Miscibility studies in poly(methyl vinyl ether)/hydroxypropylcellulose binary system in aqueous solutions and solid state

The phase separation behaviour in aqueous mixtures of poly(methyl vinyl ether) and hydroxypropylcellulose has been studied by cloud points method and viscometric measurements. The miscibility of these blends in solid state has been assessed by infrared spectroscopy; methanol vapours sorption experiments and scanning electron microscopy. The values of Gibbs energy of mixing of the polymers and their blends with methanol as well as between each other were calculated. It was found that in solid state the polymers can interact with methanol very well but the polymer-polymer interactions are unfavourable. Although in aqueous solutions the polymers exhibit some intermolecular interactions their solid blends are not completely miscible. (C) 2005 Elsevier Ltd. All rights reserved.

pH effects on the complexation, miscibility and radiation-induced crosslinking in poly(acrylic acid)-poly (vinyl alcohol) blends

The effect of pH on the complexation of poly(acrylic acid) with poly(vinyl alcohol) in aqueous solution, the miscibility of these polymers in the solid state and the possibility for crosslinking the blends using gamma radiation has been studied. It is demonstrated that the complexation ability of poly(vinyl alcohol) with respect to poly(acrylic acid) is relatively low in comparison with some other synthetic non-ionic polymers. The precipitation of interpolymer complexes was observed below the critical pH of complexation (pH(crit1)), which characterizes the transition between a compact hydrophobic polycomplex and an extended hydrophilic interpolymer associate. Films prepared by casting from aqueous solutions at different pH values exhibited a transition from miscibility to immiscibility at a certain critical pH, pH(crit2), above which hydrogen bonding is prevented. It is shown here that gamma radiation crosslinking of solid blends is efficient and only results in the formation of hydrogel films for blends prepared between pH(crit1), and pH(crit2). The yield of the gel fraction and the swelling properties of the films depended on the absorbed radiation dose and the polymer ratio.

Optimization of electroless copper plating on polyethylene films modified by surface grafting of vinyl ether of monoethanolamine

Metallized plastics have recently received significant interest for their useful applications in electronic devices such as for integrated circuits, packaging, printed circuits and sensor applications. In this work the metallized films were developed by electroless copper plating of polyethylene films grafted with vinyl ether of monoethanoleamine. There are several techniques for metal deposition on surface of polymers such as evaporation, sputtering, electroless plating and electrolysis. In this work the metallized films were developed by electroless copper plating of polyethylene films grafted with vinyl ether of monoethanoleamine. Polyethylene films were subjected to gamma-radiation induced surface graft copolymerization with vinyl ether of monoethanolamine. Electroless copper plating was carried out effectively on the modified films. The catalytic processes for the electroless copper plating in the presence and the absence of SnCl2 sensitization were studied and the optimum activation conditions that give the highest plating rate were determined. The effect of grafting degree on the plating rate is studied. Electroless plating conditions (bath additives, pH and temperature) were optimized. Plating rate was determined gravimetrically and spectrophotometrically at different grafting degrees. The results reveal that plating rate is a function of degree of grafting and increases with increasing grafted vinyl ether of monoethanolamine onto polyethylene. It was found that pH 13 of electroless bath and plating temperature 40°C are the optimal conditions for the plating process. The increasing of grafting degree results in faster plating rate at the same pH and temperature. The surface morphology of the metallized films was investigated using scanning electron microscopy (SEM). The adhesion strength between the metallized layer and grafted polymer was studied using tensile machine. SEM photos and adhesion measurements clarified that uniform and adhered deposits were obtained under optimum conditions.

Microwave-assisted hydrogel synthesis: a new method for crosslinking polymers in aqueous solutions

It has been found that hydrogels may be formed by microwave irradiation of aqueous solutions containing appropriate combinations of polymers. This new method of hydrogel synthesis yields sterile hydrogels without the use of monomers, eliminating the need for the removal of unreacted species from the final product. Results for two particularly successful combinations, poly(vinyl alcohol) with either poly(acrylic acid) or poly(methylvinylether-alt-maleic anhydride), are presented. Irradiation using temperatures of 100–150 °C was found to yield hydrogels with large equilibrium swelling degrees of 500–1000 g g−1. Material leached from both types of hydrogel shows little cytotoxicity towards HT29 cells.

Linear viscoelasticity from molecular dynamics simulation of entangled polymers

The linear viscoelastic (LVE) spectrum is one of the primary fingerprints of polymer solutions and melts, carrying information about most relaxation processes in the system. Many single chain theories and models start with predicting the LVE spectrum to validate their assumptions. However, until now, no reliable linear stress relaxation data were available from simulations of multichain systems. In this work, we propose a new efficient way to calculate a wide variety of correlation functions and mean-square displacements during simulations without significant additional CPU cost. Using this method, we calculate stress−stress autocorrelation functions for a simple bead−spring model of polymer melt for a wide range of chain lengths, densities, temperatures, and chain stiffnesses. The obtained stress−stress autocorrelation functions were compared with the single chain slip−spring model in order to obtain entanglement related parameters, such as the plateau modulus or the molecular weight between entanglements. Then, the dependence of the plateau modulus on the packing length is discussed. We have also identified three different contributions to the stress relaxation:  bond length relaxation, colloidal and polymeric. Their dependence on the density and the temperature is demonstrated for short unentangled systems without inertia.

