Application of non-isothermal cure kinetics on the interaction of poly(ethylene terephthalate) - Alkyd resin paints

Samples of paint (P), reused PET (PET-R) and paint/PET-R mixtures (PPET-R) were evaluated using DSC to verify their physical-chemical properties and thermal behavior. Films from paints and PPET-R are visually similar. It was possible to establish that the maximum amount of PET-R that can be added to paint without significantly altering its filming properties is 2%. The cure process (80-203°C) was identified through DSC curves. The kinetic parameters, activation energy (E a) and Arrhenius parameters (A) for the samples containing 0.5 to 1% of PET-R, were calculated using the Flynn-Wall-Ozawa isoconversional method. It was observed that for greater amounts of PET-R added, there is a decrease in the E a values for the cure process. A Kinetic compensation effect (KCE), represented by the equation InA=-2.70+0.31E a was observed for all the samples. The most suitable kinetic model to describe this cure process is the autocatalytic Šesták-Berggreen, model applied to heterogeneous systems. © 2007 Springer Science+Business Media, LLC.

Rheological behavior of binary aqueous solutions of poly(ethylene glycol) of 1500 g·mol-1 as affected by temperature and polymer concentration

The rheological behavior of poly(ethylene glycol) of 1500 g·mol -1(PEG1500) aqueous solutions with various polymer concentrations (w = 0.05, 0.10, 0.15, 0.20 and 0.25) was studied at different temperatures (T = 283.15, 288.15, 293.15, 298.15 and 303.15) K. The analyses were carried out considering shear rates ranging from (20 to 350) s-1, using a cone-and-plate rheometer under controlled stress and temperature. Classical rheological models (Newton, Bingham, Power Law, Casson, and Herschel-Bulkley) were tested. The Power Law model was shown suitable to mathematically represent the rheological behavior of these solutions. Well-adjusted empirical models were derived for consistency index variations in function of temperature (Arrhenius-type model; R2 > 0.96), polymer concentration (exponential model; R2 > 0.99) or the combination of both (R 2 > 0.99). Additionally, linear models were used to represent the variations of behavior index in the functions of temperature (R2 > 0.83) and concentration (R2 > 0.87). © 2013 American Chemical Society.

Síntese e caracterização de cátodos de perovskitas 'La IND.0,6''Sr IND.0,4''Fe IND.y''Co IND.1-y''O IND.3-'delta'', para células a combustível de eletrólito sólido (SOFC) operando em temperaturas intermediárias

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Density, Refractive Index, Apparent Specific Volume, and Electrical Conductivity of Aqueous Solutions of Poly(ethylene glycol) 1500 at Different Temperatures

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Water activity of aqueous solutions of ethylene oxide-propylene oxide block copolymers and maltodextrins

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Plasmid DNA partitioning and separation using poly(ethylene glycol)/poly(acrylate)/salt aqueous two-phase systems

Phase diagrams of poly(ethylene glycol)/polyacrylate/Na2SO4 systems have been investigated with respect to polymer size and pH. Plasmid DNA from Escherichia coil can depending on pH and polymer molecular weight be directed to a poly(ethylene glycol) or to a polyacrylate-rich phase in an aqueous two-phase system formed by these polymers. Bovine serum albumin (BSA) and E. coil homogenate proteins can be directed opposite to the plasmid partitioning in these systems. Two bioseparation processes have been developed where in the final step the pDNA is partitioned to a salt-rich phase giving a total process yield of 60-70%. In one of them the pDNA is partitioned between the polyacrylate and PEG-phases in order to remove proteins. In a more simplified process the plasmid is partitioned to a PEG-phase and back-extracted into a Na2SO4-rich phase. The novel polyacrylate/PEG system allows a strong change of the partitioning between the phases with relatively small changes in composition or pH. (C) 2012 Elsevier B.V. All rights reserved.

In vitro and in vivo evaluation of the biocompatibility of a calcium phosphate/poly(lactic-co-glycolic acid) composite

This study assess the effects of bioceramic and poly(lactic-co-glycolic acid) composite (BCP/PLGA) on the viability of cultured macrophages and human dental pulp fibroblasts, and we sought to elucidate the temporal profile of the reaction of pulp capping with a composite of bioceramic of calcium phosphate and biodegradable polymer in the progression of delayed dentine bridge after (30 and 60 days) in vivo. Histological evaluation of inflammatory infiltrate and dentin bridge formation were performed after 30 and 60 days. There was similar progressive fibroblast growth in all groups and the macrophages showed viability. The in vivo study showed that of the three experimental groups: BCP/PLGA composite, BCP and calcium hydroxide (Ca(OH)(2)) dentin bridging was the most prevalent (90 %) in the BCP/PLGA composite after 30 days, mild to moderate inflammatory response was present throughout the pulp after 30 days. After 60 days was observed dentine bridging in 60 % and necrosis in 40 %, in both groups. The results indicate that understanding BCP/PLGA composite is biocompatible and by the best tissue response as compared to calcium hydroxide in direct pulp capping may be important in the mechanism of delayed dentine bridge after 30 and 60 days.

