Poly(vinyl alcohol)/cellulose nanocrystal barrier membranes

In this study, barrier membranes were prepared from poly(vinyl alcohol) (PVOH) with different amounts of cellulose nanocrystals (CNXLs) as filler. Poly(acrylic acid) (PAA) was used as a crosslinking agent to provide water resistance to PVOH. The membranes were heat treated at various temperatures to optimize the crosslinking density. Heat treatment at 170 °C for 45 min resulted in membranes with improved water resistance without polymer degradation. Infrared spectroscopy indicated ester bond formation with heat treatment. Mechanical tests showed that membranes with 10% CNXLs/10% PAA/80% PVOH were synergistic and had the highest tensile strength, tensile modulus and toughness of all the membranes studied. Polarized optical microscopy showed agglomeration of CNXLs at filler loadings greater than 10%. Differential thermogravimetric analysis (DTGA) showed a highly synergistic effect with 10% CNXL/10% PAA/80% PVOH and supported the tensile test results.Transport properties were studied, including water vapor transport rate and the transport of trichloroethylene, a representative industrial toxic material. Water vapor transmission indicated that all the membranes allowed moisture to pass. However, moisture transport was reduced by the presence of both CNXLs and PAA crosslinking agent. A standard time lag diffusion test utilizing permeation cups was used to study the chemical barrier properties. The membranes containing ≥10% CNXLs or PAA showed significantly reduced flux compared to the control. The CNXLs were then modified by surface carboxylation in order to better understand the mechanism of transport reduction. While barrier performance improvements were minimal, the chemical modification improved the dispersion of the modified CNXLs which led to improved performance. Of special note was an increase in the initial degradation temperatures of both modified and unmodified systems, with the modified system showing an initial degradation temperature >100 °C higher than the cellulose alone. This may reflect more extensive crosslinking in the modified composite.     

Miscibility and orientation behavior of poly(vinyl alcohol) / poly(vinyl pyrrolidone) blends

The miscibility of poly(viny1 alcohol)/poly(vinyl pyrrolidone) (PVA/PVP) blends is investigated by differential scanning calorimetry (DSC) and wide-angle x-ray diffraction (WAXD). The molecular orientation induced by uniaxial stretching of the blends is also examined by WAXD and birefringence measurements. It is shown by the DSC thermal analysis that the polymer pair is miscible, since a single glass transition temperature (T_g) is situated between the T_gs of the two homopolymers at every composition. The T_g versus composition curve does not follow a monotonic function but exhibits a cusp point at a PVP volume fraction of a little under 0.7, as in a case predicted by Kovacs' theory. The presence of a specific intermolecular interaction between the two polymers is suggested by an observed systematic depression in the melting point of the PVA component. A negative value of the polymer-polymer interaction parameter, χ₁₂ = 0.35 (at 513 K), is estimated from a thermodynamic approach via a control experiment using samples crystallized isothermally at various temperatures. The extent of optical birefringence (Δn) of the drawn blends decreases drastically with increasing PVP content up to 80 wt %, when compared at a given draw ratio, and ultimately Δn is found to change from positive to negative at a critical PVP concentration of a little over 80 wt %. Discussion of the molecular orientation behavior takes into consideration a birefringence compensation effect in the miscible amorphous phase due to positive and negative contributions of oriented PVA and PVP, respectively.     

Rheological investigation of aqueous solutions of poly(vinyl alcohol) during ageing

The changes in viscosity and normal stress difference during the ageing of concentrated aqueous solutions of poly(vinyl alcohol) prepared at 80 °C and the effect of the procedure used in the preparation of solutions on the course of these changes are described. The results are interpreted by means of shear complianceJ _e and relaxation time ₀.     

Potassium sorbate release from poly(vinyl alcohol)-bacterial cellulose films

Active packaging materials are the subject of research because their performance exceeds that of traditional packaging. From this class, antimicrobial materials extend the shelf-life of products and reduce the risk of contamination by pathogens. In this paper, new composite materials with antimicrobial properties are obtained by using polyvinyl alcohol and bacterial cellulose powder. Potassium (2E,4E)-hexa-2,4-dienoate was used as the antimicrobial agent. The films thus obtained were characterised using Fourier-transform infrared spectroscopy and scanning electron microscopy. Mass transfer phenomena concerning the release of potassium (2E,4E)-hexa-2,4-dienoate were investigated. The results indicated that the new biocomposite films could be used as antimicrobial packaging materials.     

