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     

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     

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 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.     

Structure and processability of iodinated poly(vinyl alcohol). II. Drawability of iodinated films

The drawability of poly(vinyl alcohol) (PVA) films iodinated with 0.1, 0.3, 0.5, 1.0, and 2.0 mol/L I₂/KI aqueous solutions was examined with a tensile tester and a hand‐operated drawer at 30–150°C. The structure of the films drawn to a maximum draw ratio (MDR) and deiodinated was determined by X‐ray diffractometry, differential scanning calorimetry, and birefringence. Generally, the improvement of the drawability for the PVA film via iodination was ascertained by the increased breaking strain and decreased yield stress on the stress–strain curves when increasing the I₂/KI concentration of the aqueous solutions used in the iodination. The MDR was generally increased with the concentration of I₂/KI and the draw temperature. However, it diminished instead when close to the highest temperature and concentration of I₂/KI, which was likely due to molecular degradation by the action of iodine as an oxidizer. The variation of the structure of the films drawn and deiodinated seems to be dependent mainly upon the MDR rather than the concentration of I₂/KI. The greater the MDR was, the higher the degree of crystallinity, birefringence, and initial modulus were but the lower the melting temperature. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95:1209–1214, 2005     

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.     

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     

Role of boric acid in the formation of poly(vinyl alcohol)-iodine complexes in undrawn films

The role of boric acid in the formation of poly(vinyl alcohol) (PVA)-iodine complexes in undrawn films has been investigated by using wide-angle X-ray diffraction (WAXD) and high-resolution solid-state ¹³C NMR spectroscopy. From UV-vis absorption spectroscopy, it is confirmed that boric acid is necessary for the formation of the complexes in films that are treated with I₂/KI aqueous solutions at relatively low I₂ concentrations. The WAXD profiles indicate that, irrespective of the presence of iodine, crystallite sizes perpendicular to the chain axis become smaller by the addition of boric acid in the swelling media. Moreover, small crystallites and surficial parts of larger crystallites may be partially dissolved in the swelling process with water and boric acid suppresses the re-crystallization in the drying process with or without iodine. The ¹³C spin-lattice relaxation time analysis reveals that there exist two components called the mobile and the less mobile components in the films and the latter component, which contains the complexes and the crystalline component, is increased in the fraction by the presence of boric acid. The evaluation of the CH resonance line shows that some of the intermolecular hydrogen bonds are broken by boric acid, which increases the intramolecular hydrogen bonds. The CH₂ lineshape analysis also reveals that the gauche fraction is appreciably increased in the less mobile component by the addition of boric acid. These facts suggest that boric acid may promote the formation of PVA-iodine complexes particularly in the surficial areas of the crystallites probably by reducing the molecular mobility of the PVA chains by causing cross-linking among them.     

Polarization characteristics of poly(vinyl alcohol) films containing metal iodide

The polarization properties of iodine complex layer deposited by oxidation of poly(vinyl alcohol) (PVA) containing metal iodide were investigated. Heat-resistant polarizing films with high polarization efficiency were produced by oxidizing and stretching the PVA containing metal iodide. The results indicate that i) the polarization efficiency of a polarizing film prepared by oxidation of a PVA film containing 1 mmol or more of potassium iodide (KI)/g PVA at 0°C for 120 s in a 10 wt.-% aqueous solution of H₂O₂ and a degree of stretching of 400% is high, ii) the heat resistance of the polarizing film in this experiment is higher than that of a filter prepared from a commercial PVA film.     

Structure and processability of iodinated poly(vinyl alcohol) (III)‐structure of films iodinated in solution before casting

Films iodinated at solution before casting (IBC films) were prepared by casting aqueous solutions of 10 wt % poly(vinyl alcohol) (PVA) containing selected quantities of I₂/KI. The quantity of I₂/KI was controlled to obtain 15.2, 39.8, 83.2, 117.0, and 140.1%. The Thermogravimetry (TG) curves of the IBC film exhibited three distinct zones corresponding to the evaporation of H₂O and I₂ molecules (zone I), evaporation of I₂ and partial decomposition of side groups (? OH) (zone II), degradation of the remaining side groups and partial degradation of the main chain (zone III‐1), and degradation of the remaining main chain and the char zone corresponding to KI. The crystalline structure of the film with a weight gain of 15.2% was almost the same as that of the pure PVA, and the film with the weight gain of 140% was almost amorphous. The differential scanning calorimetry (DSC) thermograms of the IBC films with a weight gain of 15.2% and 39.8% indicated endothermic single or double peaks at around 180°C, corresponding to the crystal melting and degradation of side groups; those with weight gains of 83.2% and above indicated exothermic peaks at around 170°C, corresponding to crystallization, and broad endothermic peak at around 180–200°C, corresponding to the crystal melting and degradation of side groups. The dynamic mechanical α_a transition of the IBC film with the weight gain of 140.1% appeared at around 20°C. X‐ray diffraction and DSC analysis of deiodinated films show that the crystal structure, on deiodination of all the IBC films, regardless of crystallinity, returned to that of the pure PVA. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3497–3502, 2006     

