Martensite aging kinetics in the Cu-10 wt.%Al and Cu-10 wt.%Al-10 wt.%Ag alloys

The martensite aging kinetics in the Cu-10 wt.%Al and Cu-10 wt.%Al-10 wt.%Ag alloys was studied using microhardness measurements, classical differential thermal analysis (DTA), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX) and in-situ high-temperature X-ray diffractometry (XRD). The results for the Cu-10%Al alloy indicated a process dominated by the martensite ordering assisted by migration of quenched-in vacancies and followed by the consumption of the α phase. For the Cu-10%Al-10%Ag alloy the dominant process is the consumption of the α phase associated with a decrease in the ordering degree of the martensitic phase. © 2007 Springer Science+Business Media, LLC.

Application of non-isothermal cure kinetics on the interaction of poly(ethylene terephthalate) - Alkyd resin paints

Samples of paint (P), reused PET (PET-R) and paint/PET-R mixtures (PPET-R) were evaluated using DSC to verify their physical-chemical properties and thermal behavior. Films from paints and PPET-R are visually similar. It was possible to establish that the maximum amount of PET-R that can be added to paint without significantly altering its filming properties is 2%. The cure process (80-203°C) was identified through DSC curves. The kinetic parameters, activation energy (E a) and Arrhenius parameters (A) for the samples containing 0.5 to 1% of PET-R, were calculated using the Flynn-Wall-Ozawa isoconversional method. It was observed that for greater amounts of PET-R added, there is a decrease in the E a values for the cure process. A Kinetic compensation effect (KCE), represented by the equation InA=-2.70+0.31E a was observed for all the samples. The most suitable kinetic model to describe this cure process is the autocatalytic Šesták-Berggreen, model applied to heterogeneous systems. © 2007 Springer Science+Business Media, LLC.

Analysis of the kinetics of phase and amplitude gratings recorded in azopolymer films

In this work we use a stabilized holographic technique to study both refractive index and absorption gratings recorded in thin films made of Disperse Red 1 (DR1) embedded in an organic polymer matrix (PMMA) deposited on glass substrate. Gratings are recorded by linearly polarized illumination with the interference pattern of two crossing beams. One of the beams is phase modulated and the interference signals between the transmitted and diffracted waves are detected by a tuned lock-in amplifier. The technique allows measuring separately changes of the refractive index and the absorption coefficient during the course of the photoreaction process. The time evolution of the diffraction efficiencies during recording has shown bi-exponential kinetics for both gratings. © 2008 American Institute of Physics.

Kinetics of martensitic phase decomposition in the Cu-10wt.%Al alloy with Ag additions

The study of the kinetics of martensitic phase decomposition in the Cu-10wt.%Al alloy with Ag additions showed that the presence of Ag retarded the eutectoid decomposition reaction and enhanced martensite stabilization. This stabilization effect was attributed to Ag atoms redistribution as structure defects, increase in the numbers of Cu-Al pairs due to Ag-Al interaction and the Al atoms redistribution around one Cu atom at the sub-lattice of the martensitic crystal. © 2008 Trans Tech Publications.

Analytical model for heterogeneous crystallization kinetics of spherical glass particles

An analytical model developed to describe the crystallization kinetics of spherical glass particles has been derived in this work. A continuous phase transition from three-dimensional (3D)-like to 1D-like crystal growth has been considered and a procedure for the quantitative evaluation of the critical time for this 3D-1D transition is proposed. This model also allows straightforward determination of the density of surface nucleation sites on glass powders using differential scanning calorimetry data obtained under different thermal conditions. © 2009 The American Ceramic Society.

