Lithium ion conducting solid polymer blend electrolyte based on bio-degradable polymers

Lithium ion conducting polymer blend electrolyte films based on poly(vinyl alcohol) (PVA) and poly(vinyl pyrrolidone) (PVP) with different Mwt% of lithium nitrate (LiNO₃) salt, using a solution cast technique, have been prepared. The polymer blend electrolyte has been characterized by XRD, FTIR, DSC and impedance analyses. The XRD study reveals the amorphous nature of the polymer electrolyte. The FTIR study confirms the complex formation between the polymer and salt. The shifts in T _g values of 70 PVA–30 PVP blend and 70 PVA–30 PVP with different Mwt% of LiNO₃ electrolytes shown by DSC thermograms indicate an interaction between the polymer and the salt. The dependence of T _g and conductivity upon salt concentration has been discussed. The ion conductivity of the prepared polymer electrolyte has been found by a.c. impedance spectroscopic analysis. The PVA–PVP blend system with a composition of 70 wt% PVA: 30 wt% PVP exhibits the highest conductivity of 1·58 × 10^???6 Scm^???1 at room temperature. Polymer samples of 70 wt% PVA–30 wt% PVP blend with different molecular weight percentage of lithium nitrate with DMSO as solvent have been prepared and studied. High conductivity of 6·828 × 10^???4 Scm^???1 has been observed for the composition of 70 PVA:30 PVP:25 Mwt% of LiNO₃ with low activation energy 0·2673 eV. The conductivity is found to increase with increase in temperature. The temperature dependent conductivity of the polymer electrolyte follows the Arrhenius relationship which shows hopping of ions in the polymer matrix. The relaxation parameters (ω) and (τ) of the complexes have been calculated by using loss tangent spectra. The mechanical properties of polymer blend electrolyte such as tensile strength, elongation and degree of swelling have been measured and the results are presented.     

Flexible and Tough Poly(lactic acid) Films for Packaging Applications: Property and Processability Improvement by Effective Reactive Blending

This study demonstrates a practical means to overcome inherent brittleness problem of poly(lactic acid) (PLA) and make PLA feasible as packaging material. PLA with suitable processability is utterly required for package manufacturers, where flexible, tough PLA film is essential for packers and end users. Highly flexible PLA films with 60‐fold increase in elongation at break (Eb) over that of the neat PLA were successfully produced by integrating effective reactive blending and economical film blowing process. The ‘two‐step’ blending was used to prepare PLA compound; poly(butylene adipate‐co‐terephthalate) (PBAT – another biodegradable polymer) was first blended with 0.5–1% chain extender (epoxy‐functionalized styrene acrylic copolymer) (ESA), followed by subsequent blending with PLA in twin‐screw extruder. Blown films of reactive blend of PLA/PBAT/ESA (80/20/1) showed impressively high Eb of 250% versus a very low Eb of 4% for the neat PLA. Resulting blown films still possessed high modulus of 2 GPa, yield stress of 50–60 MPa and good toughness of ~100 MPa. Significant enhancement in the film's ductility was attributed to homogeneous blend with developed fine strand‐like structure as a result of effective in situ compatibilization and good interfacial adhesion between the PLA and PBAT. PLA/PBAT/ESA blend also offered improved processability. Resulting films had acceptable haze of ~10% for common packaging, and clearer film close to PLA (≤2%) could be obtained by designing PLA skin layers in multilayer structure. Films of PLA/PBAT/1%ESA exhibit potential as packaging material; their mechanical and optical properties are comparable with or even exceed some existing films used in the market. Copyright © 2015 John Wiley & Sons, Ltd.     

