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.

Plasma treatment maintains surface energy of the implant surface and enhances osseointegration

The surface energy of the implant surface has an impact on osseointegration. In this study, 2 surfaces: nonwashed resorbable blasting media (NWRBM; control) and Ar-based nonthermal plasma 30 days (Plasma 30 days; experimental), were investigated with a focus on the surface energy. The surface energy was characterized by the Owens-Wendt-Rabel-Kaelble method and the chemistry by X-ray photoelectron spectroscopy (XPS). Five adult beagle dogs received 8 implants (n = 2 per surface, per tibia). After 2 weeks, the animals were euthanized, and half of the implants (n = 20) were removal torqued and the other half were histologically processed (n = 20). The bone-to-implant contact (BIC) and bone area fraction occupancy (BAFO) were evaluated on the histologic sections. The XPS analysis showed peaks of C, Ca, O, and P for the control and experimental surfaces. While no significant difference was observed for BIC parameter (P > 0.75), a higher level for torque (P < 0.02) and BAFO parameter (P < 0.01) was observed for the experimental group. The surface elemental chemistry was modified by the plasma and lasted for 30 days after treatment resulting in improved biomechanical fixation and bone formation at 2 weeks compared to the control group. © 2013 Fernando P. S. Guastaldi et al.

Evaluation of degree of conversion and hardness of dental composites photoactivated with different light guide tips

Objective: The aim of this study was to evaluate the degree of conversion and hardness of different composite resins, photo-activated for 40 s with two different light guide tips, fiber optic and polymer. Methods: Five specimens were made for each group evaluated. The percentage of unreacted carbon double bonds (% C=C) was determined from the ratio of absorbance intensities of aliphatic C=C (peak at 1637 cm-1) against internal standard before and after curing of the specimen: aromatic C-C (peak at 1610 cm-1. The Vickers hardness measurements were performed in a universal testing machine. A 50 gf load was used and the indenter with a dwell time of 30 seconds. The degree of conversion and hardness mean values were analyzed separately by ANOVA and Tukey's test, with a significance level set at 5%. Results: The mean values of degree of conversion for the polymer and fiber optic light guide tip were statistically different (P<.001). The hardness mean values were statistically different among the light guide tips (P<.001), but also there was difference between top and bottom surfaces (P<.001). Conclusions: The results showed that the resins photo-activated with the fiber optic light guide tip promoted higher values for degree of conversion and hardness.

Description and phylogenetic relationships of a new species of treefrog of the Dendropsophus leucophyllatus group (Anura: Hylidae) from the Amazon basin of Colombia and with an exceptional color pattern

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

ZnO nanostructures directly grown on paper and bacterial cellulose substrates without any surface modification layer

In this report, hierarchical ZnO nano- and microstructures were directly grown for the first time on a bacterial cellulose substrate and on two additional different papers by hydrothermal synthesis without any surface modification layer. Compactness and smoothness of the substrates are two important parameters that allow the growth of oriented structures. © 2013 The Royal Society of Chemistry.

Insights of meso and micro-scale processes for the Caxiuanã forest region from high resolution simulation

Dados meteorológicos e simulações numéricas de alta resolução foram usados para estimar campos espaciais na região leste da Amazônia onde se situam a Floresta e a Baía de Caxiuanã, no Estado do Pará. O estudo foi feito para o período de Novembro de 2006, quando foi realizado o experimento de campo COBRA-PARÁ. Análises de imagens do sensor MODIS mostram a ocorrência de vários fenômenos locais como avenidas de nuvens, sistemas convectivos precipitantes, e importante influência das interfaces entre a floresta e as superfícies aquáticas. Simulações numéricas para o dia 7 de novembro de 2006 mostraram que o modelo representou bem as principais variáveis meteorológicas. Os resultados mostram que a Baía de Caxiuanã provoca importante impacto nos campos meteorológicos adjacentes, principalmente, através da advecção pelos ventos de nordeste que induzem a temperaturas do dossel mais frias a oeste da baía. Simulações de alta resolução (LES) produziram padrões espaciais de temperatura e umidade alinhados com os ventos durante o período diurno e mudanças noturnas causadas principalmente pela presença da baía e chuvas convectivas. Correlações espaciais entre os ventos de níveis médios e os fluxos verticais de calor latente mostraram que existe uma mudança de correlações negativas para as primeiras horas do dia passando para correlações positivas para o período da tarde e início da noite.

