Physico-mechanical properties of poly (vinyl alcohol), poly (vinyl alcohol)/boric acid,and poly (vinyl alcohol) nanocomposites incorporated with amino-functionalized and pristine halloysite nanotubes films

Eco-friendly poly(vinyl alcohol) (PVA), PVA/boric acid, PVA/halloysite nanotubes (HNTs), and PVA/amino-functionalized HNTs (APTES-HNTs) films were fabricated by a solution casting technique. The samples were characterized by fourier transform infrared, X-ray diffraction, differential scanning calorimetry, scanning electron microscope, and energy-dispersive spectroscopy. The characterization results proved the chemical and physical interactions between the PVA and different additives. The viscoelastic behavior of the films was evaluated by DMA and creep analysis. The storage modulus, loss factor, and both α_α and β_β transitions affected by APTES-HNTs as a potential filler to form effective cross-links. APTES-HNTs existence enhanced creep-recovery beyond expectations. Tensile and impact strength were measured to understand samples' mechanical stability. PVA/APTES-HNTs and PVA/boric acid showed more yield behavior after the elastic limit. Furthermore, the subsequent rupture and impact strength were increased significantly compared with neat PVA and PVA/HNTs. The viscoelastic and mechanical behaviors were linked to each other by the area under Tanδ curve and the work of rupture and impact strength, which their linear correlation coefficient is statistically significant at 95% confidence limits. It seems that the presence of APTES-HNTs provides new cross-links, which altered (improved) the physico-mechanical properties of PVA, offering a bionanocomposite suitable for further applications. From the literature, possible explanations are provided for these observations.     

Moisture‐induced effects on the tensile mechanical properties and glass‐transition temperature of poly(vinyl alcohol) films

In this study, the effect of sorbed water on the tensile mechanical properties of noncrosslinked, thermally treated poly(vinyl alcohol) (PVA) films was studied. The Young's modulus, elongation at break, and tensile strength of the PVA films equilibrated at different relative humidities (0–86%) are reported, together with the depression of the glass transition of the polymer at each equilibrating humidity, as determined by temperature‐modulated differential scanning calorimetry. The results indicate that drastic changes in the tensile properties were correlated with the transition of the hydrated polymer from the glassy to the rubbery state. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

The effect of physical ageing on the properties of poly(ethylene terephthalate)

Physical ageing rates of poly(ethylene terephthalate) have been measured, and ageing is interpreted to be associated with the conventional glass formation process, which occurs at a more rapid rate at higher temperatures. Ageing is accompanied by a marked change in mechanical properties, increased tensile yield stress and drawing stress, more localized yielding of the polymer and a marked decrease in impact strength. The fracture results have been attributed to the increased yield stress and a change in contribution of plane stress and plane strain conditions in the samples. Fracture surfaces show evidence of mixed modes of fracture.     

Preparation,characterization, electrical and antibacterial properties of sericin/poly(vinyl alcohol)/poly(vinyl pyrrolidone) composites

In this study, we focused on the fabrication of poly(vinyl alcohol) (PVA)/poly(vinyl pyrrolidone) (PVP)/sericin composites via a simple solution‐blending method. The composites were characterized by Fourier transform infrared (FTIR) spectroscopy, UV spectroscopy, X‐ray diffraction (XRD), scanning electron microscopy (SEM), differential scanning calorimetry, thermogravimetric analysis (TGA), and measurements of the conductivity, tensile strength, and antibacterial activity against Staphylococcus aureus. The results of FTIR and UV spectroscopy implied the occurrence of hydrogen bonding between sericin and the PVA/PVP blend. The structure and morphology, studied by XRD and SEM, revealed that the sericin particles were well dispersed and arranged in an orderly fashion in the blend. The glass‐transition temperature (T_g) of the composite was higher than that of the pure blend, and the T_g value shifted toward higher temperatures when the volume fraction of sericin increased. TGA indicated that sericin retarded the thermal degradation; this depended on the filler concentration. The mechanical and electrical properties, such as the tensile strength, alternating‐current electrical conductivity, dielectric constant, and dielectric loss of the composites, were higher than those of the pure blend, and these properties were enhanced when the concentration of sericin was increased up to 10 wt % filler content, whereas the elongation at break of the composite decreased with the addition of sericin particles. The antibacterial properties of the composite showed that sericin had a significant inhibitory effect against S. aureus. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43535.     

