壳聚糖/聚乙烯醇共混膜的氢键和相容性

采用溶液共混法制备了不同配比的壳聚糖/聚乙烯醇共混膜,通过变温FTIR、TG、DTA、DSC及XRD等对共混膜的结构、氢键相互作用、热行为和结晶性等进行研究。实验结果表明,共混膜中壳聚糖与聚乙烯醇间存在强烈的氢键相互作用。氢键的存在使壳聚糖的热稳定性提高,聚乙烯醇结晶性下降,促进壳聚糖与聚乙烯醇相容。当壳聚糖/聚乙烯醇共混膜的质量比分别为10/0、7/3、5/5、3/7和0/10时,共混膜的初始分解温度分别为244 ℃、257 ℃、260 ℃、262 ℃和285 ℃。聚乙烯醇熔融温度从193 ℃下降到173 ℃,玻璃化转变温度从74.2 ℃上升至80 ℃,结晶度Xc从3.57%下降到1.97%。     

Physicochemical and morphological evaluation of chitosan/poly(vinyl alcohol)/methylcellulose chemically cross-linked ternary blends

Chitosan/poly(vinyl alcohol)/methylcellulose (CS/PVA/MC) ternary blend was prepared and chemically cross-linked with glutaraldehyde. The prepared ternary blends were characterized by Fourier transform infrared spectroscopy (FTIR), Thermogravimetric analysis (TGA), and X-ray diffraction (XRD). The FTIR results showed that the strong intermolecular hydrogen bonds took place between CS and PVA. TGA showed the thermostability of the blend is enhanced by glutaraldehyde as crosslink agent. Results of XRD indicated that the relative crystalline of pure CS film was reduced when the polymeric network was reticulated by glutaraldehyde. Finally, the results of scanning electron microscopy (SEM) indicated that the morphology of the blend is rough and heterogenous, further it confirms the interaction between the functional groups of the blend components.     

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     

Oxidized pea starch/chitosan composite films: Structural characterization and properties

In this article, a series of oxidized pea starch/chitosan (OPS/CS) blend films were prepared by a casting and solvent evaporation method. The structure, thermal behavior, and mechanical properties of the films were investigated by means of Fourier transform infrared spectroscopy, wide‐angle X‐ray diffraction, scanning electron microscopy, thermogravimetric analysis, and tensile testing. The results suggested that, in addition to hydrogen bonding, the interactions between OPS and CS molecules were enhanced by the formation of electrostatic interaction between the negatively charged carboxyl groups on OPS and the positively charged amino groups on CS. Compared with the pea starch/chitosan (PS/CS) blend films, OPS/CS blend films exhibited significantly higher tensile strength with significantly lower elongation at break. Moreover, incorporation of CS into the OPS matrix also led to a decrease in moisture uptake by the composite film. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Effects of halloysite nanotubes and kaolin loading on the tensile,swelling, and oxidative degradation properties of poly(vinyl alcohol)/chitosan blends

[Halloysite nanotubes (HNT)]‐filled and kaolin filled composite films based on poly(vinyl alcohol) (PVA)/chitosan (CS) blend were prepared via solution casting method. Tensile properties, fracture morphology, FTIR spectra, thermal stability, swelling properties, moisture absorption, and oxidative degradation of the composite films were investigated. Addition of 0.5 wt% of filler led to the optimum tensile properties of the films. Increased roughness and tearing in the fracture surface morphology supported the tensile results. The FTIR results indicated there were physical interactions present in the composite films. Thermal stability of the composite films differed slightly where PVA/CS/HNT composite films showed better thermal stability than PVA/CS/kaolin composite films. Moreover, the presence of HNT and kaolin fillers in the blend reduced the swelling and moisture absorption properties of the films. Finally, the composite films were degraded by using Fenton's reagent. Degradation percentage of the composite films decreased with increasing filler loading. J. VINYL ADDIT. TECHNOL., 19:55–64, 2013. © 2013 Society of Plastics Engineers     

Characterization of polyvinyl alcohol/gelatin blend hydrogel films for biomedical applications