Study of biosorption of rare earth metals (La, Nd, Eu, Gd) by Sargassum sp. biomass in batch systems: Physicochemical evaluation of kinetics and adsorption models

This work evaluated kinetic and adsorption physicochemical models for the biosorption process of lanthanum, neodymium, europium, and gadolinium by Sargassum sp. in batch systems. The results showed: (a) the pseudo-second order kinetic model was the best approximation for the experimental data with the metal adsorption initial velocity parameter in 0.042-0.055 mmol.g -1.min-1 (La < Nd < Gd < Eu); (b) the Langmuir adsorption model presented adequate correlation with maximum metal uptake at 0.60-0.70 mmol g-1 (Eu < La < Gd < Nd) and the metal-biomass affinity parameter showed distinct values (Gd < Nd < Eu < La: 183.1, 192.5, 678.3, and 837.3 L g-1, respectively); and (c) preliminarily, the kinetics and adsorption evaluation did not reveal a well-defined metal selectivity behavior for the RE biosorption in Sargassum sp., but they indicate a possible partition among RE studied. © (2009) Trans Tech Publications.

Sintering temperature influence on microwave dielectric properties of TiO2-ZrO2 ceramics

Dielectric ceramics have been widely investigated and used for microwave applications such as resonators and filters. The present study deals with the influence of sintering temperature on microwave dielectric properties of TiO2 ceramics with 10, 20, and 30 wt% ZrO2. Three compositions have been developed through mixing procedures and then tested for each sintering temperature: 1500 and 1400°C. X-ray diffraction and scanning electron microscopy are carried out aiming to explain the ceramic behavior of each sample. The dielectric constants of different ceramics for both temperatures varied from 85.4 to 62.6, while their quality factor due to dielectric losses varied from 3110 to 1630. The Q decrease is attributed to the non uniform grain growth and to the obtained crystalline phases. The best microwave parameters were obtained for the ceramics sintered at 1400°C, which can be applied in microwave circuits as dielectric resonators. © (2010) Trans Tech Publications.

Use of high energy ball milling on the sintering optimization of alumina ceramics

In this work, the effect of the milling time on the densification of the alumina ceramics with or without 5wt.%Y 2O 3, is evaluated, using high-energy ball milling. The milling was performed with different times of 0, 2, 5 or 10 hours. All powders, milled at different times, were characterized by X-Ray Diffraction presenting a reduction of the crystalline degree and crystallite size as function of the milling time increasing. The powders were compacted by cold uniaxial pressing and sintered at 1550°C-60min. Green density of the compacts presented an increasing as function of the milling time and sintered samples presented evolution on the densification as function of the reduction of the crystallite size of the milled powders. © (2010) Trans Tech Publications.

SnO 2 ceramics with low electrical resistivity obtained by microwave sintering

The main aim of this study was to develop dense and conducting SnO 2 ceramics without precipitated phases on the grain boundaries, which was verified using field emission scanning microscopy (FE-SEM) coupled with an energy-dispersive X-ray spectroscopy (FE-SEM/EDS). Two sample groups were investigated, where the first sample group was doped with zinc while the second one was doped with cobalt. The ceramics were prepared using the oxides mixture method and the sintering was carried out in a conventional muffle oven as well as in microwave oven. The results obtained were found to be similar regarding the relative density for the two sintering methods while time and temperature gains were observed for the microwave sintering method. The relative densities obtained were nearly 95%, for the two sintering methods. Concerning the electrical characterization measurements-electric field x current density as well as the environment temperature, the ceramics obtained through the conventional sintering method presented non-ohmic behavior. For the microwave sintered ceramics, we observed an ohmic behavior with electrical resistivity of 1.3 Ωcm for the samples doped with ZnO/Nb 2O 5 and 2.5 Ωcm for that of the samples doped with CoO/Nb 2O 5. The FE-SEM/EDS results for the microwave sintered ceramics indicated a structure with a reduced number of pores and other phases segregated at the grain boundaries, which leads to a better conductive ceramic than the conventional oven sintered samples. The dilatometry analysis determined the muffle sintering temperature and the difference between the densification of cobalt and zinc oxides. The addition of niobium oxide resulted in the decrease in resistivity, which thus led us to conclude that it is possible to obtain dense ceramics with low electrical resistivity based on SnO 2 using commercial oxides by the oxides mixture technique and the microwave oven sintering method. Copyright © 2011 American Scientific Publishers All rights reserved.

