Phase separation in poly(vinyl alcohol)/gelatin blend systems

Blends of a commercial poly(vinyl alcohol) (a-PVA) derived from vinyl acetate and gelatin obtained from collagen were prepared by mixing aqueous solutions of both samples under various conditions. For the blend hydrogels, the depression of melting temperatures was observed at high PVA content. Similarly to the a-PVA/silk fibroin (SF) system, when the degrees of polymerization of PVA increased, the microphase separation region in a phase diagram of the blend films increased for the a-PVA/gelatin system. In the IR spectra of the blend films, no absorption bands corresponding to a conformational change of gelatin appeared. Comparison of the mechanical properties of the a-PVA/gelatin and a-PVA/SF systems, showed the interaction between PVA and gelatin molecules to be smaller than that between PVA and SF molecules. © 1999 Society of Chemical Industry     

Phase separation structure in poly(vinyl alcohol)/silk fibroin blend films

Blend films of a commercial poly(vinyl alcohol) (a-PVA) derived from vinyl acetate and silk fibroin (SF) obtained from degummed silk were prepared by mixing the aqueous solutions of both samples. A plain weave structure was recognized only in the blend films, whereas no structure was found for the superimposed films of both samples. The phase separation structure of the blend films was examined by microscopic observations elongation, tensile tests, and IR measurements. The microphase separation region increased with increase in the degree of polymerization of the PVA. In the IR spectra of the blend films with high PVA contents cast under certain conditions, the absorption peak attributed to the cross-β-form conformation of SF appeared strongly. Gelatin, a water-soluble and natural polymer, was also used for comparison with SF. The ternary phase diagram in an a-PVA/gelatin/H₂O system was obtained experimentally and the critical point was used to estimate the interaction parameter between PVA and gelatin molecules. The phase separation structure and the interaction between PVA and SF molecules were also discussed taking into consideration the results of the a-PVA/gelatin system. © 1998 SCI.     

Improving the antifouling property of poly(vinyl chloride) membranes by poly(vinyl chloride)‐g‐poly(methacrylic acid) as the additive

To improve the antifouling property of poly(vinyl chloride) (PVC) membranes, a series of poly(methacrylic acid) grafted PVC copolymers (PVC‐g‐PMAA) with different grafting degree were synthesized via one‐step atom transfer radical polymerization process utilizing the labile chlorines on PVC backbones followed by one‐step hydrolysis reaction. PVC/PVC‐g‐PMAA blend membranes with different grafting degree and copolymer content were prepared by nonsolvent induced phase separation method. The surface chemical composition, surface charge, membrane structures, wettability, permeability, separation performances and the fouling resistance of blend membranes were carefully investigated. The results indicated that the PMAA chains were segregated towards the surface and the membranes were endowed with negative charge. The hydrophilicity and permeability of the blend membranes were obviously improved. Furthermore, the antifouling ability especially at neutral or alkaline environments was also significantly increased. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42745.     

Water‐absorptive blend fibers of copoly(acrylic acid–acrylamide) and poly(vinyl alcohol)

Through the addition of N‐hydroxymethyl acrylamide as a potential crosslinker, water‐absorptive blend fibers of copoly(acrylic acid–acrylamide) and poly(vinyl alcohol) with three‐dimensional network structures were prepared with heat‐crosslinking technology after fiber formation. Fourier transform infrared, scanning electron microscopy, dynamic mechanical analysis, and thermogravimetry were used to analyze the structures and properties of the fibers. The tensile behavior and absorbent capacities of the fibers were also studied. The results showed that there were lots of chemical crosslinking points in the fibers, the compatibility of copoly(acrylic acid–acrylamide) and poly(vinyl alcohol) was perfect, and the tensile properties of the fibers could be improved effectively through stretching in a vapor bath. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3353–3357, 2006     

Films made from poly(vinyl alcohol‐co‐ethylene) and soluble biopolymers isolated from municipal biowaste

Blends were obtained from poly(vinyl alcohol‐co‐ethylene) and water‐soluble biopolymers isolated from the alkaline hydrolysate of two materials sampled from an urban waste treatment plant: that is, an anaerobic fermentation digestate and a compost. The digestate biopolymers contained more lipophilic and aliphatic C and less acidic functional groups than the compost biopolymers. Evidence was obtained for a condensation reaction occurring between the biopolymers and the synthetic polymer. The thermal, rheological, and mechanical properties of the blends were studied. Films containing a low concentration (ca. 6–7%) of biopolymers exhibited up to three times higher yield strength than the neat synthetic polymer. The films' properties were found to be dependent on the concentration and nature of the biopolymers. The results offer a scope for investigating biopolymers sourced from other biowastes and for a better understanding of the reasons for the observed effects and exploiting their full potential for modifying or replacing synthetic polymers. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41359.     

