Making polyvinyl alcohol films iodinated at solution state before casting and its application

This research focused on the manufacture a polarizing film with PVA iodinated at solution before casting (IBC) film, which was prepared by casting aqueous solutions of 10 wt % poly(vinyl alcohol) (PVA) containing boric acid with 0, 0.1, 0.5, and 1.0 mol/L of I₂/KI aqueous solution, and I₂/KI(1:2) with 0, 5, and 10 wt % of PVA. The lights of wavelengths between 450 and 700 nm were polarized in UV analysis. The degree of polarization and transmittance of the IBC polarizing film (10 wt % I₂/KI and 0.5 mol/L boric acid) are 99.9% and 43.2%, respectively. The resistance of the heat and humidity of IBC polarizing films was higher than that of commercial polarizing films, which were elucidated by changing the transmittance of the films. This can be explained by the fact that the interaction between polyiodine molecules and PVA chains as the state of IBC is higher than that of the commercial state. The effect of boric acid may be strengthened for the resistance of heat and humidity. Crosslinking by boric acid improved thermal properties of the IBC polarizing films, resulting from the increases of degradation temperature in DSC and TG analysis. And the unit cell broadening occurred, which was caused by the intrusion of boric acid into PVA chains in X-ray analysis. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation of syndiotacticity‐rich high molecular weight poly(vinyl alcohol)/iodine polarizing film with high water resistance

To enhance durability of poly(vinyl alcohol) (PVA)/iodine polarizing film under humid and warm atmospheres and to identify the effects of syndiotacticity on the polarizing efficiency (PE) and durability of PVA/iodine complex film, we prepared three high molecular weight (PVA)s with similar number‐average degree of polymerization (P_n) of 4000 and with different syndiotactic diad (s‐diad) contents of 53, 56, and 59%, respectively. It was found that syndiotacticity of PVA had a significant influence on the durability of PVA/iodine complex film in warm and humidity conditions (relative humidity of 80% and temperature of 50°C). That is, both desorption of iodine in PVA/iodine film and transmittance of film decreased with increasing syndiotacticity of PVA. In the case of PE, the values of over 99% were obtained at each optimum conditions. The change of PE (durability) of PVA/iodine complex films having P_n of 4000 and s‐diad contents of 56 and 59%, respectively, in warm and humidity conditions was almost zero, whereas those of PVA/iodine film with s‐diad content of 53% and with (P_n)s of 1700 and 4000 were about 60% and 50%, respectively, under same conditions. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Polarizer effect and structure of iodinated before and after casting poly(vinyl alcohol) film

Poly(vinyl alcohol) (PVA)/iodine polarizing film was manufactured as follows: PVA iodinated in solution before casting (IBC film) and iodinated again after casting (IBC + IAC film) and then the IBC + IAC film was drawn in boric acid aqueous solution (IBC + IAC polarizing film), to improve the durability of the polarizing film under a humid and warm atmosphere. These effects were examined by investigating the structural and optical properties of the IBC, IBC + IAC, and IBC + IAC polarizing films. In the IBC state, the PVA chain segments that combined boric acid and iodine were regarded as defects of the crystal, the formation of I₃⁻ decreased with respect to weight gain of boric acid. In the IBC + IAC state, the strength of the peak corresponding to I₃⁻ decreased and the I₅⁻ peak increased. The iodine ions penetrated into crystal of the IBC state during the IAC process and formed a new PVA/iodine complex crystal at the 2θ = 20° in the X‐ray diffraction curves. In the IBC + IAC polarizing film state, another type of polarizing film (IBC + IAC polarizing film‐H) containing I₃⁻ ions mainly was manufactured as well as the IBC + IAC polarizing film to compare the effects of the I₃⁻ and I₅⁻ ions on the durability of the polarizing films. The durability of the I₃⁻ ions that were complexed with the PVA chain was higher than the I₅⁻ ions, which could possibly be separated to I₃⁻ and I₂. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effect of boric acid treatment method on the characteristics of poly(vinyl alcohol)/iodine polarizing film