High-pressure assisted sintering of Ti-20Si-10B and Ti-10Si-5B powders

This work presents the structural characterization of Ti-10Si-5B and Ti-20Si-10B (at-%) alloys produced by high-pressure assisted sintering. Sintering was performed in air at 1100 and 1200°C for 60 s using pressure levels of 5 GPa. Structural evaluation of sintered samples was conducted by means of scanning electron microscopy and energy dispersive spectrometry. Samples were successfully consolidated after sintering, which presented theoretical density values higher than 99%. The microstructures of the sintered Ti-10Si-5B and Ti-20Si-10B alloys revealed the presence of the TiSS, TiB, TiB2, Ti5Si3, Ti5Si4, TiSi, and TiSi2.phases. A small amount of Ti6Si2B was formed after high-pressure assisted sintering of the Ti-20Si-10B alloy (5GPa, 1100°C for 60 s) indicating that equilibrium structures were not achieved during short sintering times. No oxygen and carbon contamination was detected in structures of Ti-Si-B alloys after high-pressure sintering at 1100 and 1200°C without controlled atmosphere. © (2012) Trans Tech Publications, Switzerland.

Evaluation of Sperm Kinetics and Plasma Membrane Integrity of Frozen Equine Semen in Different Storage Volumes and Freezing Conditions

In the present study, different freezing systems (Styrofoam box and Mini Digitcool ZH 400) and storage volumes (0.5- and 0.25-mL straws) were compared with regard to sperm kinetics and plasma membrane integrity of frozen and thawed semen. For that, three ejaculates from four animals were frozen in Styrofoam box and Mini Digitcool ZH 400 machine. The 0.5-mL straws were thawed at 46°C for 20 seconds, and the 0.25-mL straws were thawed at 46°C for 12 seconds. Statistical analysis was performed using program R of descriptive analysis box plot, followed by analysis of variance using PROC MIXED of SAS 9.1 package. Variances of 5% were considered as different. There was no interaction between the straw sizes and volumes; however, statistical differences were observed between the semen storage volumes. The 0.5-mL straws had higher total motility (%), progressive motility (%), average path velocity (μm/s), straight-line velocity (μm/s), curvilinear velocity (μm/s), and rapid sperm percentage (%) than the 0.25-mL straws. However, plasma membrane integrity analysis did not differ between the two straws. Thus, it is possible to conclude that equine sperm cryopreserved in 0.5-mL straws has better sperm kinetics than when stored in 0.25-mL straws. Additionally, it is possible to conclude that automated systems that enable faster freezing rates result in a seminal quality that is similar to the one obtained by the conventional system using Styrofoam boxes. © 2013 Elsevier Inc.

Photo-Fenton degradation kinetics of low ciprofloxacin concentration using different iron sources and pH

The aim of the present study was to compare the degradation kinetics of low (1 mg L-1) and high (25 mg L-1) concentrations of ciprofloxacin (CIP) aiming to decrease the concentration of additives and evaluate the pH limitation by the use of low iron concentrations and organic ligands. A parameterized kinetic model was satisfactorily fitted to the experimental data in order to study the performance of photo-Fenton process with specific iron sources (iron citrate, iron oxalate, iron nitrate) under different pH medium (2.5, 4.5, 6.5). The process modeling allowed selecting those process conditions (iron source, additives concentrations and pH medium) which maximize the two performance parameters related to the global equilibrium conversion and kinetic rate of the process. For the high CIP concentration, degradation was very influenced by the iron source, resulting in much lower efficiency with iron nitrate. At pH 4.5, highest TOC removal (0.87) was achieved in the presence of iron citrate, while similar CIP conversions were obtained with oxalate and citrate (0.98 after 10 min). For the low CIP concentration, much higher conversion was observed in the presence of citrate or oxalate in relation to iron nitrate up to pH 4.5. This behavior denotes the importance of complexation also at low dosages. Appropriate additives load (320 μM H 2O2; 6 μM Fe) resulted in a CIP conversion of 0.96 after10 min reaction with citrate up to pH 4.5. © 2013 Elsevier B.V. All rights reserved.