Properties of new polyelectrolytes based on cellulose and poly(vinyl alcohol)

Carbo- and heterochain tetrazole-containing polyelectrolytes are synthesized via a sequence of cyanoethylation reactions followed by azidation of cyanoethyl derivatives of cellulose and poly(vinyl alcohol). The products exhibit properties typical for polymers containing N-H unsubstituted tetrazole cycles.     

Heterotactic poly(vinyl alcohol)

Bulky substituents in vinyl trialkylsilyl ethers and vinyl trialkylcarbinyl ethers led to heterotactic polymers (H = 66%). The polymers were converted into poly(vinyl alcohol) (PVA) and further to poly(vinyl acetate), and tacticity was determined as poly(vinyl acetate). Vinyl triisopropylsilyl ether in nonpolar solvents yielded a heterotactic polymer with a higher percentage of isotactic triads than syndiotactic triads (Hetero-I). Vinyl trialkylcarbinyl ethers in polar solvents gave a heterotactic polymer with more syndiotactic triads than isotactic (Hetero-II). Heterotactic PVA was soluble in water and showed characteristics infrared absorptions. Interestingly, Hetero-I PVA showed no iodine color reaction, but Hetero-II showed a much more intense color reaction than a commercial PVA. The mechanism of heterotactic propagation was discussed in terms of the Markóv chain model.     

Phase behavior and gelation of solutions of poly (vinyl alcohol)

The phase behavior of poly (vinyl alcohol) dissolved in ethylene glycol and propylene glycol was studied. On cooling a solution in the low concentration range, solidification results from a combination of a liquid-liquid demixing and a crystallization or liquid-solid demixing. This conclusion is based on the results obtained from optical and calorimetric observations and is further supported by the influence of the molecular weight and the solvent quality. It also explains the melting point-crystallization relationship observed after isothermal crystallization of the polymer in presence of the solvent. The mechanism proposed for the thermoreversible gelation of these solution is confirmed.     

Miscibility and isothermal crystallization behavior of polyamide 6/poly(vinyl alcohol) blend

An investigation of miscibility and isothermal crystallization behavior of Polyamide 6 (PA6)/Poly(vinyl alcohol) (PVA) blends was conducted. Fourier transform infrared spectra (FTIR) analysis indicated that the interactions between the carbonyl groups of PA6 and hydroxyl groups of PVA increase as the weight ratios of PA6 to PVA of PA6/PVA specimens increase. This interaction between PA6 and PVA leads to their miscibility in the amorphous region and even some extent effects on their crystal phase, respectively. Further isothermal crystallization behavior of PA6/PVA indicate that the miscibility of PVA in PA6 leading difficulty in crystallization of PA6. Several kinetics equations are employed to describe the effects of PVA on the crystallization properties of PA6 in PA6/PVA blends in detail. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1360–1368, 2008     

Gelation of cellulose nanocrystal suspensions in glycerol

Aqueous suspensions of cellulose nanocrystals (NCC) produced by sulfuric acid hydrolysis of natural cellulose fibres display a number of unique properties. In addition to forming equilibrium chiral nematic phases above some critical concentration, cellulose nanocrystal suspensions tend to gel or aggregate if the stability of the suspension decreases, for example because of a decrease in the surface charge density of sulfate ester groups, or a change in the properties of the suspending medium. Direct incorporation of unmodified nanocrystals into organic media usually leads to aggregation. We have found that it is possible to circumvent this difficulty and form clear thixotropic gels of unmodified NCC in glycerol, by careful evaporation of water from aqueous glycerol suspensions of NCC. The physical gels form at a fairly low (<3 wt%) concentrations of cellulose. The initial composition of the suspension, the temperature and rate of evaporation, and the time resting at room temperature all influence the formation of thixotropic gels. Desulfation of the acid-form nanocrystals, enhanced in the glycerol-rich suspensions, is shown to be a key step in this gelation process.     

