Small-angle X-ray scattering study of the smart thermo-optical behavior of zirconyl aqueous colloids

The smart thermo-optical systems studied here are based on the unusual thermoreversible sol-gel transition of zirconyl chloride aqueous solution modified by sulfuric acid in the molar ratio Zr/SO4:3/1. The transparency to the visible light changes during heating due to light scattering. This feature is related to the aggregates growth that occurs during gelation. These reversible changes can be controlled by the amount of chloride ions in solution. The thermoreversible sol-gel transition temperature increases from 323 to 343 K by decreasing the molar ratio Cl/Zr from 7.0 to 1.3. In this work the effect of the concentration of chloride ions on the structural characteristics of the system has been analyzed by in situ SAXS measurements during the sol-gel transition carried out at 323 and 333 K. The experimental SAXS curves of sols exhibit three regions at small, medium and high scattering vectors characteristics of Guinier, fractal and Porod regimes, respectively. The radius of primary particles, obtained from the crossover between the fractal and Porod regimes, remains almost invariable with the chloride concentration, and the value (4 Angstrom) is consistent with the size of the molecular precursor. During the sol-gel transition the aggregates grow with a fractal structure and the fractal dimensionality decreases from 2.4 to 1.8. This last value is characteristic of a cluster-cluster aggregation controlled by a diffusion process. Furthermore, the time exponent of aggregate growth presents values of 0.33 and 1, typical of diffusional and hydrodynamic motions. A crossover between these two regimes is observed.

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.

A Transmission Problem for Euler-Bernoulli beam with Kelvin-Voigt Damping

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Small angle X-ray scattering study of structural changes in silica gel modified with organofunctional groups

Silica gel surfaces, organofunctionalized with 2-mercaptobenzimidazole, iminosalicylaldehyde and imidazole groups were examined using the small angle X-ray scattering technique (SAXS). From the scattering intensity data it was concluded that particles have a uniform size after the coupling reaction. The chemical treatment of the silica gel leads to an attachment of the organofunctional groups on the solid-pore interface of the silica with an increase of the mean size of the solid phase and some coalescence of the pores. © 1989.

Experimental analysis of heat recoveries with heat pipes operating in low inclination angle

Heat recovery devices are important in the optimization of thermal systems, since they can be used to reduce thermal losses to the environment. The use of heat pipes in these types of equipment can provide heat recoveries of higher efficiency, since both fluid flows are external and there are less contamination risks between the hot and cold fluids. The objective of this work is to study a heat recovery unit constructed with heat pipes and mainly, to analyze the influence of the inclination of the heat pipes on the performance of the equipment. For this analysis, a heat recovery unit was constructed which possesses 48 finned heat pipes in triangular geometry, the evaporator and condenser being of the same length. This unit was tested in an air-air system simulating a heat recovery process in which heat was supplied to the hot fluid by electrical resistances. The results have shown that there exists an inclination at which the system has a better performance, but for higher inclinations there is no significant increase of the efficiency of the system. This paper also presents the influence of inclination of heat pipes on effectiveness and NTU parameters which are important in heat exchanger design.

Pore structure characterization of kaolin, metakaolin, and their acid-treated products using small-angle X-ray scattering

Pore structure of dealuminated kaolin and metakaolin was studied by small-angle X-ray scattering (SAXS). Both parent kaolin and metakaolin have about 10% of the total pore volume provided by globular pores with 105 Å mean pore size. Their surface area is about 14 m2/g. Acid dealumination of kaolin causes an increase of its globular pore volume without an appreciable change in the mean pore size, its surface area increasing up to about 90 m2/g. Acid dealumination of metakaolin enhances the globular pore volume, although there is generation of slit-shaped pores with a narrow thickness distribution whose mean value is 14 Å. This interlayer spacing causes an increase in surface area of about 190 m2/g by SAXS. © 1994.

