Size-controlled TiO2 nanoparticles on porous hosts for enhanced photocatalytic hydrogen production

Nanocystalline TiO2 particles were successfully synthesized on porous hosts (SBA-15 and ZSM-15) via a sol-gel impregnation method. Resulting nanocomposites were characterized by XRD, TEM, BET surface analysis, Raman and UV-vis diffuse reflectance spectroscopy, and their photocatalytic activity for H2 production evaluated. XRD evidences the formation of anatase nanoparticles over both ZSM-5 and SBA-15 porous supports, with TEM highlighting a strong particle size dependence on titania precursor concentration. Photocatalytic activities of TiO2/ZSM-5 and TiO2/SBA-15 composites were significantly enhanced compared to pure TiO2, owing to the smaller TiO2 particle size and higher surface area of the former. TiO2 loadings over the porous supports and concomitant photocatalytic hydrogen production were optimized with respect to light absorption, available surface reaction sites and particle size. 10%TiO2/ZSM-5 and 20%TiO2/SBA-15 proved the most active photocatalysts, exhibiting extraordinary hydrogen evolution rates of 10,000 and 8800μmolgTiO2 -1 h-1 under full arc, associated with high external quantum efficiencies of 12.6% and 5.4% respectively under 365nm irradiation.

Glycerol valorization:dehydration to acrolein over silica-supported niobia catalysts

The catalytic dehydration of glycerol to acrolein is investigated over silica-supported niobia catalysts in a continuous fixed-bed gas-phase reactor. Various supported niobia catalysts are prepared and characterized using surface analysis and spectroscopic methods (XRD, UV-Vis, XPS, N2 adsorption), as well as with ammonia adsorption microcalorimetry. Good results are obtained with initial glycerol conversions of over 70% and with 50-70% selectivity to acrolein. We investigate the influence of changing the catalyst acid strength by varying the niobia content and catalyst calcination temperature. Glycerol conversion and acrolein selectivity depend on the surface acid strength. Catalyst deactivation by coking is also observed, but simple oxidative treatment in air restores the activity of the catalysts completely. © The Author(s) 2010.

Catalyst studies on the ring opening of tetrahydrofuran-dimethanol to 1,2,6-hexanetriol

The metal catalyzed hydrogenolysis of the biomass-derived THF-dimethanol to 1,2,6-hexanetriol using heterogeneous catalysts was investigated. Bimetallic Rh-Re catalysts (4 wt% Rh and a Re/Rh (mol. ratio of 0.5) on a silica support gave the best performance and 1,2,6-hexanetriol was obtained in 84% selectivity at 31% conversion (120 C, 80 bar, 4 h); the selectivity reaches a maximum of 92% at 80 C. The product distribution at prolonged reaction times or higher temperatures or both shows the formation of diols and mono-alcohols, indicating that the 1,2,6-hexanetriol is prone to subsequent hydrodeoxygenation reactions. Different silica supports were investigated and optimal results were obtained with an amorphous silica featuring an intermediate surface area and an average mesopore size of about 6 nm. TPR and XPS surface analysis support the presence of mixed Rh and Re particles. The redox Reδ+/ReTotal surface ratio correlates with the conversion in a volcano type dependency. Both gas phase as well as Rh200Re1OH cluster DFT calculations support an acid-metal bifunctional mechanism and explain the products distribution. © 2013 Elsevier B.V. All rights reserved.

Implications of the reduction of cutting fluid in drilling AISI P20 steel with carbide tools

The machining of hardened steel is becoming increasingly important in manufacturing processes. Machined parts made with hardened steel are often subjected to high service demands, which require great resistance and quality. The machining of this material submits the tools to high mechanical and thermal loads, which increases the tool wear and affects the surface integrity of the part. In that context, this work presents a study of drilling of AISI P20 steel with carbide tools, analyzing the effects on the process caused by the reduction of cutting fluid supply and its relation with the tool wear and the surface integrity of the piece. The major problem observed in the tests was a difficulty for chips to flow through the drill flute, compromising their expulsion from the hole. After a careful analysis, a different machining strategy was adopted to solve the problem