Polymorphic crystallization of poly(butylene adipate) and its copolymer: Effect of poly(vinyl alcohol)

The crystallization kinetics and crystalline structure of the biodegradable polymorphic polymers, poly(butylene adipate) (PBA) and poly(butylene adipate‐co‐hexamethylene adipate), in the microparticles and nanoparticles covered by poly(vinyl alcohol) (PVA), and those on the PVA substrate were investigated by differential scanning calorimetry, wide‐angle X‐ray diffraction, and Fourier transform infrared spectroscopy. Both the polymers crystallized in the particle state and on the PVA substrate showed higher crystallization temperatures in the nonisothermal melt crystallization and shorter crystallization times in the isothermal crystallization; this indicated a faster crystallization of the polymer in the particle state and on the PVA substrate than that of the bulk sample. Furthermore, the polymers in the particle state and on the PVA substrate showed the preferential formation of the β‐type crystalline form of PBA compared to the bulk one. The mechanism for the effects of the PVA layer or substrate on the crystallization kinetics and crystalline structure of PBA and its copolyesters are discussed. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39600.     

Revisiting the thermal relaxations of poly(vinyl alcohol)

The molecular dynamics of poly(vinyl alcohol) (PVA) were studied by dielectric spectroscopy and dynamic mechanical analysis in the 20–300°C range. The well-established plasticizing effect of water on the glass-transition temperature (T_g) of PVA was revisited. Improper water elimination analysis has led to a misinterpretation of thermal relaxations in PVA such that a depressed T_g for wet PVA films (ca. 40°C) has been assigned as a secondary β relaxation in a number of previous studies in the literature. In wet PVA samples, two different Vogel–Fulcher–Tammann behaviors separated by the moisture evaporation region (from 80 to 120°C) are observed in the low- (from 20 to 80°C) and high- (>120°C) temperature ranges. Previously, these two regions were erroneously assigned to two Arrhenius-type relaxations. However, once the moisture was properly eliminated, a single non-Arrhenius α relaxation was clearly observed. X-ray diffraction analysis revealed that the crystalline volume fraction was almost constant up to 80°C. However, the crystallinity increased approximately 11% when temperature increased to 180°C. A secondary β_c relaxation was observed at 140°C and was related to a change in the crystalline volume fraction, as previously reported. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Thermal and mechanical properties of poly(vinyl alcohol) plasticized with glycerol

Thermomechanical behavior of membranes based on blends of poly(vinyl alcohol) (PVA) with different weight percentage (wt %) of glycerol has been studied. Solid‐state PVA/Glycerol polymer membranes were prepared by a solution casting method. The films were studied for thermal characteristics by differential scanning calorimetry (DSC) and thermogravimetric analysis and for the mechanical properties including hardness and modulus by nanoindentation method. The dispersion of glycerol within the polymer matrix was examined using scanning electron microscopy. Fourier transform infrared spectroscopy was used to confirm the formation of hydrogen bonding between the plasticizer and PVA in their blends and also to provide information on compatibility and physical interactions between the glycerol and PVA. It was found that the thermal properties particularly the melting point (T_m) for PVA blends exhibit a reduced value proportional to the glycerol content. The hardness and elastic modulus were also found to decrease with an increase in plasticizer content. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Characterization of poly(vinyl pyrrolidone‐co‐isobutylstyryl polyhedral oligomeric silsesquioxane) nanocomposites

