Thermal and photochemical stability of poly(vinyl alcohol)/modified lignin blends

A kraft lignin derivative (KLD) obtained by reaction with p-aminobenzoic acid/phthalic anhydride was blended with poly(vinyl alcohol) (PVA) by solution casting from DMSO. PVA and PVA/KLD films were exposed to ultraviolet radiation (24, 48, and 96 h) and analyzed by thermogravimetry (TG), differential scanning calorimetry (DSC), infrared spectroscopy (FTIR), hydrogen nuclear magnetic resonance (H-1 NMR) spectroscopy, and scanning electron microscopy (SEM). PVA films show a loss of thermal stability due to irradiation. PVA/KLD reveals greater thermal stability than PVA and an increase in thermal stability after irradiation. These results suggest that the incorporation of KLD into PVA provides a gain in thermal and photochemical stability. FTIR, H-1 NMR, DSC, and TG results obtained for the blends suggest that intermolecular interactions between PVA and KLD chains are present. SEM micrographs revealed blend miscibility for a KLD blend content of up to 15 wt%, as observed at magnification of 1000 times. (c) 2005 Elsevier Ltd. All rights reserved.

Micellar modification of drug stability: analysis of the effect of hexadecyltrimethylammonium halides on the rate of degradation of cephaclor

The intra- and intermolecular rates of degradation of cephaclor were determined with and without hexadecyltrimethylammonium bromide (CTABr). Micellar-derived spectral shifts were used to measure the association of the ionic forms as well as to determine the effect of CTABr on the apparent acid dissociation constant of the antibiotic. The rate of degradation of cephaclor increased with detergent and was salt sensitive. Micellar effects were analyzed quantitatively within the frame-work of the speudophase ion exchange model. All experimental data were fitted to this model which was used to predict the combined effects of pH and detergent concentration. Micelles increased the rate of OH- attack on cephaclor; most of the effect was due to the concentration of reagents in the micellar pseudophase. The intramolecular degradation was catalyzed 25-fold by micelles, and a working hypothesis to rationalize this effect is proposed. The results demonstrate that quantitative analysis can be utilized to assess and predict effects of detergents on drug stability.

Interfacial concentrations of chloride and bromide and selectivity for ion exchange in vesicles prepared with dioctadecyldimethylammonium halides, lipids, and their mixtures

The local concentrations of chloride, Cl b, and bromide, Br b, in the interface of vesicles prepared with dioctadecyldimethylammonium chloride, DODAC, or bromide, DODAB, dipalmitoylphosphatidylcholine, DPPC, dimyristoylphosphatidylcholine, DMPC, and mixtures of DMPC, DPPC, and DODAC were determined by chemical trapping by analyzing product yields from spontaneous dediazoniation of vesicle-bound 2,6-dimethyl-4-hexadecylbenzenediazonium ion. The values of Cl b and Br b in DODAC and DODAB vesicles increase with vesicle size, in agreement with previous data showing that counterion dissociation decreases with vesicle size. Addition of tetramethylammonium chloride displaces bromide from the DODAB vesicular interface. The value for the selectivity constant for Br/Cl exchange at the DODAB vesicular interface obtained by chemical trapping was ∼2.0, well within values obtained for comparable amphiphiles. In vesicles of DPPC the values of Cl b were very sensitive to the nature of the cation and decreased in the order Ca 2+ > Mg 2+ > Li + > Na + > K + = Cs + = Rb + ≥ +. The effect of the cation becomes more important as temperature increases above the phase transition temperature, T m, of the lipid. The values of Cl b increased sigmoidally with the mol % of DODAC in vesicles prepared with DODAC/lipid mixtures. In sonicated vesicles prepared with DODAC and DMPC (or DPPC), the values of Cl b reach local concentrations measured for the pure amphiphile at 80 mol % DODAC. These results represent the first extensive study of local concentration of ions determined directly by chemical trapping in vesicles prepared with lipids, synthetic ampliiphiles, and their mixtures.