Celdilla de digestión-Lixiviación con membrana semipermeable, sistema de cerrado hermético y de control de temperatura

La invención es una celdilla de digestión-lixiviación con membrana semipermeable, sistema de cerrado hermético y de control de temperatura que es un dispositivo para pruebas de digestibilidad y lixiviación de moléculas o iones a nivel laboratorio. La invención es un diseño novedoso que permite mantener aislada la cámara interna (donde se realiza la digestión-lixiviación de materiales) de la cámara externa (donde se reciben los productos de la digestión-lixiviación) conectadas exclusivamente a través de la membrana semipermeable, de tamaño de poro intercambiable, para el paso de las moléculas o iones de tamaño deseado. La celdilla contiene un dispositivo que permite mantener un control de la temperatura en el interior de la cámara interna. Las aplicaciones de la celdilla están en laboratorios académicos o de investigación (empresas, centros de investigación, institutos, Universidades) para la realización de pruebas de digestibilidad in vitro de macromoléculas o de lixiviación de moléculas o iones.

fuzzySim: Fuzzy similarity in species distributions

fuzzySim is an R package for calculating fuzzy similarity in species occurrence patterns. It includes functions for data preparation, such as converting species lists (long format) to presence-absence tables (wide format), obtaining unique abbreviations of species names, or transposing (parts of) complex data frames; and sample data sets for providing practical examples. It can convert binary presence-absence to fuzzy occurrence data, using e.g. trend surface analysis, inverse distance interpolation or prevalence-independent environmental favourability modelling, for multiple species simultaneously. It then calculates fuzzy similarity among (fuzzy) species distributions and/or among (fuzzy) regional species compositions. Currently available similarity indices are Jaccard, Sørensen, Simpson, and Baroni-Urbani & Buser.

Hybrid materials for biomedical applications

The increased longevity of humans and the demand for a better quality of life have led to a continuous search for new implant materials. Scientific development coupled with a growing multidisciplinarity between materials science and life sciences has given rise to new approaches such as regenerative medicine and tissue engineering. The search for a material with mechanical properties close to those of human bone produced a new family of hybrid materials that take advantage of the synergy between inorganic silica (SiO4) domains, based on sol-gel bioactive glass compositions, and organic polydimethylsiloxane, PDMS ((CH3)2.SiO2)n, domains. Several studies have shown that hybrid materials based on the system PDMS-SiO2 constitute a promising group of biomaterials with several potential applications from bone tissue regeneration to brain tissue recovery, passing by bioactive coatings and drug delivery systems. The objective of the present work was to prepare hybrid materials for biomedical applications based on the PDMS-SiO2 system and to achieve a better understanding of the relationship among the sol-gel processing conditions, the chemical structures, the microstructure and the macroscopic properties. For that, different characterization techniques were used: Fourier transform infrared spectrometry, liquid and solid state nuclear magnetic resonance techniques, X-ray diffraction, small-angle X-ray scattering, smallangle neutron scattering, surface area analysis by Brunauer–Emmett–Teller method, scanning electron microscopy and transmission electron microscopy. Surface roughness and wettability were analyzed by 3D optical profilometry and by contact angle measurements respectively. Bioactivity was evaluated in vitro by immersion of the materials in Kokubos’s simulated body fluid and posterior surface analysis by different techniques as well as supernatant liquid analysis by inductively coupled plasma spectroscopy. Biocompatibility was assessed using MG63 osteoblastic cells. PDMS-SiO2-CaO materials were first prepared using nitrate as a calcium source. To avoid the presence of nitrate residues in the final product due to its potential toxicity, a heat-treatment step (above 400 °C) is required. In order to enhance the thermal stability of the materials subjected to high temperatures titanium was added to the hybrid system, and a material containing calcium, with no traces of nitrate and the preservation of a significant amount of methyl groups was successfully obtained. The difficulty in eliminating all nitrates from bulk PDMS-SiO2-CaO samples obtained by sol-gel synthesis and subsequent heat-treatment created a new goal which was the search for alternative sources of calcium. New calcium sources were evaluated in order to substitute the nitrate and calcium acetate was chosen due to its good solubility in water. Preparation solgel protocols were tested and homogeneous monolithic samples were obtained. Besides their ability to improve the bioactivity, titanium and zirconium influence the structural and microstructural features of the SiO2-TiO2 and SiO2-ZrO2 binary systems, and also of the PDMS-TiO2 and PDMS-ZrO2 systems. Detailed studies with different sol-gel conditions allowed the understanding of the roles of titanium and zirconium as additives in the PDMS-SiO2 system. It was concluded that titanium and zirconium influence the kinetics of the sol-gel process due to their different alkoxide reactivity leading to hybrid xerogels with dissimilar characteristics and morphologies. Titanium isopropoxide, less reactive than zirconium propoxide, was chosen as source of titanium, used as an additive to the system PDMS-SiO2-CaO. Two different sol-gel preparation routes were followed, using the same base composition and calcium acetate as calcium source. Different microstructures with high hydrophobicit were obtained and both proved to be biocompatible after tested with MG63 osteoblastic cells. Finally, the role of strontium (typically known in bioglasses to promote bone formation and reduce bone resorption) was studied in the PDMS-SiO2-CaOTiO2 hybrid system. A biocompatible material, tested with MG63 osteoblastic cells, was obtained with the ability to release strontium within the values reported as suitable for bone tissue regeneration.