Four types of polyvinyl alcohol (PVA)/iodine complex films were made using different boric acid treatments to prepare polarizing films having high durability under humid and warm atmospheres and to identify the effects of the boric acid treatment method on the formation of the PVA/iodine polarizing film. The four types of films were a PVA iodinated film(I), a PVA film that was iodinated and then treated with boric acid(I‐B), a PVA film that was treated with boric acid and then iodinated(B‐I), and a PVA film that was simultaneously treated with iodine and boric acid(I+B). The concentrations of I₂/KI were 0.03, 0.05, and 0.07 mol/L, and the concentrations of boric acid were 0.1, 0.3, and 0.5 mol/L. Comparing four type films treated with 0.05 mol/L I₂/KI and 0.5 mol/L boric acid, the conformation of PVA/iodine complexes for I‐B film were larger than the others. The degrees of polarization (ρ) of all of the films increased to very high levels (99.9%↑). The durability of I‐B was superior to B‐I or I+B, and the change in the ρ was below 5% because the boric acid treated after iodine treatment reduced the molecular mobility of the PVA/iodine complex chains through intracrosslinking, so that the PVA/iodine complex could not easily collapse. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Effect of boric acid and heat treatment for the formation of poly(vinyl alcohol)/iodine complex films iodinated at solution before casting

This study examined the role of boric acid and the effect of heat treatment on PVA‐iodine polarizing films prepared in the solution state before casting (IBC) of PVA/iodine/boric acid films. The films were prepared by casting aqueous solutions of 10 wt % poly(vinyl alcohol) (PVA) containing boric acid with 0, 0.1, 0.3, and 0.5 mol/l of I₂/KI aqueous solution, and I₂/KI(1 : 2) with 5 wt % of PVA. The effect of boric acid and heat treatment on the durability of the IBC PVA polarizing sheet films was investigated by UV–vis absorption spectroscopy. Boric acid was found to be essential for the complex formation in PVA/iodine solutions at relatively low I₂/KI concentrations and high temperatures. The strength of the complex peak at ∼ 600 nm in UV–vis absorption spectra increased with increasing boric acid concentration. With increasing heating temperature over 90°C the intensity of the peak at 600 nm corresponding to the complex decreased due to the evaporation of I₂ decomposed from I₅⁻, but the peak at 355 nm corresponding to free I₂·I₃⁻ was remained unchanged. From heat treatment at 150°C, the intensity of the peak at 600 nm decreased but the intensity of the complex peak (600 nm) of the sample with 0.5 mol/l boric acid was unaffected. The transmittance and degree of polarization for the films increased and decreased with increasing heat treatment time under heat and a humid atmosphere, respectively. However, this tendency decreased with increasing boric acid concentration and heat treatment. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Role of molecular weight of atactic poly(vinyl alcohol) (PVA) in the polarizing efficiency of PVA/azo dye complex film with high durability

To precisely identify the effect of molecular weight of atactic poly(vinyl alcohol) (a‐PVA) on the durability and polarizing efficiency (PE) of a‐PVA/dye polarizing film, we prepared two (a‐PVA)s with similar syndiotactic diad contents of 54.0%, degrees of saponification of 99.9%, and with different number‐average degrees of polymerization [(P_n)s] of 1700 and 4000, respectively. Through a series of experiments, it was found that molecular weight of a‐PVA had a significant influence on the durability of a‐PVA/dye film in heat and humidity conditions (relative humidity of 80% and temperature of 90°C). That is, both desorption of dye in a‐PVA/dye film and transmittance of film decreased with increasing molecular weight of PVA. The change of PE (durability) of a‐PVA/dye film in heat and humidity conditions was limited to about below 5%. The change of PE of PVA/dye film having P_n of 4000 especially was limited to 1%, whereas that of a‐PVA/iodine film with P_n of 4000, was almost 80% under the same condition. Also, transmittance of the drawn a‐PVA/dye film was far higher than that of the undrawn one. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 967–974, 2005     

Preparation and characterization of carbon films prepared from poly(vinyl alcohol) containing metal oxide and nano fibers with iodine pretreatment