Swelling behavior of a blend hydrogel made of poly(allylguanidino-co-allylamine) and poly(vinyl alcohol)

A hydrogel was prepared by mixing poly(allylguanidino-co-allylamine) hydrochloride (PAG) with poly(vinyl alcohol) (PVA) and repeatedly freezing and thawing the blend. The swelling behavior of the hydrogel was investigated as a function of the pH and ionic strength of the medium. In a salt-free aqueous medium, a size of the hydrogel was reduced below pH 3 and above pH 10, but the size was little affected in the pH range 3 ≈ 10. In a medium of constant ionic strength (μ = 0.1), the hydrogel's pH response was different: it was significantly reduced in size above pH 9, but the size was affected only moderately below pH 9. When the ionic strength of medium was varied at a fixed pH, the size change of the hydrogel was gradual. All these phenomena could be understood by observing that PAG displayed multiple protonation states due to pH and that the electrostatic interactions among the charges on the polymer backbone are shielded by the added electrolyte as the ionic strength of the medium is raised.     

Characterization of poly(vinyl alcohol) during the emulsion polymerization of vinyl acetate using poly(vinyl alcohol) as emulsifier

During the emulsion polymerization of vinyl acetate (VAc) using poly(vinyl alcohol) (PVA) as stabilizer and potassium persulfate as initiator, the VAc reacts with PVA forming PVA-graft-PVAc. When the grafted polymer reaches a critical size it becomes water-insoluble and precipitates from the aqueous phase contributing to the formation of polymer particles. Since particle formation and therefore the properties of the final latex will depend on the degree of grafting, it is important to quantify and to characterize the grafted PVA. In this work, the quantitative separation and characterization of the grafted water-insoluble PVA was carried out by a two-step selective solubilization of the PVAc latex, first with acetonitrile to separate PVAc homopolymer, followed by water to separate the water-soluble PVA from the remaining acetonitrile-insoluble material. After the separation, the water-soluble and water-insoluble PVA were characterized by Fourier Transform Infrared (FTIR) spectroscopy and ¹H and ¹³C nuclear magnetic resonance (NMR) analyses, from which the details of the PVA-graft-PVAc structure were obtained. © 1996 John Wiley & Sons, Inc.     

Rheological and dynamic-mechanical behavior of carbon nanotube/vinyl ester-polyester suspensions and their nanocomposites

Rheological properties of vinyl ester-polyester resin suspensions containing various amounts (0.05, 0.1 and 0.3 wt.%) of multi walled carbon nanotubes (MWCNT) with and without amine functional groups (-NH₂) were investigated by utilization of oscillatory rheometer with parallel plate geometry. Dispersion of corresponding carbon nanotubes within the resin blend was accomplished employing high shear mixing technique (3-roll milling). Based on the dynamic viscoelastic measurements, it was observed that at 0.3 wt.% of CNT loadings, storage modulus (G′) values of suspensions containing MWCNTs and MWCNT-NH₂ exhibited frequency-independent pseudo solid like behavior especially at lower frequencies. Moreover, the loss modulus (G″) values of the resin suspensions with respect to frequency were observed to increase with an increase in contents of CNTs within the resin blend. In addition, steady shear viscosity measurements implied that at each given loading rate, the resin suspensions demonstrated shear thinning behavior regardless of amine functional groups, while the neat resin blend was almost the Newtonian fluid. Furthermore, dynamic mechanical behavior of the nanocomposites achieved by polymerizing the resin blend suspensions with MWCNTs and MWCNT-NH₂ was investigated through dynamic mechanical thermal analyzer (DMTA). It was revealed that storage modulus (E′) and the loss modulus (E″) values of the resulting nanocomposites increased with regard to carbon nanotubes incorporated into the resin blend. In addition, at each given loading rate, nanocomposites containing MWCNT-NH₂ possessed larger loss and storage modulus values as well as higher glass transition temperatures (T_g) as compared to those with MWCNTs. These findings were attributed to evidences for contribution of amine functional groups to chemical interactions at the interface between CNTs and the resin blend matrix. Transmission electron microscopy (TEM) studies performed on the cured resin samples approved that the dispersion state of carbon nanotubes with and without amine functional groups within the matrix resin blend was adequate. This implies that 3-roll milling process described herein is very appropriate technique for blending of carbon nanotubes with a liquid thermoset resin to manufacture nanocomposites with enhanced final properties.     