Thermo-gravimetric analysis (TGA) after different exposures of high density polyethylene (HDPE) and poly vinyl chloride (PVC) geomembranes

This paper presents the results of thermogravimetric analysis (TGA) tests in PVC (1.0; 2.0 mm) and HDPE (0.8; 2.5 mm) geomembranes exposed to weathering and leachate after 30 months. The aim of this paper is the comparison of fresh and exposed samples to assess the degradation process concerning the total loss of mass of geomembranes. The exposure was conducted in accordance with the recommendations of ASTM standards. The TGA tests were carried out according to ASTM D6370 and E2105. Results show, for instance, that for PVC geomembrane the largest reductions of plasticizers occurred for samples exposed to weathering. The loss of plasticizers after the exposure contributed to the decrease of deformation and consequent increase in stiffness. TGA tests shows to be a valuable tool to control the quality of the materials. © 2012 ejge.

Altering the adsorptive and electronic properties of Pt through poly(vinyl alcohol) adsorption

In the present paper we investigated the effect of adsorbed PVA on Pt electrodes on classic electrochemical processes such as hydrogen UPD, oxygen reduction and CO electro-oxidation. Upon adsorption PVA blocks roughly 50% of the hydrogen sites and can not be removed from the Pt surface through cycling in the potential range of 0.05-1.0 V vs. RHE. Potentiodynamic experiments under controlled hydrodynamic conditions provided by rotating disk electrode experiments showed a negative impact of the adsorbed PVA on the oxygen reduction reaction (ORR). Cyclic-voltammetry results revealed that not even CO was able to remove PVA from the Pt surface. Regarding the oxidation of CO, the adsorbed polymer positively shifted the CO oxidation peak potential, therefore higher potentials are required to free the Pt surface from CO poisoning. In situ Fourier transform infrared spectroscopy evidenced that the presence of PVA shifted the linearly bound CO frequency toward higher wavenumbers, a process found to be independent of the Pt surface orientation. In situ electrochemical X-ray absorption spectroscopy results showed that PVA also impacted the electronic properties of platinum by decreasing the occupancy of the Pt conducting 5d band. Our findings clearly support the efforts toward understanding the nature of the interaction between polymers and metallic surfaces as well as the impact on technological applications (e.g. in PEMFCs). © 2013 Elsevier Ltd. All rights reserved.

The Effects of Weathering Exposure on the Physical, Mechanical, and Thermal Properties of High-density Polyethylene and Poly (Vinyl Chloride)

This paper presents results describing the physical, mechanical, and thermal properties (melt flow index - MFI and oxidative induction time - OIT) of high density polyethylene and poly (vinyl chloride) after weathering exposure (6, 12, 18, and 30 months). The materials exposed were geomembranes of two thicknesses: 1.0 and 2.0 mm (PVC) and 0.8 and 2.5 mm (HDPE). The climate parameters (average) obtained were 25 degrees C (temperature), 93 mm (precipitation), 66% (relative humidity), and 19 MJ/m(2). day (intensity of global radiation). Some results showed, for instance, that the behavior of the geomembranes changed after the exposures. A few minor variations in physical properties occurred. The density and thickness, for instance, varied 0.5-1.0% (average) for both the PVC and HDPE geomembranes. The mechanical properties changed as a function of the period of exposure. In general, some decreases were verified by the deformation of PVC. The samples became more rigid. In contrast, HDPE geomembranes became more ductile. Despite the variations in elasticity, some increases in deformability were verified. An MFI test showed some degradation in HDPE geomembranes. OIT tests revealed small values for both intact and exposed samples.

Thermal analysis of coordination compounds. Part 1. Thermodecomposition of nickel(II) triphenylphosphine complexes with halides, nitrate, and thiocyanate

The compounds [NiX 2(PPh 3) 2] (where X is Cl -, Br -, I -, NO - 3, NCS -; and PPh 3 is triphenylphosphine) were prepared and characterized by infrared and atomic absorption spectroscopies and by carbon and hydrogen analyses. Simultaneous thermogravimetric (TG) and derivative thermogravimetric (DTG) curves of these complexes were recorded in air. The decrease in mass observed indicates conversion of the complexes to oxides. The thermal decomposition of the halogen and nitrate complexes occurred in a number of steps; the thiocyanate complex decomposed in a single step. © 1994.

