Kinetics of Isothermal and Nonisothermal Crystallization of Poly(ethylene oxide) (PEO) in PEO/Fatty Acid Blends

In this work, isothermal and nonisothermal crystallization kinetics of poly(ethylene oxide) (PEO) and PEO in PEO/fatty acid (lauric and stearic acid) blends, that are used as thermal energy storage materials, was studied using differential scanning calorimetry (DSC) data. The Avrami equation was adopted to describe isothermal crystallization of PEO and nonisothermal crystallization was analyzed using both the modified Avrami approach and Ozawa method. Avrami exponent (n) for PEO crystallization was in the range 1.08–1.32 (10–90% relative crystallinity), despite of spherulites formation, while for PEO in PEO/fatty acid blends n was between 1.61 and 2.13. Hoffman and Lauritzen theory was applied to calculate the activation energy of nucleation (K_g) – the lowest value of K_g was observed for pure PEO, despite of heterogeneous nucleation of fatty acid crystals in PEO/fatty acid blends. For nonisothermal crystallization of PEO in PEO/lauric acid (1:1 w/w) and PEO/stearic acid (1:3 w/w) blends, secondary crystallization occurred and values of the Avrami exponent were 2.8 and 2.0, respectively. The crystallization activation energies of PEO were determined to be ?260 kJ/mol for pure PEO, ?538 kJ/mol for PEO/lauric acid blend, and ?387 kJ/mol for PEO/stearic acid blend for isothermal crystallization and ?135,6 kJ/mol, ?114,5 kJ/mol, and ?92,8 kJ/mol, respectively, for nonisothermal crystallization.     

Maleic Acid–alt–Styrene Copolymer as Compatibilizer for Poly(Ethylene Oxide)-Poly(Styrene)Blends

Maleic acid-alt-styrene (MAaS) copolymer with number-average molecular weight [Mbar] _n = 2500 was used as a compatibilizer in blends of poly(ethylene oxide) (PEO) and poly(styrene) (PS). PEO with weight-average molecular weight [Mbar] _w = 10⁵ (PEO₁₀₀) and two PS samples with [Mbar] _w = 9 × 10⁴ and 4 × 10⁵, respectively (PS₉₀ and PS₄₀₀, respectively) were used. A depression of the melting temperature T _m of PEO in blends containing MAaS relative to pure PEO and PEO/PS blends was observed. The melting enthalpy ΔH _m for the PEO/PS blends containing MAaS was lower than those of pure PEO and PEO/PS blends without compatibilizer. The crystallization kinetics of PEO and the blends were studied by differential scanning calorimetry (DSC) at different crystallization temperatures T _c. Flory-Huggins interaction parameters χ₁₂ for the blends were estimated. Their values are in good agreement with those obtained for similar systems and suggest that the free energy of mixing ΔG _mix should be negative. Polarized optical microscopy shows differences in the macroscopic homogeneity of the blends containing compatibilizer that could be attributed to a compatibilization process.     

A novel PEO-based blends solid polymer electrolytes doping liquid crystalline ionomers

A novel PEO-based blends solid polymer electrolytes doping liquid crystalline ionomers (LCI), PEO/PMMA/LiClO₄/LCI, and PEO/LiClO₄/LCI were prepared by solution casting technology. Scanning electron microscope (SEM) and energy-dispersive spectroscopy (EDS) analysis proved that LCI uniformly dispersed into the solid electrolytes and restrained phase separation of PEO and PMMA. Differential scanning calorimetry (DSC) results showed that LCI decreases the crystallinity of blends solid polymer electrolytes. Thermogravimetric analysis (TGA) proved LCI not only improved thermal stability of PEO/PMMA/LiClO₄ blends but also prevent PEO/PMMA from phase separation. Infrared spectra results illustrated that there exists interaction among Li⁺ and O, and LCI that promotes the synergistic effects between PEO and PMMA. The EIS result revealed that the conductivity of the electrolytes increases with LiClO₄ concentration in PEO/PMMA blends, but it increases at first and reaches maximum value of 2.53?×?10^?4 S/cm at 1.0 % of LCI. The addition of 1.0 % LCI increases the conductivity of the electrolytes due to that LCl promoting compatibility and interaction of PEO and PMMA. Under the combined action of rigidity induced crystal unit, soft segment and the terminal ionic groups in LCI, PEO/PMMA interfacial interaction are improved, the reduction of crystallinity degree of PEO leads Li⁺ migration more freely.     