E-MA-GMA三嵌段共聚物对聚乳酸的增韧改性

在聚乳酸(PLA)中加入不同比例的乙烯-丙烯酸乙酯-甲基丙烯酸缩水甘油酯三嵌段共聚物(E-MA-GMA)对其进行增韧改性。用傅立叶变换红外光谱仪和旋转流变仪分别对体系的反应进行表征;用熔融指数测量仪和旋转流变仪对体系的流变性能进行表征;同时测试材料力学性能并观察样条微观结构以考察E-MA-GMA对PLA的增韧效果。结果表明:E-MA-GMA的环氧官能团与PLA的端羧基和端羟基发生反应,使得共聚物与PLA有一定的相容性,PLA的冲击性能得到了明显的提高,含20%E-MA-GMA(质量分数)的共混物冲击强度较纯PLA提高了329.7%。     

Toughening of brittle poly(lactide) with hyperbranched poly(ester-amide) and isocyanate-terminated prepolymer of polybutadiene

Abstract  

The use of polylactide (PLA) in durable applications is currently being hampered by its brittleness and low impact strength. In this study, the effects on mechanical properties of two potential toughening agents for PLA, i.e., hydroxyl-terminated hyperbranched poly (ester amide) and isocyanate-terminated prepolymer of butadiene (ITPB), alone and in combination, are investigated with the aim of making tough PLA blends for use in durable non-food applications such as automotive interior. Synergistic effects in impact strength were observed in PLA ternary blends containing hyperbranched polymer (HBP) and ITPB. Impact strength of the PLA/HBP/ITPB ternary blend was improved by over 86 %, while the elongation at break was increased by over 100 %. Physical and chemical interactions between the hydroxyl-terminated HBP and the ITPB may be responsible for the observed synergistic effect and improvements in impact strength. Tensile, flexural, thermal, and thermo-mechanical properties of the PLA/HBP blends with varying amounts of the ITPB were studied. Scanning electron microscopy images showed evidence of stretched polymer which may indicate that the fracture behavior of PLA changed from brittle to ductile in the PLA/HBP/ITPB ternary blends.     

MFC-structured biodegradable poly(l-lactide)/poly(butylene adipate-co-terephatalate) blends with improved mechanical and barrier properties

Both polylactide (PLA) and poly(butylene adipate-co-terephthalate) (PBAT) are biodegradable polymers. They are thermoplastics which can be processed using conventional polymer processing methods. In this study, microfibrillar-reinforced composites (MFC) based on PLA/PBAT (PLA/Ecoflex^®) blends in different weight ratios were prepared under industry-relevant conditions by melt extrusion followed by continuous cold drawing of the extrudates. Strip-like specimens (films) and plates (laminates) of the drawn blends were prepared by compression molding (CM) at processing temperature above the melting temperature (T _m) of PBAT, but below T _m of PLA. SEM and WAXS observations show that the extruded blend components are isotropic, but become highly oriented after drawing, and they are converted into MFC-structured polymer–polymer composites after CM. An effect of PLA microfibrils on the non-isothermal crystallization of the Ecoflex during cooling from the melt, associated with the formation of crystalline regions of the matrix around the fibrils, was observed. Depending on the blend composition, the compression-molded samples possess a 3- to 7-time higher tensile strength as well as a 15–30 higher modulus than the neat Ecoflex. In addition, the MFC-structured plates exhibited superior barrier properties compared to the neat Ecoflex, e.g., the oxygen permeability decreased by up to 5 times.     

超韧尼龙6体系的流变与力学行为EI

马来酸酐接枝聚烯烃类热塑弹性体 (TPEg)对尼龙 6有显著的增韧效果。研究了基体粘度和界面改性剂 (CE-96 )的使用对尼龙 6 / TPEg共混体系缺口冲击强度的影响。在 TPEg分散相粘度大于尼龙 6基体粘度情况下 ,TPEg对高粘度尼龙 6的增韧效果明显好于低粘度尼龙体系。CE- 96的加入通过增大尼龙 6基体粘度和增强界面偶联显著地改善了 TPEg分散质量。在给定的分散相含量下 ,分散相颗粒尺寸的减小更有利于引发基体剪切屈服 。     

Structure and properties of polylactide/natural rubber blends

Polylactide, PLA, is a biodegradable thermoplastic polyester derived from biomass that has restricted packaging applications due to its high brittleness and poor crystallisation behaviour. Here, new formulations based on natural rubber–PLA blends have been developed. The processing windows, temperature, time, and rotor rate, and the rubber content have been optimised in order to obtain a blend with useful properties. The rubber phase was uniformly dispersed in the continuous PLA matrix with a droplet size range from 1.1 to 2.0 μm. The ductility of PLA has been significantly improved by blending with natural rubber, NR. The elongation at break improved from 5% for neat PLA to 200% by adding 10 wt% NR. In addition, the incorporation of NR not only increased the crystallisation rate but also enhanced the crystallisation ability of PLA. These materials are, therefore, very promising for industrial applications.     

