Study of the polyvinyl chloride polymer structure in relation to migration of residual vinyl chloride monomer by inverse gas chromatography

The polyvinyl chloride (PVC) polymer structure was studied using inverse gas chromatography (IGC). The specific retention volume (Vg°) of a vinyl chloride monomer (VCM) probe, as well as the thermodynamic parameters of the interaction between PVC and VCM were calculated. Changes in Vg°, free energy(ΔG°_s), enthalpy (ΔH°_s) and entropy (ΔS°_s) observed as the temperature and the amount of VCM decreased, clearly indicate that the PVC—VCM interaction was both concentration and temperature dependent. The Vg° and thermodynamic parameters also varied with changes in polymer structure. Data were interpreted in terms of the active site hypothesis. Active sites in the PVC matrix strongly bind VCM at low enough concentrations and temperatures. Inferably, migration of VCM from PVC packaging materials containing very low concentrations of residual monomer should be for all practical purposes, essentially zero, particularly at low temperatures.     

In vitro iontophoretic release of lithium chloride and lidocaine hydrochloride from polymer electrolytes

Ionically conducting polymers, frequently known as polymer electrolytes, are potential candidates as hosts for drugs to be delivered iontophoretically. The iontophoretic delivery of lithium or lidocaine from polymer electrolyte films through a cellophane membrane was examined using different delivery current regimes. Thin, mechanically strong, polymer electrolyte films were fabricated from poly(ethylene oxide) (PEO) with lithium chloride or lidocaine hydrochloride. Experiments showed that iontophoretic transport of both lithium chloride and lidocaine hydrochloride might be achieved from these PEO-based films. Cation transport number determinations give values for PEO-based films of about 0.4 for lithium chloride systems and 0.12 for lidocaine hydrochloride systems. The mechanism of transport from these PEO-based polymer electrolyte films allows the delivery of ionic salts such as lithium chloride and lidocaine hydrochloride to be controlled solely by current, thus providing a system that can deliver precise amounts of drug.     

Fabrication of flexible polymer dispersed liquid crystal films using conducting polymer thin films as the driving electrodes

Conducting polymers exhibit good mechanical and interfacial compatibility with plastic substrates. We prepared an optimized coating formulation based on poly(3,4-ethylenedioxythiophene) (PEDOT) and 3-(trimethoxysilyl)propyl acrylate and fabricated a transparent electrode on poly(ethylene terephthalate) (PET) substrate. The surface resistances and transmittance of the prepared thin films were 500-600 Ω/□ and 87% at 500 nm, respectively. To evaluate the performance of the conducting polymer electrode, we fabricated a five-layer flexible polymer-dispersed liquid crystal (PDLC) device as a PET-PEDOT-PDLC-PEDOT-PET flexible film. The prepared PDLC device exhibited a low driving voltage (15 VAC), high contrast ratio (60:1), and high transmittance in the ON state (60%), characteristics that are comparable with those of conventional PDLC film based on indium tin oxide electrodes. The fabrication of conducting polymer thin films as the driving electrodes in this study showed that such films can be used as a substitute for an indium tin oxide electrode, which further enhances the flexibility of PDLC film.     

Gold nanorods as nanotransducers to monitor the growth and swelling of ultrathin polymer films

In this work, we demonstrate that plasmonic nanostructures can be employed as nanoscale transducers to monitor the growth and phase transitions in ultrathin polymer films. In particular, gold nanorods with high refractive index sensitivity (~150 nm/refractive index unit (RIU)) were employed to probe the growth and swelling of polyelectrolyte multilayers (PEM). By comparing the wavelength shift and extinction intensity increase of the localized surface plasmon resonance (LSPR) of the gold nanorods coated with PEM in air and water, the swelling of PEM was estimated to be 26% ± 6%. The swelling was quantitatively confirmed with independent thickness measurement of PEM in dry and swollen states using AFM. The deployment of shape-controlled metal nanostructures with high refractive index sensitivity represents a novel and facile approach for monitoring the phase transition in polymers with nanoscale resolution.     

