EVOH nanocomposite films with enhanced barrier properties under high humidity conditions

To improve the oxygen and water vapor barrier properties of ethylene vinyl alcohol, EVOH/EFG nanocomposite films under high humidity conditions, we successfully prepared highly exfoliated graphite (EFG) containing a monolayer or a few layers of graphene via rapid heating treatment and ultrasonication as confirmed by Fourier transform infrared spectroscopy (FTIR), scanning electron microscope (SEM), elemental analysis (EA), and nitrogen adsorption–desorption analysis. Six different EVOH/EFG nanocomposite films containing as‐prepared EFG were prepared via a solvent blend method and their physical and barrier properties at different relative humidities were investigated as a function of EFG content. Depending on the EFG content, oxygen transmission rate (OTR) decreased from 3.7 to 0.1 cc/m²/day at dry condition, and the difference in OTR between dry condition and humid condition decreased from 6.5 to 2.3 cc/m²/day. Barrier properties of the EVOH/EFG nanocomposite films were strongly dependent on their chemical structure and morphology. Crystallinity, tortuous path length, and hydrophobicity of EVOH/EFG nanocomposite films were enhanced by the addition of EFG. However, the thermal stability and glass transition temperature of the nanocomposite films were not improved by incorporation of EFG due to the weak interaction between EVOH and EFG. To maximize the performance of EVOH/EFG nanocomposite films, the compatibility of the polymer matrix and fillers needs to be improved. POLYM. COMPOS., 35:644–654, 2014. © 2013 Society of Plastics Engineers     

Effect of solvent interactions on swelling and microstructure of amphiphilic polyurethane networks

Amphiphilic polyurethane (PU) ionomer networks were synthesized by urethane acrylate anionomer (UAA) precursor chains. These networks were prepared with water, dioxane (DO), and dimethyl sulfoxide (DMSO) and exhibited very different swelling behaviors in water/DO (UAADG) and water/DMSO (UAASG) solvent mixtures, which was due to the different solvent interactions between water/DO and water/DMSO. The additional important factor influencing the swelling behavior in water/aprotic solvent mixtures was the hydrophilicity of the UAA networks, which was different than the water–UAA network interaction. The microstructure of UAA networks prepared with the water/aprotic solvent mixtures was greatly influenced by the water–solvent interactions. Unlike the water/DO mixtures, which had a relatively weak water–DO interaction, the strong water–DMSO interaction largely restricted the ability of DMSO to solvate the UAA chain, which resulted in an increase in the aggregation of the hydrophobic segment and the hydrophilic/hydrophobic microphase separation. Thus, UAASG and UAADG networks showed very different swelling behaviors in the same swelling medium because of the microstructural difference between these gels, which was confirmed by dynamic mechanical measurements. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 608–620, 2001     

Influence of the ethylene–(methacrylic acid)–Zn2+ ionomer on the thermal and mechanical properties of blends of poly(propylene) (PP)/ethylene–(vinyl alcohol) copolymer (EVOH)

The thermal and mechanical properties and the morphologies of blends of poly(propylene) (PP) and an ethylene–(vinyl alcohol) copolymer (EVOH) and of blends of PP/EVOH/ethylene–(methacrylic acid)–Zn²⁺ ionomer were studied to establish the influence of the ionomer addition on the compatibilization of PP/EVOH blends and on their properties. The oxygen transmission rate (O₂TR) values of the blends were measured as well. PP and EVOH are initially incompatible as was determined by tensile tests and scanning electronic microscopy. Addition of the ionomer Zn²⁺ led to good compatibility and mechanical behaviour was improved in all blends. The mechanical properties on extruded films were studied for 90/10 and 80/20 w/w PP/EVOH blends compatibilized with 10 % of ionomer Zn²⁺. These experiments have shown that the tensile properties are better than in the injection‐moulded samples. The stretching during the extrusion improved the compatibility of the blends, diminishing the size of EVOH domains and enhancing their distribution in the PP matrix. As was to be expected, the EVOH improved the oxygen permeation of the films, even in compatibilized blends. Copyright © 2004 Society of Chemical Industry     

Preparation and characterization of poly(ethylene‐co‐vinyl alcohol) membranes via thermally induced liquid–liquid phase separation