Synthesis and optimization of P(MMA-BA-MAA)/PEG-based polymer gel electrolytes

A polymer gel electrolyte based on poly(methyl methacrylate-butyl acrylate-methacrylic acid)/polyethylene glycol 400 blend (P(MMA-BA-MAA)/PEG400) was successfully prepared by a simple and efficient procedure. The optimal ionic conductivity was achieved to be 3.12 mS cm^?1 at the temperature of 30 °C when the electrolyte has the composition of 20 wt% P(MMA-BA-MAA)/PEG400 blend, 0.6 M NaI, and 0.06 M I₂ in the solvent γ-butyrolactone (GBL). For tuning the ionic conductivity, various additives were introduced into the polymer gel electrolytes. The measured values of open circuit voltage, short circuit current, and total photovoltaic efficiency indicates that the adding of pyridine (PY) leads to better performance of the final dye-sensitized solar cells (DSSCs), while the adding of Guanidine thiocyante (GuSCN) leads to a worse one. 4-Tert-butylpyridine (TBP) additive takes a more complex effect on the performance of the final DSSCs. For polymer gel electrolyte with 0.5 M pyridine, the final fabricated dye-sensitized solar cell has overall energy conversion efficiency (η) of 3.63 % (0.16 cm² active area) under AM 1.5 at irradiation of 100 mW cm^?2, which reached the level of the liquid electrolyte based device (η = 3.83 % at 0.16 cm² active area). Meanwhile, this gel electrolyte exhibits well long-term stability. The mechanism analysis revealed the dependences of ionic conductivity on the concentration of polymer and NaI and the temperatures.     

Effect of membrane hydrophilization on ultrafiltration performance for biomolecules separation

This paper compares the performance of different hydrophilization methods to prepare low fouling ultrafiltration (UF) membranes. The methods include post-modification with hydrophilic polymer and blending of hydrophilic agent during either conventional or reactive phase separation (PS). The post-modification was done by photograft copolymerization of water-soluble monomer, poly(ethylene glycol) methacrylate (PEGMA), onto a commercial polyethersulfone (PES) UF membrane. Hydrophilization via blend polymer membrane with hydrophilic additive was performed using non-solvent induced phase separation (NIPS). In reactive PS method, the cast membrane was UV-irradiated before coagulation. The resulting membrane characteristic, the performance and hydrophilization stability were systematically compared. The investigated membrane characteristics include surface hydrophilicity (by contact angle /CA/), surface chemistry (by FTIR spectroscopy), and surface morphology (by scanning electron microscopy). The membrane performance was examined by investigation of adsorptive fouling and ultrafiltration using solution of protein or polysaccharide or humic acid. The results suggest that all methods could increase the hydrophilicity of the membrane yielding less fouling. Post-modification decreased CA from 44.8 ± 4.2^o to 37.8 ± 4.2^o to 42.5 ± 4.3^o depending on the degree of grafting (DG). The hydrophilization via polymer blend decreased CA from from 65^o to 54^o for PEG concentration of 5%. Nevertheless, decreasing hydraulic permeability was observed after post-modification as well as during polymer blend modification. Stability examination showed that there was leaching out of modifier agent from the membrane matrix prepared via conventional PS after 10 days soaking in both water and NaOH. Reactive PS could increase the stability of the modifier agent in membrane matrix.     

Studies on electrical conductivity and dielectric behaviour of PVdF–HFP–PMMA–NaI polymer blend electrolyte

Polymer blend electrolytes composed of poly(vinylidene fluoride-co-hexafluoro-propylene), poly(methyl methacrylate) and 1·0 M NaI as salt have been synthesized using solution caste technique by varying the PVdF(HFP)–PMMA blend concentration ratio systematically. A.c. impedance studies were performed to evaluate the ionic conductivity of the polymer electrolyte films. The highest ionic conductivity at room temperature for [PVdF(HFP)–PMMA(4:1)](20 wt%) – [NaI(1·0 M)](80 wt%) system is found to be 1·67 × 10^???2 S cm^???1. XRD studies reveal complete complexation of the salt in the polymeric blend systems. The temperature dependence conductivity has been performed in the range of 303–373 K and it is observed that it obeys the Arrhenius behaviour. It has been observed that the dielectric constant, ε _r and dielectric loss, ε _i, increases with temperature in the lower frequency region and is almost negligible in the higher frequency region. This behaviour can be explained on the basis of electrode polarization effects. Plot of real part, M _r and imaginary part, M _i vs frequency indicates that the systems are predominantly ionic conductors. The phenomenon suggests a plurality of relaxation mechanism.     