In the present investigation, attempt was made to prepare blend hydrogel by esterification of polyvinyl alcohol with gelatin. The blend hydrogel was further converted into films by the conventional solution‐casting method. These films were characterized by FTIR, DSC, and X‐ray diffraction studies. The refractive index and viscosity of different composition of the blends were measured in the solution phase of the material. The mechanical properties of the blend films were measured by tensile test. Swelling behavior of the blend hydrogel was also studied. The FTIR spectrum of the blend film indicated complete esterification of the free carboxylic group of gelatin. The DSC results indicate that the addition of gelatin with PVA changes the thermal behavior like melting temperature of PVA, which may be due to the miscibility of PVA with gelatin. The interaction of gelatin with PVA molecule changes the crystallite parameters and the degree of crystallinity. The crystallinity of the blend film was mainly due to gelatin. The comparison of viscosity indicated an increase in the segment density within the molecular coil. The results revealed the changes observed in the properties of the gel, and it enhances the gel formation at viscoelastic phase of the material. The blend film had sufficient strength and water‐holding capacity. The results obtained indicated that the blend film could be used for various biomedical applications such as wound dressing and drug‐delivery systems. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Poly (vinyl alcohol)/polylactic acid blend film with enhanced processability,compatibility, and mechanical property fabricated via melt processing

Poly (vinyl alcohol)/polylactic acid (PVA/PLA) blend film, which is environment friendly and has potential applications in food and electronic packaging fields, was fabricated by melt extrusion casting. Fourier transform infrared spectroscopy analysis confirmed the formation of the hydrogen bonding between PLA and PVA, which improved the compatibility of PLA with PVA, making PLA uniformly dispersed in PVA matrix as small spheres, even when PLA content increase to 15 wt%. In this way, the original hydrogen bond network among PVA was disturbed and the chain mobility of PVA was activated, endowing PVA/PLA blends with lower melt viscosity than bot modified PVA and PLA, and the blend films with the increased crystallinity, mechanical property, and water resistance. Compared with PVA film, the crystallinity, tensile strength and Young's modulus of the blend film with 15 wt% PLA, respectively, increased by 15.1%, 9 and 51 MPa, and the water contact angle enlarged from 23° to 60°.     

Blend films from chitosan and konjac glucomannan solutions

Blend films were prepared by blending 7 wt % konjac glucomannan (KGM) aqueous solution with 2 wt % chitosan (CH) in acetate solution and dried at 40°C for 4 h to obtain the transparent films. Their structure and properties were studied by infrared (IR), wide‐angle X‐ray diffraction (WAXD), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and differential thermal analysis (DTA). Crystallinities of the blend films decreased with the increase of konjac glucomannan. The thermostability, tensile strength, and breaking elongation of the blend films in dry state were obviously higher than those of both konjac glucomannan and chitosan films. Tensile strength of the dry blend film achieved 73.0MPa when the weight ratio of chitosan to konjac glucomannan was 7:3. The structure analysis indicated that there is a strong interaction between konjac glucomannan and chitosan resulted from intermolecular hydrogen bonds. The water solubility of the blend films was improved by blending with konjac glucomannan, so they have promising applications to soluble antiseptic coating of pills. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 509–515, 2000     

Bio‐nanocomposite films based on cellulose nanocrystals filled polyvinyl alcohol/chitosan polymer blend

Bio‐nanocomposite films based on polyvinyl alcohol/chitosan (PVA/CS) polymeric blend and cellulose nanocrystals (CNC) were prepared by casting a homogenous and stable aqueous mixture of the three components. CNC used as nanoreinforcing agents were extracted at the nanometric scale from sugarcane bagasse via sulfuric acid hydrolysis; then they were characterized and successfully dispersed into a PVA/CS (50/50, w/w) blend to produce PVA/CS–CNC bio‐nanocomposite films at different CNC contents (0.5, 2.5, 5 wt %). Viscosity measurement of the film‐forming solutions and structural and morphological characterizations of the solid films showed that the CNC are well dispersed into PVA/CS blend forming strong interfacial interactions that provide an enhanced load transfer between polymer chains and CNC, thus improving their properties. The obtained bio‐nanocomposite films are mechanically strong and exhibit improved thermal properties. The addition of 5 wt % CNC within a PVA/CS blend increased the Young's modulus by 105%, the tensile strength by 77%, and the toughness by 68%. Herein, the utilization of Moroccan sugarcane bagasse as raw material to produce high quality CNC has been explored. Additionally, the ability of the as‐isolated CNC to reinforce polymer blends was studied, resulting in the production of the aforementioned bio‐nanocomposite films with improved properties. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42004.     

