chitosan and containing phenolic compounds have properties that therefore allow their application as active packaging. In addition, chitosan is an excellent polymer for packaging as it presents biodegradability, biocompatibility and, non-toxicity.

Preparation and characterization of chitosan-based nanocomposite hybrid polymer electrolyte membranes for fuel cell application

The aim of the work was to synthesize nanocomposite membranes based on sulfonated chitosan and PEO blends containing sulfonated silica dioxide (s-SiO2) nanoparticles and investigated their morphological, structural, mechanical, and thermal properties. The electrolytes were characterized by SEM, FTIR, XRD, TG analysis, and water contact angle. FTIR analysis confirmed the presence of chitosan, PEO, SiO2, and sulfonic acid groups through the chitosan matrix in which the components used had good compatibility. The mechanical and thermal studies emphasized that strong interactions occurred between sulfonated chitosan, PEO, and s-SiO2. Blending sulfonated chitosan with PEO and the addition of s-SiO2 nanoparticles enhanced the hydrophilic property of chitosan membranes. The s-chitosan /PEO-based nanocomposites containing 7.5 wt% of s-SiO2 nanoparticles showed the remarkable improvements in ultimate tensile strength values and an increase in conductivity compared to the chitosan/PEO with s-SiO2 membranes in the order of 10−2 S/cm at room temperature.

Block copolymer compatibilization driven frustrated crystallization in electrospun nanofibers of polystyrene/poly(ethylene oxide) blends

The confined crystallization behaviour of poly(ethylene oxide) (PEO) has been studied in electrospun nanofibers of the phase-separated blends of polystyrene (PS) and PEO compatibilized with polystyrene-block-poly(ethylene oxide) (PS-b-PEO) block copolymer. The PS was present as the majority component such that the electrospun nanofibers consisted of PEO domains dispersed in the PS matrix. The phase separation in the blend occurred under the radial constraint of the nanofibers which led to the formation of small-sized fibrillar PEO domains. The use of block copolymer compatibilizer resulted in a noticeable decrease in the PEO domain size in the as-spun nanofibers. Moreover, the decrease in the domain size and domain connectivity was more substantial in the thermally annealed blend nanofibers due to the suppression of the domain coalescence mechanism resulting from the localization of the PS-b-PEO block copolymer at the interface. Consequently, the fraction of PEO domains crystallizing via homogeneous nucleation increased in the compatibilized blend nanofibers due to the presence of higher number of heterogeneity free PEO domains and disruption in their spatial connectivity. Interestingly, in the compatibilized blend nanofibers consisting of low molecular weight PEO, additional crystallization event attributed to surface nucleation was observed. The surface nucleation, plausibly, resulted from the formation of wet-brush structures where the PEO homopolymers homogeneously wet the PEO blocks present at the interface. In such a scenario, the PEO crystallization occurred via surface nucleation at the domain interface. The surface nucleated crystallization was absent in the compatibilized blend nanofibers composed of high molecular weight PEO presumably due to the formation of morphology with dry-brush structures.

Poly (ethylene oxide) (PEO)-based, sodium ion-conducting‚ solid polymer electrolyte films, dispersed with Al2O3 filler, for applications in sodium ion cells

The studies on solid polymer electrolyte (SPE) films with high ionic conductivity suitable for the realization of all solid-state Na-ion cells‚ form the focal theme of the work presented in this paper. The SPE films are obtained by the solution casting technique using the blend solution of poly (ethylene oxide) (PEO) with ethylene carbonate (EC) and propylene carbonate (PC) and complexed with sodium nitrate. Structural and thermal studies of SPE films are done by XRD, FTIR spectroscopy, and TGA techniques. Surface morphology of the films is studied using the FESEM. The ionic conductivity of SPE films is determined from the electrochemical impedance spectroscopy studies. For the SPE film with 16 wt% of NaNO3 used for reacting with the polymer blend of PEO with EC and PC, the ionic conductivity obtained is around 1.08 × 10−5 S cm−1. Addition of the Al2O3 as the filler material is found to enhance the ionic conductivity of the SPE films. The studies on the Al2O3 modified SPE film show an ionic conductivity of 1.86 × 10–4 S cm−1, which is one order higher than that of the SPE films without the filler content. For the SPE film dispersed with 8 wt% of Al2O3, the total ion transport number observed is around 0.9895, which is quite impressive from the perspective of the applications in electrochemical energy storage devices. From the cyclic voltammetry studies, a wide electrochemical stability window up to 4 V is observed, which further emphasizes the commendable electrochemical behavior of these SPE films.