Polymer assisted preferential growth of PbS and PbS:Mn nanorods: structural and optical properties

We report here the structural and optical properties of PbS and PbS:Mn nanorods (diameter 30–80 nm) grown in a polymer (polypyrrole) matrix. X-ray diffraction data of nanorods clearly reveals preferential growth of PbS nanorods with a strong lattice distortion from a bulk cubic to tetragonal one. The strain introduced lattice distortion is inherent to the growth process and strongly depends on polymer concentration. The polymer concentration is found to play an important role in controlling the structural properties. The effect of Mn²⁺ incorporation into PbS lattice shows no appreciable change in the structural properties. Optical absorption behaviors in such PbS and PbS:Mn nanorods are also reported. The absorption peak energy shows blue-shift with increase in Mn²⁺ concentration to some critical value beyond which red-shift is observed.     

Solution blow spinning: parameters optimization and effects on the properties of nanofibers from poly(lactic acid)/dimethyl carbonate solutions

Solution blow spinning (SBS) is a process to produce non-woven fiber sheets with high porosity and an extremely large amount of surface area. In this study, a Box–Behnken experimental design (BBD) was used to optimize the processing parameters for the production of nanofibers from polymer solutions consisting of poly(lactic acid) (PLA) dissolved in dimethyl carbonate. In addition, a comparative study between SBS fibers and cast film was performed to verify the influence of the SBS process on the crystallinity and thermal properties of PLA. The PLA concentration in polymer solutions was the most significant parameter affecting fiber diameter. The BBD analysis revealed that small diameter fibers were best obtained by a combination of 8 % w/v PLA concentration, 80 psi air pressure, and a feed rate of 50 µL min^?1. The comparative study showed that both the SBS and the film casting processes increased the PLA crystallinity. However, the PLA films had a higher degree of crystallinity compared with the fibers made by the SBS process (39 and 17 %, respectively), which was attributed to the high shear created at the SBS nozzle inducing orientation and chain alignment. During the fiber formation, crystals formed with varied morphology including the α′-crystals, which have a less ordered structure and lower thermal stability compared to the α-crystals. The lower thermal stability of SBS fibers compared to the films can be explained by the lower degree of crystallinity and also by the higher surface area which can accelerate the weight loss process.     

Manufacture of a hydrophobic CaO/polylactic acid composite

In this study, the surface of calcium oxide (CaO) was modified with n-octadecyltrichlorosilane [CH₃(CH₂)₁₆CH₂SiCl₃] to obtain modified calcium oxide (CaO-M). CaO and CaO-M were melt-blended with polylactic acid (PLA) to prepare PLA/CaO and PLA/CaO-M, respectively. Moisture absorption measurement showed that the surface of modified CaO was changed from hydrophilic to hydrophobic. CaO and PLA had a tendency to agglomerate after blending, whereas the blend of CaO-M and PLA showed no signs of agglomeration, and the distribution of CaO-M in PLA was homogeneous. In addition, CaO-M had a heterogeneous nucleation effect on PLA, which effectively inhibited cold crystallization and promoted crystallization of PLA. In conclusion, CaO-M can be used as a nucleating agent of PLA.     