Study on the structure and processibility of the iodinated poly(vinyl alcohol). I. Thermal analyses of iodinated poly(vinyl alcohol) films

To get more information on the structure of iodinated poly(vinyl alcohol) (PVA), thermal analyses of unoriented and oriented PVA films were conducted. Unoriented and oriented PVA films iodinated with aqueous solutions at selected concentrations were carried out by thermogravimetry (TG) and differential scanning calorimetry (DSC). The TG curves for the iodinated film shows four or five weight‐loss zones associated with degradation and evaporation of excess I₂ molecules and I₂ molecules from I, partial OH side groups on PVA, and I₂ from I, the remaining OH groups and the partial main chains, the remaining main chains, and a very small amount of residue from PVA. The char of KI salts remained. By investigating the TG results, it was identified that the amount of I ions increased with increasing I₂/KI up to 65%, but above that weight gain, the rate of increase diminished and the amount of I ions from the I ions increased. The TG curve for the oriented film was very similar to that for the unoriented film except for its greater weight loss at zone I due to narrow space in amorphous region. The DSC thermogram of iodinated films indicated two peaks at 145°C and 160–170°C, corresponding to the melting of crystals and the degradations of OH groups and main chains, respectively. The maximum temperatures of peaks were much lower than that of the untreated one. ©2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2407‐2415, 2004     

On the poly(vinyl alcohol)–iodine complexes

The color development due to the complex formation of poly(vinyl alcohol) (PVA) with iodine increased with increasing syndiotacticity of PVA. Isotactic PVA showed no color development. The color development of syndiotacticity-rich PVA film decreased with increasing annealing temperature for films before complexization, whereas that of atactic (commercial) PVA increased with it. Lower temperatures, the elongation of complex film, and the presence of boric acid enhanced the absorbance at 600 nm due to I^?₅. The complexes are assumed to be made by incorporation of polyiodines into aggregates of syndiotactic sequences in PVA. The polarizability and electric conductivity of complex films are investigated. © 1993 John Wiley & Sons, Inc.     

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     

Study on the structure of nylon 6 films iodinated before forming. III. Fine structure variation of the amorphous film through deiodination

Amorphous nylon 6 film iodinated before forming with an aqueous solution of 1.0N iodine–potassium iodide (I₂/KI) was deiodinated by dipping in water/ethylene glycol (EG) solutions of sodium thiosulfate with various EG contents and temperatures, washed with water, and dried at ambient condition. Structural variation through deiodination and the effects of the deiodination conditions were investigated by X‐ray diffractometry and differential scanning calorimetry. The degree of swelling of the films immediately after deiodination and the time required to complete the deiodination were generally increased and decreased, respectively, with increasing temperature and EG content. The amorphous iodinated film was crystallized through deiodination. The α‐crystal formation became easier with increasing temperature and EG content in the solution. The crystallinity of the films was higher after drying than before drying, suggesting that the drying induced further crystallization without any significant conversion of crystal type. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Role of adsorbed iodine into poly(vinyl alcohol) films drawn in KI/I2 solution

We have investigated the microstructure of the poly(vinyl alcohol) (PVA) films using small- and wide-angle X-ray scattering (SAXS and WAXS, respectively) techniques. The samples were uniaxially drawn in water or KI/I₂ aqueous solution and then dried in an air-oven at 333 K for 1 h prior to SAXS and WAXS measurements. It was found that for the films drawn in KI/I₂ solution PVA chains in the microfibrillar structure are more extended upon the film drawing compared to the case of the films drawn in pure water, which is resulted from the correlation function analysis on the SAXS data. Adsorbed iodines into the film were anticipated to act as junction points between the microfibrils via the formation of the PVA-iodine complexes.     