This research focused on the combination of catalyst effect of metal oxide, thermal conductive effect of carbon nano fibers and iodine pretreatment during carbonization of polymer precursor in order to prepare tough carbon films. Poly(vinyl alcohol) (PVA) composites containing metal oxide (Fe₃O₄) and vapor-grown carbon fibers (VGCFs) were prepared by gelation/crystallization method with the freezing/thawing technique. The dry gel films as precursor were pretreated in the atmosphere of vapor iodine, and then heat-treated at 600-1200 °C. The combined effect of iodine, Fe₃O₄ and VGCF on the carbonization of PVA was analyzed with thermo-gravimetric analysis, X-ray diffraction, and scanning electron microscope in details. Iodine pretreatment for 24 h significantly promoted the dehydration of PVA, and resulted the carbon film with a high crystallinity. Fe₃O₄ as catalyst facilitated the carbonization of PVA at a low temperature of 800-900 °C. The addition of VGCFs was found to play an important role to prepare tough films by mild carbonization due to its high thermal conductivity. The degree of graphitization in the carbon film depended on the filler contents, pretreatment conditions and carbonization conditions. The graphitization degrees for G- and T-components in the film were investigated on the basis of X-ray diffraction intensity distribution from the (0 0 2) plane.     

Improved ferroelectric properties in KBiFe2O5-polymer composite film

Composite films of KBiFe₂O₅ and PVA were prepared with a varied weight percentage of PVA by spin coating method on platinised silicon wafer. The composite films were characterised for dielectric and ferroelectric properties in comparison to pure KBiFe₂O₅thick film. The frequency dependent permittivity measurement indicated a higher contribution of space charge/interfacial polarization in KBiFe₂O₅ thick film than that in the KBiFe₂O₅ -PVA composite films. The ferroelectric properties in composite films were enhanced due to the reduction in leakage current and they showed well saturated polarization hysteresis loops. The remanent polarization value in KBiFe₂O₅ -PVA composite film (Pr?=?3.7?μC/cm²) was found to be 2.5 times higher than that of the pure KBiFe₂O₅ film (Pr?=?1.45?μC/cm²) and with the increase in PVA percentage, the remanent polarization values also increased. The space charge dominated conduction in pure KBiFe₂O₅ became transformed to field assisted ionic conduction in the KBiFe₂O₅ composite films. The polymeric matrix in KBiFe₂O₅ composites helped in reducing the leakage current of pure KBiFe₂O₅ by four orders of magnitude and further reduced with the increase in the PVA content in the composite. The composite films showed fatigue free polarization even after 10⁸ switching cycles whereas the polarization degradation in KBiFe₂O₅ film was 30% around 10⁸switching cycles.     

Effect of magnesium chloride hexahydrate on thermal and mechanical properties of starch/PVA films

Starch/poly(vinyl alcohol) (PVA) blend films were prepared from the aqueous solutions containing starch, PVA and magnesium chloride hexahydrate (MgCl₂.6H₂O). The interaction between MgCl₂.6H₂O and starch/PVA was studied by Fourier transform infrared spectroscopy. The plasticising effect of MgCl₂.6H₂O on starch/PVA film was studied by scanning electron microscopy (SEM), X-ray diffraction, thermogravimetric analysis, dynamic mechanical analysis and tensile testing respectively. The water content of starch/PVA films increased with the content of MgCl₂.6H₂O. The absorbed water can act as the plasticiser for starch/PVA film. The crystals of starch and PVA were destroyed, and the crystallinity of starch/PVA film decreased with the plasticising effect of MgCl₂.6H₂O and water. SEM micrographs showed that the compatibility between starch and PVA improved with the addition of MgCl₂.6H₂O. The toughness of starch/PVA film increased with the content of MgCl₂.6H₂O.     