Enhancement of water barrier properties of cassava starch-based biodegradable films using silica particles

Biodegradable films are used in a variety of applications, including packaging. However, their use is limited due to their high moisture and water sensitivity. In this work, cassava starch (CS) was blended with poly(vinyl alcohol) (PVA). Silica particles (SiO₂) were incorporated to increase the hydrophobicity of the blend by intermolecular interaction through hydrogen bonding between the three components. Instead of a plasticizer or crosslinker, a small amount of triethylamine was added to eliminate residual acetate groups in PVA. The miscibility of CS and PVA phases was confirmed by smooth fracture surfaces and a single glass transition temperature. When SiO₂ content was below 5% (wt), the particles were well dispersed in a continuous phase of polymer matrix. At this loading of SiO₂, the increase in tensile strength was as high as 170% and in elongation-at-break, 250%. All loadings of SiO₂ increased thermal stability of the blend films because silanol groups on the surface of SiO₂ particles formed effective interfacial interactions with hydroxyl groups of the polymers. These interactions also prevented the ingress of water molecules, significantly increasing the hydrophobicity of the films. The water contact angle increased as high as 113° and moisture absorbency and water solubility were low. These highly hydrophobic, photodegradable, biodegradable CS/PVA/SiO₂ films show great potential as a low-cost, eco-friendly material.

     

Development of biopolymer composite films based on chicory extract reinforced polyvinyl alcohol/chitosan blend via green approach for flexible optoelectrical devices

Biopolymer blend composite films based on polyvinyl alcohol (PVA) and chitosan (CS) incorporated with varying amounts of chicory extract (CE) have been developed by the green solution casting technique. The impact of CE content on structural, thermal, mechanical and electrical properties was thoroughly examined. The existence of intermolecular interactions in the blend composite was confirmed by Fourier-transform infrared and ultraviolet spectroscopy. The x-ray diffraction pattern proved the successful preparation of PVA/CS/CE composite film. The scanning electron microscopy images of the composites showed shape and grain size for the different bio-filler contents. The thermal transition temperature of the blend composites was significantly improved by the addition of CE extract deduced from differential scanning calorimetry. The dielectric study showed that the permittivity remarkably increases with decreasing frequency and maximum dielectric constant was observed for 15 wt% loading. The activation energy obtained from the AC conductivity decreased as the temperature increased. The addition of CE extract improved the hardness and tensile strength of the PVA/CS blend composite in comparison with a pristine pure blend. The controllable mechanical, thermal, optical, and electrical characteristics of the PVA/CS blend composite suggest that it might be an attractive optical material for the advancement of futuristic flexible-type optoelectronic and energy storage systems.     

Preparation and characterization of conductive poly(vinyl alcohol)/polyaniline doped by dodecyl benzene sulfonic acid (PVA/PANDB) blend films

In this study a solution‐blend method is adopted to prepare conductive poly(vinyl alcohol)/polyaniline doped by dodecyl benzene sulfonic acid (PVA/PANDB) blend films. Emeraldine base (EB)‐type polyaniline (PANI) is dissolved in N‐methyl‐2‐pyrrolidinone (NMP) and then blended with PVA/dodecyl benzene sulfonic acid (DBSA) solution by various amounts. It is found that the electrical conductivity and the thermal degradation onset temperature of the PVA/PANDB blend film are increased as the amount of EB‐type PANI solution is increased. Fourier transform infrared (FTIR) spectra show that the intensity of the characteristic peak of the functional groups in the blend film is significantly changed as the amount of EB‐type PANI is changed. From optical microscopy examination, it indicates that the amount and size of green particles are increased with increasing the amount of EB‐type PANI solution. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3415–3422, 2007     

Characterization of films from chitosan and quaternized poly(4‐vinyl‐N‐butyl) pyridine solutions

All Blend films were prepared from a mixture of 2 wt % chitosan in acetate solution and 4 wt % quaternized poly(4‐vinyl‐N‐butyl) pyridine (QPVP) in aqueous solution and dried at room temperature for 72 h to obtain the films. Their structure and properties were studied by infrared (IR), wide‐angle X‐ray diffraction (WXRD), scanning electron microscopy (SEM), thermogravimetric analysis (TG), and differential scanning calorimetry (DSC). Crystallinities of the blend films decreased with the increase of QPVP when weight of QPVP content was less than 15.0 wt %. The thermostability, tensile strength, and breaking elongation of the films in dry state were better than those of chitosan film. Tensile strength of the blend film dried at 40°C under vacuum for 24 h achieved 56.38 MPa when the weight ratio of chitosan to QPVP was 9 : 1. The structural analysis indicated that there was a strong interaction between chitosan and QPVP resulting from strong adhesion between both polymers. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 559–566, 2004     