Study on the phase behavior of ethylene–vinyl acetate copolymer and poly(methyl methacrylate) blends by in situ polymerization

This study examines the phase behavior of ethylene–vinyl acetate copolymer (EVA) and poly(methyl methacrylate) (PMMA) blends during MMA polymerization. The ternary PMMA/MMA/EVA mixtures are considered to create a triangular phase diagram, which responds the phase changes during polymerization. The phase changes during MMA polymerization are also examined by optical microscope and photometer. Since the PMMA and EVA are well‐known immiscibles, the polymer solution undergoes phase separation at the initial stage of the MMA polymerization. Additionally, the phase inversion occurs as the conversion of MMA between 13.8 and 20.8%. On the other hand, the EVA‐graft‐PMMA, which can reduce the dispersed EVA particle size, is induced efficiently by taking tert‐butyl peroctoate (t‐BO) as initiator during MMA polymerization. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1001–1008, 2003     

Synthesis and surface characterization of poly(methyl methacrylate)‐block‐polydimethylsiloxane copolymers from macroazoinitiator

Poly(methyl methyacrylate)‐block‐polydimethylsiloxane (PMMA‐b‐PDMS) copolymers with various compositions were synthesized with PDMS‐containing macroazoinitiator (MAI), which was first prepared by a facile one‐step method in our lab. Results from the characterizations of X‐ray photoelectron spectroscopy (XPS), contact angle measurements, and atomic force microscopy (AFM) showed that the copolymer films took on a gradient of composition and more PDMS segments enriched at the film surfaces, which then resulted in the low surface free energy and little microphase separation at the film surfaces. By contrast, transmission electron microscopy (TEM) analysis demonstrated that distinct microphase separation occurred in bulk. Slight crosslinking of the block copolymers led to much steady morphology and more distinct microphase separation, in particularly for copolymers with low content of PDMS. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Preparation and characterization of poly(vinyl alcohol) and gelatin blend films

Poly(vinyl alcohol) (PVA) is a water-soluble polymer that has been studied intensively because of several interesting physical properties that are useful in technical applications, including biochemical and medical applications. In this article, we report the effects of the addition of gelatin on the optical, microstructural, thermal, and electrical properties of PVA. Pure and PVA/gelatin blend films were prepared with the solution-casting method. These films were further investigated with Fourier transform infrared (FTIR), differential scanning calorimetry (DSC), X-ray diffraction (XRD), ultraviolet–visible (UV–vis) spectroscopy, and dielectric measurements. The FTIR spectrum shows a strong chemical interaction between PVA and gelatin molecules with the formation of new peaks. These peaks are due to the presence of gelatin in the blend films. The DSC results indicate that the addition of gelatin to PVA changes the thermal behavior, such as the melting temperature of PVA, and this shows that the blends are compatible with each other. This also shows that the interaction of gelatin and PVA molecules changes the crystallite parameters and the degree of crystallinity, and this supports the XRD results. The UV–vis optical study also reflects the formation of the complex and its effect on the microstructure of the blend film. Moreover, the addition of gelatin also gives rise to changes in the electrical properties of PVA/gelatin blend films. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation of PVDF/poly(tetrafluoroethylene‐co‐vinyl alcohol) blend membranes with antifouling propensities via nonsolvent induced phase separation method