Dynamics of the interaction between body fluid and Ti cp: the influence of surface functionalization in the first stages of osseointegration

INTRODUCTION: Regenerative therapies using biomaterials require accurate information on interactions between the implanted material and the human body. To improve the process of bone regeneration it is necessary to obtain a better understanding of the influence of the surfaces on the early stages of osseointegration. This work aims to investigate the dynamic interaction between simulated body fluid (SBF) and titanium surfaces (Ti cp) immediately after their first contact. METHODS: Ti cp samples were passed through physicochemical treatments after immersion in acid solution, alkaline solution and solutions containing TiO2 and Ca2+, to obtain three different surfaces. These were characterized by electron microscopy and free energy estimates. The evaluation of the interaction with SBF was performed by measuring the dynamic contact angles after contacting the surfaces. RESULTS: The effects of SBF wettability were more significant on surfaces according to high energy estimates. A comparative analysis of the three types of surfaces showed that fluid spreading was greater in samples with greater polar components, indicating that the surface nature influences interactions in the early stages of osseointegration. CONCLUSION: The results indicate the influence of polar interactions in the dynamic wettability of the SBF. It is possible that these interactions can also influence cellular viability on surfaces. Based on these results, new experiments are being designed to improve the presented methodology as a tool for the evaluation of biomaterials without the need for in vivo experiments.

Bond strength of composite to dentin: effect of acid etching and laser irradiation through an uncured self-etch adhesive system

This study evaluated the effect on micro-tensile bond strength (mu-TBS) of laser irradiation of etched/unetched dentin through an uncured self-etching adhesive. Dentinal surfaces were treated with Clearfil SE Bond Adhesive (CSE) either according to the manufacturer's instructions (CSE) or without applying the primer (CSE/NP). The dentin was irradiated through the uncured adhesive, using an Nd: YAG laser at 0.75 or 1 W power settings. The adhesive was cured, composite crowns were built up, and the teeth were sectioned into beams (0.49 mm(2)) to be stressed under tension. Data were analyzed using one-way ANOVA and Tukey statistics (alpha = 5%). Dentin of the fractured specimens and the interfaces of untested beams were observed under scanning electron microscopy (SEM). The results showed that non-etched irradiated surfaces presented higher mu-TBS than etched and irradiated surfaces (p < 0.05). Laser irradiation alone did not lead to differences in mu-TBS (p > 0.05). SEM showed solidification globules on the surfaces of the specimens. The interfaces were similar on irradiated and non-irradiated surfaces. Laser irradiation of dentin through the uncured adhesive did not lead to higher mu-TBS when compared to the suggested manufacturer's technique. However, this treatment brought benefits when performed on unetched dentin, since bond strengths were higher when compared to etched dentin.

Effect of Resin Cement Type on the Microtensile Bond Strength to Lithium Disilicate Ceramic and Dentin Using Different Test Assemblies

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Radiant exposure effects on physical properties of methacrylate - and silorane-composites

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

Analysing the fate of nanopesticides in soil and the applicability of regulatory protocols using a polymer-based nanoformulation of atrazine

For the first time, regulatory protocols defined in the OECD guidelines were applied to determine the fate properties of a nanopesticide in two agricultural soils with contrasting characteristics. The nanoformulation studied had no effect on the degradation kinetics of atrazine indicating that (1) the release of atrazine from the polymer nanocarriers occurred rapidly relative to the degradation kinetics (half-lives 36-53 days) and/or that (2) atrazine associated with the nanocarriers was subject to biotic or abiotic degradation. Sorption coefficients, derived from a batch and a centrifugation technique at a realistic soil-to-solution ratio, were higher for the nanoformulated atrazine than for the pure active ingredient. Results indicate that the nanoformulation had an effect on the fate of atrazine. However, since the protocols applied were designed to assess solutes, conclusions about the transport of atrazine loaded onto the nanocarriers should be made extremely cautiously. The centrifugation method applied over time (here over 7 days) appears to be a useful tool to indirectly assess the durability of nanopesticides under realistic soil-to-solution ratios and estimate the period of time during which an influence on the fate of the active ingredient may be expected. More detailed investigations into the bioavailability and durability of nanopesticides are necessary and will require the development of novel methods suitable to address both the "nano" and "organic" characteristics of polymer-based nanopesticides.

