Dynamic scale theory for characterizing surface morphology of layer-by-layer films of poly(o-methoxyaniline)

The dynamic scale theory and fractal concepts are employed in the characterization of surface morphological properties of layer-by-layer (LBL) films from poly(o-methoxyaniline) (POMA) alternated with poly(vinyl sulfonic acid) (PVS). The fractal dimensions are found to depend on the procedures to fabricate the POMA/PVS multilayers, particularly with regard to the drying procedures. LBL films obtained via drying in ambient air show a more homogeneous surface, compared to films dried under vacuum or a flow of nitrogen, due to a uniform rearrangement of polymer molecules during solvent evaporation.

Influence of solution treatment on the adsorption and morphology of poly(o-methoxyaniline) layer-by-layer films

It is shown that the adsorption and morphological properties of layer-by-layer films of poly(o-methoxyaniline) (POMA) alternated with poly(vinyl sulfonic acid) (PVS) are affected dramatically by different treatments of the POMA solutions employed to prepare the films. Whereas the dimension of the globular structures seen by atomic force microscopy increases non monotonically during film growth in parent POMA solution, owing to a competition of adsorption/desorption processes, it changes monotonically for the fractionated POMA. The roughness of the latter films depends on the concentration of the solution and saturates at a given size of the scan window. This allowed us to apply scaling laws that indicated a self-affine mechanism for adsorption of the treated POMA.

Adsorption processes in layer-by-layer films of poly(o-methoxyaniline): the role of aggregation

In this work we investigate the effect from the solution concentration on aggregation in layer-by-layer (LBL) films of poly(omethoxyaniline) (POMA) alternated with poly(vinyl sulfonic acid). Films are adsorbed on hydrophilized glass substrates and characterized with UV-Vis spectroscopy and atomic force microscopy. The formation of aggregates is favored in more concentrated solutions, leading to an increase in the diameter of the domains. This is caused by stronger polymer-polymer interactions under high concentrations. The size of POMA aggregates in solution is estimated to be larger than in LBL films, which is surprising because one should expect aggregates from solution to coalesce into larger aggregates in the deposited films. This unexpected result may be explained by a swelling effect of aggregates in the aqueous POMA solutions, consistent with other reports in the literature which consider the aggregates in solution to be made up of smaller aggregates. Upon adsorption on a solid substrate to form the LBL film, a molecular reorganization probably takes place, resulting in smaller aggregates. It is also found that the size distribution of the POMA domains in the LBL films is determined by the concentration of the solution. (C) 2002 Elsevier B.V. B.V. All rights reserved.

Diffusion-controlled growth of aggregates in layer-by-layer films of poly(o-methoxyaniline)

The adsorption process in layer-by-layer (LBL) films of poly(o-methoxyaniline) alternated with poly(vinyl sulfonic acid) is explained using the Avrami equation. This equation was used due to its mathematical simplicity and adequate description of experimental data in real polymer systems. The Avrami parameters are a convenient means to represent empirical data of crystallization, and if microscopic knowledge is available these parameters can also be associated with adsorption mechanisms. The growth of spherulites in the LBL films was studied as a function of time using atomic force microscopy and the data were used to estimate the number and radii of aggregates, from which the Avrami parameters were determined. We find that the adsorption mechanism may correspond to a tri dimensional, diffusion-controlled growth, with increasing nucleation rate, consistent with results from kinetics of adsorption.

Ftalato de di-(2-etilexila) (DEHP) em bolsas de PVC para soluções parenterais de grandes volumes

Large volume parenteral solutions (LVPS) are widely used as vehicles for intravenous administration of drugs and polyvinyl chloride (PVC) flexible bags are, nowadays, the plastic containers most commonly used to pack and drip-feed LVPS. An advantage of using bags is that they collapse flat and thus reduce the risk of airborne contamination and embolism caused by air in the bloodstream. They are mainly used in hospitals. This review deals with some important aspects of the PVC packaging containing the plasticizer DEHP, generally used to pack LVPS. The interaction between drug and package is discussed, with an emphasis on the migration of DEHP from the PVC bag to LVPS containing the immunosuppressant cyclosporin, and toxicological aspects are considered.