Poly(vinylidene fluoride) (PVDF) was blended with a new amphiphilic copolymer, poly(tetrafluoroethylene‐co‐vinyl alcohol) [poly(TFE‐VA)], via non‐solvent induced phase separation (NIPS) method to make membranes with superior antifouling properties. The effects of the VA/TFE segment ratio of the copolymer and the copolymer/PVDF blend ratio on the properties of the prepared membranes were studied. Membranes with similar water permeabilities, surface pore sizes, and rejection properties were prepared and used in bovine serum albumin (BSA) filtrations with the same initial water flux and almost the same operating pressure, to evaluate the sole effect of membrane material on fouling propensity. While the VA/TFE segment ratio strongly affected the membrane antifouling properties, the effects of the copolymer/PVDF blending ratio were not so drastic. Membrane surface hydrophilicity increased, and BSA adsorption and fouling decreased upon blending a small amount of amphiphilic copolymer with a high VA/TFE segment ratio with PVDF (copolymer/PVDF blending ratio 1:5). © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43780.     

Morphology and rheological behavior of maltene–polymer blends. I. Effect of partial hydrogenation of poly(styrene‐block‐butadiene‐block‐styrene‐block)‐type copolymers

Because of the importance of the maltene–polymer interaction for the better performance of polymer‐modified asphalts, this article reports the effects of the molecular characteristics of two commercial poly(styrene‐block‐butadiene‐block‐styrene‐block) (SBS) polymers and their partially hydrogenated derivatives [poly{styrene‐block[(butadiene)_1?x–(ethylene‐co‐butylene)_x]‐block‐styrene‐block} (SBEBS)] on the morphology and rheological behavior of maltene–polymer blends (MPBs) with polymer concentrations of 3 and 10% (w/w). Each SBEBS and its parent SBS had the same molecular weight and polystyrene block size, but they differed from each other in the composition of the elastomeric block, which exhibited the semicrystalline characteristics of SBEBS. Maltenes were obtained from Ac‐20 asphalt (Pemex, Salamanca, Mexico), and the blends were prepared by a hot‐mixing procedure. Fluorescence microscopy images indicated that all the blends were heterogeneous, with polymer‐rich and maltene‐rich phases. The rheological behavior of the blends was determined from oscillatory shear flow data. An analysis of the storage modulus, loss modulus, complex modulus, and phase angle as a function of the oscillatory frequency at various temperatures allowed us to conclude that the maltenes behaved as pseudohomogeneous viscoelastic materials that could dissipate stress without presenting structural changes; moreover, all the MPBs were more viscoelastic than the neat maltenes, and this depended on both the characteristics and amount of the polymer. The MPBs prepared with SBEBS were more viscoelastic and possessed higher elasticity than those prepared with SBS. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Soil burial test for poly(ethylene‐co‐vinyl alcohol)‐graft‐polycaprolactone

The ring‐opening polymerization of ε‐caprolactone was carried out with poly(ethylene‐co‐vinyl alcohol) as a macroinitiator to synthesize poly(ethylene‐co‐vinyl alcohol)‐graft‐polycaprolactone (EVOH‐g‐PCL). A simple low‐density polyethylene (LDPE)/polycaprolactone (PCL) (64/36) blend lost 5.3 wt % of its original weight after 90 days of a soil burial test. However, the elongation at break of the LDPE/PCL blend remained almost invariable even after the solid burial test because the tensile properties depended mostly on the LDPE phase on account of the poor interaction between the continuous LDPE matrix and the dispersed PCL phase. For EVOH‐g‐PCL, the elongation at break decreased drastically as a result of the soil burial test, and the reduction of the elongation at break was more pronounced for EVOH‐g‐PCL with a higher PCL concentration, even though the weight loss of EVOH‐g‐PCL after the soil burial test was as low as 1.2–1.3% and was nearly independent of the PCL concentration. Few holes were observed in EVOH‐g‐PCL when the PCL concentration was less than 26 wt % after an accelerated hydrolysis experiment at 60°C for 7 days in a 0.1M KOH solution. In contrast, the hydrolysis formed small holes in EVOH‐g‐PCL with a PCL concentration of 36 wt %. The LDPE/PCL blend was much better percolated, as a result of the hydrolysis, than EVOH‐g‐PCL with the same PCL concentration; the soil burial test showed the same results. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1064–1071, 2005     

Poly(styrene‐block‐butadiene‐block‐styrene‐block‐butadiene) and poly(styrene‐block‐butadiene‐block‐methyl methacrylate) copolymers as compatibilizers in PPO–SAN blends. I. Morphology and fracture behavior

