Characterization of poly(N-vinyl-2-pyrrolidone)s with broad size distributions

We report on the characterization of the solution structure of poly(N-vinyl-2-pyrrolidone)s (PVP) by small-angle X-ray scattering (SAXS) and by online coupling of asymmetrical flow field-flow fractionation (A4F), SAXS and dynamic light scattering (DLS). The commercial products PVP K30 and PVP K90 with nominal molar masses of 40 × 10³ and 360 × 10³ g mol⁻¹, respectively, were investigated separately and as binary mixture. Detailed information for all polymer fractions is available on the polymer contour lengths and the diffusion coefficients. Key areas of applications for the A4F-SAXS-DLS coupling are seen in comparison to static light scattering for polymers with radii of gyration smaller than 10 nm, for which only SAXS produces precise analytical results on the size of the polymers in solution.     

Water sorption and desorption in 2-hydroxyethylmethacrylate/methylmethacrylate copolymers

Cross-linked copolymers of 2-hydroxyethylmethacrylate/methylmethacrylate HEMA/MMA) with different HEMA contents have been prepared. Water sorption and desorption kinetics have been studied at a temperature of 37°C. The results indicate that the rate controlling step of sorption and desorption is the Fickian diffusion in the swollen polymer. The diffusion coefficient is a function of the water concentration and decreases to zero below a critical value of water content, which depends on the HEMA content.     

Sorption and diffusion of water vapor in poly(ethylene terephthalate) film

The sorption and diffusion of water vapor in poly(ethylene terephthalate) (PET) film were measured by applying a thermogravimetric analyzer (TG‐DTA), which customarily has been used to detect the weight loss of a sample with the increase of temperature under a given atmosphere. In this case, we detected the weight gain of PET film by sorption of water vapor under a given humidity at a constant temperature. Sorption‐rate curves were successfully obtained in spite of the low solubility of PET film and the presence of Fickian‐type curves. The solubility was better described according to the dual‐mode sorption model. The diffusion coefficients were determined in their initial slopes by the short‐time method. We found that the diffusion coefficient depended on vapor pressure. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 67–74, 2000     

Direct UV photocrosslinking of poly(N-vinyl-2-pyrrolidone) (PVP) to produce hydrogels

Hydrogels for biomedical purposes, made from synthetic polymers as starting materials and free of co-adjuvant molecules, have been produced almost exclusively by high-energy radiative processes. On the other hand, UV photocrosslinking of such materials has been used in conjunction of monomers and/or photoinitiators. This work was addressed to the analysis of poly(N-vinyl-2-pyrrolidone) (PVP) submitted to direct photocrosslinking in aqueous solution, using low pressure Hg lamp (λ_em=254 nm). The process efficiency was evaluated, and the properties of the hydrogel formed were determined. The product thus formed has similar micro- and macroscopic properties, as compared to hydrogels produced by high-energy radiation and presents no cytotoxicity. These results demonstrated the viability of using this method as a versatile alternative to hydrogel production, broadening the possibility of its production where high-energy radiation facilities are not available.     

Electrically conductive hydrogel composites made of polyaniline nanoparticles and poly(N-vinyl-2-pyrrolidone)

A novel electrically conductive composite material, consisting of polyaniline (PANI) nanoparticles dispersed in a polyvinyl pyrrolidone (PVP) hydrogel, was prepared ‘in situ’ by water dispersion polymerisation (DP) of aniline using PVP as steric stabiliser, followed by γ-irradiation induced crosslinking of the PVP component. Conversion yield of aniline into PANI particles was determined via HPLC and gas chromatography, while structural confirmation of the synthesised polymer was sought by FTIR. Morphology and dimensions of PANI particles into the coloured, optically transparent hydrogel was determined by electronic microscopy; moreover, swelling behaviour of composite hydrogels in different buffer solutions was investigated by gravimetric measurements and compared to that of pure PVP hydrogels.Cyclic voltammetry experiments were carried out both on these hydrogels and on the parent aqueous dispersions, at different pH values of the suspending/swelling medium, while conductivity of the composite hydrogels was derived from Impedance Spectroscopy; in both cases results were compared to those relative to hydrogels containing commercial-grade PANI particles.     

