Photoinduced birefringence at low temperatures in Langmuir-Blodgett films of azobenzene-functionalized copolymers

The temperature dependence has been investigated for the photoinduced birefringence in Langmuir-Blodgett (LB) films from the azocopolymer 4-[N- ethyl -N-(2-hydroxyethyl)] amino-2'-chloro-4'-nitroazobenzene (MMA-DR13) mixed with cadmium stearate. The buildup and relaxation of the birefringence in the range from 20 to 296 K were fitted with a Kohlrausch-Williams-Watts (KWW) function, with a beta-value of 0.78-0.98 for the build-up and 0.18-0.27 for the decay. This is consistent with a distribution of time constants for the kinetics of the birefringence processes. The maximum birefringence increased with increasing temperature up to 120 K because the free volume fluctuation also increased with temperature. Above 120 K, the birefringence decreased with temperature as thermal diffusion dominates. In the latter range of temperature, an Arrhenius behavior is inferred for both build-up and decay of birefringence. In each case two activation energies were obtained: 0.8 and 5 kJ/mol for the build-up and 10 and 30 kJ/mol for the decay. The energies for the build-up are much lower than those associated with motion of the polymer chain, which means that the dynamics is governed by the orientation of the chromophores. For the decay, local motion of lateral groups of the polymer chains becomes important as the activation energies are within the range of gamma-relaxation energies. (C) 2003 Elsevier B.V. B.V. All rights reserved.

Small-angle X-ray and nuclear-magnetic resonance study of siloxane-PMMA hybrids prepared by the sol-gel process

Transparent siloxane-polymethylmethacrylate (PMMA) hybrids were synthesized by the sol-gel process through hydrolysis of methacryloxyproyltrimethoxysilane (TMSM), tetramethoxysilane (TMOS) and polymerization of methylmethacrylate (MMA) using benzol peroxide (BPO) as catalyst. These composites have a good chemical stability due to the presence of covalent bonds between the inorganic (siloxane) and organic (PMMA) phases. The effects of siloxane content, pH of the initial sol and BPO content on the structure of the dried gels were analyzed by small-angle X-ray scattering (SAXS). SAXS results revealed the presence of an interference (or correlation) peak at medium q-range for all compositions, suggesting that siloxane groups located at the ends of PMMA chains form isolated clusters that are spatially correlated. The average intercluster distance - estimated from the q-value corresponding to the maximum in SAXS spectra - decreases for samples prepared with increasing amount of TMSM-TMOS. This effect was assigned to the expected increase in the number density of siloxane groups for progressively higher siloxane content. The increase of BPO content promotes a more efficient polymerization of MMA monomers but has no noticeable effect on the average intercluster distance. High pH favors polycondensation reactions between silicon species of both TMOS and TMSM silicon alcoxides, leading to a structure in which all siloxane clusters are bonded to PMMA chains. This effect was confirmed by Si-29 nuclear-magnetic resonance (NMR) measurements.

Effects of Synthesis Conditions on the Nanostructure of Hybrid Sols Produced by the Hydrolytic Condensation of (3-Methacryloxypropyl)trimethoxysilane

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Effect of Surface Treatments on the Bond Strength between Composite Resin and Acrylic Resin Denture Teeth

Purpose: This investigation studied the effects of 3 surface treatments on the shear bond strength of a light-activated composite resin bonded to acrylic resin denture teeth. Materials and Methods: The occlusal surfaces of 30 acrylic resin denture teeth were ground flat with up to 400-grit silicon carbide paper. Three different surface treatments were evaluated: (1) the flat ground surfaces were primed with methyl methacrylate (MMA) monomer for 180 seconds; (2) light-cured adhesive resin was applied and light polymerized according to the manufacturer's instructions; and (3) treatment 1 followed by treatment 2. The composite resin was packed on the prepared surfaces using a split mold. The interface between tooth and composite was loaded at a cross-head speed of 0.5 mm/min until failure. Results: Analysis of variance indicated significant differences between the surface treatments. Results of mean comparisons using Tukey's test showed that significantly higher shear bond strengths were developed by bonding composite resin to the surfaces that were previously treated with MMA and then with the bonding agent when compared to the other treatments. Conclusion: Combined surface treatment of MMA monomer followed by application of light-cured adhesive resin provided the highest shear bond strength between composite resin and acrylic resin denture teeth.