Porous membranes were prepared through the thermally induced phase separation of poly(ethylene‐co‐vinyl alcohol) (EVOH)/glycerol mixtures. The binodal temperature and dynamic crystallization temperature were determined by optical microscopy and differential scanning calorimetry measurements, respectively. It was determined experimentally that the liquid–liquid phase boundaries were shifted to higher temperatures when the ethylene content in EVOH increased. For EVOHs with ethylene contents of 32–44 mol %, liquid–liquid phase separation occurred before crystallization. Cellular pores were formed in these membranes. However, only polymer crystallization (solid–liquid phase separation) occurred for EVOH with a 27 mol % ethylene content, and the membrane morphology was the particulate structure. Scanning electron microscopy showed that the sizes of the cellular pores and crystalline particles in the membranes depended on the ethylene content in EVOH, the polymer concentration, and the cooling rate. Furthermore, the tendency of the pore and particle sizes was examined in terms of the solution thermodynamics of the binary mixture and the crystallization kinetics. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 853–860, 2003     

Use of a sodium ionomer as a compatibilizer in polypropylene/high‐barrier ethylene–vinyl alcohol copolymer blends: The processability of the blends and their physical properties

The effect of a sodium ionomer (ion.Na⁺) on the compatibility of polypropylene (PP)/high‐barrier ethylene–vinyl alcohol copolymer (EVOH) blends was studied in terms of the thermal, mechanical, and optical properties and morphology. The rheological behavior, tensile tests, and morphology of the binary blends showed that the miscibility of EVOH with PP was very poor. The miscibility of the polymers improved with the ionomer addition. In general, the ion.Na⁺ concentration did not alter the thermal behavior of the blends, but it did improve the ductility of the injection‐molded specimens. Scanning electron micrographs displayed better adhesion between the PP and EVOH phases in the samples with the ionomer. The mechanical improvement was better in the film samples than in the injection‐molded samples. A 90/10 (w/w) PP/EVOH film with 5% ion.Na⁺ and an 80/20 (w/w) PP/EVOH film with 10% ion.Na⁺ presented better global properties than the other blends studied. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1763–1770, 2004     

Effect of the ethylene content of poly(ethylene-co-vinyl alcohol) on the formation of microporous membranes via thermally induced phase separation

Porous poly(ethylene-co-vinyl alcohol) (EVOH) membranes were prepared via thermally induced phase separation. The effect of the EVOH ethylene content on the membrane morphology and solute rejection property was investigated. For EVOHs with ethylene contents of 27–44 mol %, polymer crystallization (solid–liquid phase separation) occurred, and the membrane morphology was the particulate structure. However, the liquid–liquid phase separation occurred before crystallization for EVOH with a 60 mol % ethylene content. Cellular pores were formed in this membrane. For the particulate membranes, higher solute rejection and lower water permeance were obtained for EVOH with a lower ethylene content. The membrane formed by the liquid–liquid phase separation showed a sharper solute rejection change with a change in the solute radius than the particulate membranes did. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2583–2589, 2001     

Properties of gels obtained by freezing/thawing of poly(vinyl alcohol)/water/dimethyl sulfoxide solutions

Melting points of poly(vinyl alcohol) (PVA) gels obtained by repeated freezing/thawing cycles of the solutions in mixed solvents of water and dimethyl sulfoxide (DMSO) were measured. PVA solutions in 1–30 and 90 vol % DMSO froze at ?40°C. The melting point of a gel increased with an increase in freezing/thawing cycles for all the solutions frozen and with an increase in freezing time in 10–30 vol % DMSO. The solutions in 1–5 vol % DMSO gelled even at very low polymer concentration of 1.0 g/dL by repeated freezing/thawing. The melting point of all the gels with a 5% polymer concentration reached ca. 73°C after 14 freezing/thawing cycles except for the gels in 90 vol % DMSO. However, the melting point of the gels with the same polymer concentration prepared at ?40°C using an unfrozen mixed solvent in 60 vol % DMSO was ca. 77°C and the largest. The maximum apparent enthalpy of fusion of the gels prepared by repeated freezing/thawing was ca. 40 kcal/mol. The gels in 90 vol % DMSO were transparent independent of cycles where as those in 1–80 vol % DMSO were opaque. The degree of opaqueness increased with decreasing DMSO content.     

Infrared Spectroscopic Investigation of Hydrogen Bonding in EVOH Containing PVA Fibers

Fibers of poly(vinyl alcohol) (PVA) containing ethylene‐vinyl alcohol copolymer (EVOH) are made by gel spinning. By using IR spectroscopy, the hydrogen bonds of the PVA/EVOH fibers with different EVOH content and different draw ratio are discussed. The peaks in the neighborhood of 3 400 cm^–1 and the peaks near 3 600 cm^–1 are used to analyze the hydroxyl absorption engaged in hydrogen bonds and the free hydroxyl absorption, respectively. As for PVA/EVOH films, with increasing EVOH content the H‐bond is gradually weakened. As for fibers, however, with increasing EVOH content the strength of the H‐bond increases, while the number of H‐bonds is decreased. Similarly, with increasing draw ratio of the PVA/EVOH fibers, the strength of H‐bond increases, while the number of H‐bonds seems decreased. Higher EVOH content in the PVA/EVOH fibers causes a higher maximum draw ratio because of weakening of the H‐bond. However, higher draw ratio does not always cause better mechanical properties of PVA/EVOH fibers.     