An IR study on ion-specific and solvent-specific swelling of poly(N-vinyl-2-pyrrolidone) gel

Swelling degrees of poly(N-vinyl-2-pyrrolidone) (PVP) gel were measured in aqueous salt solutions and in water/organic solvent mixtures to find marked ion- and solvent-specificities. In order to investigate any correlation of those specificities with hydration or solvation of PVP, IR spectra band of the CO group was monitored by means of ATR method both for PVP gel and the relevant solution systems. Dependence of the peak frequency on the swelling ratio suggested that hydration of PVP carbonyl group in deswollen gel systems is different from that in the corresponding solution systems. In the solution systems, PVP carbonyl band showed a high-wavenumber shift for deswollen systems, which can be well correlated with changes in water proton charge through ionic hydration and with Gutmann's acceptor number of organic solvents. In the deswollen gel systems, the CO band showed a low-wavenumber shift, suggesting a strong hydration or doubly hydrated state. This unexpected behavior was interpreted by assuming an intermolecular hydrogen bond of two carbonyl groups intermediated by water molecules.     

Fluorescence polarization and rheological studies of the poly(N-vinyl-2-pyrrolidone) hydrogels produced by UV radiation

Poly(N-vinyl-2-pyrrolidone) hydrogels produced by direct ultraviolet irradiation of PVP aqueous solution leads to crosslinking through pyrrolidinone moiety photolysis. Generally, hydrogel physical properties, like crosslinking density, pore size, swelling capacity, storage and loss moduli are obtained by swelling and rheological tests. However, relations between anisotropy obtained by fluorescence polarization studies and these properties have not been addressed for hydrogel systems. In this work we show that there is a correlation between the data obtained from anisotropy and rheological experiments, since both of them are related with crosslinking density of the hydrogels. These results reveal that fluorescence polarization spectroscopy is a promising tool for understanding the structure of hydrogels.     

Characterization and water vapor sorption property of ABA‐type triblock copolymers derived from polyimide and poly(methyl methacrylate)

The characterization of ABA‐type triblock copolymer films derived from polyimide (PI) macroinitiator and poly(methyl methacrylate) (PMMA) synthesized by atom transfer radical polymerization was investigated by focusing on different block lengths of PMMA. The hydrophobic property tends to increase with increasing PMMA content in the triblock copolymers, while the PMMA blocks enhance the charge transfer interaction between the PI segments. The water vapor sorption measurement of triblock copolymers was determined at 35 °C. The water vapor solubility of triblock copolymers tends to decrease with increasing PMMA content. In addition, linear correlations were observed between the solubility and polymer‐free volume and polymer molecular polarity in triblock copolymers as well as in other conventional polymer families. According to Zimm?Lundberg analysis, the PMMA block segments in the triblock copolymers accelerate water vapor clustering due to the high mobility of PMMA. The mobility of PMMA block segments strongly affected not only physical properties but also the water vapor solubility of the triblock copolymers. The ABA triblock copolymerization composed of PI and PMMA is one of the effective ways to improve the hydrophobic property. © 2013 Society of Chemical Industry     

Synthesis, characterization and thermodynamic properties of poly(3-mesityl-2-hydroxypropyl methacrylate-co-N-vinyl-2-pyrrolidone)

Poly(3-mesityl-2-hydroxypropyl methacrylate-co-N-vinyl-2-pyrrolidone) P(MHPMA-co-VP) was synthesized in 1, 4-dioxane solution using benzoyl peroxide (BPO) as initiator at 60 °C. The copolymer was characterized by ¹H ¹³C NMR, FT-IR, DSC, TGA, size exclusion chromatography analysis (SEC) and elemental analysis techniques. According to SEC, the number-average molecular weight (M_n), weight-average molecular weight (M_w) and polydispersity index (PDI) values of PMHPMA-co-VP were found to be 58,000, 481,000 g/mol and 8.26, respectively. According to TGA, carbonaceous residue value of PMHPMA-co-VP was found to be 6% at 500 °C. Also, some thermodynamic properties of PMHPMA-co-VP such as the adsorption enthalpy, ΔH_a, molar evaporation enthalpy, ΔH_v, the sorption enthalpy, , sorption free energy, , sorption entropy, , the partial molar free energy, , the partial molar heat of mixing, , at infinite dilution was determined for the interactions of PMHPMA-co-VP with selected alcohols and alkanes by inverse gas chromatography (IGC) method in the temperature range of 323-463 K. According to the specific retention volumes, , the weight fraction activity coefficients of solute probes at infinite dilution, , and Flory-Huggins interaction parameters, between PMHPMA-co-VP-solvents were determined in 413-453 K. According to and , selected alcohols and alkanes were found to be non-solvent for PMHPMA-co-VP at 413-453 K. The glass transition temperature, T_g, of the PMHPMA-co-VP found to be 370 and 363 K, respectively, by IGC and DSC techniques, respectively.     