Acrylonitrile-butadiene-styrene toughened nylon 6: The influences of compatibilizer on morphology and impact properties

Polymer alloys have been used as an alternative to obtain polymeric materials with unique physical properties. Generally, the polymer mixture is incompatible, which makes it necessary to use a compatibilizer to improve the interracial adhesion. Nylon 6 (PA6) is an attractive polymer to use in engineering applications, but it has processing instability and relatively low notched impact strength. In this study, the acrylonitrile-butadiene-styrene (ABS) triblock copolymer was used as an impact modifier for PA6. Poly(methyl methacrylate-co-maleic anyhydride) (MMA-MA) and poly(methyl methacrylate-co-maleic methacrylate) (MMA-GMA) were used as compatibilizers for this blend. The morphology and impact strength of the blends were evaluated as a function of blend composition and the presence of compatibilizers. The blends compatibilized with maleated copolymer exhibited an impact strength up to 800 J/m and a morphology with ABS domains more efi8ciently dispersed. Moderate amounts of MA functionality in the compatibilizer (∼5%) and small amounts of compatibilizer in the blend (∼5%) appear sufficient to improve the impact properties and ABS dispersion. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87.

Effect of compatibilizer in acrylonitrile-butadiene-styrene toughened nylon 6 blends: Ductile-brittle transition temperature

The ductile-brittle transition temperatures were determined for compatibilized nylon 6/acrylonitrile-butadiene-styrene (PA6/ABS) copolymer blends. The compatibilizers used for those blends were methyl methacrylate-co-maleic anhydride (MMA-MAH) and MMA-co-glycidyl methacrylate (MMA-GMA). The ductile-brittle transition temperatures were found to be lower for blends compatibilized through maleate modified acrylic polymers. At room temperature, the PA6/ABS binary blend was essentially brittle whereas the ternary blends with MMA-MAH compatibilizer were supertough and showed a ductile-brittle transition temperature at -10°C. The blends compatibilized with maleated copolymer exhibited impact strengths of up to 800 J/m. However, the blends compatibilized with MMA-GMA showed poor toughness at room temperature and failed in a brittle manner at subambient temperatures.

Thermal properties of nylon6/ABS polymer blends: Compatibilizer effect

Nylon6/ABS binary blends are incompatible and need to be compatibilized to achieve better performance under impact tests. Poly(methyl methacrylate/maleic anhydride) (MMA-MA) is used in this work to compatibilize in situ nylon6/ABS immiscible blends. The MA functional groups, from MMA-MA copolymers, react with NH2 groups giving as products nylon molecules grafted to MMA-MA molecules. Those molecular species locate in the nylon6/ABS blend interfacial region increasing the local adhesion. MMA-MA segments are completely miscible with the SAN rich phase from the ABS. The aim of this work is to study the effects of ABS and compatibilizing agent on the melting and crystallization of nylon6/ABS blends. This effect has been investigated by differential scanning calorimetry (DSC) and dynamic mechanical thermal analysis (DMTA). Incorporation of this compatibilizer and ABS showed little effect on the melting behavior of the PA6 crystalline phase, in general. DMTA analysis confirmed the system immiscibility and showed evidence of compatibility between the two phases, nylon6 and ABS, produced by MMA-MA copolymer presence. The nylon6/ABS blend morphology, observed by transmission electron microscopy (TEM), changes significantly by the addition of the MMA-MA compatibilizer. A better dispersion of ABS in the nylon6 phase is observed. © 2004 Kluwer Academic Publishers.