Poly(vinyl pyrrolidone‐co‐isobutyl styryl polyhedral oligomeric silsesquioxane)s (PVP–POSS) were synthesized by one‐step polymerization and characterized using FTIR, high‐resolution ¹H‐NMR, solid‐state ¹³C‐NMR, ²⁹Si‐NMR, GPC, and DSC. The POSS content can be controlled by varying the POSS feed ratio. The T_g of the PVP–POSS hybrid is influenced by three main factors: (1) a diluent role of the POSS in reducing the self‐association of the PVP; (2) a strong interaction between the POSS siloxane and the PVP carbonyl, and (3) physical aggregation of nanosized POSS. At a relatively low POSS content, the role as diluent dominates, resulting in a decrease in T_g. At a relatively high POSS content, the last two factors dominate and result in T_g increase of the PVP–POSS hybrid. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2208–2215, 2004     

Poly(ɛ‐caprolactone)/polyhedral oligomeric silsesquioxane hybrids: Crystallization behavior and thermal degradation

Biodegradable organic–inorganic hybrids based on poly(?‐caprolactone) (PCL) and polyhedral oligomeric silsesquioxane (POSS) with 5.3–21.3 wt % POSS were synthesized via ring‐opening polymerization (ROP). Chemical structures of the polymers were characterized by proton nuclear magnetic resonance (¹H NMR), fourier transform infrared spectroscopy (FTIR), and gel permeation chromatography (GPC). X‐ray diffraction (XRD) analysis illustrated that both POSS and PCL segment in POSS/PCL hybrids could crystallize and form two well‐separated crystalline phases except in the one with low content of POSS (5.3 wt %). Melting behavior and non‐isothermal crystallization kinetics of POSS/PCL hybrids were studied by differential scanning calorimeter (DSC). The results indicated that the POSS segment suppressed crystallization of the PCL segment to some extent. Polarizing optical microscope (POM) images showed that POSS/PCL hybrids with the highest POSS loading (21.3 wt %) possessed “snowflake” shape crystals whereas the ones with relatively low POSS loading exhibited classic spherulites. Thermogravimetry (TG) measurement revealed that thermal degradation of POSS/PCL hybrids proceeded by four‐step while PCL homopolymers degraded by a single step. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44113.     

Epoxy hybrid composites cured with octaaminophenyl polyhedral oligomeric silsesquioxane

Polyhedral oligomeric silsesquioxane-containing hybrids of epoxy resins are prepared via the cocuring reaction between octaaminophenyl polyhedral oligomeric silsesquioxane (OAPS) and brominated epoxy resin (EP). The gel time, dispersion, thermal properties, mechanical properties, water absorption, and dielectric properties of the OAPS/EP composites are studied. The gel time of the 1 wt % OAPS composites is significantly higher compared with that of the epoxy resin control. Wide angle X-ray diffraction and scanning electron microscopy show that, at the molecular level, the appropriate amount of POSS cages was dispersed in the epoxy matrix because the POSS monomer participated in the crosslinking reaction. The thermal and mechanical properties of the composites are enhanced as 1 wt % OAPS was added to the epoxy system. The water absorption of the 1 wt % OAPS composite significantly declines. The dielectric constant of the 1 wt % OAPS composite is 0.5 less than that of the epoxy resin control in the range of 100 Hz–40 MHz. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Effect of metal oxides added onto polyvinyl alcohol via pulsed underwater plasma on their thermal,electrical and dielectric properties

Flexible electronics require materials with high breakdown strength, high dielectric constant, and thermal stability. These conditions are met by composites based on polymers and metal oxides. In this article, we present a new one-step method for producing composites based on water-soluble polyvinyl alcohol (PVA) and metal oxides (AlOOH, CuO, and ZnO). The source of oxides is underwater plasma. The oxides are introduced into the polymer matrix when plasma is exposed to the polymer solution. The results of X-ray, IR, and SEM analysis showed that metal oxides are embedded in the polymer. Differential scanning calorimetry measurements have shown that the glass transition temperature depends on the oxide being incorporated. The electrical properties of polymer composites were studied by current–voltage characteristics. Dielectric properties were measured in the range of 25–10⁶ Hz. The properties of obtained PVA + metal oxide showed that using underwater plasma is a suitable method for producing composites for electronic devices.     