Poly(N-vinyl-2-pyrrolidone) hydrogel production by ultraviolet radiation: new methodologies to accelerate crosslinking

Poly(N-vinyl-2-pyrrolidone) hydrogels produced by high-energy radiation relies on water radiolysis as a primary process leading to crosslinks. Conversely, ultraviolet direct irradiation into PVP leads to crosslinking trough pyrrolidinone moiety photolysis. However, this process showed to be rather inefficient. This work describes the crosslinking of poly(N-vinyl-2-pyrrolidone) based on hydrogen peroxide photolysis, therefore mimicking water radiolysis, using UV-C (e.g. low pressure Hg lamp) or UV-A radiation sources. The process efficiency and the properties of the hydrogel formed are discussed and compared with other methods of hydrogel production.     

Sorption and transport of water vapor in glassy poly(acrylonitrile)

Sorption data for H₂O in glassy poly(acrylonitrile)(PAN) are presented for a range of relative vapor pressures at temperatures from 20 to 50°C. Simple dual mode sorption, involving “hole-filling” and molecular solution appears to dominate the low activity region of sorption. Based on the clustering analysis suggested by Zimm and Lundberg, pronounced clustering of penetrant appears to occur above a relative pressure of 0.6. The form of the effective concentration-dependent diffusion coefficient for H₂O in PAN, determined by analysis of steady state permeation data, suggests that water in the microvoids and clusters has a lower mobility than the molecularly dissolved water in the polymer matrix. Time lag measurements at high upstream relative water vapor pressures suggest that the transient state permeation has a non-Fickian character due to relaxations which occur slowly to accommodate the clustering process.     

The use of volume-averaging techniques to predict temperature transients due to water vapor sorption in hygroscopic porous polymer materials

Volume-averaging techniques developed for modeling drying processes in porous materials offer a convenient framework for analyzing vapor sorption in porous hygroscopic polymeric materials. Because of the large temperature changes associated with water vapor sorption in these materials (from 10° to 20°C), sorption/diffusion processes are best characterized through the coupled differential equations describing both the transport of energy and mass through the porous structure. Experimental and numerical results are compared for a variety of natural and man-made porous polymeric materials (textiles) using the volume-averaging technique. Boundary heat and mass transfer coefficients and assumptions about thermal radiative properties of the experimental apparatus are shown to influence results obtained with the numerical solution method. © 1997 John Wiley & Sons, Inc.

1 This article is a US Government work and, as such, is in the public domain in the United States of America.

J Appl Polym Sci 64: 493–505, 1997     

Preferential interactions of poly(N-vinyl-2-pyrrolidone) in the binary mixture water/CdCl2

The poly(N-vinyl-2-pyrrolidone)(PVP)(2)/water(1)/CdCl₂(3) ternary system has been studied by viscometry, densimetry and atomic absorption spectrophotometry. In this system a preferential adsorption of Cd²⁺ at all solvent compositions studied and a conformational transition at 4mM of salt, the concentration at which a preferential adsorption minimum of Cd²⁺ in exhibited, are observed. The PVP/Cd²⁺ bound molar ratio is 0·23. CdCl₂ behaves as a salting-in agent for the macromolecule. The binary solvent mixture is thermodynamically more favourable at salt concentrations greater than 10 mM of CdCl₂.     

Application of FTIR spectroscopy to determine transport properties and water-polymer interactions in polypropylene (PP)/poly(ethylene-co-vinyl alcohol) (EVOH) blend films: Effect of poly(ethylene-co-vinyl alcohol) content and water activity

This paper reports the use of FTIR spectroscopy along with gravimetric analysis to simultaneously study water sorption, transport properties and water-polymer interactions in PP/EVOH films at 25 °C, as a function of EVOH content and water vapour activity. The results indicate the existence of two different mechanisms, below (dual-mode) and above a critical concentration value close to the clustering limit activity. Several spectroscopically distinguishable “types” of sorbed water molecules with different diffusion rates have been detected, and their evolution as a function of the penetrant concentration followed. The main changes in the water structure take place from the clustering limit activity onwards. Significant differences both in the state of water and diffusion sequence of free/bound water have been found between 90/10 PP/EVOH films and blends with EVOH content ≥20%, suggesting not only composite-dependence but also morphology-dependence.     