Effect of hydrogen bonding on characterization of polyamide 612 and ethylene vinyl alcohol copolymer blends

Hydrogen bonding interaction in the blends of polyamide 612 (PA⁶¹²)/ethylene vinyl alcohol copolymer (EVOH) and the effect of the hydrogen bonds on the characterization of PA⁶¹²/EVOH were investigated. Fourier transform infrared spectra (FTIR) analysis indicated that the interactions between the carbonyl groups of PA⁶¹² and hydroxyl groups of EVOH increase as the content of EVOH in PA⁶¹²/EVOH specimens increase. This interaction between PA⁶¹² and EVOH leads to their miscibility to some extent in the amorphous region and even some effects on their crystal phase, respectively. Further isothermal crystallization behavior of PA⁶¹²/EVOH indicates that the hydrogen bonding between PA⁶¹² and EVOH leading difficulty in crystallization of PA⁶¹². Several kinetics equations are employed to describe the effects of EVOH on the crystallization properties of PA⁶¹² in PA⁶¹²/EVOH blends in detail. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Thermoreversible gelation of a polystyrene–poly(ethylene/butylene)–polystyrene triblock copolymer in n‐octane/4‐methyl‐2‐pentanone solutions

The thermoreversible gelation of a triblock copolymer polystyrene‐block‐poly(ethylene/butylene)‐block‐polystyrene in n‐octane and two solvent mixtures of n‐octane and 4‐methyl‐2‐pentanone with a high n‐octane content has been studied. n‐Octane and 4‐methyl‐2‐pentanone are selective solvents for the middle poly(ethylene/butylene) block and the end polystyrene blocks, respectively. The influence of the solvent composition on the sol–gel transition and the mechanical properties of the gels was studied. The gel formation temperature increased with the copolymer concentration and the n‐octane content in the solvent system. The mechanical properties of the different gels were studied through oscillatory shear measurements. The concentration dependence of the elastic storage modulus showed an exponent close to that expected for gels in good solvents (2.25) that possess a structure similar to those of chemical networks. © 2002 Society of Chemical Industry     

Gels of syndiotacticity-rich poly(vinyl alcohol)–water/dimethyl sulfoxide or – water/ethylene glycol solutions

Gels of syndiotacticity-rich poly(vinyl alcohol) (s-PVA) in mixed solvents of water/dimethyl sulfoxide (DMSO) or water/ethylene glycol (EG) were made by chilling at the temperatures of 0–70°C from those solutions with the polymer concentrations below 10g/dL. The melting points of the gels were measured warming the gel from the gelling temperature (T_gel) at a constant heating rate. The apparent enthalpy of fusion of a junction of gel, ΔH was estimated from the relation between the apparent melting temperature and the polymer concentration. The s-PVA gels made from the mixtures of the water/lower contents of DMSO or EG had a minimum at lower T_gel and a maximum ΔH at a higher T_gel. On the other hand, the s-PVA gels made from the mixtures of the water/higher contents of them had nearly a maximum ΔH at a higher T_gel. From those results, it was considered that the former gels received a high thermal history while the latter gels received only slight thermal history.     

Deformation and fracture behavior of polypropylene–ethylene vinyl alcohol blends compatibilized with ionomer Zn2+

This work investigated the deformation and fracture behavior of polypropylene–ethylene vinyl alcohol (PP/EVOH) blends compatibilized with ionomer Zn²⁺. Uniaxial tensile tests and quasistatic fracture experiments were performed for neat PP and for 10 and 20 wt % EVOH blends with different ionomer contents. The addition of EVOH copolymer to PP led to an increase in the Young's modulus whereas the yield strength was decreased with the EVOH content as a consequence of the higher stiffness of EVOH and the poor interfacial adhesion between PP and EVOH, respectively. Furthermore, the incorporation of EVOH into PP promoted stable crack growth. Neat PP displayed nonlinear load‐displacement behavior with some amount of slow crack growth preceding unstable brittle fracture, whereas most PP/EVOH blends exhibited “pseudostable” fracture characterized by slow crack growth that could not be externally controlled. All blends exhibited lower resistance to crack initiation than PP but the fracture propagation resistance was significantly improved. For 10 wt % EVOH blends, the resistance to crack initiation was roughly constant with the ionomer content up to 5%, then it increased with the further addition of compatibilizer. Conversely, for 20 wt % EVOH blends, the resistance to crack initiation appeared to be independent of the ionomer content. The better resistance to crack initiation exhibited by the 10 wt % EVOH blends could be attributed to a higher level of compatibilization in these blends. By contrast, 20 wt % EVOH blends with ≤2% ionomer content showed completely stable crack growth. In addition, J–R curves and valid plane strain fracture toughness values for these blends could also be determined. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1271–1279, 2005     