Study on the structure of nylon 6 films iodinated before forming. II. Investigation of the crystallization behavior through thermal analysis

Two kinds of amorphous nylon 6 films iodinated before forming from the powders iodinated with 0.2N and 1.0N I₂/KI aqueous solutions were prepared by a melt‐press, and isothermally treated at 20 to 80°C for 1 day to 20 days. Thermal analyses were performed to investigate mainly the crystallization behavior on the treatment. The DSC thermograms for the treated films exhibit three temperature‐groups of endothermic peaks at 60 ～ 70°C, 105 ～ 120°C, and higher than 150°C, which may be associated with the melting of the complex crystal, the relaxed γ‐crystal, and the relaxed α‐crystal, respectively. The film containing less I₂/KI and treated at the higher temperature exhibits the peaks associated with the more stable type of crystal. The peak temperature generally increases with the treating temperature and time. On the occasion of there being two peaks associated with the γ‐crystal and the α‐crystals, ΔH for the α‐crystal increases while that for the γ‐crystal decreases with increasing the treating time. The TG curves indicate two temperature‐zones of weight loss by the volatilization of I₂ from I₅^? and the decompositions of I₃^? and nylon 6. With increasing treating temperature, the % weight loss by the volatilization of I₂ decreases, and consequently the temperature of the weight loss by the decomposition of nylon 6 increases. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1062–1069, 2004     

Conductivity studies of poly (vinyl alcohol)-iodine complex membrane

Summary The conductivities of polymers like poly (vinyl alcohol) (PVA) and its iodine complex membranes are reported here. PVA-iodine complex membrane was prepared by dipping PVA film into an I₂–KI solution. The formation of the complex membrane was confirmed by IR spectra. Conductivities were determined from 30 to 300 °C with a frequency ranges from 42 Hz to 500 KHz in solid state. It was observed that iodine is known to act as a catalyst for dehydration of PVA. A possible mechanism for the dehydration of PVA catalyzed by iodine is also explained.     

Role of boric acid for a poly (vinyl alcohol) film as a cross-linking agent: Melting behaviors of the films with boric acid

We have investigated the role of boric acid as a cross-linking agent for a poly (vinyl alcohol) (PVA) film when the film is immersed in boric acid aqueous solution. DSC results show that the films with boric acid exhibit the higher glass transition temperatures than that of the PVA film without boric acid, when the films are dried after immersing in boric acid aqueous solutions with various boric acid concentrations, implying that boric acid penetrating into the films slows down the PVA molecular motion. Furthermore, simultaneous small-angle X-ray scattering and wide-angle X-ray diffraction measurements were performed on the melting processes of the PVA films with boric acid. We found that the crystallite size increase originated from melting and recrystallization do not occur for the PVA films with boric acid, whereas in the case of the PVA without boric acid the crystallite size is enlarged in both directions parallel and perpendicular to the chain axis via melting and recrystallization on melting. These indicate that chemical reactions of boric acid to the PVA molecular chains in amorphous regions resulted in cross-linking points take place in boric acid aqueous solutions, inhibiting recrystallization on melting, because the cross-links slow down the PVA molecular motion and must not be included in the crystalline domains.     

Water stability of high‐molecular‐weight (HMW) syndiotacticity‐rich poly(vinyl alcohol) (PVA)/HMW atactic PVA/iodine complex blend films

To precisely identify the effect of blend ratios of syndiotacticity‐rich poly(vinyl alcohol) (s‐PVA)/atactic PVA (a‐PVA) on the water stability of s‐PVA/a‐PVA/iodine complex blend films, we prepared two PVAs with similar number‐averaged degrees of polymerization of 4000 and degrees of saponification of 99.9% and with different syndiotactic diad contents of 58.5 and 53.5%, respectively. The desorption behavior of iodine in s‐PVA/a‐PVA/iodine complex films in water was investigated in terms of the solubility of s‐PVA/a‐PVA blend films in water. The degree of solubility of s‐PVA/a‐PVA blend films with s‐PVA content over 50% in water at 70°C was limited to about 10–20%, whereas that of s‐PVA/a‐PVA blend films with s‐PVA content of 10% was 85% under the same conditions. The degree of iodine desorption of complex blend films decreased with increasing s‐PVA content. The degree of iodine desorption of s‐PVA/a‐PVA drawn film with s‐PVA content of 90% was limited to 7%, regardless of the soaking temperature from 30 to 70°C. The desorption of iodine in water was strongly affected by the dissolution of blends. Moreover, the stability of iodine in the drawn s‐PVA/a‐PVA/iodine blend films in hot water was far superior to that of the undrawn film. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1435–1439, 2004     

Starch crosslinked with poly(vinyl alcohol) by boric acid

Starch was crosslinked with poly(vinyl alcohol) (PVA) by boric acid. A suitable plasticizer and defoamer were added to obtain the brei. A film from the starch and PVA (SP film) was prepared by casting. The effects of various factors, such as the crosslinking temperature, the PVA content, and the amounts of glycerol and boric acid, on the tensile strength and breaking elongation were studied. The results showed that the SP film prepared by boric acid crosslinking had excellent mechanical properties. The film‐forming properties, transmittance, and water resistance of the SP film were also investigated. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1394–1397, 2005