Ester‐amide based on ricinoleic acid as a novel primary plasticizer for poly(vinyl chloride)

Utilization of ricinoleic acid as a raw material for the synthesis of green plasticizer would offer an alternative to the phthalate plasticizers. Ester‐amide of ricinoleic acid was synthesized by a two‐step reaction with dibutyl amine and benzoic acid; and then utilized as primary plasticizer in PVC. Ester‐amide plasticizer was added up to 40 phr in PVC; and the prepared PVC sheets were characterized for mechanical, X‐ray diffraction, thermal, rheological, colorimetric, and exudation properties. Addition of the ester‐amide plasticizer demonstrated good incorporation and plasticizing performance in PVC. Viscosity of PVC decreased with increased addition of ester‐amide plasticizer. The dark color of the synthesized plasticizer could have constraints on its application areas; however, the prepared samples illustrated negligible weight loss in the exudation test, attributed to better compatibility between them brought about by the ester, tertiary amide and polarizable benzene ring in the ester‐amide plasticizer with the C‐Cl polar linkage in PVC. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41913.     

Influence of hydrogen bonding interaction on the damping properties of poly(n‐butyl methacrylate)/small molecule hybrids

The hydrogen bonding interactions between poly(n‐butyl methacrylate) and a series of low molecular weight phenols containing two to four hydroxyl groups with different steric effects were investigated by differential scanning calorimetry and Fourier‐transform infrared spectroscopy. Results showed that the hydrogen bonding strength between the two components varies greatly according to the steric effects of the phenolic hydroxyl group. As the size of the group beside the hydroxyl increases, the hydrogen bond strength weakens. The glass transition temperature of binary hybrid systems was put into relation with the corresponding hydrogen bonding interaction strength. Strong hydrogen bonding strength increased T_g to higher values than that predicted by the linear additivity rule; by contrast, T_g of hybrid systems with weak hydrogen bonds showed linear changes. All of the samples showed linear variations at low concentrations of small molecules. The damping properties of five systems were analyzed by dynamic mechanical analysis. Either the loss factor or area of tan δ peak of the five systems increased compared with that of the pure polymer, thereby showing great improvements in the damping properties of the poly(n‐butyl methacrylate)/small molecule hybrid material. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41954.     

Effects of water on drawability,structure, and mechanical properties of poly(vinyl alcohol) melt‐spun fibers

Poly(vinyl alcohol) (PVA) melt‐spun fibers with circular cross‐section and uniform structure, which could support high stretching, were prepared by using water as plasticizer. The effects of water content on drawability, crystallization structure, and mechanical properties of the fibers were studied. The results showed that the maximum draw ratio of PVA fibers decreased with the increase of water content due to the intensive evaporation of excessive water in PVA fibers at high drawing temperature. Hot drying could remove partially the water content in PVA as‐spun fibers, thus reducing the defects caused by the rapid evaporation of water and enhancing the drawability of PVA fibers at high drawing temperature. The decreased water content also improved the orientation and crystallization structure of PVA, thus producing a corresponding enhancement in the mechanical properties of the fibers. When PVA as‐spun fibers with 5 wt % water were drawn at 180 °C, the maximum draw ratio of 11 was obtained and the corresponding tensile strength and modulus reached ～0.9 GPa and 24 GPa, respectively. Further drawing these fibers at 215 °C and thermal treating them at 220 °C for 1.5 min, drawing ratio of 16 times, tensile strength of 1.9 GPa, and modulus of 39.5 GPa were achieved. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45436.     