Ion dynamics in NaBF4 salt-complexed PVC–PEO blend polymer electrolytes: correlation between average ion hopping length and network structure

Electrical transport properties of a series of NaBF4 salt-doped PVC–polyethylene oxide blend polymer electrolytes are studied using impedance spectroscopy. X-ray diffraction, Fourier transform infrared spectroscopy, and differential scanning calorimetry are implemented to characterize the structural properties of the electrolytes. The characterization data clearly indicate that the interaction between the dopant salt and the polymer host substantially influences the overall crystallinity of the electrolytes. Experimental frequency-dependent complex conductivity and loss tangent data are analyzed using a physical model to extract separately the mobile ion concentration and ion mobility of the charge carriers and the type of their thermal activation. The average hopping length of free ions, which essentially controls the macroscopic ion transport within the electrolytes, is found to be strongly correlated to the network structure of the electrolytes. Both the dc conductivity and free ion mobility are observed to be strongly coupled with the segmental dynamics of blend polymer host over the entire range of ion content studied.

Elasticity patterns induced by phase-separation in polymer blend films

Systematical studies on the impact of the thickness of thin films composed of polystyrene (PS) or poly(ethylene oxide) (PEO) on the effective elasticity of polymer-decorated soft polydimethylsiloxane substrate were performed. For both investigated polymer films, elasticity parameter was determined from force-displacement curves recorded using atomic force microscopy. Effective stiffness of supported film grows monotonically with film thickness, starting from the value comparable to the elasticity of soft support and reaching plateau for polymer layers thicker than 200nm. In contrary, for films cast on hard support no significant thickness dependence of elasticity was observed and the value of elasticity parameter was similar to the one of the substrate. Based on these results, non-conventional method to produce elasticity patterns of various shapes and dimensions induced by phase-separation process in symmetric and asymmetric PS:PEO blend films on soft support was demonstrated. Elevated PS domains were characterized by elasticity parameter 2 times higher than lower PEO matrix. In contrary, adhesion force was increased more than 3 times for PEO regions, as compared to PS areas.

Crystallization behavior of crystalline/crystalline polymer blends under confinement in electrospun nanofibers of polystyrene/poly(ethylene oxide)/poly(ε-caprolactone) ternary mixtures.

We have studied the crystallization behavior of crystalline/crystalline blends of poly(ethylene oxide) (PEO) and poly(ε-caprolactone) (PCL) in electrospun nanofibers fabricated from ternary blends of polystyrene (PS), PEO, and PCL, where PS was present as the majority component. It was demonstrated previously that PEO in PS/PEO binary blend nanofibers with a low PEO weight fraction (≦0.2) crystallized predominantly through homogenous nucleation due to the small PEO domain size which excluded the presence of heterogeneities (Soft Matter, 2016, 12, 5110). Here, it was found that PCL in PS/PCL binary blend nanofibers exhibited similar behavior, but at a much lower weight fraction of PCL (≦0.1) due to the presence of an inherently higher concentration of heterogeneities in the PCL homopolymer. In the PS/PEO/PCL ternary blend nanofibers, where the combined weight fraction of PEO and PCL was kept at 0.2 or less, the crystallization of the two components took place separately through both heterogeneous and homogenous nucleation mechanisms. The phase segregated crystallization behavior was further confirmed by the melting behavior of the blend nanofibers and wide angle X-ray diffraction (WAXD) measurements. Most significantly, the homogenous nucleation of both PEO and PCL was suppressed whereas the heterogeneous nucleation was enhanced in the ternary blend nanofibers even at very low weight fraction of PEO or PCL. This was plausibly attributed to the coupling between the crystallization and the liquid-liquid phase separation (LLPS) of the PEO/PCL mixture dispersed in the PS matrix during non-isothermal cooling of the blend nanofibers. Furthermore, it was observed that thermal treatment of the PS/PEO/PCL blend nanofibers above the glass transition temperature of PS further promoted the heterogeneous nucleation-initiated crystallization of PEO because of a complex interplay between Plateau-Rayleigh instability-induced domain breakup and its further coalescence and demixing within the PEO/PCL domains embedded in the PS matrix.