Corrosion-fatigue life of commercially pure titanium and Ti-6Al-4V alloys in different storage environments

Statement of problem. Removable partial dentures are affected by fatigue because of the cyclic mechanism of the masticatory system ansi frequent insertion and removal. Titanium and its alloys have been used in the manufacture of denture frameworks; however, preventive agents with fluorides are thought to attack titanium alloy surfaces.Purpose. This study evaluated, compared, analyzed the corrosion-fatigue life of commercially pure titanium and Ti-6Al-4V alloy in different storage environments.Material and methods. For each metal, 33 dumbbell rods, 2.3 mm in diameter at the central segment, were cast in the Rematitan system. Corrosion-fatigue strength test was carried out through a universal testing machine with a load 30% lon er than the 0.2% offset yield strength and a combined influence of different: environments: in air at room temperature, with synthetic saliva, and with fluoride synthetic saliva. After failure, the number of cycles were recorded, and fracture surfaces were examined with on SEM.Results. ANOVA and Tukey's multiple comparison rest indicated that Ti-6Al-4V alloy achieved 21,269 cycles (SD = 8,355) against 19,157 cycles (SD = 3,624) for the commercially purr Ti. There were no significant differences between either metal in the corrosion-fatigue life for dry specimens, but when the solutions were present, the fatigue life was significantly reduced, probably because of the product-ion of corrosion pits caused by superficial reactions.

Effect of surface and heat treatments on the biaxial flexural strength and phase transformation of a Y-TZP ceramic

To evaluate the effect of grinding and airborne-particle abrasion on the biaxial flexural strength (BFS) and phase transformation of a Y-TZP ceramic, and examine whether sintering the veneering porcelain renders the previous heat treatment recommended by the manufacturer unnecessary. Materials and Methods: Lava zirconia specimens (N = 108) were obtained with the following dimensions: 14.0 mm diameter × 1.3 mm thickness (n = 36) and 14.0 mm × 1.6 mm (n = 72). The thicker specimens were ground with diamond burs under irrigation and received (heat-treated groups) or not (non-heat-treated groups) a heat treatment (1000°C for 30 min) prior to the four firing cycles applied to simulate the sintering of the veneering porcelain. All specimens were air abraded as follows (n = 12): 1) 30-μm silica-modified Al2O3 particles (Rocatec Soft); 2) 110-μm silica-modified Al2O3 particles (Rocatec Plus); and 3) 120-μm Al2O3 particles, followed by Rocatec Plus. Three specimens of each group were analyzed by x-ray diffraction (XRD) to assess the monoclinic phase content (%). The BFS test was performed in a mechanical testing machine (Instron 8874). Data (MPa) were analyzed by two-way ANOVA (grinding × airborne-particle abrasion and heat treatment × airborne-particle abrasion) and Tukey's post-hoc test (α = 0.05). The strength reliability was analyzed using the Weibull distribution. Results: Grinding significantly decreased the BFS of the non-heat-treated groups (p < 0.01). Within the ground groups, the previous heat treatment did not influence the BFS (p > 0.05). Air abrasion only influenced the BFS of the ground/heat-treated groups (p < 0.01). For the non-heat-treated groups, the grinding did not decrease the Weibull modulus (m), but it did decrease the characteristic strength (σ0). For Rocatec Soft and 120-μm Al2O3 particles + Rocatec Plus, the heat-treated groups presented lower m and higher σ0 than the ground/non-heat-treated groups. The independent variables did not seem to influence phase transformation. Air-abraded surfaces presented higher monoclinic zirconia content than the as-sintered and ground surfaces, which exhibited similar content. Conclusion: Even under irrigation, grinding compromised the Y-TZP ceramic strength. The sintering of the veneering porcelain rendered the previous heat treatment recommended by the manufacturer unnecessary. Airborneparticle abrasion influenced the strength of heat-treated zirconia.