Fabrication of highly monodisperse CeO2@poly(methyl silsesquioxane) microspheres and their application in UV‐shielding films

Highly monodisperse CeO₂@poly(methyl silsesquioxane) (PMSQ) microspheres were successfully prepared by a facile chemical precipitation technique. The structures and properties of CeO₂@PMSQ were analyzed by Fourier transform infrared spectroscopy, X‐ray diffraction, and scanning electron microscopy techniques. We confirmed that the PMSQ microspheres were uniformly coated by CeO₂ nanoparticles, with about an 8 nm crystallite diameter. Then, CeO₂@PMSQ was incorporated into a poly(vinyl alcohol) (PVA) matrix to fabricate PVA/CeO₂@PMSQ composite films by the casting of homogeneous solutions. The thermal and optical properties of the composite films were investigated by thermogravimetric analysis and UV–visible spectroscopy. The results show the high UV‐shielding efficiency of the composites: for a film containing 2.5 wt % CeO₂@PMSQ microspheres, about 80% UV light at wavelengths between 200 and 360 nm was absorbed, whereas the optical transparency in the visible region still remained very high. The addition of CeO2@PMSQ microspheres improved the thermal stability of the PVA films. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45065.     

Effect of boric acid treatment on the crystallinity and drawability of poly(vinyl alcohol)–iodine complex films

A film iodinated at solution state before casting (BIBC film) and a film iodinated after casting (BIAC film) were prepared by casting an aqueous solution of poly(vinyl alcohol) (PVA) including I₂/KI and boric acid, and by successively soaking the PVA film in aqueous solutions of boric acid and I₂/KI, respectively. The boric acid-induced and I₂/KI-induced weight gains relative to the PVA were 3, 5, 7, and 10%, and 3, 5, 10, and 20%, respectively. The effects of boric acid and iodine on the crystallinity and drawability of the films were investigated. Although the crystalline structure of the BIAC films was not affected by boric acid, the boric acids in the PVA solution containing I₂/KI may have formed intra-molecular cross-links on the PVA chain to accelerate the formation of the PVA–iodine complex evenly, and subsequently interrupt the PVA crystallization through the BIBC film formation to render the resultant film slightly crystalline or practically amorphous. This occurred even at a much lower I₂/KI-induced weight gain (20%) than the minimum weight gain (125%) at which the iodinated at solution state before casting film without boric acid indicated a practically amorphous state. The maximum draw ratio of the films generally decreased with increasing boric acid content, which was mainly attributed to the increase of the extended segments of the PVA chains in the amorphous region due to the cross-links formed with the boric acids. The maximum draw ratios of the BIBC films tended to decrease more severely than those of the BIAC films.     

Oxygen barrier properties of biaxially oriented polypropylene/polyvinyl alcohol blend films

The biaxially oriented PP/PVA blend film was prepared and had the higher oxygen barrier property by about 130 times than that of a biaxially oriented PP film. When the viscosity ratio (η_d(PVA)/η_m(PP)) decreased, the dispersed PVA phase was developed into platelets during stretching process. Oxygen permeability was dependent on the number and size of PVA platelet. However, the Oxygen permeability was not sensitively changed in above 25 wt% of PVA. To obtain excellent barrier property, the optimum amount of plasticizer and initiator was required. A pasticizer was related to the size and degree of crystallization of PVA platelet. An initiator played the role of a compatibilizer. The oxygen barrier was enhanced with increasing the viscosity of PP and draw ratio. The higher viscosity of PP was advantageous for preventing the delamination of a blend film, and the moisture vapor permeability was not affected with the laminar structure. As a result, the biaxially oriented PP/PVA blend film had the potential of substituting for the PVDC coated BOPP film.     

Poly (vinyl alcohol)/graphene oxide nanocomposite films and hydrogels prepared by gamma ray

ABSTRACT

Poly (vinyl alcohol)/graphene oxide (PVA/GO) gamma irradiated nanocomposite films and hydrogels were prepared. In composite films, GO was initially irradiated by gamma ray in order to improve interactions between GO and PVA. The film containing 1?wt-% GO was very strong where tensile modulus and tensile yield strength were 45 and 115% higher than those of pure PVA. In the second set of experiments PVA/GO hydrogels were made by irradiating PVA/GO suspensions by gamma ray at various doses. It was an interesting finding that GO increased the gel portion of hydrogels through contribution of H-bonds between PVA and GO. The hydrogels prepared at 20?kGy had remarkable water swelling ratio that reached as high as 20 at water temperature of 80°C. The hydrogel metal ion adsorption capability was tested on Cu²⁺ ions. It was shown that the GO contributed significantly to the adsorption capacity of PVA hydrogels.     