Hierarchical modeling of entangled polymers

We demonstrate that it is possible to link multi-chain molecular dynamics simulations with the tube model using a single chain slip-links model as a bridge. This hierarchical approach allows significant speed up of simulations, permitting us to span the time scales relevant for a comparison with the tube theory. Fitting the mean-square displacement of individual monomers in molecular dynamics simulations with the slip-spring model, we show that it is possible to predict the stress relaxation. Then, we analyze the stress relaxation from slip-spring simulations in the framework of the tube theory. In the absence of constraint release, we establish that the relaxation modulus can be decomposed as the sum of contributions from fast and longitudinal Rouse modes, and tube survival. Finally, we discuss some open questions regarding possible future directions that could be profitable in rendering the tube model quantitative, even for mildly entangled polymers

Defining Structure in Electrospun Polymer Fibres

We use a combination of microscopy, x-ray scattering and neutron scattering to show how structure develops in micro and nano-size polymer fibres prepared by electrospinning. The technique has been applied to a range of different polymers, an amorphous system (polystyrene), a crystallisable polymer (poly-epsilon-caprolactone), a composite systems (polyethylene oxide or poly vinyl alcohol containing polypyrrole) and consider the possibility of self assembly (gelatin).

Microscopic Mechanisms of Strain Hardening in Glassy Polymers

The mechanisms underlying the increase in stress for large mechanical strains of a polymer glass, quantified by the strain-hardening modulus, are still poorly understood. In the present paper we aim to elucidate this matter and present new mechanisms. Molecular-dynamics simulations of two polymers with very different strain-hardening moduli (polycarbonate and polystyrene) have been carried out. Nonaffine displacements occur because of steric hindrances and connectivity constraints. We argue that it is not necessary to introduce the concept of entanglements to understand strain hardening, but that hardening is rather coupled with the increase in the rate of nonaffine particle displacements. This rate increases faster for polycarbonate, which has the higher strain-hardening modulus. Also more nonaffine chain stretching is present for polycarbonate. It is shown that the inner distances of such a nonaffinely deformed chain can be well described by the inner distances of the worm-like chain, but with an effective stiffness length (equal to the Kuhn length for an infinite worm-like chain) that increases during deformation. It originates from the finite extensibility of the chain. In this way the increase in nonaffine particle displacement can be understood as resulting from an increase in the effective stiffness length of the perturbed chain during deformation, so that at larger strains a higher rate of plastic events in terms of nonaffine displacement is necessary, causing in turn the observed strain hardening in polymer glasses.

Solvent Effects on the Formation of Nanoparticles and Multilayered Coatings Based on Hydrogen-Bonded Interpolymer Complexes of Poly(acrylic acid) with Homo- and Copolymers of N-Vinyl Pyrrolidone

The formation of hydrogen-bonded interpolymer complexes between poly(acrylic acid) and poly(N-vinyl pyrrolidone) as well as amphiphilic copolymers of N-vinyl pyrrolidone with vinyl propyl ether has been studied in aqueous and organic solutions. It was demonstrated that introduction of vinyl propyl ether units into the macromolecules of the nonionic polymer enhances their ability to form complexes in aqueous solutions due to more significant contribution of hydrophobic effects. The complexation was found to be a multistage process that involves the formation of primary polycomplex particles, which further aggregate to form spherical nanoparticles. Depending on the environmental factors (pH, solvent nature), these nanoparticles may either form stable colloidal solutions or undergo further aggregation, resulting in precipitation of interpolymer complexes. In organic solvents, the intensity of complex formation increases in the following order: methanol < ethanol < isopropanol < dioxane. The multilayered coatings were developed using layer-by-layer deposition of interpolymer complexes on glass surfaces. It was demonstrated that the solvent nature affects the efficiency of coating deposition.

Linear nucleation of polymers

The use of high-melting fibres as linear nuclei for quiescent polymeric melts is instrumental in providing the superior mechanical properties of polymeric self-composites. It also has inherent advantages in the elucidation of fundamental aspects of polymeric crystallization and self-organization, not least in allowing systematic microscopic studies of polymeric crystallization from nucleation through to the growth interface. This has demonstrated explicitly that lamellae develop in two distinct ways, for slower and faster growth, depending on whether fold packing has or has not time to order before the next molecular layer is added with only the former leading to banded growth in linear polyethylene. Other gains in understanding concern cellulation and morphological instability, internuclear interference, isothermal lamellar thickening and banded growth being a consequence of the partial relief of initial surface stress. (c) 2006 Elsevier Ltd. All rights reserved.