Segmentos anátomo-cirúrgicos arteriais do rim de cutia (Dasyprocta prymnolopha)

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Testicular arteries systematization based on different levels of scrotal configuration in caprines

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Hydroalumination of Thioacetylenes: A Versatile Generation and Reactions of -Aluminate Sulfides Intermediates

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

Comportamento de adesão da madeira de um híbrido clonal de Eucalyptus urophylla x Eucalyptus grandis proveniente de três condições de manejo

This study aimed to evaluate the adhesion ability of eucalyptus lumber from three tillage systems, using adhesives: resorcinol formaldehyde and two adhesives in water emulsion based on vinyl poly-acetate. The management systems were characterized by three strata, the stratum one (E1) characterized by wood from coppice and 70 months of age, the stratum two (E2) characterized by wood and retirement age of 166 months and stratum three (E3), also characterized by retirement at 70 months of age. The wood was derived from a random mixture of the first two sawn logs, each three feet from the base, which comprised three treatments on the adhesive used. We evaluated the shear strength by compression tests and the percentage of wood failure in the glue line. Based on the results obtained, it can be said that the adhesion had satisfactory performance with all the resins used, and the average values of shear strength of the glue line were shown to be equivalent to the shear strength of solid wood only for the samples which adhered with 'Wonderbond' adhesive and also provide higher values for wood failure (97.64%). The highest density present in the wood of the second stratum (E2) influenced only sticking with the resorcinol formaldehyde resin. For polyvinyl acetate (Cascorez 2590), shear values decreased in the third management condition (E3).

LDPE/EVA Composites for Antimicrobial Properties

Composites with antimicrobial activity are of great interest nowadays and the development of titanium dioxide with these functional properties presents interest in academic and industrial sectors.An approach to develop PE composite containing silver microparticles to have an antimicrobial effect is presented. To obtain such antimicrobial composites, LDPE/EVA were processed with Ag particles on TiO2 particles as inorganic carrier substance. Titanium dioxide nanoparticles (P-25) were covered with silver particles using Turkevich Method or citrate reduction method. The Ag/TiO2 particles were dispersed at concentration of 0,8 wt% and 1% wt% in LDPE/ethylene vinyl acetate copolymer (EVA)-(50% w/w) at the melt state in a Haake torque Rheometer. Silver microparticles were characterized with UV-Vis Spectroscopy. The composites thus prepared were characterized through XRD, Ares Rheometer, Scanning Electronic Microscopy (SEM) and JIS Z 2801 antimicrobial tests to study the effects of the addition of particles on rheological properties, morphological behavior and antimicrobial properties. The results showed that incorporation of silver/titanium dioxide particles on composites obtained systems with differents dispersions. The Ag/TiO2 particles showed uniform distribution of Ag on TiO2 particles as observed by SEM-EDX and antimicrobial tests according to JIS Z 2801 shows excellent antimicrobial properties.

The influence of preparation method of OC1OC6-PPV films on the photo-oxidation process

Poly(p-phenylene vinylene) (PPV) derivatives are well known for their applications in polymer light emitting diodes (PLEDs). PPV derivatives are highly susceptible to photo-oxidation though, which is mainly caused by the scission of the vinyl double bond on the polymer backbone. In this work, we show that Langmuir-Blodgett (LB) films are less degraded than cast films of a PPV derivative (OC1OC6-PPV). Both films had similar thickness (similar to 50 nm) to allow for a more realistic comparison. Degradation was monitored with UV-vis and FTIR spectroscopies. The results indicated that cast films were completely degraded in ca. 400 min, while LB took longer time, i.e. about four times the values for the cast films. The differences can be attributed to the more compact morphology in the LB than in the cast films. With a compact morphology the diffusion of oxygen in the LB film is hampered and this causes a delay in the degradation process. (c) 2006 Elsevier Ltd. All rights reserved.

Structure and Physical Properties of EVA/Starch Precursor Materials for Foaming Applications

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

Nanocompósitos eletroativos de poli-o-metoxianilina e polissacarídeos naturais

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