Fabrication and characterization of polymer blends consisting of cationic polyallylamine and anionic polyvinyl alcohol

Thin sheets of polyallylamine (PAAm) and polyvinyl alcohol (PVA) blend were prepared by employing solution casting technique for potential membranes application. The blends were characterized by Fourier transform infrared (FTIR) and ¹H-NMR spectroscopy, scanning electron microscopy, thermogravimetric analysis, ultraviolet–visible spectroscopy, X-ray diffraction, and mechanical properties. The zeta potential, conductivity and rheological properties of PAAm/PVA blends were also studied. The FTIR spectrum reveals that the C–H asymmetric stretching vibration band of PVA at 2,928 cm^?1 disappeared in all the blend samples. Thermal stability of the blend membrane was better than pure polymers. The crystallinity of the PAAm/PVA blends was decreased, which may be due to the entanglement of PAAm in to PVA chains, which is also responsible for the improvement in the mechanical properties of the blends. Zeta potential decreases where as the conductivity increases as a function of temperature. Hydrophilicity is improved by addition of PVA to PAAm, which may be due to hydroxyl group of PVA. The blend solution shows non-Newtonian character of the liquid. By applying shear stress, increase in the effect of rarefaction was observed. The knowledge about the investigated parameters will be of vital importance for use of the blended material in membrane applications, especially where CO₂ separation is in focus. The membrane performance (separation properties) of the PAAm/PVA blended material is, however, not reported in the current article.     

Infrared and conductivity studies on blends of PMMA/PEO based polymer electrolytes

Poly(methylmetacrylate)/poly(ethylene oxide) (PMMA/PEO) based polymer electrolytes were synthesized using the solution cast technique. Four systems of PMMA/PEO blends based polymer electrolytes films were investigated:

1. PMMA/PEO system,
2. PMMA/PEO + ethylene carbonate (EC) system,
3. PMMA/PEO + lithium hexafluorophosphate (LiPF₆) system and
4. PMMA/PEO + EC + LiPF₆ system.

The polymer electrolytes films were characterized by Impedance Spectroscopy and Fourier Transform Infrared Spectroscopy (FTIR). The FTIR spectra show the complexation occurring between the polymers, plasticizer and lithium salt. The FTIR results give further insight in the conductivity enhancement of PMMA/PEO blends based polymer electrolytes.     

聚合物O-PPV的链间相互作用的研究

近年来,聚对苯乙炔(PPV)及其衍生物作为一类性能优良的电致发光材料而受到人们的广泛关注[1].这是因为聚合物发光材料能通过化学裁剪方法来改善发光效率、颜色、成膜性等特性.载流子形成激子以及激子的辐射和非辐射衰减过程向来是聚合物发光二极管(LEDs)发光的重要环节,因此研究聚合物的光物理过程对提高器件的发光特性是非常重要的.     

Preparation and Properties of Polyvinyl Alcohol/Collagen Hydrogel

Hydrogel scaffolds based on poly(vinyl alcohol) (PVA) collagen films were prepared by a chemical cross-linking method. The effects of the contents of PVA and cross-linker on compressive strength and swelling ratio were studied, and the effect of the pH value of the immersion medium on the swelling ratio was also investigated. The results showed that the introduction of PVA improved the compressive strength of PVA/collagen hydrogel, and the swelling ratio of the hydrogel scaffold increased with increasing PVA content in the blends. With increasing cross-linker content, the swelling ratio decreased; however, the compressive strength increased. The swelling ratio of PVA/collagen scaffold increased when pH was decreased. In conclusion, swelling ratio and compressive strength in PVA/collagen blends can be controlled by variation of their contents, cross-linking agent content, and pH value.     

Properties of nano-ZnO/poly(vinyl alcohol)/poly(ethylene oxide) composite thin films

A series of poly(vinyl alcohol)/nano-ZnO composites were prepared by dispersing nano-ZnO in aqueous solutions containing mixtures of the biodegradable polymers poly(vinyl alcohol) (PVA) and poly(ethylene oxide) (PEO), and composite thin films were prepared by casting. The introduction of nano-ZnO into PVA/PEO mixed solutions significantly decreased the resistivity of the solutions. Ultraviolet absorption, thermal behaviour and visco-elastic properties of the thin films were determined as a function of nano-ZnO content up to 15 wt%. Optimum film properties were obtained with 1 wt% nano-ZnO, higher proportions of nano-ZnO resulting in agglomeration of ZnO particles and deterioration in film properties. The Forouhi and Bloomer model was used for the modelling of ZnO thin films.     