Numerical simulation of viscous three-dimensional flow over aerospace vehicles using Euler/boundary-layer zonal approach

This paper presents a viscous three-dimensional simulations coupling Euler and boundary layer codes for calculating flows over arbitrary surfaces. The governing equations are written in a general non orthogonal coordinate system. The Levy-Lees transformation generalized to three-dimensional flows is utilized. The inviscid properties are obtained from the Euler equations using the Beam and Warming implicit approximate factorization scheme. The resulting equations are discretized and approximated by a two-point fmitedifference numerical scheme. The code developed is validated and applied to the simulation of the flowfield over aerospace vehicle configurations. The results present good correlation with the available data.

Comparative study using small-angle x-ray scattering and nitrogen adsorption in the characterization of silica xerogels and aerogels

A comparative study using small-angle x-ray scattering (SAXS) and nitrogen adsorption has been carried out in the structural characterization of silica xerogels and aerogels, obtained from tetraethoxysilane sonohydrolysis. The specific surface and the mean pore size as measured by both the techniques were found to be in notable agreement in all cases for aerogels and xerogels. According to the SAXS data, aerogels at 500 °C exhibit a mass fractal structure with fractal dimension D∼2.4 in the range between the correlation length ξ∼5.3 nm and a∼0.75 nm. An experimental method to probe the mass fractal structure of aerogels from exclusively nitrogen adsorption isotherms has been presented. For aerogels at 500 °C, we have found D∼2.4 in the range between the pore width 2rξ∼33 nm and 2ra∼4.5 nm, which is in notable agreement with the SAXS results (D ∼2.4, ξ∼5.3 nm, a∼0.75 nm) if we assign the pore width 2r probed by the Kelvin equation in the adsorption method to the Bragg distance 2π/q associated to the correlation length 1/q probed by SAXS.

Small-angle x-ray scattering study of the structural evolution of the drying of sonogels with the liquid phase exchanged by acetone

The structural evolution on the drying of wet sonogels of silica with the liquid phase exchanged by acetone, obtained from tetraethoxisilane sonohydrolysis, was studied in situ by small-angle x-ray scattering (SAXS). The periods associated to the structural evolution as determined by SAXS are in agreement with those classical ones established on basis of the features of the evaporation rate of the liquid phase in the obtaining of xerogels. The wet gel can be described as formed by primary particles (microclusters), with characteristic length a ∼ 0.67 nm and surface which is fractal, linking together to form mass fractal structures with mass fractal dimension D=2.24 in a length scale ξ∼6.7 nm. As the network collapses while the liquid/vapor meniscus is kept out of the gel volume, the mass fractal structure becomes more compacted by increasing D and decreasing ξ, with smoothing of the fractal surface of the microclusters. The time evolution of the density of the wet gels was evaluated exclusively from the SAXS parameters ξ, D, and a. The final dried acetone-exchanged gel presents Porod's inhomogeneity length of about 2.8 nm and apparently exhibits an interesting singularity D →3, as determined by the mass fractal modeling used to fit the SAXS intensity data for the obtaining of the parameters ξ and D.

Compensatory canine angulation in angle class II and III patients

Abstract: The aim of this study was to evaluate the occurence of compensation in mesiodistal axial inclinations of canines in skeletal malocclusions patients. The sample consisted of 25 Angle Class II, division 1 malocclusion (group 1) and 19 Angle Class III malocclusion patients (group 2). After measurement of dental angulations through a method that associates plaster model photography and AutoCad software, comparisons between the groups were performed by T-test for independent samples. Results showed that there was no statistically significant difference (p ≤ 0.05) between groups, when maxillary canine angulations were compared. Regarding the mandibular canines, there was a statistically significant difference in dental angulation, expressed by 3.2° for group 1 and 0.15° for group 2. An upright position tendency for mandibular canines was observed in the Angle Class III sample. This configures a pattern of compensatory coronary positioning, since the angulation of these teeth makes them occupy less space in the dental arch and consequently mandibular incisors can be in a more retracted position in the sagittal plane.