A new approach to the fabrication of ZnO ultrathin films from annealing ZnS nanoparticulate films

The ZnO ultrathin films were fabricated from annealing the ZnS nanoparticulate films. By the layer by layer self-assembly technique, we constructed the ZnS nanoparticulate films from alternating layers of ZnS nanoparticles and polydiallyldimethylammonium chloride (PDDA). The result of the emission spectra indicated that PDDA played a role of passivator. Annealing the ZnS/PDDA films at different temperatures led to the changes in absorption. The SEM images showed that the preannealed film was composed of the uniformly distributing domains, while on the annealed film, there exist some holes formed by the burning of the organic components. The EDS confirmed that ZnS could be converted to ZnO at 500 °C.     

The contributions of erosion, swelling, and porosity to theophylline release kinetics from Cissus populnea polymer matrices

The variable factors of erosion rate, swelling rate, and porosity were used in studying the release patterns of theophylline from our Cissus populnea polymer (CPP) matrices under the different factor combinations given by a simple 2ⁿ factorial experimental design. The zero-order slopes and correlation coefficients representing release rate and linearity, respectively, as obtained from both the nonsteady state and steady state were statistically treated. It appears that the nonsteady-state analysis is more suitable for studying the effects of individual factors, while the steady-state analysis appears more suitable for studying interaction effects of the factors. The study also showed that erosion is the main mechanism by which theophylline is released from the matrices, while swelling is responsible for maintaining linearity in the zero-order release curves. A careful examination of the statistical results shows some functional relationships between the factors, which should be considered in designing more detailed factorial experiments to enable the establishment of equation models for predicting the release profile of theophylline from our CPP matrices under any given dissolution condition.     

Pattern replication examined with integral geometry approach: application to ion milling of polymer blend films

An extension of the integral geometry approach, proposed to characterize pattern replication, was used to compare quantitatively the surface pattern of spin-cast polymer blend films with that replicated in their substrate by ion milling. The original and replicated patterns, recorded with atomic force microscopy (AFM) and analyzed in terms of the Minkowski measures plotted as a function of height, were characterized by the vertical extent and lateral morphological measures. Good, moderate, and far from ideal replication was discussed for various types (island-, hole-dominated, and bicontinuous, respectively) of the original pattern, formed by binary (deuterated) polystyrene mixtures with polyisoprene and poly(n-butyl methacrylate).     

Cross-linked cationic polymer microparticles: effect of N-trimethyl chitosan chloride on the release and permeation of ibuprofen

Microparticles made by cross-linking hydrophilic polymers, such as chitosan, have been used to modify the release rate of a loaded drug. In this study a polymer with fixed positive charges, N-trimethyl chitosan chloride (TMC), was used in combination with chitosan to formulate microparticles to investigate its effects on drug release rate and transport across intestinal epithelial cells. The microparticles were prepared by cross-linking these cationic polymer(s) using sodium citrate as the ionic cross-linker. This process was done under homogenization and ultrasonication to control the size of the particles. The addition of TMC to the chitosan microparticles resulted in an increase in particle size of the microparticles and an increase in ibuprofen release rate as compared to the microparticles containing chitosan alone. Permeation of ibuprofen across Caco-2 cell monolayers, after administration of a suspension of the microparticles to the apical side, was not significantly different for the microparticles containing TMC as compared to those consisting of chitosan alone. It was concluded that release of TMC molecules from the microparticles was probably not sufficient to interact with the intestinal epithelial cells in order to change the permeation of the released drug.     

Meso-patterning of thin polymer films by controlled dewetting: from nano-droplet arrays to membranes

Controlled dewetting of thin polymer films on physically heterogeneous substrates is employed as a new soft lithography route to obtain various types of ordered meso-scale structures, including nano-membranes and ordered arrays of nano-droplets. Dewetting of a thin polymer film on a defect free homogeneous surface occurs by a randomly placed collection of holes and droplets with a well-defined spacing. In contrast, on a physically patterned surface, strong influence of the underlying pattern is observed on the dewetting pathways as well as on the ordering and size of the resulting meso-scale structures. The imposed periodicity of the substrate pattern vis-à-vis the spinodal length scale of dewetting provides a powerful tool for the morphology and size control. The thickness of the film and the kinetics of dewetting are the other important parameters that govern the morphology of the resulting structures.     