Carbon-carbon bond formation methods for the preparation of shape-persistent architectures

Carbon-rich, conjugated organic scaffolding is a popular basis for functional materials, especially for electronic and photonic applications. However, synthetic methods for generating these types of materials lack diversity and, in many cases, efficiency; the insistence of investigators focusing on the properties of the end product, rather than the process in which it was created, has led to the current state of the relatively homogeneous synthetic chemistry of functional organic materials. Because of this, there is plenty of room for improvement at the most basic level. Problems endemic to the preparation of carbon-rich scaffolding can, in many cases, be solved with modern advances in synthetic methodology. We seek to apply this synthesis-focused paradigm to solve problems in the preparation of carbon-rich scaffolds. Herein, the development and utilization of three methodologies: iridium-catalyzed arene C-H borylation; zinc- mediated alkynylations; and Lewis acid promoted Mo nitride-alkyne metathesis, are presented as improvements for the preparation of carbon-rich architectures. In addition, X-ray crystallographic analysis of two classes of compounds are presented. First, an analysis of carbazole-containing arylene ethynylene macrocycles showcases the significance of alkyl chain identity on solid-state morphology. Second, a class of rigid zwitterionic metal-organic compounds display an unusual propensity to crystallize in the absence of inversion symmetry. Hirshfeld surface analysis of these crystalline materials demonstrates that subtle intermolecular interactions are responsible for the overall packing motifs in this class of compounds.

Detection Of Explosives On The Surface Of Banknotes By Raman Hyperspectral Imaging And Independent Component Analysis.

The aim of this study was to develop a methodology using Raman hyperspectral imaging and chemometric methods for identification of pre- and post-blast explosive residues on banknote surfaces. The explosives studied were of military, commercial and propellant uses. After the acquisition of the hyperspectral imaging, independent component analysis (ICA) was applied to extract the pure spectra and the distribution of the corresponding image constituents. The performance of the methodology was evaluated by the explained variance and the lack of fit of the models, by comparing the ICA recovered spectra with the reference spectra using correlation coefficients and by the presence of rotational ambiguity in the ICA solutions. The methodology was applied to forensic samples to solve an automated teller machine explosion case. Independent component analysis proved to be a suitable method of resolving curves, achieving equivalent performance with the multivariate curve resolution with alternating least squares (MCR-ALS) method. At low concentrations, MCR-ALS presents some limitations, as it did not provide the correct solution. The detection limit of the methodology presented in this study was 50μgcm(-2).