Viscoelastic behaviors and molecular motions of highly syndiotactic poly(vinyl alcohol) fibers

The viscoelastic behavior and molecular motion of highly syndiotactic poly(vinyl alcohol) (S‐PVA) fibers with a dyad syndiotacticity (r) of 69% were studied by dynamic mechanical thermal analysis and wide‐angle X‐ray diffraction and compared with those of atactic poly(vinyl alcohol) (A‐PVA) fibers with r = 54%. The β_c dispersion, based on the molecular motion of the chain molecules in the crystalline regions, was observed for A‐PVA around 120–140 °C, and the only primary (α_c) dispersion was observed for S‐PVA around 180 °C. The thermal expansion coefficients for the a and c axes of the A‐PVA crystal changed discontinuously around 120 °C, which corresponded to the β_c dispersion. For S‐PVA, the coefficient for the (002) plane changed discontinuously around 100 °C, similarly to A‐PVA, but that for the (100) plane remained unchanged between 20 and 220 °C. These results showed that the intermolecular hydrogen bonding of S‐PVA was stronger in the direction of the a axis than in the other directions, suppressing the β_c dispersion. The storage modulus and thermal expansion coefficient of the (020) plane (molecular axis) of S‐PVA decreased markedly around 180 °C, and this indicated that the α_c dispersion was due to the torsional motion of the molecular chains in the crystalline regions. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 800–808, 2004     

Thermal decomposition behavior of poly(propylene carbonate) in poly(propylene carbonate)/poly(vinyl alcohol) blend

Journal of Thermal Analysis and Calorimetry - To provide guidance for the practical thermal processing and applications of poly(propylene carbonate)/poly(vinyl alcohol) (PPC/PVA) blend, an...     

Impedance spectroscopy of chitosan/poly(vinyl alcohol) films

Journal of Solid State Electrochemistry - Polymer films were cast from aqueous solutions of chitosan (CS) and poly(vinyl alcohol) (PVA) in employing tetraethoxysilane (TEOS) as a crosslinking...     

Preparation of electrospun chitosan/poly(vinyl alcohol) membranes

Electrospinning of chitosan from its solutions in 2% aqueous acetic acid was studied by adding poly(vinyl alcohol) (PVA) as a “guest” polymer. Properties of the chitosan/PVA solutions including viscosity, conductivity, and surface tension were measured, and effects of the polymer concentration, chitosan/PVA mass ratio and processing parameters (applied voltage, flow rate, capillary-to-collector distance) on the electrospinnability of chitosan/PVA were investigated. Analyses of scanning electron micrographs and transmission electron micrographs suggested that the chitosan/PVA ultrafine fibers were often obtained along with beads, and chitosan was located in the elctrospun fibers as well as in the beads. Uniform chitosan/PVA fibers with an average diameter of 99 ± 21 nm could be prepared from a 7% chitosan/PVA solution in 40:60 mass ratio. Results of Fourier transform infrared spectroscopy and X-ray diffraction demonstrated that there were possible hydrogen bonds between chitosan and PVA molecules, which could weaken the strong interaction in chitosan itself and facilitate chitosan/PVA electrospinnability. The electrospun chitosan/PVA membranes showed higher water uptake and would have potential applications in wound dressings.     

The solvation of poly(vinyl alcohol)

The possible incorporation of water molecules within the crystal structure of poly(vinyl alcohol) is discussed. Modelling of the crystal structure suggested that water could be incorporated without severe disruption, and the effect on the X-ray powder diffraction trace was simulated. The effect of variation in tacticity is discussed in terms of the nature of the hydrogen bonding. Simulated traces are compared with experimental data from atactic samples in which a change in the diffraction peak intensities is observed for samples crystallised with water present. This is compared with samples produced from nonaqueous solutions.     

Long branching in poly(vinyl acetate) and poly(vinyl alcohol). II. Polymerization of vinyl acetate in the presence of crosslinked poly(vinyl alcohol)

It is a common view that poly(vinyl acetate) has many branches at the acetyl side group, but that the corresponding poly(vinyl alcohol) has little branching. In order to study the branching in poly(vinyl acetate) and poly(vinyl alcohol) which is formed by chain transfer to polymer, the polymerization of ¹⁴C-labeled vinyl acetate in the presence of crosslinked poly(vinyl acetate), which was able to be decrosslinked to give soluble polymers, was investigated at 60°C and 0°C. This system made it possible to separate as well as to distinguish the graft polymer from the newly polymerized homopolymer. Furthermore, the degree of grafting onto the acetoxymethyl group and onto the main chain were estimated. It became clear that, in the polymerization of vinyl acetate, chain transfer to the polymer main chain takes place about 2.4 times as frequently at 60°C as that to the acetoxy group and about 4.8 times as frequently at 0°C.