Effect of a Polymeric Protective Coating on Optical and Electrical Properties of Poly(p-phenylene vinylene) Derivatives

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Avaliação do ciclo de vida dos tubos de PVC produzidos no Brasil

Naturally characterizes the human being the interference in the environment to ensure their survival and also convenience. After numerous environmental accidents caused by unbridled pursuit of this goal, the concern about providing for current needs without compromising the ability of the future generations to supply their own, gained space. In order to contribute to sustainable development the Life Cycle Assessment (LCA) was implemented. This tool is based on the concept that if the environmental impacts of a product or service are known, it is possible to take better decisions concerning its environmental aspects. The purpose of this research is to conduct the LCA of polyvinyl chloride (PVC), the world’s second most consumed thermoplastic. The methodology described in NBR ISO 14040 and NBR ISO 14044 was followed. As a result, the LCA of polyvinyl chloride produced in Brazil was obtained, and, therefore, the inventory of the product in question adapted to Brazilian reality. The research can be applied to various studies considering that actions were taken to ensure that it represents the Brazilian reality. Moreover, the procedures were described to guarantee the greatest transparency possible

Understanding the mechanical and biodegradation behaviour of poly(hydroxybutyrate)/rubber blends in relation to their morphology

In this work poly(hydroxybutyrate/poly(vinyl butyral)- co-(vinyl alcohol)-co(vinyl acetate) (or ethylene propylene diene monomer rubber) blends were prepared by conventional processing techniques (extrusion and injection moulding). A droplet type morphology was obtained for P(3HB)/PVB blends whereas P(3HB)/EPDM blends presented some extent of co-continuous morphology. In addition, rubbery domains were much smaller in the case of PVB. These differences in morphology are discussed taking into account solubility parameters and rheological behaviours of each component. For both blends, the increase of elastomer ratio led to a decrease of Young's modulus but an increase in elongation at break and impact strength. The latter increased more in the case of P(3HB)/EPDM blends although the rubbery domains were larger. These results are explained in the light of the glass transition of the rubber and the presence of plasticizer in the case of PVB. The addition of elastomer also resulted in an increase of P(3HB) biodegradation rate, especially in the case of EPDM. It is assumed that, in this case, the size and morphology of the rubbery domains induce a geometrical modification of the erosion front which leads to an increase of the interface between P(3HB) phase and the degradation medium and consequently to an apparently faster biodegradation kinetics of PHB/rubber blends. Copyright (C) 2011 Society of Chemical Industry

Platinum nanoparticles incorporated in silsesquioxane for use in LbL films for the simultaneous detection of dopamine and ascorbic acid

We describe the preparation of platinum nanoparticles (PtNPs) using the 3-n-propylpyridinium silsesquioxane chloride (SiPy+Cl-) as a nanoreactor and stabilizer. The formation of PtNPs was monitored by UV-Vis spectroscopy by measuring the decrease in the intensity of the band at 375 nm, which is attributed to the electronic absorption of PtCl62- ions. TEM images of Pt-SiPy+Cl- nanohybrid indicated an average size of 3-40 nm for PtNPs. The Pt-SiPy+Cl- was used as a polycation in the preparation of layer-by-layer films (LbL) on a glass substrate coated with fluorine-doped tin oxide (FTO) alternating with the polyanion poly(vinyl sulfonic acid) (PVS). The films were electrochemically tested in sulfuric acid to confirm the deposition of Pt-SiPy+Cl- onto the LbL films, observing the adsorption and desorption of hydrogen (E-pa = 0.1 V) and by the redox process of formation for PtO with E-pa = 1.3 V and E-pc = 0.65 V. FTIR and Raman spectra confirmed the presence of the PVS and Pt-SiPy+Cl- in the LbL films. A linear increase in the absorbance in the UV-Vis spectra of the Pt-SiPy+Cl- at 258 nm (pi -> pi* transition of the pyridine groups) with a number of Pt-SiPy+Cl-/PVS or PVS/SiPy+Cl- bilayers (R = 0.992) was observed. These LbL films were tested for the determination of dopamine (DA) in the presence of ascorbic acid (AA) with a detection limit (DL) on the order of 2.6 x 10(-6) mol L-1 and a quantification limit (QL) of 8.6 x 10(-6) mol L-1. The films exhibited a good repeatability and reproducibility, providing a potential difference of 550 mV for the oxidation of DA with AA interferent.

Effect of a polymeric protective coating on optical and electrical properties of poly (p-phenylene vinylene) derivatives

The resistance to photodegradation of poly [(2-methoxy-5-n-hexyloxy)-p-phenylene vinylene] (OC1OC6-PPV) films was significantly enhanced by the use of poly(vinyl alcohol) 99% hydrolyzed as protective coating. The deposition of poly(vinyl alcohol) onto OC1OC6-PPV films did not affect the absorption and the emission spectra of the luminescent polymer. The protected film showed 5% drop on the absorbance at 500nm after 270 hours of light exposure while the unprotected film completely degraded in the same conditions. The conductivity of the protected film remained stable (around 7 × 10-10 S/m) while the value for the unprotected one dropped around two orders of magnitude after 100 hours of light exposure.