Effect of surface and heat treatments on the biaxial flexural strength and phase transformation of a y-tzp ceramic

To evaluate the effect of grinding and airborne-particle abrasion on the biaxial flexural strength (BFS) and phase transformation of a Y-TZP ceramic, and examine whether sintering the veneering porcelain renders the previous heat treatment recommended by the manufacturer unnecessary. Materials and Methods: Lava zirconia specimens (N = 108) were obtained with the following dimensions: 14.0 mm diameter × 1.3 mm thickness (n = 36) and 14.0 mm × 1.6 mm (n = 72). The thicker specimens were ground with diamond burs under irrigation and received (heat-treated groups) or not (non-heat-treated groups) a heat treatment (1000°C for 30 min) prior to the four firing cycles applied to simulate the sintering of the veneering porcelain. All specimens were air abraded as follows (n = 12): 1) 30-μm silica-modified Al2O3 particles (Rocatec Soft); 2) 110-μm silica-modified Al2O3 particles (Rocatec Plus); and 3) 120-μm Al2O3 particles, followed by Rocatec Plus. Three specimens of each group were analyzed by x-ray diffraction (XRD) to assess the monoclinic phase content (%). The BFS test was performed in a mechanical testing machine (Instron 8874). Data (MPa) were analyzed by two-way ANOVA (grinding × airborne-particle abrasion and heat treatment × airborne-particle abrasion) and Tukey's post-hoc test (α = 0.05). The strength reliability was analyzed using the Weibull distribution. Results: Grinding significantly decreased the BFS of the non-heat-treated groups (p < 0.01). Within the ground groups, the previous heat treatment did not influence the BFS (p > 0.05). Air abrasion only influenced the BFS of the ground/heat-treated groups (p < 0.01). For the non-heat-treated groups, the grinding did not decrease the Weibull modulus (m), but it did decrease the characteristic strength (σ0). For Rocatec Soft and 120-μm Al2O3 particles + Rocatec Plus, the heat-treated groups presented lower m and higher σ0 than the ground/non-heat-treated groups. The independent variables did not seem to influence phase transformation. Air-abraded surfaces presented higher monoclinic zirconia content than the as-sintered and ground surfaces, which exhibited similar content. Conclusion: Even under irrigation, grinding compromised the Y-TZP ceramic strength. The sintering of the veneering porcelain rendered the previous heat treatment recommended by the manufacturer unnecessary. Airborneparticle abrasion influenced the strength of heat-treated zirconia.

Effect of particle size on the flexural strength and phase transformation of an airborne-particle abraded yttria-stabilized tetragonal zirconia polycrystal ceramic.

Statement of problem Because airborne-particle abrasion is an efficient method of improving the bond at the zirconia-cement interface, understanding its effect on the strength of yttria-stabilized tetragonal zirconia polycrystal is important. Purpose The purpose of this study was to evaluate the effect of the particle size used for airborne-particle abrasion on the flexural strength and phase transformation of a commercially available yttria-stabilized tetragonal zirconia polycrystal ceramic. Material and Methods For both flexural strength (20.0 × 4.0 × 1.2 mm) (n=14) and phase transformation (14.0-mm diameter × 1.3-mm thickness) (n=4), the zirconia specimens were made from Lava, and their surfaces were treated in the following ways: as-sintered (control); with 50-μm aluminum oxide (Al2O3) particles; with 120-μm Al2O3 particles; with 250-μm Al2O3 particles; with 30-μm silica-modified Al2O3 particles (Cojet Sand); with 120-μm Al2O3 particles, followed by 110-μm silica-modified Al2O3 particles (Rocatec Plus); and with Rocatec Plus. The phase transformation (%) was assessed by x-ray diffraction analysis. The 3-point flexural strength test was conducted in artificial saliva at 37°C in a mechanical testing machine. The data were analyzed by 1-way ANOVA and the Tukey honestly significant difference post hoc test (α=.05). Results Except for the Cojet Sand group, which exhibited statistically similar flexural strength to that of the as-sintered group and for the group abraded with 250-μm Al2O3 particles, which presented the lowest strength, airborne-particle abrasion with the other particle sizes provided the highest values, with no significant difference among them. The as-sintered specimens presented no monoclinic phase. The groups abraded with smaller particles (30 μm and 50 μm) and those treated with the larger ones (110 μm and/or 120 μm particles and 250 μm) exhibited percentages of monoclinic phase that varied from 4% to 5% and from 8.7% to 10%. Conclusions Except for abrasion with Cojet Sand, depending on the particle size, zirconia exhibited an increase or a decrease in its flexural strength. Airborne-particle abrasion promoted phase transformation (tetragonal to monoclinic), and the percentage of monoclinic phase varied according to the particle size.