Influence of Blend Composition on Crystallization of Poly(L-Lactic Acid)/Poly (Ethylene Oxide) Crystalline/Crystalline Blends

The effect of blend composition on crystallization morphology and behavior of a crystalline/crystalline blend, poly(l-lactic acid) (PLLA)/poly(ethylene oxide) (PEO), during slow, non-isothermal crystallization was studied by polarized light microscopy (PLM) connected with a hot-stage and differential scanning calorimetry (DSC). The results showed that all of the PLLA/PEO blends produced spherulites which gradually became bigger and looser, as well as coarser, with the increment of the PEO content, indicating that the PEO crystals was resided in the interlamellar or interfibrillar (between clusters of commonly oriented lamellae) regions of the PLLA spherulites. In the (25/75) and (10/90) blends, the nucleation and growth processes of the PEO spherulites could be clearly observed in the pre-existing PLLA spherulites. The onset crystallization temperature and the melting point of one component decreased with increasing the content of the other one owing to the good miscibility of the two components in the non-crystalline state and the interaction between their macromolecules, indicating that the crystallization of each component was influenced by the other one.     

Interfacial morphology and friction properties of thin PEO and PEO/PAA blend films

The scanning force microscope (SFM) was used to investigate morphology of poly(ethylene oxide) (PEO) and poly(acrylic acid) (PAA) blend. The effect of solvent and dewetting in surface structure of PEO film was reported. The results manifested that the crystallization of PEO could be suppressed completely in ultrathin region via using chloroform as a solvent, and the branched-like crystallization was recovered after dewetting. Also, the effect of thickness, the ratio of PEO/PAA and dewetting in surface morphology of PEO-PAA blend films were investigated. These results showed that the crystallization was highly dependent on the ratio of PEO/PAA and the thickness of blend film. Furthermore, we assembled the PEO/PAA layer-by-layer film by spin-casting method for the first time, which exhibited highly efficiency. As a complementary tool, we also used lateral force microscopy (LFM) to explore surface information of these films. The result was indicative of interfacial constraints in ultrathin region, and also was supported by the results showing the spin-casting PEO/PAA blends rather than heterogeneous mixture.     

Dielectric spectroscopy and viscosity studies of aqueous poly(ethylene oxide) and poly(vinyl pyrrolidone) blend

The complex dielectric function, electric modulus, impedance and ac electrical conductivity behaviour of aqueous solutions of 5 wt% poly(ethylene oxide) (PEO) and poly(vinyl pyrrolidone) (PVP) and their different volume percent blends were investigated in the frequency range 20 Hz to 1 MHz at 15, 30 and 45 °C. It is found that the real part of dielectric function of these blends at 1 MHz decreases with the increase of PEO concentration and their dc electrical conductivity has strong correlation with the electrode polarization relaxation time. The static permittivity, ionic conductivity, electrode polarization relaxation time and apparent viscosity have linear behaviour with temperature variation at fixed volume concentration of the aqueous polymers blend. The viscosity of these aqueous polymeric blends increases with the increase of PEO concentration. The behaviour of hydrogen bond interactions between the polar segments of PEO and PVP were explored from the comparative change in dielectric parameters and viscosity of the two phase aqueous polymeric systems.     

Conductivity studies of poly(ethylene oxide)(PEO)/poly(vinyl alcohol) (PVA) blend gel polymer electrolytes for dye-sensitized solar cells

Poly(ethylene oxide)(PEO)–poly(vinyl alcohol) (PVA) blend-based gel polymer electrolytes (GPEs) have been prepared by blending equal weights of PEO and PVA in ethylene carbonate (EC), dimethyl sulfoxide (DMSO), tetrabutylammonium iodide (TBAI), and iodine crystals (I₂). The conductivity, diffusion coefficient, number density, and ion mobility of the electrolytes have been calculated from the impedance data obtained from electrochemical impedance spectroscopy (EIS) measurements. The GPE with the composition of 7.02 wt%, PVA, 7.02 wt% PEO, 30.11 wt% ethylene carbonate (EC), 30.11 wt% DMSO, 24.08 wt% TBAI and 1.66 wt% I₂ exhibits the highest conductivity of 5.5 mS cm^?1 at room temperature. Dye-sensitized solar cells (DSSCs) with configuration fluorine tin oxide (FTO)/titanium dioxide/N3-dye/GPE/platinum/FTO have been fabricated and tested under the white light of intensity 100 mW cm^?2. The DSSC containing the highest conducting GPE exhibits the highest power conversion efficiency, η of 5.36 %.     