Genome Survey Sequence Analysis and Identification of Homologs of Major Surface Protease (gp63) Genes in Trypanosoma rangeli

In this study, 222 genome survey sequences were generated for Trypanosoma rangeli strain P07 isolated from an opossum (Didelphis albiventris) in Minas Gerais State, Brazil. T. rangeli sequences were compared by BLASTX (Basic Local Alignment Search Tool X) analysis with the assembled contigs of Leishmania braziliensis, Leishmania infantum, Leishmania major, Trypanosoma brucei, and Trypanosoma cruzi. Results revealed that 82% (182/222) of the sequences were associated with predicted proteins described, whereas 18% (40/222) of the sequences did not show significant identity with sequences deposited in databases, suggesting that they may represent T. rangeli-specific sequences. Among the 182 predicted sequences, 179 (80.6%) had the highest similarity with T. cruzi, 2 (0.9%) with T. brucei, and 1 (0.5%) with L. braziliensis. Computer analysis permitted the identification of members of various gene families described for trypanosomatids in the genome of T. rangeli, such as trans-sialidases, mucin-associated surface proteins, and major surface proteases (MSP or gp63). This is the first report identifying sequences of the MSP family in T. rangeli. Multiple sequence alignments showed that the predicted MSP of T. rangeli presented the typical characteristics of metalloproteases, such as the presence of the HEXXH motif, which corresponds to a region previously associated with the catalytic site of the enzyme, and various cysteine and proline residues, which are conserved among MSPs of different trypanosomatid species. Reverse transcriptase-polymerase chain reaction analysis revealed the presence of MSP transcripts in epimastigote forms of T. rangeli.

Surface integrity analysis in the super duplex stainless steel ASTM-A890 after machining

The purpose of this paper was to study the main effects of the turning in the superficial integrity of the duplex stainless steel ASTM A890-6A. The tests were conducted on a turning centre with carbide tools and the main entrances variables were: tool material class, feed rate, cutting depth, cutting speed and cutting fluid utilisation. The answers were analysed: microstructural analysis by optical microscopy and x-ray diffraction, cutting forces measurements by a piezoelectric dynamometer, surface roughness, residual stress by x-ray diffraction technique and the microhardness measurements. The results do not show any changes in the microstructural of the material, even when the greater cutting parameters were used. The smaller feed rate (0.1 mm/v), smaller cutting speed (110 m/min) and the greater cutting depth (0.5 mm) provided the smaller values for the tensile residual stress, the smaller surface roughness and the greater microhardness.

Comparative analysis of root surface smear layer removal by different etching modalities or erbium:yttrium-aluminum-garnet laser irradiation. A scanning electron microscopy study

The purpose of this study was to evaluate the effect of erbium:yttrium-aluminum-garnet (Er:YAG) laser (2.94 mu m) irradiation on the removal of root surface smear layer of extracted human teeth and to compare its efficacy with that of citric acid, ethylenediamine tetra-acetic acid (EDTA), or a gel containing a mixture of tetracycline hydrochloride (HCl) and citric acid, using scanning electron microscopy (SEM). Thirty human dentin specimens were randomly divided into six groups: G1 (control group), irrigated with 10 ml of physiologic saline solution; G2, conditioned with 24% citric acid gel; G3, conditioned with 24% EDTA gel; G4, conditioned with a 50% citric acid and tetracycline gel; G5, irradiated with Er:YAG laser (47 mJ/10 Hz/5.8 J/cm(2)/pulse); G6, irradiated with Er:YAG laser (83 mJ/10 Hz/10.3 J/cm(2)/pulse). Electron micrographs were obtained and analyzed according to a rating system. Statistical analysis was conducted with Kruskal-Wallis and Mann-Whitney tests (P < 0.05). G1 was statistically different from all the other groups; no statistically significant differences were observed between the Er:YAG laser groups and those undergoing the other treatment modalities. When the two Er:YAG laser groups were compared, the fluency of G6 was statistically more effective in smear layer removal than the one used in G5 (Mann-Whitney test, P < 0.01). Root surfaces irradiated by Er:YAG laser had more irregular contours than those treated by chemical agents. It can be concluded that all treatment modalities were effective in smear layer removal. The results of our study suggest that the Er:YAG laser can be safely used to condition diseased root surfaces effectively. Furthermore, the effect of Er:YAG laser irradiation on root surfaces should be evaluated in vivo so that its potential to enhance the healing of periodontal tissues can be assessed.