Surfactant-assisted intercalation of high molecular weight poly(ethylene oxide) into vanadyl phosphate di-hydrate

A high molecular weight poly(ethylene oxide)/layered vanadyl phosphate di-hydrate intercalation compound was synthesized via the surfactant-assisted approach. Results confirmed that surfactant molecules were replaced with the polymer, while the lamellar structure of the matrix was retained, and that the material presents high specific surface area. In addition, intercalation produced a more thermally stable polymer as evidenced by thermal analysis. (C) 2011 Elsevier Ltd. All rights reserved.

Partitioning and extraction of collagenase from Penicillium aurantiogriseum in poly(ethylene glycol)/phosphate aqueous two-phase system

Purification of collagenase produced by Penicillium aurantiogriseum URM4622 was carried using a PEG/phosphate aqueous two-phase system (ATPS). A 2(3)-full experimental design was used to investigate the influence of PEG molar mass, PEG concentration and phosphate concentration on the selected responses, namely partition coefficient, activity yield and purification factor. The ATPS was composed of PEG (molar mass of 550, 1500 and 4000 g/mol) at concentrations of 15.0, 17.5 and 20.0% (w/w) and phosphate at concentrations of 12.5, 15.0 and 17.5% (w/w). The best results of one-step extraction of collagenase from the fermentation broth (partition coefficient of 1.01, activity yield of 242% and purification factor of 23.5) were obtained at pH 6.0 using 20.0% (w/w) PEG 550 and 17.5% (w/w) phosphate. The results of this preliminary study demonstrate that the selected ATPS is satisfactorily selective for the extraction of such a collagenase. (C) 2012 Elsevier B.V. All rights reserved.

The Influence of Osteoblast Differentiation Stage on Bone Formation in Autogenously Implanted Cell-Based Poly(Lactide-Co-Glycolide) and Calcium Phosphate Constructs

We tested the hypothesis that the osteoblast differentiation status of bone marrow stem cells (BMSCs) combined with a three-dimensional (3D) structure modulates bone formation when autogenously implanted. Rat BMSCs were aspirated, expanded, and seeded into a 3D composite of poly(lactide-co-glycolide) and calcium phosphate (PLGA/CaP) to produce a hybrid biomaterial. Calvarial defects were implanted with (1) scaffold without cells (SC/NC), (2) scaffold and BMSCs (SC + BMSC), (3) scaffold and osteoblasts differentiated for 7 days (SC + OB7), and (4) for 14 days (SC + OB14). After 4 weeks, there was more bone formation in groups combining scaffold and cells, SC + BMSC and SC + OB7. A nonsignificant higher amount of bone formation was observed on SC + OB14 compared with SC/NC. Additionally, more blood vessels were counted within all hybrid biomaterials, without differences among them, than into SC/NC. These findings provide evidences that the cell differentiation status affects in vivo bone formation in autogenously implanted cell-based constructs. Undifferentiated BMSCs or osteoblasts in early stage of differentiation combined with PLGA/CaP scaffold favored bone formation compared with plain scaffold and that one associated with more mature osteoblasts.

Compatible blends of thermoplastic starch and hydrolyzed ethylene-vinyl acetate copolymers

Ethylene-vinyl acetate copolymer (EVA) with 19% of vinyl acetate and its derivatives modified by hydrolysis of 50 and 100% of the initial vinyl acetate groups were used to produce blends with thermoplastic starch (TPS) plasticized with 30 wt% glycerol. The blends were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy. X-ray diffraction, water absorption, stress-strain mechanical tests, dynamic mechanical analysis and thermogravimetric analysis. In contrast to the blends with unmodified EVA. those made with hydrolyzed EVA were compatible, as demonstrated by the brittle fracture surface analysis and the results of thermal and mechanical tests. The mechanical characteristics and water absorption of the TPS were improved even with a small addition (2.5 wt%) of hydrolyzed EVA. The glass transition temperature rose with the degree of hydrolysis of EVA by 40 and 50 degrees, for the EVA with 50 and 100% hydrolysis, respectively. The addition of hydrolyzed EVA proved to be an interesting approach to improving TPS properties, even when very small quantities were used, such as 2.5 wt%. (C) 2012 Elsevier Ltd. All rights reserved.