Morphological, mechanical and thermal properties of nylon 6/ABS blends using glycidyl methacrylate-methyl methacrylate copolymers

Nylon6 is an attractive polymer for engineering applications because it has reactive functionality through amine and carboxyl end groups that are capable of reacting. For this reason, it has been used a lot in polymeric blends. Blends of nylon6/ABS (acrylonitrile-butadiene-styrene) were produced using glycidyl methacrylate-methyl methacrylate (GMA-MMA) copolymers as compatibilizer. The binary blends were immiscible and exhibited poor mechanical properties that stemmed from the unfavorable interactions among their molecular segments. This produced an unstable coarse phase morphology and weak interfaces between the phases in the solid state. The presence of the copolymer in the blends clearly led to a more efficient dispersion of the ABS phase and consequently optimized Izod impact properties. However, the compatibilized blend showed poor toughness at room temperature and failed in a brittle manner at subambient temperatures. © 2005 Springer Science + Business Media, Inc.

Effect of ridge lap surface treatment and thermocycling on microtensile bond strength of acrylic teeth to denture base resins

This study evaluated the effect of denture base polymer type (heat- and microwave-polymerized), ridge lap surface treatment (with and without methyl methacrylate-MMA etching) and thermocycling on the microtensile bond strength (mTBS) of Biotone acrylic teeth. Flat-ground, ridge-lap surface of posterior artifcial teeth were bonded to cylinders of each denture base resin, resulting in the following groups (n=6): G1a - Clássico/with MMA etching; G1b - Clássico/without MMA etching; G2a - OndaCryl/with MMA etching; G2b - OndaCryl/without MMA etching. Rectangular bar specimens with a cross-sectional area of 1 mm 2 were prepared. Half of the bars in each group were thermocycled (5,000 cycles between 4°C and 60°C). mTBS testing was performed in an universal testing machine at a crosshead speed of 0.5 mm/min. Data were analyzed statistically by three-way ANOVA (a=0.05). There was no statisti-caly signifcant difference (p>0.05) for the factors (resin, surface treatment,and thermocycling) or their interactions. The mean mTBS values (MPa) and standard deviations were as follows: Thermocycling - G1a: 41.00 (14.00); G1b: 31.00 (17.00); G2a: 50.00 (27.00); G2b: 40.00 (18.00); No thermocycling - G1a: 37.00 (14.00); G1b: 43.00 (25.00); G2a: 43.00 (14.00); G2b: 40.00 (27.00). The mTBS of Biotone artifcial teeth to the denture base acrylic resins was not infuenced by the polymer type, surface treatment or thermocycling.

Evaluation of yield advantage indexes in carrot-lettuce intercropping systems

The aim of this study was to estimate the effect of the association between carrot and lettuce crops in several intercropping systems through different yield advantage indexes, as well as to assess which system is better for the environmental resources management with respect to productivity and economic indicators. A 'group balanced block' experimental design was used, with four replications. Cultivars of lettuce crispleaf ('Lucy Brown', 'Tainá', 'Laurel' and 'Verônica') and looseleaf ('Babá de Verão', 'Maravilha das Quatro Estações', 'Elisa' and 'Carolina') groups were evaluated in intercropping systems with 'Alvorada' and 'Brasilia' carrot cultivars. The land equivalent ratio (LER) and yield efficiency index (YEI) were estimated, besides economic indicators such as gross (GI) and net (NI) income, modified monetary advantage (MMA), return rate (RR) and profit margin (PM). The evaluated indexes showed that carrot is the dominant and lettuce the dominated crop. Higher biological/agronomic efficiency indexes and economic indicators were observed in intercropping systems with 'Brasilia' carrot as component crop and that based on the crispleaf lettuce group.