半胱氨酸作为耦联剂制备的纳米银膜上的SERS研究

在直流10V电压下电解聚乙烯醇和硝酸银的混合液3h制备纳米银胶,将经过半胱氨酸修饰后的载玻片浸入银胶24h制得纳米银膜。用紫外可见分光光度计对银胶进行了观测,由于其吸收峰半高宽较窄可知银胶中纳米银颗粒粒径分布较为均匀。同时,使用扫描电镜对银膜进行了表征。通过对半胱氨酸分子SERS信号的分析得出了纳米银粒子在玻璃表面上可能的组装方式。以结晶紫(Crystal Violet)和孔雀石绿(Malachite Green)作为探测分子,采用便携式拉曼光谱仪测得两种分子不同浓度下的SERS谱。发现该方法所制得的纳米银膜有很好的表面增强效果。最后分析了半胱氨酸分子SERS信号对探针分子光谱的影响。     

Preparation and dispersive mechanism of highly dispersive ultrafine silver powder

Using ascorbic acid as the reducing agent, AgNO₃ as the source of Ag, the ultrafine silver powder was prepared by liquid-phase reduction method. The optimal conditions to prepare the ultrafine silver powder were obtained by studying the effects of following factors, such as the selection of dispersant, the doses of dispersant and pH, on the dispersibility of silver powder under other constant conditions. The pure ultrafine silver powder with quasi-spherical shape and mean size of 1.15 μm was synthesized under the optimal conditions of polyvinyl alcohol (PVA) as disperser, PVA/AgNO₃ mass ratio of 4:100 and pH 7 while maintaining other conditions exactly in the same circumstances, such as AgNO₃ concentration of 0.20 mol L⁻¹, ascorbic acid concentration of 0.15 mol L⁻¹ and reaction temperature of 40 °C. The ultrafine silver powder was characterized by SEM and XRD. And a PVA dispersive mechanism for preparing highly dispersive ultrafine silver powder, proved by the ultraviolet spectra, is that PVA absorbed on the surface of silver particles by coordination bond preventing the silver particles from diffusion and aggregation. In addition, the steric effect may help to reduce aggregation.     

Nanostructured Thermosetting Blends of Phenolic Thermosets and Poly(ethylene oxide)‐block‐poly(propylene oxide)‐block‐poly(ethylene oxide) Triblock Copolymer

The amphiphilic triblock copolymer, poly(ethylene oxide)‐block‐poly(propylene oxide)‐block‐poly(ethylene oxide) (PEO‐b‐PPO‐b‐PEO) was incorporated into novolac resin to prepare thermosetting blends. The morphology of the thermosetting blends was investigated by means of atomic force microscopy (AFM) and small‐angle x‐ray scattering (SAXS) and the nanostructures were obtained. It was identified that the reaction‐induced phase separation occurred in the blends of phenolic thermosets with the model poly(propylene oxide) (PPO), whereas poly(ethylene oxide) (PEO) was miscible with novolac resin after and before the curing reaction. In terms of miscibility and phase behavior of the subchains of the triblock copolymer with novolac resin, it was demonstrated that the formation of nanostructures in the thermosets followed a mechanism of reaction‐induced microphase separation.     

Shape Memory Properties of Melt-Blended Olefin Block Copolymer (OBC)/Ethylene-Vinyl Acetate Blends

The completely crosslinked shape memory polymer blends (SMPs) traditionally suffer from recycling problems due to their network structure. In this paper we describe the thermal, mechanical, and shape memory behavior of physical blends of OBC (Olefin block copolymer) and EVA (Ethylene-vinyl acetate copolymer), with and without modification of one or both of the components, prepared using a melt-blending method. These behaviors of the modified blends, based on maleated OBC (OBC-g-MA) and/or vinyltriethoxysilane (VTEOS) modified EVA, included OBC/EVA-g-VTEOS, OBC-g-MA/EVA, and OBC-g-MA/EVA-g-VTEOS blends; they were investigated to compare with the OBC/EVA blend. The SEM (scanning electron microscopy) observations showed that the compatibility of the silane and maleic anhydride modified OBC/EVA blends were better than that of the unmodified OBC/EVA blend. The crystallization temperatures of OBC and EVA in the modified blends were higher than those in the neat blend. The OBC-g-MA/EVA-g-VTEOS blend had the highest modulus and thermal stability of all investigated blend systems due to the numerous interactions between maleic anhydride and silane. The shape memory performance, as defined by the shape fixity ratio (R_f) and shape recovery ratio (R_r), was higher for the modified blends of one or both of the modified components than that for the OBC/EVA blend. These modified blends were readily reprocessible, like thermoplastic vulcanizates, and still retained shape memory behavior, in contrast with the fully crosslinked shape memory polymer blends; thus they were also improved in terms of the environmental aspects of processing.     