Elaboration and Characterization of Nano-Biocomposites Based on Plasticized Poly(Hydroxybutyrate-Co-Hydroxyvalerate) with Organo-Modified Montmorillonite

Nano-biocomposites based on a biodegradable bacterial copolyester, poly(hydroxybutyrate-co-hydroxyvalerate), have been elaborated with an organo-modified montmorillonite (OMMT) clay as nanofiller, and acetyl tributyl citrate as plasticizer. The corresponding (nano)structures, thermal and mechanical properties, permeability, and biodegradability have been determined. Polyhydroxyalkanoates are very thermal sensitive then to follow the degradation the corresponding matrices have been analyzed by size exclusion chromatography. The results indicate that the addition of the plasticizer decreases the thermo-mechanical degradation, during the extrusion. These nano-biocomposites show an intercalated/exfoliated structure with good mechanical and barrier properties, and an appropriated biodegradation kinetic. Intending to understand the changes in the thermal properties, the nano-biocomposites were characterized by thermal gravimetric analysis and differential scanning calorimetry. The presence of the OMMT clay did not influence significantly the transition temperatures. However, the filler not only acted as a nucleating agent which enhanced the crystallization, but also as a thermal barrier, improving the thermal stability of the biopolymer. The results indicated that the addition of the plasticizer reduces the glass transition temperature and the crystalline melting temperature. The plasticizer acts as a processing aid and increases the processing temperature range (lower melting temperature).

Hofmeister effects on the colloidal stability of poly(ethylene glycol)-decorated nanoparticles

The colloidal stability of poly(ethylene glycol)-decorated poly(methyl methacrylate), PMMA/Tween-20, particles was investigated by means of phase separation measurements, in the presence of sodium fluoride (NaF), sodium chloride, sodium bromide, sodium nitrate, or sodium thiocyanate (NaSCN) at 1.0 mol L-1. Following Hofmeister's series, the dispersions of PMMA/Tween-20 destabilized faster in the presence of NaF than with NaSCN. After the phase separation, the systems were homogenized and except for the dispersions in NaF, re-dispersed particles took longer to destabilize, indicating that anions adsorbed on the particles, creating a new surface. Except for F- ions, the adsorption of anions on the polar outmost shell was evidenced by means of tensiometry and small-angle X-ray scattering measurements. Fluoride ions induced the dehydration of the polar shell, without affecting the polar shell electron density, and the formation of very large aggregates. A model was proposed to explain the colloidal behavior in the presence of Hofmeister ions.

Chain extension of poly (ethylene terephthalate) by reactive extrusion with secondary stabilizer

Poly(ethylene tereftalate) (PET) is a polymer highly susceptible to the hydrolytic reactions that occur during applications and mainly in thermomechanical processing. These reactions lead to the decrease of molecular weight of the polymer, limiting the recycling number of the material. The reactive extrusion of the PET in presence of chain extenders is an alternative to recover mechanical and rheological properties that were depreciated by the polymer degradation. In this study, PET wastes from nonwoven fabrics production were extruded in presence of the secondary stabilizer Irgafos 126 (IRG) on variable concentrations. The results showed that Irgafos 126 increased molecular weight, decreased crystallinity and changed processing behavior of the PET, similarly to the effects produced by the well-known chain extender pyromellitic dianhydride (PMDA), showing that the secondary stabilizer Irgafos 126 can also act as a chain extender for the PET.

Effect of Prior Photodegradation on the Biodegradation of Polypropylene/Poly(3-hydroxybutyrate) Blends

In this work, the effect of blend composition and previous photodegradation on the biodegradation of polypropylene/ poly(3-hydroxybutyrate) (PP/PHB) blends was studied. The individual polymers and blends with or without the addition of poly(ethylene-co-methyl acrylate- co-glycidyl methacrylate) [P(E-MA-GMA)] as a compatibilizer (in the case of 80/20 blend) were exposed to UV light for 4 weeks and their biodegradation was evaluated. The biodegradation of PHB phase within the blends was hindered as PHB was the dispersed phase and PP fibrous particles were observed at the surface of the blend samples after biodegradation. Previous photodegradation lessened PHB biodegradation but enhanced the biodegradation of PP and the blends within the biodegradation time studied. Photodegradation resulted in cracks at the surface of PP and the blends, which probably facilitated the biotic reactions due to an easier access of the enzymes to deeper polymer layers. It also resulted in a decrease of molecular weight of PP phase and formation of carbonyl and hydroxyl groups which were consumed during biodegradation. Size exclusion chromatography analysis revealed that only the short chains of PP were consumed during biodegradation.