Properties of soy protein isolate/poly(vinyl alcohol) blend “green” films: Compatibility,mechanical properties,and thermal stability

Blend films from nature soy protein isolates (SPI) and synthetical poly(vinyl alcohol) (PVA) compatibilized by glycerol were successfully fabricated by a solution‐casting method in this study. Properties of compatibility, mechanical properties, and thermal stability of SPI/PVA films were investigated based on the effect of the PVA concentration. XRD tests confirm that the SPI/PVA films were partially crystalline materials with peaks of 2θ = 20°. And, the addition of glycerol will insert the crystalline structure and destroy the blend microstructure of SPI/PVA. Differential scanning calorimetry (DSC) tests show that SPI/PVA blend polymers have a single glass transition temperature (T_g) between 80 and 115.0°C, which indicate that SPI and PVA have good compatibility. The tension tests show that SPI/PVA films exhibit both higher tensile strength (σ_b) and percentage elongation at break point (P.E.B.). Thermogravimetric analysis (TGA) and water solubility tests show that SPI/PVA blend polymer has more stable stability than pure SPI. All the results reflect that SPI/PVA/glycerol blend film provides a convenient and promising way to prepare soy protein plastics for practical application. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Influence of Syzygium cumini leaves extract on morphological,thermal, mechanical,and antimicrobial properties of PVA and PVA/chitosan blend films

In the present work, poly(vinyl alcohol)/Syzygium cumini leaves extract (PSN) and poly(vinyl alcohol)/chitosan/S. cumini leaves extract blend films were prepared by solution casting technique. The films were characterized by using scanning electron microscopy, atomic force microscopy, X‐ray diffraction study, Fourier transform infrared spectroscopy, thermogravimetric analysis, and universal testing machine. The results indicated that the appreciable physical interaction at lower concentrations of S. cumini leaves extract in the PVA and PVA/chitosan films contribute to the smooth uniform morphology, increased the degree of crystallinity, degradation temperature, and improved mechanical properties. Further, films were analyzed with water contact angle analyzer which illustrates that blend films were hydrophilic (PSN‐1) and hydrophobic (PCS‐1) in nature. However, blend films were also subjected to the antimicrobial study, which revealed that inclusion of S. cumini leaves extracts significantly enhanced the antibacterial activity in the PVA and PVA/chitosan film. With all of these results, fabricated blends can find potential applications in packaging material to extend the shelf life of foodstuffs. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46188.     

Heterogeneous method of chitosan film preparation: Effect of multifunctional acid on film properties

The heterogeneous crosslinking method was applied to chitosan films with citric acid to observe and understand the effect of a multifunctional acid at a low concentration on film properties. Neat and neutralized chitosan films and films containing 15% (w/w) citric acid (denoted as CA films) were characterized by mechanical, water vapor permeability (WVP), and thermogravimetric analysis tests. The CA films displayed a higher tensile strength by 10%, lower WVP by 30%, and higher thermal stability, compared to neutralized films. The crystalline structure converted back from tendon to Type II after the addition of citric acid, as determined by X-ray diffraction. Neat films displayed a lower water contact angle (72°) compared to neutralized and CA films (78°–79°). The heterogeneous method was also applied to incorporate a plasticizer into a neutralized film to potentially observe the glass transition using dynamic mechanical analysis. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48648.     

Novel blend microspheres of poly(vinyl alcohol) and succinyl chitosan for controlled release of nifedipine

Water-soluble succinyl chitosan (SCS) was synthesized by reacting succinic anhydride with –OH and –NH₂ reactive groups of chitosan (CS). The blend hydrogel microspheres were prepared from SCS with poly(vinyl alcohol) (PVA) by water-in-oil (w/o) emulsion cross-linking using glutaraldehyde (GA) as the cross-linking agent. Nifedipine (NFD), an antihypertensive drug having a plasma half-life of 2 h, was encapsulated giving encapsulation efficiency up to 92 % and its release was extended up to 12 h. Scanning electron microscopy (SEM) confirmed the spherical nature and smooth surfaces of the microspheres, while Fourier transform infrared spectroscopy (FTIR) confirmed succinylation of CS and chemical stability of NFD in the matrix. Thermogravimetry (TGA) and differential scanning calorimetry (DSC) characterized the SCS and the blend hydrogel microspheres. X-ray diffraction (XRD) and DSC were also used to study the crystalline or amorphous nature of NFD. Swelling and in vitro release experiments performed in pH 1.2 and 7.4 buffer media showed a dependence of blend composition, extent of cross-linking and pH of the media. The mechanism of drug release as analyzed by an empirical equation, suggested non-Fickian trends.     