Destruction of percolative network using green synthesized gold nanoparticles: Formation of high dielectric material

Gold nanoparticles (AuNPs) of about 5 nm in diameter were biosynthesized at room temperature (300 K). The PVA/2.5 wt% KH₂PO₄ or KDP composite film and PVA/2.5 wt% KDP/AuNPs nanocomposite films with different concentrations of AuNPs were prepared. Interestingly, addition of 0.05 wt% of AuNPs to the PVA/2.5 wt% KDP percolative composite film destroys percolative behavior of this composite film. Furthermore, the PVA/2.5 wt% KDP/0.05 wt% AuNPs nanocomposite film exhibited high room temperature dielectric permittivity (ε′ ∼ 590 at 1 kHz). The behavior of AC conductivity (σ_ac) of the nanocomposite films indicated correlated barrier hopping type of conduction mechanism. The Cole–Davidson dielectric response becomes evident as the interfacial polarization process acquires a more symmetric form, tending to Debye relaxation. High value of ε′ promises direct application in capacitors. Moreover, the novel feature of destroying the percolative behavior by AuNPs may be applied even in other systems.     

Fourier transform infrared study of polypyrrole–poly(vinyl alcohol) conducting polymer composite films: Evidence of film formation and characterization

The electrochemical preparation of polypyrrole (PPY)–poly(vinyl alcohol) (PVA) conducting polymer composite films on an indium–tin oxide glass electrode from an aqueous solution containing a pyrrole monomer, a p‐toluene sulfonate electrolyte, and a PVA insulating polymer is reported. The prepared PPY–PVA composite films were characterized by Fourier Transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), and conductivity measurements. The FTIR study showed that the composite of PPY and PVA formed through bond formation between PVA and the p‐toluene sulfonate dopant anion. The conductivity data of PPY–PVA showed that with increasing PVA concentration in the pyrrole solution, the conductivity of the prepared PPY–PVA film increased up to a certain level due to an increase in conjugation length, and later, it decreased with further increases in the PVA concentration in the solution due to a decrease in conjugation length. This was supported by the FTIR band intensity I₁₅₆₀/I₁₄₈₀. The TGA results show that the PPY–PVA polymer composite film was thermally more stable than the PPY film. A shielding effectiveness of 45.6 dB was exhibited by the PPY–PVA composite film in the microwave frequency range. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4107–4113, 2006     

Modification of poly(vinyl alcohol) films by the addition of magnesium chloride hexahydrate

Poly(vinyl alcohol) (PVA) films modified with Magnesium chloride hexahydrate (MgCl₂·6H₂O) were prepared by casting method. The prepared films were characterized by X‐ray diffraction measurements (XRD), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and mechanical testing. It was found that the presence of MgCl₂·6H₂O had considerable effects on the crystallinity, thermal, and mechanical properties of PVA films. The crystallization of PVA film was interrupted and the degree of crystallinity of PVA film decreased with the addition of MgCl₂·6H₂O. The glass transition temperature of PVA film decreased with the addition of MgCl₂·6H₂O. After modifying with MgCl₂·6H₂O, PVA film became soft, with lower tensile strength and higher elongation at break. The presence of MgCl₂·6H₂O could significantly increase the moisture content of PVA films and this may be the cause of the plasticizing. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Structure,electrical and optical properties of (PVA/LiAsF6) polymer composite electrolyte films

In this work, Li⁺ ion conducting polymer composite electrolyte films (PECs) were prepared based on poly (vinyl alcohol) (PVA), lithium hexafluoro arsenate (LiAsF₆), and ceramic filler TiO₂ using solution cast technique. The XRD and FTIR spectra were used to determine the complexation of the PVA polymer with LiAsF₆ salt. The ionic conductivities of the (PVA + LiAsF₆) and (PVA + LiAsF₆ + TiO₂) films have been determined by the A.C. impedance measurements in the temperature range 320–440 K. The maximum conductivity was found to be 5.10 × 10^?4 S cm^?1 for PVA:LiAsF₆ (75:25) + 5 wt% TiO₂ polymer composite film at 320 K. The calculation of Li⁺ ion transference number was carried out by the combination of A.C. impedance and D.C. polarization methods and is found to be 0.52 for PVA:LiAsF₆ (75:25) + 5 wt% TiO₂ film. Optical properties such as direct energy gap, indirect energy gap, and optical absorption edge values were investigated in pure PVA and salt complexed PVA films from their optical absorption spectra in the wavelength range of 200–600 nm. The absorption edge was found at 5.76 eV for undoped film, while it is observed at 4.87 and 4.70 eV for 20 and 25 wt% LiAsF₆ doped films, respectively. The direct band gaps for these undoped and salt doped PVA films were found to be 5.40, 5.12, and 4.87 eV, respectively, whereas the indirect band gaps were determined as 4.75, 4.45, and 4.30 eV. POLYM. ENG. SCI., 2010. © 2009 Society of Plastics Engineers     