Oxygen barrier properties of polyketone/EVOH blend films and their resistance to moisture

Polyketone (PK) has excellent chemical and mechanical properties, but its use in food packaging is limited due to its oxygen barrier properties being insufficient for high-barrier film applications. To improve its oxygen barrier properties, PK has been blended with ethylene vinyl alcohol copolymer (EVOH), which is one of the highest oxygen barrier polymers in use today. The oxygen barrier properties under both dry and humid conditions, as well as the mechanical properties of PK/EVOH blend films were investigated in this study. These novel PK/EVOH blend films exhibited unusually low oxygen permeability values from 0.3 to 0.16 cc 20 μm m⁻² day⁻¹ atm⁻¹ with increasing EVOH content from 30 to 70 wt%, which are even lower than those of the ideal laminar model that expresses the theoretical minimum permeability values attainable for blended barrier films. These high oxygen barrier properties of PK/EVOH blend films can conceivably be attributed to the combination of two dominant effects: a tortuous diffusion path through the EVOH domains in the PK matrix and hydrogen bonding interactions between PK and EVOH. Furthermore, in high-humidity environments with retorting, the PK/EVOH blend films exhibited superior resistance to moisture over EVOH. Immediately after the retorting test, the oxygen permeability of the high-barrier PK/EVOH blend films with an EVOH content of 30–40 wt% increased by less than 3× the pre-retorting value, as opposed to 74× for EVOH. In addition, PK/EVOH blend films displayed superior stretching characteristics, with a breaking strain of over 300%, which are valuable for flexible packaging applications.     

Solvent‐specific swelling behavior of poly(allylamine) gel

Poly(allylamine) (PAlAm) gel was prepared by γ‐ray irradiation. Swelling behavior of the charged PAlAm gels having Cl^? and NO₃^? counter‐ions (PAlAmHCl and PAlAmHNO₃, respectively) was investigated in aqueous organic solvent mixtures as functions of solvent species (dimethylsulfoxide (DMSO), methanol (MeOH), ethanol (EtOH), 2‐propanol (2PrOH), tert‐butanol (tert‐BuOH), acetone, tetrahydrofuran (THF) and dioxane) and the concentration. With increasing solvent concentration, the gels (except for the DMSO system) showed a sharp deswelling comparable to the volume phase transition. The solvent specificity for the PAlAmHNO₃ gel transition was correlated with the dielectric constant of the organic solvents, while that for the PAlAmHCl gel suggested that solvency for the counter anion is another important factor. Copyright © 2004 Society of Chemical Industry     

Blends of poly(propylene) and polyacetal compatibilized by ethylene vinyl alcohol copolymers

Polymer blends of poly(propylene) (PP) and polyacetal (polyoxymethylene, POM) with ethylene vinyl alcohol (EVOH) copolymers were investigated by differential scanning calorimetry (DSC), rheological, tensile, and impact measurements, Fourier transform infrared spectroscopy (FTIR), and scanning electron microscopy (SEM). The PP–POM–EVOH blends were extruded with a co‐rotating twin‐screw extruder. The ethylene group in the EVOH is partially miscible with PP, whereas the hydroxyl group in the EVOH can form hydrogen bonding with POM. The EVOH tends to reside along the interface, acting as a surfactant to reduce the interfacial tension and to increase the interfacial adhesion between the blends. Results from SEM and mechanical tests indicate that a small quantity of the EVOH copolymer or a smaller vinyl alcohol content in the EVOH copolymer results in a better compatibilized blend in terms of finer phase domains and better mechanical properties. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1471–1477, 2003     

Solvent-, ion- and pH-specific swelling of poly(2-acrylamido-2-methylpropane sulfonic acid) superabsorbing gels