Perturbation of a nonautonomous problem in ℝn

In this paper, we prove a stability result about the asymptotic dynamics of a perturbed nonautonomous evolution equation in ℝn governed by a maximal monotone operator. Copyright © 2013 John Wiley & Sons, Ltd. Copyright © 2013 John Wiley & Sons, Ltd.

Evaluation of sample preparation procedures and krypton as an interference standard probe for arsenic speciation by HPLC-ICP-QMS

Different conditions of extraction using water, a methanol-water mixture and nitric acid solutions were evaluated for speciation of As(iii), As(v), DMA and MMA in plant samples that previously received As(v) after being sown and emergence was investigated. Microwave-assisted extraction (MAE) using diluted nitric acid solutions was also performed for arsenic extraction from chicken feed samples. The separation and determination of arsenic species were performed using HPLC-ICP-MS. The interference standard method (IFS) using 83Kr+ as the IFS probe was employed to minimize spectral interferences caused by polyatomic species, such as 40Ar 35Cl+. The extraction procedures tested presented adequate extraction efficiencies (90%), and the four arsenic species evaluated were found in plant samples. Extractions with diluted nitric acid solution at 90 °C were the most efficient strategy, with quantitative recoveries for all four As species in plant tissues. On the other hand, the methanol-water mixture was the solvent with the lowest extraction efficiency (50-60%). For chicken feed samples, MAE at 100 °C for 30 min resulted in an extraction efficiency of 97% and only As(v) was found, without any species interconversion. The IFS method contributed to improving precision and limits of detection and quantification for all tested extraction procedures. Significant improvements on accuracy were obtained by applying the IFS method and recoveries between 77 and 94%, and 82 and 93% were obtained for plant extracts and chicken feed samples, respectively. This journal is © 2013 The Royal Society of Chemistry.

Temporomandibular joint condylar changes following maxillomandibular advancement and articular disc repositioning

Purpose To evaluate condylar changes 1 year after bimaxillary surgical advancement with or without articular disc repositioning using longitudinal quantitative measurements in 3-dimensional (3D) temporomandibular joint (TMJ) models. Methods Twenty-seven patients treated with maxillomandibular advancement (MMA) underwent cone-beam computed tomography before surgery, immediately after surgery, and at 1-year follow-up. All patients underwent magnetic resonance imaging before surgery to assess disc displacements. Ten patients without disc displacement received MMA only. Seventeen patients with articular disc displacement received MMA with simultaneous TMJ disc repositioning (MMA-Drep). Pre- and postsurgical 3D models were superimposed using a voxel-based registration on the cranial base. Results The location, direction, and magnitude of condylar changes were displayed and quantified by graphic semitransparent overlays and 3D color-coded surface distance maps. Rotational condylar displacements were similar in the 2 groups. Immediately after surgery, condylar translational displacements of at least 1.5 mm occurred in a posterior, superior, or mediolateral direction in patients treated with MMA, whereas patients treated with MMA-Drep presented more marked anterior, inferior, and mediolateral condylar displacements. One year after surgery, more than half the patients in the 2 groups presented condylar resorptive changes of at least 1.5 mm. Patients treated with MMA-Drep presented condylar bone apposition of at least 1.5 mm at the superior surface in 26.4%, the anterior surface in 23.4%, the posterior surface in 29.4%, the medial surface in 5.9%, or the lateral surface in 38.2%, whereas bone apposition was not observed in patients treated with MMA. Conclusions One year after surgery, condylar resorptive changes greater than 1.5 mm were observed in the 2 groups. Articular disc repositioning facilitated bone apposition in localized condylar regions in patients treated with MMA-Drep. © 2013 American Association of Oral and Maxillofacial Surgeons.

Educação ambiental e a construção da cidadania: agenda 21 escolar - um caminho?

Pós-graduação em Educação - IBRC

Reação de genótipos de tangerinas a Alternaria alternata e Elsinoe fawcettii: resistência, suscetibilidade e acúmulo de metabólitos

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