Tetracycline hydrochloride (TCH)-loaded drug carrier based on PLA:PCL nanofibre mats: experimental characterisation and release kinetics modelling

The experimental characterisation of electrospun poly(lactic acid) (PLA):poly(ε-caprolactone) (PCL) as drug carriers, at five blend ratios from 1:0, 3:1, 1:1, 1:3 and 0:1, was holistically investigated in terms of their morphological structures, crystallinity levels and thermal properties. A widely used antibiotic tetracycline hydrochloride (TCH) was loaded to prepared fibrous mats at TCH concentrations of 1 and 5 wt%. The additional TCH into PLA:PCL better facilitates the reduction of fibre diameter than polymer blends. Increasing the TCH concentration from 1 to 5 wt% was found to result in only a modest decrease in the crystallinity level, but a significant increase in the crystallisation temperature (T _c) for PLA within PLA:PCL blends. The infrared spectra of fibre mats confirm the successful TCH encapsulation into fibrous networks. The first order and Zeng models for drug release kinetics were in better agreement with experimental release data, indicating the release acceleration of TCH with increasing its concentration. In a typical case of PLA:PCL (1:1) loaded with 5 wt% TCH, the fibre mats apparently demonstrate more wrinkled and floppy structures and increased fibre diameters and decreased inter-fibrous spaces after 7-day in vitro fibre degradation, as opposed to those obtained after 3-h degradation.     

Cheaper membrane materials for microalgae dewatering

Among different strategies to reduce costs in microalgae dewatering process via cross-flow filtration, the one related to membrane material was investigated in order to be decreased. Several materials were tested, starting with the ones commonly used in membrane technology [ceramic, polysulfone (PSf) and polyacrylonitrile (PAN)] to the ones generally employed in packaging industry [acrylonitrile butadiene styrene (ABS), glycol-modified polyethylene terephthalate (PETG) and polylactic acid (PLA)], the latter being considerably cheaper. Experiments carried out showed promising results in terms of permeabilities for PSf–Pluronic^® F127 blended membranes and PAN membranes (11 ± 1 L/h/m²/bar and 22 ± 1 L/h/m²/bar, respectively, instead of 2 ± 2 L/h/m²/bar of PSf membranes), but with high related costs. PLA membranes showed good mechanical properties, biodegradability and price, but low permeability values (5 ± 1 L/h/m²/bar). PETG membranes showed attractive results in terms of costs and permeability, but poor mechanical properties. The polymer that offered the best results was the ABS that reached membrane permeabilities of 19 ± 1 L/h/m²/bar, maintaining good mechanical properties while filtering the microalgae Phaeodactylum tricornutum Bohlin. Thus, a novel functionality was found for these not so common polymers in microalgae dewatering. This indicates that use of these materials could also be considered in other aqueous micro/ultrafiltration applications. In addition, the biodegradable PLA polymer introduces a new concept of cheap and environmental friendly membrane in this application.     

Rapidly stopping hemorrhage by enhancing blood clotting at an opened wound using chitosan/polylactic acid/polycaprolactone wound dressing device

Doxycycline and monosodium glutamate (MSG) loaded chitosan (CHI)/polylactic acid (PLA)/polycaprolactone (PCL) blend film was studied as a model device to deliver drug to targeted human organ which in this case was the skin with opened wound. The CHI/PLA/PCL blend film containing 60 % CHI, 28 % PLA, and 12 % PCL exhibited the good properties for making the dressing device. It was observed that doxycycline/MSG loaded CHI/PLA/PCL blend film could rapidly deliver both doxycycline and MSG at the high release percentage approaching 100 % loaded. MSG accelerated blood clotting and fibrin formation; thus, it exhibited the good hemostatic activity. The antibacterial activity of doxycycline loaded CHI/PLA/PCL blend film against Staphylococcus aureus and Escherichia coli as model bacteria was investigated. Doxycycline release played the crucial role in bacterial inhibition as observed from the lowest bacterial cell dry weight observed when compared with the control bacterial culture or the bacterial cultures with the presence of other films studied.     

A study on compatibilization of AES/PA6 blends

Polyblends of Nylon 6 and AES were prepared and their mechanical properties and phase morphology examined. Two compatibilization techniques were evaluated: addition of a suitable block copolymer: poly(styrene-co-maleic anhydride) (SMA); AES functionalization with maleic anhydride (MA) through reactive extrusion. As a preliminary test for the compatibilizing efficiency, SMAs and PA6 were compounded in a Brabender mixer, recording the torque during the operations and evaluating, by solvent extraction, the amount of SMA grafted to PA6. However, when moving to the ternary blends AES/SMA/PA6, the highest value of notched lzod impact strength (290 J m^–1 versus 20 J m^–1) was found for an SMA sample containing 24% MA, which did not show the highest reactivity with PA6 in the preliminary test run. This finding suggests that not only the reactivity towards PA6, but also the miscibility with AES phase (the highest for the SMA product with 24% MA) must be taken into account when designing the best performing compatibilizer. On the other hand, AES functionalization with MA and DCP proved to be more successful and the resulting 50/50 blend with PA6 exhibited an outstanding value of notched Izod impact strength (1050 J m^–1)     