Hybrid Randomly Electrospun Poly(lactic-co-glycolic acid):Poly(ethylene oxide) (PLGA:PEO) Fibrous Scaffolds Enhancing Myoblast Differentiation and Alignment.

Cellular responses are regulated by their microenvironments, and engineered synthetic scaffolds can offer control over different microenvironment properties. This important relationship can be used as a tool to manipulate cell fate and cell responses for different biomedical applications. We show for the first time in this study how blending of poly(ethylene oxide) (PEO) to poly(lactic-co-glycolic acid) (PLGA) fibers to yield hybrid scaffolds changes the physical and mechanical properties of PLGA fibrous scaffolds and in turn affects cellular response. For this purpose we employed electrospinning to create fibrous scaffolds mimicking the basic structural properties of the native extracellular matrix. We introduced PEO to PLGA electrospun fibers by spinning a blend of PLGA:PEO polymer solutions in different ratios. PEO served as a sacrificial component within the fibers upon hydration, leading to pore formation in the fibers, fiber twisting, increased scaffold disintegration, and hydrophilicity, decreased Young's modulus, and significantly improved strain at break of initially electrospun scaffolds. We observed that the blended PLGA:PEO fibrous scaffolds supported myoblast adhesion and proliferation and resulted in increased myotube formation and self-alignment, when compared to PLGA-only scaffolds, even though the scaffolds were randomly oriented. The 50:50 PLGA:PEO blended scaffold showed the most promising results in terms of mechanical properties, myotube formation, and alignment, suggesting an optimal microenvironment for myoblast differentiation from the PLGA:PEO blends tested. The explored approach for tuning fiber properties can easily extend to other polymeric scaffolds and provides a valuable tool to engineer fibrillar microenvironments for several biomedical applications.

An investigation into the use of polymer blends to improve the printability of and regulate drug release from pharmaceutical solid dispersions prepared via fused deposition modeling (FDM) 3D printing

FDM 3D printing has been recently attracted increasing research efforts towards the production of personalized solid oral formulations. However, commercially available FDM printers are extremely limited with regards to the materials that can be processed to few types of thermoplastic polymers, which often may not be pharmaceutically approved materials nor ideal for optimizing dosage form performance of poor soluble compounds. This study explored the use of polymer blends as a formulation strategy to overcome this processability issue and to provide adjustable drug release rates from the printed dispersions. Solid dispersions of felodipine, the model drug, were successfully fabricated using FDM 3D printing with polymer blends of PEG, PEO and Tween 80 with either Eudragit E PO or Soluplus. As PVA is one of most widely used polymers in FDM 3D printing, a PVA based solid dispersion was used as a benchmark to compare the polymer blend systems to in terms of processability. The polymer blends exhibited excellent printability and were suitable for processing using a commercially available FDM 3D printer. With 10% drug loading, all characterization data indicated that the model drug was molecularly dispersed in the matrices. During in vitro dissolution testing, it was clear that the disintegration behavior of the formulations significantly influenced the rates of drug release. Eudragit EPO based blend dispersions showed bulk disintegration; whereas the Soluplus based blends showed the ‘peeling’ style disintegration of strip-by-strip. The results indicated that interplay of the miscibility between excipients in the blends, the solubility of the materials in the dissolution media and the degree of fusion between the printed strips during FDM process can be used to manipulate the drug release rate of the dispersions. This brings new insight into the design principles of controlled release formulations using FDM 3D printing.

Single Chain Dynamic Structure Factor of Linear Polymers in an All-Polymer Nano-Composite

We present neutron spin echo (NSE) experiments on the single chain dynamic structure factor of long poly(ethylene oxide) (PEO) linear chains in the presence of poly(methyl methacrylate)-based single-chain nanoparticles (SCNPs). A complementary structural characterization of the system discards a significant interpenetration of the components and reveals a close to globular conformation of the SCNPs when surrounded by PEO chains. Analogous NSE measurements on blends of PEO with the linear precursor chains of the SCNPs are taken as a reference for the dynamics study. For short times (below approximately 5 ns) PEO in both mixtures exhibits slowed down Rouse dynamics with respect to bulk PEO behavior. The similar deceleration observed in both environments suggests this effect to be due to the large dynamic asymmetry in the mixtures as evidenced by DSC experiments. More interestingly, the NSE results at longer times reveal a spectacular increase of the explored volume of PEO chains in the all-polymer nanocompo...