Transparent and thermally stable improved poly (vinyl alcohol)/Cloisite Na/ZnO hybrid nanocomposite films: Fabrication,morphology and surface properties

A series of poly(vinyl alcohol)/Cloisite Na⁺-Tyrosine/Zinc oxide (PVA/Cloisite Na⁺-Tyr/ZnO) bionanocomposites were prepared by dispersing ZnO nanoparticles in solution containing mixture of the PVA and modified Cloisite Na⁺. Structure of nanocomposite coatings was investigated by X-ray diffraction and Fourier-transform infrared spectroscopy. The thermal stability and optical properties of bionanocomposite were characterized by thermogravimetric analysis and UV–vis spectroscopy, respectively. The introduction of ZnO nanoparticles into PVA/Cloisite Na⁺-Tyr mixed solutions significantly increased the thermal stability of the obtained films. The results revealed that the high UV-shielding efficiency of the composites: for a film containing 6.0 wt% of ZnO nanocrystals, over 92% of UV light at wavelengths of 368 nm was absorbed while the optical transparency in the visible region was slightly below that of a PVA/Cloisite Na⁺-Tyr film.     

Photoconductivity of poly(vinyl alcohol) films with Fe3+ complexes and ESR study of their structures

We have studied whether photoconductivity is observed in polymer films containing the first transition metal complexes. Polymers investigated were poly(vinyl alcohol) (PVA), polyacrylamide, poly(acrylic acid), poly(vinyl pyrrolidone), and polyethylene glycol. Transition metal salts used were CrCl₃, MnCl₂, FeCl₃, CoCl₂, NiCl₂, FeBr₃, Fe(NO₃)₃, Fe₂(SO₄)₃, and Fe(ClO₄)₃. Only in the PVA–FeCl₃ film was relatively large photoconductivity due to the photoreduction of Fe³⁺ observed. ESR spectra indicate that an Fe³⁺ ion is chelated with two in-plane OH residues of PVA and coordinated with three Cl^?ions on the meridian. UV irradiation causes an electron transfer from Cl^? to Fe³⁺. The produced chlorine atom extracts an electron from the oxygen of a neighboring OH residue. The unpaired electron thus formed can move from one oxygen to another through hydrogen bonding. In other words, the photoconductivity is due to holes produced in the network of PVA hydrogen bonding by the reduction of Fe³⁺. Finally, we have tried to explain why the photoconductivity is observed only in the PVA–FeCl₃ film.     

Color change of an iodinated poly(vinyl alcohol) film by physical deformation

The color change of an iodinated poly(vinyl alcohol) (PVA) film caused by physical deformation was investigated in this study. The color of a PVA film soaked in an aqueous potassium iodide (KI)/I₂ solution was light yellow, but it turned light blue when the film was physically deformed. The ultraviolet–visible absorption spectrum of the iodinated PVA film extended uniaxially in air was measured at various extension levels. Without deformation, the film showed UV absorption bands at 210, 290, and 360 nm. However, under deformation, the film showed new visible light absorption bands at 440 and 620 nm. From the UV–vis absorption spectra of several iodinated solutions, we found that the absorption wavelength of iodine was affected by the cohesive energy of the solvents. The KI/I₂ diethyl ether solution showed an absorption band at 460 nm, and this provided a clue to understanding the color change of the PVA–iodine complexes caused by physical deformation. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43036.