Evaluation of the effect of the concentration of plasticizer di(2-ethylhexyl) phthalate on the quantity of residual monomer vinyl chloride in PVC chest drainage tubes

The effect of amount of plasticizer di(2-ethylhexyl) phthalate (DEHP) amount on the amount of residual monomer vinyl chloride (VC) was determined in samples of plasticised polyvinyl chloride (PVC) with different concentration of plasticiser (22.32-33.05%), before and after sterilisation by a titrimetric method. The titrimetric method was used to determine the VC concentration in a KMnO4 solution where the samples were kept immersed under the same conditions for 2 h. The influence of PVC film extracts with different amounts of DEHP on mouse fibroblast cells L-929 in a culture medium was evaluated by using quantitative tests: the amount of cells (protein determination), viability (MTT test) and proliferation (incorporation of bromodeoxyuridine (BrDU). The amount of vinyl chloride before and after heat sterilisation at 120 degrees C for 30 min was found to be almost the same for all samples and without any dependence on the concentration of DEHP. The extracts of the PVC films which were tested have no toxic effect on cells in a culture medium.     

Wetting behavior of polymer coated nanoporous anodic alumina films: transition from super-hydrophilicity to super-hydrophobicity

We show that nanoporous anodic alumina films, with pore diameters in the range 10-80 nm, can be transformed from being very hydrophilic (or super-hydrophilic) to very hydrophobic (or super-hydrophobic) by coating the surface with a thin (2-3 nm) layer of a hydrophobic polymer. This dramatic transformation happens as a result of the interplay between surface morphology and surface chemistry. The coated surfaces exhibit 'sticky' hydrophobicity as a result of ingress of water into the pores by capillary action. The wetting parameters (contact angle and contact angle hysteresis) exhibit qualitatively different dependences on pore diameters in coated and uncoated films, which are explained by invoking appropriate models for wetting.     

Statistical approach to synthesise biogenic silica nanoparticles from rice husk and conjugated with Justicia adhatoda extract as green,slow‐release biocide

Biogenic silica synthesised from rice husk was used as a controlled release system of an eco‐friendly biocide consisting of a Justicia adhatoda extract. Fourier‐transform infrared spectroscopy (FTIR) indicated the presence of ester bonds between the silica support and the conjugated Justicia adhatoda extract. Surface area analysis and microscopy confirmed a high level of Justicia adhatoda extract loading in the silica support. The phytochemical investigation of Justicia adhatoda was done by Gas chromatography–mass spectrometry (GC‐MS) spectroscopy. Moreover, compared with the naked biogenic silica nanoparticles, a better thermal stability was determined for the conjugated system of the extracted compounds. Trial of kinetic release of silica: Justicia adhatoda ∼29% of loaded Justicia adhatoda was released within 1 h and then the rate of release became slow. Net release of Justicia adhatoda was observed up to 50% within 7 h. The Justicia adhatoda compounds released from silica also showed the improved mortality rate against stored product pest rice weevil (Sitophilus oryzae).     

Immobilization of biomaterials to nano-assembled films (self-assembled monolayers, Langmuir-Blodgett films, and layer-by-layer assemblies) and their related functions

For utilization of highly sophisticated functions of biomaterials in nano-scale functional systems, immobilization of biomaterials on artificial devices such as electrodes via thin film technology is one of the most powerful strategies. In this review, we focus on three major organic ultrathin films, self-assembled monolayers (SAM), Langmuir-Blodgett (LB) films, and layer-by-layer (LBL) assemblies, and from the viewpoints of biomaterial immobilization, typical examples and recent progresses in these film technologies are described. The SAM method allows facile contact between biomaterials and man-made devices, and well used for bio-related sensors. In addition, recent micro-fabrication techniques such as micro-contact printing and dip-pen nanolithography were successfully applied to preparation of biomaterial patterning. A monolayer at the air-water interface, which is a unit structure of LB films, provides a unique environment for recognition of aqueous biomaterials. Recognition and immobilization of various biomaterials including nucleotides, nucleic acid bases, amino acids, sugars, and peptides were widely investigated. The LB film can be also used for immobilization of enzymes in an ultrathin film on an electrode, resulting in sensor application. The LBL assembling method is available for wide range of biomaterials and provides great freedom in designs of layered structures. These advantages are reflected in preparation of thin-film bio-reactors where multiple kinds of enzymes sequentially operate. LBL assemblies were also utilized for sensors and drug delivery systems. This kind of assembling structures can be prepared on micro-size particle and very useful for preparation of hollow capsules with biological functions.     