Rheological/thermal properties of poly(ethylene terephthalate) modified by chain extenders of pyromellitic dianhydride and pentaerythritol

Due to low molecular weight and wide molecular weight distribution, polyethylene terephthalate (PET) shows weak melt strength properties. In this study, the synergistic effect of using different types of chain extenders and catalyst on rheological behavior of PET has been investigated. Long-chain branching is known as a suitable method for developing the structure of PET during reactive melt processing. Thus, pyromellitic dianhydride (PMDA) and pentaerythritol (PENTA) were added to the fiber grade PET. The best formulation was determined based on rheological results, which revealed an improvement in both storage modulus and complex viscosity of PMDA-modified samples. Samples containing 1.5% PMDA and 0.5% PENTA exhibited the best rheological properties. Also, dibutyltin dilaurate (DBTDL) acted as an accelerator for chain extension reaction during reactive melt blending. Subsequently, the rheological properties were improved by increasing the chain extending rate. Moreover, thermal properties such as crystallization and melting temperatures and the degree of crystallinity for modified PET were investigated by differential scanning calorimetry.     

Evolution of mechanical properties during cure for out‐of‐autoclave carbon‐epoxy prepregs

Extent of cure and rheological properties were obtained for out‐of‐autoclave materials, Cycom 5320‐8HS and Cycom 5320‐PW, for the manufacturer recommended cure cycle using differential scanning calorimeter and encapsulated sample rheometer (ESR), respectively. Rheological properties from ESR were further used in designing the cure cycles to study the evolution of mechanical properties. Five panels were cured at different cure stages using the designed cure cycles and coupons were tested for short beam shear and combined loading compression properties at different cure stages. To correlate the mechanical properties with its respective glass transition temperature, dynamic mechanical analyzer was used to obtain the glass transition temperature for the coupons obtained from the respective panels. Statistical results showed significant difference in short beam shear and combined loading compression properties up to vitrification, however, no significant difference was observed on these mechanical properties after vitrification. The observed linear trend between degree of cure (DOC) and glass transition temperature (T_g) was validated using DiBenedetto relation. Linearly increasing trend between DOC and glass transition temperature (T_g) for different cure states suggests that both DOC and T_g can be used interchangeably to define the state of material. A good correlation was observed between material cure state and the mechanical properties. A mathematical model was also proposed to determine the short beam shear and combined loading compression properties based on material cure state. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41548.     

Electrical,mechanical, structural,and thermal behaviors of polymeric gel electrolyte membranes of poly(vinylidene fluoride‐co‐hexafluoropropylene) with the ionic liquid 1‐butyl‐3‐methylimidazolium tetrafluoroborate plus lithium tetrafluoroborate

Polymeric gel electrolyte membranes based on the polymer poly(vinylidene fluoride‐co‐hexafluoropropylene) [P(VdF–HFP)] with different weight percentages of the ionic liquid (IL) 1‐butyl‐3‐methylimidazolium tetrafluoroborate plus 0.3M lithium tetrafluoroborate (LiBF₄) salt were prepared and characterized by scanning electron microscopy, X‐ray diffraction, differential scanning calorimetry, thermogravimetric analysis, Fourier transform infrared (FTIR) spectroscopy, complex impedance spectroscopy, pulse echo techniques, and Vickers hardness (H) testing. After the incorporation of the IL plus the salt solution in the P(VdF–HFP) polymer, the melting temperature, glass‐transition temperature (T_g), degree of crystallinity, thermal stability, elastic modulus (E), and hardness (H) gradually decreased with increasing content of the IL–salt solution as a result of complexation between the P(VdF–HFP) and IL. This was confirmed by FTIR spectroscopy. A part of the IL and LiBF₄ were found to remain uncomplexed as well. The ionic conductivity (σ) of the polymeric gel membranes was found to increase with increasing concentration of the IL–salt solution. The temperature‐dependent σs of these polymeric gel membranes followed an Arrhenius‐type thermally activated behavior. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41456.     