Composite doped emeraldine–polyethylene oxide-bonded lithium-ion nano-tin anodes with electronic–ionic mixed conduction

Mixed-conducting lithium-ion doped emeraldine polyaniline (PAni)–polyethylene oxide (PEO) blends have been developed to achieve an optimal electronic–ionic conductivity balance in nano-tin composite anodes. Electrochemical evaluation was performed on the anodes with differing electrode preparation procedures, doping methods and PEO contents. Results indicate that both good electronic and ionic conductivity in the binder are required for rapid lithium insertion/extraction and low polarization. This doped PAni–PEO polymer blend is an attractive binder for high capacity composite anodes with low polarization.     

Surface properties of UV-irradiated poly(vinyl alcohol) films containing small amount of collagen

The surface properties of poly(vinyl alcohol) (PVA) films in the presence of 1%, 3% and 5% of collagen before and after UV-irradiation have been studied by atomic force microscopy (AFM) and by contact angle measurements. PVA films have been obtained by solvent evaporation from water solution of PVA and PVA containing small amount of collagen. After drying, the samples were irradiated with UV light wavelength λ = 254 nm in air. Surface properties before and after UV-irradiation were observed using AFM. Contact angles of two liquids: diiodomethane (D) and glycerol (G) on polymeric films were measured at constant temperature using goniometer.The results have shown that the contact angle and the surface free energy for PVA films were altered by UV-irradiation. These alterations indicate photooxidation and an increase of polarity of the surface. The comparison of surface properties of PVA films and PVA containing collagen points out that collagen is more sensitive to photooxidation than PVA and PVA/collagen blends. PVA films containing collagen easier undergo photooxidation process with formation of new polar groups than pure PVA films.     

Thermally Stimulated Depolarization Current and Thermal Analysis Studies of Gamma Irradiated Lithium‐Salt/Polymer Electrolyte Blends

Thermally stimulated depolarization current (TSDC) and thermal analysis studies of gamma irradiated LiOH/PVA blends were done. To study the mechanisms of conduction and TSDC in poly(vinyl alcohol) (PVA) and LiOH/PVA blends, short circuit TSDC at a polarizing temperature 353 K with a polarizing field of 3 kV cm^?1 have been analyzed in the temperature range 300–410 K. Two peaks are evident from the global TSDC measurements on the pure PVA homopolymer. Meanwhile, in all blended samples; there is only one broad peak with a shoulder on the high temperature side due to the relaxation of the poly‐blend system. The temperature dependence, 300–408 K, of the current density (J) for pure PVA and its blended samples has been studied. It was observed that J values increase dramatically with increasing temperature (in the low temperature region from 300–340 K) owing to the formation of local ordered regions in the otherwise disordered amorphous matrix of PVA. Further increase in the temperature caused a marginal increase in J values. The temperature dependence of the specific heat for all samples was measured. A linear increase of C _p was observed with an increase in temperature, which is ascribed to the increase in lattice vibration of linear macromolecules and consequently, increases in the number of internal degree of freedom of phonons.     

水稻白叶枯病菌生理小种在纳米银膜上的表面增强拉曼光谱初探

用硝酸银和聚乙烯醇混合溶液作为电解液,把载玻片放入电解液中,用银棒作为电极在直流电压下电解1 h,使载玻片在电解出的银胶中静置12 h后,取出晾干,即得制备的银膜。用便携式拉曼光谱仪测得在银膜上的白叶枯病菌7个生理小种的表面增强拉曼光谱(SERS)。7个生理小种分别是1-YN1, 2-YN7, 3-YN11, 4-GD414, 5-SCYC6, 6-HEN11, 7-FWJ, 7个生理小种的SERS谱在峰位及峰的相对强度上都有很多差别。这可用于生理小种的鉴别。因为银膜上的纳米银颗粒是银胶中银颗粒的聚合体,这种聚合体大大缩小了纳米银之间的距离,从而产生了很强的电磁增强作用。电解法制备的银膜价格低廉,增强效果好,普通实验室便可以制备。此研究为快速、方便检测白叶枯病菌不同生理小种提出了一种新的方法,对白叶枯病的防治具有重要的意义。