The Mode of Action of Recombinant Mycobacterium tuberculosis Shikimate Kinase: Kinetics and Thermodynamics Analyses

Tuberculosis remains as one of the main cause of mortality worldwide due to a single infectious agent, Mycobacterium tuberculosis. The aroK-encoded M. tuberculosis Shikimate Kinase (MtSK), shown to be essential for survival of bacilli, catalyzes the phosphoryl transfer from ATP to the carbon-3 hydroxyl group of shikimate (SKH), yielding shikimate-3-phosphate and ADP. Here we present purification to homogeneity, and oligomeric state determination of recombinant MtSK. Biochemical and biophysical data suggest that the chemical reaction catalyzed by monomeric MtSK follows a rapid-equilibrium random order of substrate binding, and ordered product release. Isothermal titration calorimetry (ITC) for binding of ligands to MtSK provided thermodynamic signatures of non-covalent interactions to each process. A comparison of steady-state kinetics parameters and equilibrium dissociation constant value determined by ITC showed that ATP binding does not increase the affinity of MtSK for SKH. We suggest that MtSK would more appropriately be described as an aroL-encoded type II shikimate kinase. Our manuscript also gives thermodynamic description of SKH binding to MtSK and data for the number of protons exchanged during this bimolecular interaction. The negative value for the change in constant pressure heat capacity (ΔCp) and molecular homology model building suggest a pronounced contribution of desolvation of non-polar groups upon binary complex formation. Thermodynamic parameters were deconvoluted into hydrophobic and vibrational contributions upon MtSK:SKH binary complex formation. Data for the number of protons exchanged during this bimolecular interaction are interpreted in light of a structural model to try to propose the likely amino acid side chains that are the proton donors to bulk solvent following MtSK:SKH complex formation. © 2013 Rosado et al.

Sintering of porous alumina obtained by biotemplate fibers for low thermal conductivity applications

In this research report, a sintering process of porous ceramic materials based on Al2O3 was employed using a method where a cation precursor solution is embedded in an organic fibrous cotton matrix. For porous green bodies, the precursor solution and cotton were annealed at temperatures in the range of 100-1600°C using scanning electron microscopy (SEM) and thermogravimetric (TG) analysis to obtain a porous body formation and disposal process containing organic fibers and precursor solution. In a structure consisting of open pores and interconnected nanometric grains, despite the low porosity of around 40% (calculated geometrically), nitrogen physisorption determined a specific surface area of 14m2/g, which shows much sintering of porous bodies. Energy dispersive X-ray (EDX) and X-ray diffraction (XRD) analytical methods revealed a predominant amount of α-Al2O3 in the sintered samples. Thermal properties of the sintered Al2O3 fibers were obtained by using the Laser Flash which resulted in the lower thermal conductivity obtained by α-Al2O3 and therefore improved its potential use as an insulating material. © 2012 Elsevier Ltd.

Structure and kinetics of formation of APTS/GPTS-derived organic/inorganic hybrids

The structure and the kinetics of formation of APTS/GPTS-derived organic/inorganic hybrids were studied in situ by small-angle-X-ray scattering. The data were interpreted in terms of a process of primary particles formation and growth of mass-fractal clusters. At the very early stage, the population of the nonfractal primary particles (D = 3) increases with time. As the mass-fractal clusters appear (D < 3) as a result of the aggregation process, the radius of gyration, Rg, of the clusters increases on average. At advanced stages of aggregation, the clusters grow in a mechanism in which the number of particles per clusters increases while the number of clusters diminishes with time, in such a way that the correlation volume of the clusters, Vc, fulfills the relationship Vc â̂ R g D, in agreement with a mass-fractal character of the clusters. These results supporting a cluster-cluster aggregation process, together with the typically very low value found for the mass-fractal dimension D, are in favor of a diffusion-controlled cluster aggregation mechanism. © 2013 American Chemical Society.