Glass transition and cold crystallization in carbon dioxide treated poly(ethylene terephthalate)

An amorphous poly(ethylene terephthalate) (aPET) and a semicrystalline poly(ethylene terephthalate) obtained through the annealing of aPET at 110°C for 40 min (aPET‐110‐40) were treated in carbon dioxide (CO₂) at 1500 psi and 35°C for 1 h followed by treatment in a vacuum for various times to make samples containing various amount of CO₂ residues in these two CO₂‐treated samples. Glass transition and cold crystallization as a function of the amount of CO₂ residues in these two CO₂‐treated samples were investigated by temperature‐modulated differential scanning calorimetry (TMDSC) and dynamic mechanical analysis (DMA). The CO₂ residues were found to not only depress the glass‐transition temperature (T_g) but also facilitate cold crystallization in both samples. The depressed T_g in both CO₂‐treated poly(ethylene terephthalate) samples was roughly inversely proportional to amount of CO₂ residues and was independent of the crystallinity of the poly(ethylene terephthalate) sample. The nonreversing curves of TMDSC data clearly indicated that both samples exhibited a big overshoot peak around the glass transition. This overshoot peak occurred at lower temperatures and was smaller in magnitude for samples containing more CO₂ residues. The TMDSC nonreversing curves also indicated that aPET exhibited a clear cold‐crystallization exotherm at 120.0°C, but aPET‐110‐40 exhibited two cold‐crystallization exotherms at 109.2 and 127.4°C. The two cold crystallizations in the CO₂‐treated aPET‐110‐40 became one after vacuum treatment. The DMA data exhibited multiple tan δ peaks in both CO₂‐treated poly(ethylene terephthalate) samples. These multiple tan δ peaks, attributed to multiple amorphous phases, tended to shift to higher temperatures for longer vacuum times. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Enhanced nonisothermal and isothermal cold crystallization kinetics of biodegradable poly(l‐lactide) by trisilanolisobutyl‐polyhedral oligomeric silsesquioxanes in their nanocomposites

In this work, the nonisothermal and isothermal cold crystallization behaviors of poly(l ‐lactide) (PLLA)/trisilanolisobutyl‐polyhedral oligomeric silsesquioxanes (tsib‐POSS) nanocomposites with low tsib‐POSS contents were fully investigated. For all the samples, the variations of heating rate and the tsib‐POSS loading may influence the nonisothermal cold crystallization of PLLA. During the nonisothermal crystallization kinetics study, the Ozawa equation failed to fit the nonisothermal crystallization process of PLLA, while the Tobin equation could fit it well. For the isothermal crystallization kinetics study, the crystallization rates of all the samples increased with increasing crystallization temperature. The cold crystallization activation energy of PLLA was increased with 1 wt % tsib‐POSS. Moreover, the addition of tsib‐POSS and the increment of tsib‐POSS loading could increase the crystallization rate of PLLA, indicating the nucleating agent effect of tsib‐POSS. However, the crystallization mechanism and crystal structure of PLLA remained unchanged in the nanocomposites. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43896.     

Dielectric and thermal studies of segmental dynamics in silica/PDMS and silica/titania/PDMS nanocomposites

Effects of silica and silica/titania nanoparticles on glass transition and segmental dynamics of poly(dimethylsiloxane) (PDMS) were studied for composites of a core–shell type using differential scanning calorimetry, thermally stimulated depolarization current, and dielectric relaxation spectroscopy techniques. Strong interactions between the filler and the polymer suppress crystallinity (T_c, X_c) and affect significantly the evolution of the glass transition in the nanocomposites. The segmental relaxation associated with the glass transition consists of three contributions, arising, in the order of decreasing mobility, from the bulk (unaffected) amorphous polymer fraction (α relaxation), from polymer chains restricted between condensed crystal regions (α_c relaxation), and from the semi‐bound polymers in an interfacial layer with strongly reduced mobility due to interactions with surface hydroxyls of silica and silica/titania nanoparticles (α′ relaxation). The evolution of surface affected CH₃ groups, as well as the degree of interaction of PDMS molecules with surface hydroxyl groups as a function of treatment temperature, was assessed by Fourier transform infrared spectroscopy, thermogravimetry and differential thermal analysis. The effectiveness of silica/PDMS and silica/titania/PDMS nanocomposites as hydrophobic coatings was investigated by static contact angle measurements. It was shown that the presence of titania nanoparticles and adsorbed PDMS promotes the hydrophobic properties of the PDMS coating after treatment in the 80–650°C range. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41154.