Preparation and characterization of films based on crosslinked blends of gum acacia,polyvinylalcohol, and polyvinylpyrrolidone-iodine complex

In an attempt to develop iodine-release systems based on polymeric blend for biomedical applications, our research group prepared blends of gum acacia (GA), polyvinylalcohol (PVA), and polyvinylpyrrolidone-iodine (PVP-I) complex. The blends of GA/PVA and GA/PVA/PVP-I prepared from the aqueous solutions of the polymers were crosslinked with glutaraldehyde to increase the water resistance of the films and to improve their thermal and mechanical properties. The crosslinked GA/PVA and GA/PVA/PVP-I blend films were characterized by FTIR spectroscopy, DSC, and TGA. The swelling behavior of the prepared blends was investigated and crosslinked GA/PVA blend films were found to be pH sensitive. The properties of PVP-I containing blends differed from those prepared without it probably due to the formation of an intermolecular interaction between PVP-I and the hydroxy-polymers. The results indicated that after crosslinking the blends showed improvement in water resistance, thermal, and mechanical properties. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effect of nano-SiO2 on the compatibility of PVA/RSF blend

A series of poly(vinyl alcohol) (PVA)/regenerated silk fibroin (RSF)/nano-silicon dioxide (nano-SiO₂) blend films were prepared by solution casting method, in which nano-SiO₂ was obtained via sol?Cgel process. The structure, properties, and morphology of the films related to the compatibility were investigated by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), differential scanning calorimetry (DSC), and thermogravimetric analysis (TGA). XRD peaks of PVA/RSF/nano-SiO₂ (1.0?wt?%) blends decreased in intensity indicated that formation of PVA and RSF crystal lattices was hindered by nano-SiO₂ particles. FTIR spectroscopy analysis of PVA/RSF/nano-SiO₂ films confirmed that both Si?CO?CC linkage and hydrogen bonding were formed among PVA, RSF, and nano-SiO₂. SEM showed that there was no obvious phase separation in PVA/RSF/nano-SiO₂ (1.0?wt?%) film although small uniform blur particles can still be found. In addition, TEM showed nano-particles were well dispersed through the PVA/RSF polymer matrix. Besides, the observed shift in glass transition temperatures (T _g) and improvement in thermal properties of composite films suggested the enhanced compatibility due to interfacial bonding and intermolecular interactions. Therefore, these results indicated that the compatibility of PVA/RSF was improved effectively by the addition of nano-SiO₂.     

Miscibility and phase structure of binary blends of poly(L‐lactide) and poly(vinyl alcohol)

Blend films of poly(L ‐lactide) (PLLA) and poly(vinyl alcohol) (PVA) were obtained by evaporation of hexafluoroisopropanol solutions of both components. The component interaction, crystallization behavior, and miscibility of these blends were studied by solid‐state NMR and other conventional methods, such as Fourier transform infrared (FTIR) spectra, differential scanning calorimetry (DSC), and wide‐angle X‐ray diffraction (WAXD). The existence of two series of isolated and constant glass‐transition temperatures (T_g's) independent of the blend composition indicates that PLLA and PVA are immiscible in the amorphous region. However, the DSC data still demonstrates that some degree of compatibility related to blend composition exists in both PLLA/atactic‐PVA (a‐PVA) and PLLA/syndiotactic‐PVA (s‐PVA) blend systems. Furthermore, the formation of interpolymer hydrogen bonding in the amorphous region, which is regarded as the driving force leading to some degree of component compatibility in these immiscible systems, is confirmed by FTIR and further analyzed by ¹³C solid‐state NMR analyses, especially for the blends with low PLLA contents. Although the crystallization kinetics of one component (especially PVA) were affected by another component, WAXD measurement shows that these blends still possess two isolated crystalline PLLA and PVA phases other than the so‐called cocrystalline phase. ¹³C solid‐state NMR analysis excludes the interpolymer hydrogen bonding in the crystalline region. The mechanical properties (tensile strength and elongation at break) of blend films are consistent with the immiscible but somewhat compatible nature of these blends. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 762–772, 2001