The toughness behavior of PPO–SAN blends with the modifier poly(styrene‐block‐butadiene) (SBSB) and with poly(styrene‐block‐butadiene‐block‐methyl methacrylate) copolymers (SBM) under impact loading conditions has been investigated. The observed morphology of blends compatibilized with SBM, in which the rubber phase discontinuously accumulated at the PPO–SAN interface, correlated with about 20 times higher energy dissipation up to maximum force and about seven times higher deformation capacity compared to pure PPO–SAN blends. In contrast, the fracture behavior of the SBSB‐modified blends was not as strongly dependent on the rubber content. It is especially noteworthy that although the SBM modification resulted in a strong increase in toughness of the PPO–SAN blends, no decrease in stiffness could be found with up to 15% rubber additions. The values of Young's moduli remained at the same high level of the nonmodified material. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 2037–2045, 2000     

Solution and solid‐state blend compatibility of poly(vinyl alcohol) and poly(methyl methacrylate)

The blend miscibility of poly(vinyl alcohol) and poly(methyl methacrylate) in N,N′‐dimethylformamide solution was investigated by viscosity, density, ultrasonic velocity, refractive index, and UV and fluorescence spectra studies. Differential scanning calorimetry and scanning electron microscopy were used to confirm the blend miscibility in the solid state. Blends were compatible when the concentration of poly(vinyl alcohol) was greater than 60 wt %. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2415–2421, 2006     

Release of salicylic acid through poly(vinyl alcohol)/poly(vinyl pyrrolidone) and poly(vinyl alcohol‐g‐N‐vinyl‐2‐pyrrolidone) membranes

A controlled release profile of salicylic acid (SA) for transdermal administration has been developed. Poly (vinyl alcohol) (PVA) and Poly(vinyl alcohol)/Poly(vinyl pyrrolidone) (PVP) blended preparations were used to prepare the membranes by solvent‐casting technique. The release of the drug from the membranes was evaluated at in vitro conditions. The effects of PVA/PVP (v/v) ratio, pH, SA concentration and temperature were investigated. 60/40 (v/v) PVA/PVP ratio was found to be the best ratio for the SA release. Increase in pH and temperature was observed to increase the transport of SA. Instead of blending PVA with PVP, N‐Vinyl‐2‐pyrrolidone (VP) was grafted onto the PVA and the delivery performance for SA was compared with that of the blended PVA/PVP membranes. Grafted membranes gave higher transport percentages than the blended membranes. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:1244–1253, 2006     

Reaction‐induced phase separation in poly(vinyl acetate)/polyester blend

In blends of unsaturated polyester (UP), poly (vinyl acetate) (PVAc), and styrene, a reaction‐induced phase separation occurs upon curing that is due to the crosslinking between styrene and the UP molecules. The evolution of the morphology was observed by optical microscopy on a heated stage. Light transmission was used in parallel to precisely detect the onset of phase separation and the formation of microvoids. Using Fourier transform IR spectroscopy in the same conditions, the conversions at phase separation and at microvoiding were evaluated. Phase separation occurs at a very low degree of conversion and microvoiding develops at around 60% of conversion. The final morphology of the blend was investigated by scanning electron microscopy. The relative influences of the cure temperature, the concentration in PVAc, and the molecular weight of PVAc were investigated. It was confirmed that the early stages of the reaction at high temperature determine the final morphology of the blends. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3877–3888, 2006     

Solid terpolymer electrolyte based on poly(vinyl butyral‐co‐vinyl alcohol‐co‐vinyl acetate) incorporated with lithium salt and tetraglyme for EDLCs