Homopolymer hydrogel of 2-acrylamido-2-methylpropane sulfonic acid (AMPS) and its nanocomposite counterpart were prepared to study their swelling properties. The hydrogels showed ability to absorb and retain electrolytes as well as binary mixtures of water and organic solvents (i.e., methanol, ethanol, acetone, ethylene glycol (EG), polyethylene glycol, N-methyl-2-pyrrolidone (NMP), and dimethylsulfoxide (DMSO). The nanocomposite gel exhibited lower swelling in all solvent compositions in comparison with non-composite gel. Unlike conventional acrylic acid-based hydrogels, the poly(AMPS) gels showed superabsorbing capacity in pure ethanol, methanol, EG, DMSO and NMP. Meanwhile, swelling capacity of poly(AMPS) hydrogel in DMSO-water mixtures was surprisingly found to be even higher than that in water. This extraordinary superswelling behavior was explained based on the interactions involved in solvation as well as the solubility parameters. The gels showed pH-independent superabsorbency in a wide range of pH (3–11). Saline-induced swelling transitions were also investigated and the ionic interactions were confirmed by FTIR spectroscopy.     

Stretchable calix[4]arene-based gels by induction of water

This study focused on controlling the stretching property of gels. This resilience is dependent on the water content in the calix[4]arene-based gel solvent system, where the stretching property of gels could be controlled upon the addition of water. The storage (G′) and loss (G″) moduli of the calix[4]arene-based gels prepared in solvent systems with different water contents were investigated via rheological measurements. By the strain sweeps, the values of G′ decreased, while tan-delta increased with water content in the solvent system. In addition, a significant changes in the G′ and G″ values were observed upon the addition of water by frequency sweeps. In particular, the decrease in the G″ value of the gel prepared from the 1,3-alternated calix[4]arene derivative ( HC4 ) and diisocyanate linker ( HDI ) in DMSO/H₂O mixed solvent (8:2 v/v) was approximately 5-fold larger than that of the gel prepared in 100% DMSO. Thus, this novel approach would useful for the development of new soft materials with finely controllable mechanical properties.     

Permeation of oxygen and water vapor through EVOH films as influenced by relative humidity

The transport properties of oxygen and water vapor through EVOH films as functions of relative humidity (RH) and temperature were studied. The results of oxygen and water vapor permeation demonstrated that temperature and RH markedly affected barrier properties of these films. In general, the EVOH films had minimal oxygen and water vapor permeabilities at a low RH, attributed to the reduced mobility of the polymer resulting from strong interactions between small water molecules and the polymeric matrix at low RH. Beyond 75% RH, the permeabilities increased considerably. In addition, the barrier performance of the EVOH films was found to be dependent on their ethylene content and orientation. From the experimental data, semiempirical equations describing oxygen transmission rates (O₂TR) as functions of RH and temperature were developed. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1866–1872, 2001     

Water effect on the morphology of EVOH copolymers

The effect of water on the morphology of four ethylene vinyl alcohol copolymers (EVOH) with different ethylene contents was studied by differential scanning calorimetry (DSC). EVOH film samples equilibrated in controlled atmospheres at different relative humidities (RH) and 23°C were analyzed. Under dry conditions, the glass transition temperature (T_g) was unaffected by copolymer ethylene content. As RH increases, T_g decreases. It seems that the presence of water within the polymer matrix results in plasticization of the polymer. T_g varies from around 50°C (dry) to below room temperature. EVOH copolymers are glassy polymers when dry and rubbery polymers at high RHs. Fox and Gordon–Taylor's equations well describe T_g depletion at low water uptake, although severe water gain results in a considerable T_g decrease, which is not predicted by these theories. Melting temperature, T_m, and enthalpy, ΔH_m, were also analyzed. When dry, T_m decreases as ethylene content increases. No significant water effect was found on either T_m or ΔH_m. Hence, crystallinity seems to be unaffected by water presence. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1201–1206, 1999     

Effects of solvent adsorption on solution properties of poly(vinyl alcohol)/dimethylsulfoxide/water ternary systems

In this study, the solvent adsorption phenomena of poly(vinyl alcohol) (PVA) in cosolvent mixtures of dimethylsulfoxide (DMSO; solvent 1) and water (solvent 2) were investigated. Typically, this cosolvent mixture could form hydrogen‐bonded DMSO/(water)₂ complexes, involving one DMSO and two water molecules. Because of the complex formation in the cosolvent mixtures, PVA chains preferentially adsorb water molecules at DMSO mole fraction X₁ < 0.33, but preferentially adsorb DMSO molecules at X₁ > 0.33. The preferential adsorption of DMSO (a good solvent for PVA) could cause the relatively extended conformation of PVA chains in solutions because of the increase in excluded volume effect. Because of various interactions between PVA chains and cosolvent mixtures, the aggregation and gelation behaviors of PVA solutions were significantly affected by the composition of cosolvent mixture. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 3211–3217, 2004