Crystallization behaviour of poly(ethylene oxide) under confinement in the electrospun nanofibers of polystyrene/poly(ethylene oxide) blends.

We have studied the confined crystallization behaviour of poly(ethylene oxide) (PEO) in the electrospun nanofibers of the phase-separated blends of polystyrene (PS) and PEO, where PS was present as the major component. The size and shape of PEO domains in the nanofibers were considerably different from those in the cast films, presumably because of the nano-dimensions of the nanofibers and the extensional forces experienced by the polymer solution during electrospinning. The phase-separated morphology in turn influenced the crystallization behaviour of PEO in the blend nanofibers. At a PEO weight fraction of ≥0.3, crystallization occurred through a heterogeneous nucleation mechanism similar to that in cast blend films. However, as the PEO weight fraction in the blend nanofibers was reduced from 0.3 to 0.2, an abrupt transformation of the nucleation mechanism from the heterogeneous to predominantly homogenous type was observed. The change in the nucleation mechanism implied a drastic reduction of the spatial continuity of PEO domains in the nanofibers, which was not encountered in the cast film. The melting temperature and crystallinity of the PEO crystallites developed in the nanofibers were also significantly lower than those in the corresponding cast films. The phenomena observed were reconciled by the morphological observation, which revealed that the phase separation under the radial constraint of the nanofibers led to the formation of small-sized fibrillar PEO domains with limited spatial connectivity. The thermal treatment of the PS/PEO blend nanofibers above the glass transition temperature of PS induced an even stronger confinement effect on PEO crystallization.

X-RD, SEM, FT-IR, DSC Studies of Polymer Blend Films of PMMA and PEO

Poly (methylmetacrylate)-Poly(ethylene oxide) (PMMA-PEO) polymers blend films were prepared using the solution casting method. The polymer thin films were characterized by X-ray difraction (XRD), Scanning Electron Microscopy (SEM), FTIR and differential scanning calorimetry (DSC) technique. The amorphous or crystalline nature of polymers has been confirmed by XRD analysis. The PMMA surface morphology shows rough surface and micro pore structure. Appearance of rough surface in SEM micrograph of pure PEO was suggested several crystalline domains. The surface morphology changes severely when PEO added to PMMA polymer, which shows the development of surface morphology from smooth to rough with increasing of PEO concentration in PMMA. FT-IR data shows that some of the bands found to be shifted and intensities of some of the bands are decreased and some are disappeared with the addition of PEO to PMMA when compared to pure PMMA and PEO, which suggests the coordination/ interaction between PMMA and PEO matrixes. DSC results showed that the melting temperatures (Tm) of PMMA and PEO blend decreases when compared to pure PEO, PMMA.

Hydrophobic/hydrophilic P(VDF‐TrFE)/PHEA polymer blend membranes

ABSTRACTPolymer blend membranes have been obtained consisting of a hydrophilic and a hydrophobic polymers distributed in co‐continuous phases. In order to obtain stable membranes in aqueous environments, the hydrophilic phase is formed by a poly(hydrohyethyl acrylate), PHEA, network while the hydrophobic phase is formed by poly(vinylidene fluoride‐co‐trifluoroethylene) P(VDF‐TrFE). To obtain the composites, in a first stage, P(VDF‐TrFE) is blended with poly(ethylene oxyde) (PEO), the latter used as sacrificial porogen. P(VDF‐TrFE)/PEO blend membranes were prepared by solvent casting at 70°C followed by cooling to room temperature. Then PEO is removed from the membrane by immersion in water obtaining a P(VDF‐TrFE) porous membrane. After removing of the PEO polymer, a P(VDF‐TrFE) membrane results in which pores are collapsed. Nevertheless the pores reopen when a mixture of hydroxethyl acrylate (HEA) monomer, ethyleneglycol dimethacrylate (as crosslinker) and ethanol (as diluent) is absorbed in the membrane and subsequent polymerization yields hybrid hydrophilic/hydrophobic membranes with controlled porosity. The membranes are thus suitable for lithium‐ion battery separator membranes and/or biostable supports for cell culture in biomedical applications. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016, 54, 672–679

Effect of PEO molecular weight on the miscibility and dynamics in epoxy/PEO blends.