Open circuit reactions complicating the electroprecipitation of poly(vinylferricinium) films from methylene chloride

We describe an electrochemical quartz crystal microbalance interfacial gravimetric study of the electroprecipitation and dissolution of PVF+ClO4- (PVF = poly(vinylferrocene)) films exposed to methylene chloride solutions. Film deposition is diffusion controlled by the supply of PVF from the solution. Film solvent content is markedly dependent upon the deposition potential. The self-exchange process between surface-bound ferricinium sites and solution-phase ferrocene sites, which is responsible for film deposition under conditions of positive applied potential, is also responsible for film dissolution under open circuit conditions. Dependent upon the deposition potential, releasing the electrode from potential control may (not) result in transient deposition processes that temporarily increase surface coverage. Under all conditions, opening the circuit ultimately leads to reductive stripping of the film by solution-phase PVF. The dissolution rate is independent of applied potential, and is not limited by electron transfer at the outer film interface or by electron (and coupled ion) transport within the film; we speculate that polymer-based processes, such as chain disentanglement, are rate limiting.     

An attempt to use scratch tests to predict the residual lifetime of unplasticised poly(vinyl chloride) pipes

This paper reports on a procedure that can potentially predict the residual lifetime of low-pressure uPVC pipes in a non-destructive way. Ageing of these materials is characterised by a change in yield stress and fracture behaviour. The search for a method being able to non-destructively evaluate the yield stress and the fracture behaviour led to the study of scratching of the polymer surface. According to an extensive study by Atkins and Liu, the scratching behaviour is a function of yield stress, fracture toughness and the attack angle of the cutting tool.Experiments reported in this paper give an evaluation of the scratched area as a function of the attack angle for uPVC samples having different ageing times. Existing analyses for metals are adapted for polymer specific properties, such as the pronounced strain rate dependence of yield stress and visco-elastic recovery. The suggested adaptations are successful in the sense that the resulting analysis is capable of describing the forces during scratching and the resulting cross-sectional area of the groove. Although the scratching technique was not able to discriminate between differences in the scratch force or cross-sectional area of the groove of the different ageing times, it was possible to get an estimate of the fracture toughness from the analysis. Therefore, scratching is a promising technique to determine the fracture toughness for ductile materials for which it is difficult to obtain accurate results with conventional techniques.     

Use of proteins to minimize the physical aging of EUDRAGIT sustained release films

The objective of this study was to investigate the influence of two proteins, albumin and type B gelatin, on the physical aging of EUDRAGIT® RS 30 D and RL 30 D coated theophylline pellets. The physicomechanical properties of sprayed films, thermal properties of cast films, influence of proteins on the zeta potential and particle size of the dispersion, and the release of proteins from cast films under simulated dissolution conditions were investigated. The release rate of theophylline decreased significantly over time from pellets coated with an acrylic dispersion containing 10% albumin when there was no acidification of the acrylic dispersion; however, when pellets were coated with an acidified EUDRAGIT®/albumin dispersion, the theophylline release rate was stable for dosage forms stored in the absence of humidity. The drug release rate was faster for pellets coated with acrylic dispersions containing 10% gelatin compared to the albumin-containing formulations. When sprayed films were stored at 40°C/75% RH, the water vapor permeability decreased significantly for both EUDRAGIT® films and those containing EUDRAGIT® and albumin; however, there was no significant change in this parameter when 10% gelatin was present. Albumin was released from the acrylic films when the pH of the dissolution media was below the isoelectric point of the protein while no quantitative release of gelatin was observed in pH 1.2 or 7.4 media. The effect of gelatin to prevent the decrease in drug release rate was due to stabilization in water vapor permeability of the film. Acidification of the polymeric dispersion resulted in electrostatic repulsive forces between albumin and the acrylic polymer, which stabilized the drug release rate when the dosage forms were stored in aluminum induction sealed containers at both 40°C/75% RH and 25°C/60% RH.     

Development of an experimental technique to assess the permeability of metal coated polymer films

The experimental time required to measure water vapour permeability of barrier film using the cup method is extremely long. In this study, a new technique is proposed, based on light transmission. This fast and accurate method was first validated using model films constituted of aluminized PET (polyethylene terephthalate) with aluminium layers of different thicknesses (<100 nm). It was possible to show that the ‘illuminating’ method could advantageously be employed to control the film’s barrier properties during their fabrication. In a second step, the method was tentatively used to measure the changes in barrier properties over time, when the samples are submitted to severe hydrothermal ageing (70 °C, 90% relative humidity [RH]). It was concluded that the complex degradation mechanism prevents accurate measurement while ageing.