In situ capacitance measurements for in-plane water vapor transport in paint films

A capacitance technique has been adapted to study in-plane water vapor transport in paint films. The technique requires an application of electrical contact materials on the paint film surface for capacitance measurements by electrochemical impedance spectroscopy (EIS). The capacitance obtained by EIS using Cu tape and Ag paste as the contact materials are presented. A direct comparison of capacitance and gravimetric measurements demonstrates that the change in the coating capacitance is quantitatively correlated with the total amount of in-plane water vapor transported in paint films. The water vapor diffusion coefficient derived from the capacitance technique agrees with one from the gravimetric method.     

Miscible blends of poly(n-vinyl-2-pyrrolidone) with poly(3-chloropropyl methacrylate), poly(2-bromoethyl methacrylate) and poly(2-iodoethyl methacrylate)

Summary Poly(N-vinyl-2-pyrrolidone) is miscible with poly(3-chloropropyl methacrylate), poly(2-bromoethyl methacrylate) and poly(2-iodoethyl methacrylate) as shown by the optical clarity and the glass transition behaviour of the blends. The miscible blends degrade before phase separation could be induced by heating. The three T_g-composition curves can be fitted by the Gordon-Taylor equation. The implication of the Gordon-Taylor k parameters of the blends is discussed.     

Diffusion and sorption of benzene vapor through polybutadiene‐, polybutadiene/styrene‐, and polybutadiene/acrylonitrile‐based polyurethanes

A series of polyurethane (PU) films made from toluene diisocyanate (TDI), 1,4‐butanediol (BDO), and hydroxyl‐terminated polybutadiene (HTPB), hydroxyl terminated polybutadiene/styrene (HTBS), or hydroxyl terminated polybutadiene/acrylonitrile (HTBN) was synthesized by solution polymerization. The absorption of benzene vapor was found mainly in the soft phase. The equilibrium adsorption (M_∞) was reduced with increasing hard segment content for all the PUs. The values of M_∞ were in the sequence of HTBN‐PUs > HTBS‐PUs > HTPB‐PUs, which could be explained by the different interaction parameters between soft segments and benzene. The HTBN‐PU film showed the lowest degree of phase segregation and had more hard segments intermixed in the soft phase, restricting the movement of soft segments, and therefore resulted to non‐Fickian behavior, while the HTPB‐PU is antithetical. FTIR and atomic force microscopy were utilized to identify the hydrogen bonding behavior and morphology change of the PU films before and after the absorption of benzene vapor. The tensile strength of the HTBN‐PUs showed a greater decrease than that of HTBS‐PUs and HTPB‐PUs after absorbing benzene vapor. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2984–2991, 2004     

Development of poly(vinylidene fluoride) hollow-fiber membranes for the treatment of water/organic vapor mixtures

Attempts were made to spin hollow-fiber membranes from poly(vinylidene fluoride) (PVDF) material by the dry–wet phase inversion method. Hollow fibers so prepared were characterized for various parameters and by electron microscopic techniques. Membranes were also tested for the separation of water/1-propanol mixtures in vapor phase. It was found that the hollow fibers were water selective despite the fact that PVDF material is hydrophobic. Intrinsically organic selective property of PVDF material was proved by coating a porous polyetherimide membrane with a PVDF layer, which resulted in enhancement of 1-propanol permeation while suppressing the permeation of water. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65:1263–1270, 1997     

High temperature behavior of HfSiO4 subjected to calcium-magnesium-alumina-silicate (CMAS) and high-velocity water vapor

HfSiO₄ is considered as a candidate for environmental barrier coating (EBC), but there is a lack of comprehensive evaluation of its resistance against corrosive medium. We herein study the behavior of HfSiO₄ against CMAS melt and high-velocity water vapor. HfSiO₄ shows poor resistance to CMAS attack. Si diffusion occurs during CMAS attack, which leads to the formation of HfO₂ and CaSi₂O₅. HfSiO₄ decomposes to form SiO₂ and HfO₂ under the scouring of water vapor, in which SiO₂ forms volatile hydroxide and is taken away by high-velocity steam. HfSiO₄ is not the preferred system for surface layer of EBC system and is expected to be used as intermediate transition layer.