In this work, the effect of poly(ethylene oxide) (PEO) molecular weight in blends of epoxy (ER) and PEO on the miscibility, inter-chain weak interactions and local dynamics were systematically investigated by multi-frequency temperature modulation DSC and solid-state NMR techniques. We found that the molecular weight (M(w)) of PEO was a crucial factor in controlling the miscibility, chain dynamics and hydrogen bonding interactions between PEO and ER. A critical PEO molecular weight (M(crit)) around 4.5k was found. PEO was well miscible with ER when the molecular weight was below M(crit), where the chain motion of PEO was restricted due to strong inter-chain hydrogen bonding interactions. However, for the blends with high molecular weight PEO (M(w) > M(crit)), the miscibility between PEO and ER was poor, and most of PEO chains were considerably mobile. Finally, polarization inversion spin exchange at magic angle (PISEMA) solid-state NMR experiment further revealed the different mobility of the PEO in ER/PEO blends with different molecular weight of PEO at molecular level. Based on the DSC and NMR results, a tentative model was proposed to illustrate the miscibility in ER/PEO blends.

Release of allyl isothiocyanate from mustard seed meal powder entrapped in electrospun PLA–PEO nonwovens

Defatted mustard seed meal powder (MSMP) is a natural source of allyl isothiocyanate (AITC) — a potent antimicrobial volatile released from Brassicaceae plants when a glucosinolate (sinigrin) in the plant tissues is hydrolyzed in a myrosinase-catalyzed reaction. This study demonstrated the feasibility of entrapping MSMP particles in nonwovens produced by electrospinning poly(lactic acid)–poly(ethylene oxide) (PLA–PEO) blends into ultrafine fibers. Although MSMP particles were larger than the electrospun PLA–PEO fibers, results from scanning electron microscopy showed that the mustard seed particles were physically entrapped and uniformly dispersed within the nonwovens. Moreover, the surface of the MSMP was fully covered by the polymer blend. By changing the PLA–PEO blend ratio, AITC release rate and quantity released could be manipulated readily. Specific interactions between PLA, PEO and MSMP were not detected with Fourier transform infrared spectroscopy. However, differential scanning calorimetry showed that components from MSMP interfered with the chain packing of the crystalline phases of both polymers, lowering their melting temperatures. In view of the well-established antimicrobial properties of AITC, the RH-sensitive MSMP-containing nonwovens potentially can be useful in active food packaging applications. Further studies involving specific foods will shed light on the extent by which the active nonwovens affect product shelf-life.

Polymer-ionic liquid ternary systems for Li-battery electrolytes: Molecular dynamics studies of LiTFSI in a EMIm-TFSI and PEO blend.

This paper presents atomistic molecular dynamics simulation studies of lithium bis(trifluoromethane)sulfonylimide (LiTFSI) in a blend of 1-ethyl-3-methylimidazolium (EMIm)-TFSI and poly(ethylene oxide) (PEO), which is a promising electrolyte material for Li- and Li-ion batteries. Simulations of 100 ns were performed for temperatures between 303 K and 423 K, for a Li:ether oxygen ratio of 1:16, and for PEO chains with 26 EO repeating units. Li(+) coordination and transportation were studied in the ternary electrolyte system, i.e., PEO16LiTFSI⋅1.0 EMImTFSI, by applying three different force field models and are here compared to relevant simulation and experimental data. The force fields generated significantly different results, where a scaled charge model displayed the most reasonable comparisons with previous work and overall consistency. It is generally seen that the Li cations are primarily coordinated to polymer chains and less coupled to TFSI anion. The addition of EMImTFSI in the electrolyte system enhances Li diffusion, associated to the enhanced TFSI dynamics observed when increasing the overall TFSI anion concentration in the polymer matrix.