Study of the structure–property relationships in a high impact and shape memory polyester by the stereoisomer selection of the cyclobutane diol monomer

The diol and dicarboxylic acid in polyester synthesis are significant independent variables that relate directly to the structure–property-dependent variables of polyesters. The choice of the stereoisomers of the diol in the polyester synthesis can significantly alter the mechanical and thermal performance. Terephthalate polyesters prepared from the proper ratio of 2,2,4,4-tetramethyl-1,3-cyclobutanediol (CBDO) and 1,3-propanediol have superior impact resistance when compared to ballistics grade polycarbonate. In addition these polymers exhibit very strong self-healing behavior that is activated by heat. These copolymers were all produced with a mixture of cis and trans isomers with a ratio of 43/57, respectively. This study reports research conducted to determine the structure–property relationships that can be attributed to the stereoisomers of the CBDO monomer. The polyester prepared with 99 % cis (CBDO) monomer has significantly improved mechanical and thermal performance when compared with the polyester prepared with a 43:57 mixture of cis and trans isomers or 100 % trans isomer. Thermal gravimetric analysis and differential scanning calorimetry demonstrated that the cis CBDO polymer exhibit a much higher T _g (99 °C for cis and 69 °C for the trans 84.5 °C for the mixed polymer) and better thermal stability than the trans form of the polymer (onset of decomposition of trans at 345 and 360 °C for cis). Dynamic mechanical analysis and the Notched Izod demonstrated that the cis form of the polymer was much tougher than the trans form. Wide angle X-ray diffraction showed that the trans form was semicrystalline and the cis form was amorphous. The Notched Izod impact was 1070 J/m for the cis CBDO-based copolymer with the trans form having an impact factor of 841 J/m with the mixed polymer exhibiting an intermediate value of 944 J/M. Molecular modeling supports the experimental evidence that the choice of stereoisomers for the diol significantly influences the molecular architecture of the polyesters. The molecular architecture of polyesters in addition to polar attraction and molecular weight variables provides a dramatic increase in mechanical and thermal performance.     

Impact fracture toughness of hollow glass bead-filled polypropylene composites

The notched Izod impact properties of polypropylene (PP) filled with hollow glass beads (HGB) have been measured at room temperature to identify the effects of the particle contents, size and its distribution on them in the present paper. The mean diameters of the particles were 11, 35, and 70 μm, and named TK10, TK35 and TK70 respectively. The surface of the particles was pretreated with silane coupling agent. The results showed that the notched Izod impact strength (σ _I) of the filled systems increased gently with increasing the volume fraction (φ _f) of the fillers when φ _f was less than 15%, and then it decreased. When φ _f was 10%, σ _I decreased with an increase of the mean diameter of the particles. Furthermore, the impact fracture surface of the specimens was observed by using a scanning electron microscope (SEM). The improvement of the impact toughness of the composites might be mainly attributed to the shear yielding first of the matrix around the beads to absorb relevant deformation energy under impact load.     

高密度聚乙烯官能化和增容作用的研究

通过红外光谱分析、与水的接触角测定、力学性能测定,研究了空气中不同环境温度下紫外线辐照对高密度聚乙烯(HDPE)结构与性能的影响以及紫外辐照官能化HDPE对HDPE/聚乙烯醇(PVA)纤维体系的增容作用。实验结果表明,紫外辐照后,HDPE分子链上引入了—C(C=O)CH₃,—CH₂C(=O)CH₂—,—C(=O)O—等含氧官能团,实现了HDPE的官能化。提高环境温度可提高HDPE官能化速度。紫外辐照后,HDPE的杨氏模量和拉伸屈服强度提高,但断裂伸长率和缺口冲击强度下降。官能化HDPE对HDPE/PVA纤维共混体系有增容作用,增容后的共混物的拉伸屈服强度提高和缺口冲击强度得到提高。