Effect of nozzle angle and air-jet parameters in air-assisted sprayer on biological effect of soybean asian rust chemical protection

Aiming at improving the efficiency control of Phakopsora pachyrhizi, this research evaluated different application techniques, using spray deposits and yield parameters of soybean crop. Two experiments were carried out in the experimental area of FCA/UNESP - Botucatu, SP, Brazil, in the soybean crop, Conquista variety, in the 2006/2007 season. The first experiment was arranged in random blocks with eight treatments and four replications. The treatments were conducted in factorial arrangement 4×2 (four air levels 0, 9, 11 and 29 km/h combined at two nozzle angles 0 and 30°) using AXI 110015 nozzles. Ten plants on each plot were selected for sampling spray deposits. Artificial targets were fixed on plants, two in the top and another two in the bottom part of plants (abaxial and adaxial leaf surface each one). For deposit evaluations, a cupric tracer was used and the amount of deposits was determined by a spectrophotometer. The second experiment was carried out in the same place and the treatments were of the same arrangement as the previous experiment, including control treatment (untreated plants). The spraying with triazole fungicide was realized in R2 and R5.2 growth stages of soybean with 142 l/ha spray volume. The nozzle angled of 30° combined with maximum air speed promoted the highest spray deposits on the soybean crop and influenced positively the control of the soybean Asian rust as well in the productivity of this crop.

Influence of convergence angle of tooth preparation on the fracture resistance of Y-TZP-based all-ceramic restorations

Objective: To investigate the influence of the convergence angle of tooth preparation on the fracture load of Y-TZP-based ceramic (YZ-Vita YZ) substructure (SB) veneered with a feldspathic porcelain (VM9-Vita VM9). Methods: Finite element stress analysis (FEA) was performed to examine the stress distribution of the system. Eighty YZ SB were fabricated using a CAD-CAM system and divided into four groups (n = 20), according to the total occlusal convergence (TOC) angle: G6-6° TOC; G12-12° TOC; G20-20° TOC; and G20MOD-20° TOC with modified SB. All SB were veneered with VM9, cemented in a fiber reinforced epoxy resin die, and loaded to failure. Half of the specimens from each group (n = 10) were cyclic fatigued (106 cycles) before testing. Failure analysis was performed to determine the fracture origin. Data were statistically analyzed using Anova and Tukey's tests (α = 0.05). Results: The greatest mean load to fracture value was found for the G20MOD, which was predicted by the FEA. Cyclic fatigue did not significantly affect the load of fracture. Catastrophic failure originating from the internal occlusal surface of the SB was the predominant failure mode, except for G20MOD. Significance: The YZ-VM9 restorations resisted greater compression load than the usual physiological occlusal load, regardless of the TOC angle of preparations. Yet, the G20MOD design produced the best performance among the experimental conditions evaluated. © 2013 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Small-angle X-ray scattering and structural modeling of full-length: Cellobiohydrolase I from Trichoderma harzianum

Cellobiohydrolases hydrolyze cellulose releasing cellobiose units. They are very important for a number of biotechnological applications, such as, for example, production of cellulosic ethanol and cotton fiber processing. The Trichoderma cellobiohydrolase I (CBH1 or Cel7A) is an industrially important exocellulase. It exhibits a typical two domain architecture, with a small C-terminal cellulose-binding domain and a large N-terminal catalytic core domain, connected by an O-glycosylated linker peptide. The mechanism by which the linker mediates the concerted action of the two domains remains a conundrum. Here, we probe the protein shape and domain organization of the CBH1 of Trichoderma harzianum (ThCel7A) by small angle X-ray scattering (SAXS) and structural modeling. Our SAXS data shows that ThCel7A linker is partially-extended in solution. Structural modeling suggests that this linker conformation is stabilized by inter- and intra-molecular interactions involving the linker peptide and its O-glycosylations. © 2013 Springer Science+Business Media Dordrecht.