The influence of PVC wrapping on the performance of two laser fluorescence devices on occlusal surfaces in vitro

OBJECTIVE: The aim of this study was to determine the influence of polyvinyl chloride (PVC) wrapping on the performance of two laser fluorescence devices (LF and LFpen) by assessing tooth occlusal surfaces. BACKGROUND DATA: Protection of their tips may influence LF measurements. To date there are no studies evaluating the influence of this protection on the performance of the LFpen on permanent teeth, or comparing it to the original LF device. MATERIALS AND METHODS: One hundred nineteen permanent molars were assessed by two experienced dentists using the LF and the LFpen devices, both with and without PVC wrapping. The teeth were histologically prepared and assessed for caries extension. RESULTS: The LF values with and without PVC wrapping were significantly different. For both LF devices, the sensitivity and accuracy were lower when the PVC wrapping was used. The specificity was statistically significantly higher for the LFpen with PVC. No difference was found between the areas under the ROC curves with and without PVC wrapping. The ICC showed excellent interexaminer agreement. The Bland and Altman method showed a range between the upper and the lower limits of agreement of 63.4 and 57.8 units for the LF device, and 49.4 and 74.2 for the LFpen device, with and without PVC wrapping, respectively. CONCLUSIONS: We found an influence of the PVC wrapping on the performance of the LF and LFpen devices. However, since its influence on detection of occlusal caries lesions is considered for, the use of one PVC layer is suggested to avoid cross-contamination in clinical practice.

Study of the emissions from pyrolytic and oxidative thermal decomposition of PVC

Polyvinyl chloride (PVC) is one of the plastics most extensively used due to its versatility. The demand of PVC resin in Europe during 2012 reached 5000 ktonnes1. PVC waste management is a big problem because of the high volume generated all over the world and its chlorine content. End-of-life PVC is mainly mixed with municipal solid waste (MSW) and one common disposal option for this is waste-to-energy incineration (WtE). The presence of plastics such as PVC in the fuel mix increases the heating value of the fuel. PVC has two times higher energy content than MSW ‒around 20 MJ/kg vs 10 MJ/kg, respectively. However, the high chlorine content in PVC resin, 57 wt.%, may be a source for the formation of hazardous chlorinated organic pollutants in thermal processes. Chlorine present in the feedstock of WtE plants plays an important role in the formation of (i) chlorine (Cl2) and (ii) hydrochloric gas (HCl), both of them responsible for corrosion, and (iii) chlorinated organic pollutants2. In this work, pyrolytic and oxidative thermal degradation of PVC resin were carried out in a laboratory scale reactor at 500 ºC in order to analyze the influence of the reaction atmosphere on the emissions evolved. Special emphasis was put on the analysis of chlorinated organic pollutants such as polychlorodibenzo-p-dioxins (PCDDs), polychlorodibenzofurans (PCDFs) and other related compounds like polychlorobenzenes (PCBzs), polychlorophenols (PCPhs) and polycyclic aromatic hydrocarbons (PAHs). Another objective of this work was to compare the results with those of a previous work3 in which emissions at different temperatures in both pyrolysis and combustion of another PVC resin had been studied; in that case, experiments for PCDD/Fs emissions had been performed only at 850 ºC.

Performance Assessment of a Polymer Electrolyte Membrane Electrochemical Reactor under Alkaline Conditions – A Case Study with the Electrooxidation of Alcohols

A novel polymer electrolyte membrane electrochemical reactor (PEMER) configuration has been employed for the direct electrooxidation of propargyl alcohol (PGA), a model primary alcohol, towards its carboxylic acid derivatives in alkaline medium. The PEMER configuration comprised of an anode and cathode based on nanoparticulate Ni and Pt electrocatalysts, respectively, supported on carbonaceous substrates. The electrooxidation of PGA was performed in 1.0 M NaOH, where a cathode based on a gas diffusion electrode was manufactured for the reduction of oxygen in alkaline conditions. The performance of a novel alkaline anion-exchange membrane based on Chitosan (CS) and Poly(vinyl) alcohol (PVA) in a 50:50 composition ratio doped with a 5 wt.% of poly (4-vinylpyridine) organic ionomer cross-linked, methyl chloride quaternary salt resin (4VP) was assessed as solid polymer electrolyte. The influence of 4VP anionic ionomer loading of 7, 12 and 20 wt.% incorporated into the electrocatalytic layers was examined by SEM and cyclic voltammetry (CV) upon the optimisation of the electroactive area, the mechanical stability and cohesion of the catalytic ink onto the carbonaceous substrate for both electrodes. The performance of the 4VP/CS:PVA membrane was compared with the commercial alkaline anion-exchange membrane FAA −a membrane generally used in direct alcohol alkaline fuel cells- in terms of polarisation plots in alkaline conditions. Furthermore, preparative electrolyses of the electrooxidation of PGA was performed under alkaline conditions of 1 M NaOH at constant current density of 20 mA cm−2 using a PEMER configuration to provide proof of the principle of the feasibility of the electrooxidation of other alcohols in alkaline media. PGA conversion to Z isomers of 3-(2-propynoxy)-2-propenoic acid (Z-PPA) was circa 0.77, with average current efficiency of 0.32. Alkaline stability of the membranes within the PEMER configuration was finally evaluated after the electrooxidation of PGA.