Caries Resistance of Lased Human Root Surface with 10.6 mu m CO(2) Laser-Thermal, Morphological, and Microhardness Analysis

Although the cariostatic effects of CO(2) laser on enamel have been shown, its effects on root surface demineralization remains uncertain. The objectives of this in vitro research was to establish safe parameters for a pulsed 10.6 mu m CO(2) laser and to evaluate its effect on morphological features of the root surface, as well as on the reduction of root demineralization. Ninety-five human root surfaces were randomly divided into five groups: G1-No treatment (control); G2-2.5 J/cm(2); G3-4.0 J/cm(2); G4-5.0 J/cm(2); and G5-6.0 J/cm(2). Intrapulpal temperature was evaluated during root surface irradiation by a thermocouple and morphological changes were evaluated by SEM. After the surface treatment, the specimens were submitted to a 7-day pH-cycling model. Subsequently, the cross-sectional Knoop microhardness values were measured. For all irradiated groups, intrapulpal temperature changes were less than 1.5 degrees C. Scanning electron microscopy images indicated that fluences as low as 4.0 J/cm(2) were sufficient to induce morphological changes in the root surface. Additionally, for fluences reaching or exceeding 4.0 J/cm(2), laser-induced inhibitory effects on root surface demineralization were observed. It was concluded that laser energy density in the range of 4.0 to 6.0 J/cm(2) could be applied to a dental root to reduce demineralization of this surface without compromising pulp vitality.

Ultrastructural Analysis of Radicular Dentine Surface Submitted to CO(2) Laser at Different Parameters

Background: There are no reported studies comparing different parameter settings of the CO(2) laser and irradiation direction considering their effect on the morphology of radicular dentine surface. Purpose: To evaluate the alterations of radicular dentine (cervical, middle, and apical thirds) irradiated with CO(2) laser at different potencies and irradiation directions. Study Design: Roots of 35 canines were prepared and randomly distributed according to the laser potency: GI: no laser treatment (control) (n = 5); GII, 2 W (n = 10); GIII: 4 W (n = 10); GIV: 6 W (n = 10). Each group (excepting GI) was divided in two subgroups according to the irradiation distance (n = 5): (A) parallel and (B) perpendicular to the root canal walls. The roots were splited longitudinally and analyzed by scanning electron microscopy in a qualiquatitative way. The scores were submitted to Kruskal-Wallis and Dunn`s tests. Results: No significant statistical differences were observed among root canal thirds (P > 0.05). The specimens irradiated with 2 W were statistically different (P < 0.05) from those irradiated with 4 and 6 W, which were statistically similar between themselves (P > 0.05). With 2, 4, and 6 W at in parallel irradiation and 2 W in perpendicular direction, the surface showed a fissured aspect. With 4 W in perpendicular direction and 6 W in parallel and perpendicular direction, surface was modified by laser action and exhibited fused areas. Conclusions: The intensity of the effects is dependent on the laser-irradiation dosimetries. Alterations were more intense when higher parameters were used. Microsc. Res. Tech. 72:737-743, 2009. (C) 2009 Wiley-Liss, Inc.

On-line analysis of froth surface in coal and mineral flotation using JKFrothCam

The personal computer revolution has resulted in the widespread availability of low-cost image analysis hardware. At the same time, new graphic file formats have made it possible to handle and display images at resolutions beyond the capability of the human eye. Consequently, there has been a significant research effort in recent years aimed at making use of these hardware and software technologies for flotation plant monitoring. Computer-based vision technology is now moving out of the research laboratory and into the plant to become a useful means of monitoring and controlling flotation performance at the cell level. This paper discusses the metallurgical parameters that influence surface froth appearance and examines the progress that has been made in image analysis of flotation froths. The texture spectrum and pixel tracing techniques developed at the Julius Kruttschnitt Mineral Research Centre are described in detail. The commercial implementation, JKFrothCam, is one of a number of froth image analysis systems now reaching maturity. In plants where it is installed, JKFrothCam has shown a number of performance benefits. Flotation runs more consistently, meeting product specifications while maintaining high recoveries. The system has also shown secondary benefits in that reagent costs have been significantly reduced as a result of improved flotation control. (C) 2002 Elsevier Science B.V. All rights reserved.