Solid terpolymer electrolytes (STEs) consist of different ratios of poly(vinyl butyral-co-vinyl alcohol-co-vinyl acetate) (PVBVA) and bis(trifluoromethane) sulfonamide lithium salt (LiTFSi) were prepared and the ionic conductivity of the prepared STEs was evaluated. The optimized STE (denoted as STE 20) was further doped with various amount of tetraglyme (10, 20, and 30 wt % and denoted as G10, G20, and G30, respectively). G20 enhanced the ionic conductivity from 6.22 (for STE 20) to 21.9 µS cm⁻¹. This enhancement is due to the presence of abundant oxygen-containing functional group in tetraglyme that provides more charge carrier mobility in the polymer matrix. The structure and complexation of the materials are authenticated via X-ray diffraction and Fourier transform infrared spectroscopy analysis. The performance of electric double layer capacitors based on activated carbon (AC) fabricated with STE 20 (AC/STE 20/AC) and G20 (AC/G 20/AC) were studied via cyclic voltammetry, galvanostatic charge–discharge, and electrochemical impedance spectroscopy. AC/G 20/AC achieved the maximum specific capacitance of 10.20 F/g [which is higher than AC/STE 20/AC (9.30 F/g)] with 75% of specific capacitance retention after 1500 cycles. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45902.     

Glycerol‐plasticized spirulina–poly(vinyl alcohol) films with improved mechanical performance

Spirulina–poly(vinyl alcohol) (PVA)–glycerol (SPG) films with improved mechanical performance, especially tensile strength (TS) and the elongation at break (EAB), are fabricated by a casting method. The integrity, color, solubility, microstructure, thermal properties, tensile strength, and compatibility of the SPG films are assessed. SPG films became smooth, homogeneous, and flexible after plasticizing with glycerol. The presence of PVA and hydrogen bonding of PVA with glycerol and spirulina protein improves the water resistance of SPG films by decreasing water absorption of spirulina protein and decreasing water diffusion through the films. The amount of carbonaceous residues decreases from 31% to 14% because of the co‐pyrolysis of spirulina, PVA, and glycerol. TS increases from 2.5 to 26 Mpa and modulus from 53 to 610 Mpa with increasing PVA content. Glycerol enhances film flexibility and EAB up to 50%. Spirulina can be composited with hydrophilic polymers to fabricate compatible, processable and thermally recyclable films with desirable mechanical performance. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44842.     

Compatibilized blends of PVC/PA12 and PVC/PP containing poly(lauryl lactam‐block‐caprolactone)

Specially designed block copolymers have played a role as compatibilizing agents in the system of immiscible polymer blends. We applied lauryl lactam (LA)–caprolactone (CL) block copolymer [P(LA‐b‐CL)] as a compatibilizing agent for immiscible poly(vinyl chloride) (PVC) blends with various polymers. These blends possess high thermal performance and toughness. We investigated the effect of P(LA‐b‐CL) as a compatibilizing agent for immiscible PVC blends with poly(ω‐lauryl lactam) [polyamide 12 (PA12)]. We also described the invention of a new compatibilizing agent system involving P(LA‐b‐CL) for PVC/polypropylene (PP) blends. The mechanical and thermal properties of (1) PVC/PA12 blend compatibilized with P(LA‐b‐CL) and (2) PVC/PP blend compatibilized with P(LA‐b‐CL)/PA12/maleic anhydride–modified PP were both enhanced. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1983‐1992, 2004     

Effects of different porous fillers on interfacial properties of poly (vinyl alcohol) hybrid films

Poly(vinyl alcohol) (PVA)-based hybrids have demonstrated broad liquid separation applications but separation performances are constrained by the compatibility between fillers and polymer, and thus it is essential to study the interfacial properties of these hybrids. In this work, PVA hybrids with four different porous fillers have been fabricated and characterized with Fourier transform infrared, X-ray diffraction, Scanning electron microscope, swelling and contact angle tests. Swelling results show that PVA has a degree of swelling (DS) of 79% in water but the swelling is compressed after adding fillers and the DS for PVA hybrids has decreased by 19%, 17%, 15%, and 9% for 30 wt% loading of ZIF-8, UiO-66, Hβ and ZSM-5, respectively. For methanol and its 10 wt% aqueous solution, similar swelling results are obtained due to mutual interactions among the filler, polymer and test liquids. Based on water and glycerol contact angle results, the surface energy of PVA is estimated to be 40.56 Nm⁻¹ and it drops to 27.39 Nm⁻¹ after adding less hydrophilic ZIF-8 or rise to 48.56 Nm⁻¹ after introducing more hydrophilic ZSM-5. The high-film hydrophilicity and then large surface energy have rendered methanol/water sorption selectivity of PVA hybrids decrease to some extent or vice versa.