Preparação de catalisadores para reações de esterificação do ácido oleico baseados em matrizes polímericas sulfonadas POLI(1- FENILETILENO) (PS) e POLI(1-CLOROETILENO) (PVC)

Chemical modification of polymer matrices is an alternative way to change its surface properties. The introduction of sulfonic acid groups in polymer matrices alter properties such as adhesion, wettability, biocampatibility, catalytic activity, among others. This paper describes the preparation of polymeric solid acid based on the chemical modification of poly (1-fenietileno) (PS) and Poly (1-chloroethylene) (PVC) by the introduction of sulfonic acid groups and the application of these polymers as catalysts in the esterification reaction of oleic acid with methanol. The modified materials were characterized by Infrared Spectroscopy, Elemental Analysis and titration acid-base of the acid groups. All techniques confirmed the chemical changes and the presence of sulfur associated with sulfonic acid groups or sulfates. The modified polymers excellent performance in the esterification reaction of oleic acid with methanol a degree of conversion higher than 90% for all investigated polymers (modified PS and PVC (5% w / w)), with a mass ratio of oleic acid: methanol 1:10 to 100 ° C. The best performance was observed for the modified PVC catalyst (PVCS) which showed low degree of swelling during the reactions is recovered by filtration different from that observed for polystyrene sulfonate (PSS). Given these facts, the PVCS was employed as a catalyst in the esterification reaction of oleic acid in different times and different temperatures to obtain the kinetic parameters of the reaction. Experimental data show a great fit for pseudo-homogeneous model of second order and activation energy value of 41.12 kJ mol -1, below that found in the literature for the uncatalyzed reaction, 68.65 kJ mol -1 .The PVCS exhibits good catalytic activity for 3 times of reuse, with a slight decrease in the third cycle, but with a conversion of about 78%. The results show that solid polymeric acid has good chemical stability for the application in esterification reaction of commercial importance with possible application in the biodiesel production. The advantages in use of this system are the increased reaction rate at about 150 times, at these test conditions, the replacement of sulfuric acid as a catalyst for this being the most corrosive and the possibility of reuse of the polymer for several cycles.

Synthesis and study of conductivity behaviour of blended conducting polymer films irradiated with swift heavy ions of silicon

In recent times, blended polymers have shown a lot of promise in terms of easy processability in different shapes and forms. In the present work, polyaniline emeraldine base (PANi-EB) was doped with camphor sulfonic acid (CSA) and combined with the conducting polymer polyfluorene (PF) as well as the insulating polymer polyvinyl chloride (PVC) to synthesize CSA doped PANi-PF and PANi-PVC blended polymers. It is well known that PANi when doped with CSA becomes highly conducting. However, its poor mechanical properties, such as low tensile, compressive, and flexural strength render PANi a non-ideal material to be processed for its various practical applications, such as electromagnetic shielding, anti-corrosion shielding, photolithography and microelectronic devices etc. Thus the search for polymers which are easily processable and are capable of showing high conductivity still continues. PANi-PVC blend was prepared, which showed low conductivity which is limiting factor for certain applications. Therefore, another processable polymer PF was chosen as conducting matrix. Conducting PF can be easily processed into various shapes and forms. Therefore, a blend mixture was prepared by using PANi and PF through the use of CSA as a counter ion which forms a "bridge" between the two polymeric components of the inter-polymer complex. Two blended polymers have been synthesized and investigated for their conductivity behaviour. It was observed that the blended film of CSA doped PANi-PVC showed a room temperature electrical conductivity of 2.8 × 10-7 S/cm where as the blended film made by CSA doped PANi with conducting polymer PF showed a room temperature conductivity of 1.3 × 10-5 S/cm. Blended films were irradiated with 100 MeV silicon ions with a view to increase their conductivity with a fluence ranging from 1011 ions to 1013 per cm2 from 15 UD Pelletron accelerator at NSC, New Delhi.