Experimental study of phase equilibria in the systems Fe-Zn-O and Fe-Zn-Si-O at metallic iron saturation

The reported experimental work on the systems Fe-Zn-O and Fe-Zn-Si-O in equilibrium with metallic iron is part of a wider research program that combines experimental and thermodynamic computer modeling techniques to characterize zinc/lead industrial slags and sinters in the system PbO-ZnO-SiO2-CaO-FeO-Fe2O3. Extensive experimental,investigations using high-temperature equilibration and quenching techniques followed by electron probe X-ray microanalysis (EPMA) were carried out. Special experimental; procedures were developed to enable accurate measurements in these ZnO-containing systems to be performed in equilibrium with metallic iron; The systems Fe-Zn-O and FeZn-Si-O were experimentally investigated in equilibrium with metallic iron in the temperature ranges 900 degreesC to 1200 degreesC (1173 to 1473 K) and from 1000 degreesC to 1350 degreesC (1273 to 1623 K), respectively. The liquidus surface in the system Fe-Zn-Si-O in equilibrium with metallic iron was characterized in the composition ranges 0 to 33 wt pet ZnO and 0 to 40 wt pet SiO2. The wustite (Fe,Zn)O, zincite (Zn,Fe)O, willemite (Zn,Fe)(2)SiO4, arid fayalite: (Fe,Zn)(2)SiO4 solid solutions in equilibrium with metallic iron were measured.

Experimental study of phase equilibria in the PbO-MgO-SiO2 system

Equilibrium phase relations in the PbO-Al2O3-SiO2 system have been investigated experimentally by means of high-temperature equilibration, quenching, and electron probe X-ray microanalysis (EPMA). The system has 21 primary phase fields including three monoxides (PbO, Al2O3, and SiO2), seven binary compounds (Al6Si2O13, PbAl2O4, PbAl12O19, Pb2Al2O5, PbSiO3, Pb2SiO4, and Pb4SiO6), and eleven ternary compounds (PbAl2Si2O8, Pb3Al10SiO20, Pb4Al2Si2O11, Pb4Al4SiO12, Pb4Al4Si3O16, Pb4Al4Si5O20, Pb5Al2Si10O28, Pb6Al2Si6O21, Pb8Al2Si4O19, Pb12Al2Si17O49, and Pb12Al2Si20O55). Three new ternary compounds, Pb4Al4SiO12, Pb4Al4Si5O20, and Pb12Al2Si17O49, were observed and characterized by EPMA. No extensive solid solution in any of the compounds was found in the present study. The liquidus isotherms were experimentally determined in most of the primary phase fields in the temperature range from 923 to 1873 K, and the ternary phase diagram of the PbO-Al2O3-SiO2 System has been constructed.

Age gelation of UHT milk - A review

Gelation of UHT milk during storage (age gelation) is a major factor limiting its shelf-life. The gel which forms is a three-dimensional protein matrix initiated by interactions between the whey protein beta -lactoglobulin and the kappa -casein of the casein micelle during the high heat treatment. These interactions lead to the formation of a beta -lactoglobulin-kappa -casein complex (beta kappa -complex). A feasible mechanism of age gelation is based on a two-step process; in the first step, the beta kappa -complexes dissociate from the casein micelles due to the breakdown of multiple anchor sites on kappa -casein, and in the second step, these complexes aggregate into a three-dimensional matrix. When a critical volume concentration of the beta kappa -complex is attained, a gel of custard-like consistency is formed. Significant factors which influence the onset of gelation include the nature of the heat treatment, proteolysis during storage, milk composition and quality, seasonal milk production factors and storage temperature. In this review, age gelation is discussed in terms of these factors, causative mechanisms and procedures for controlling it.

An insight into the thermostability of a pair of xylanases: the role of hydrogen bonds

Xylanases are enzymes that are very tolerant to temperature. Their potential use in several biotechnological applications, such as animal food manufacture and pulp bleaching, is due to their intrinsic thermostability. The present report deals with two xylanases, the mesophilic xylanase from Bacillus circulans, BCX, and the thermophilic xylanase from Thermomyces lanuginosus,TLX. These enzymes belong to family 11, and they are the most structurally similar mesophilic-thermophilic pair. Molecular dynamics simulations were employed to investigate the factors responsible for the different thermostabilities exhibited by these structurally similar enzymes. Their active site is their most rigid region, and it is equally rigid at all temperatures. Inter and intramolecular interactions, hydrogen bonds in particular, are the key to the main differences between BCX and TLX. The intramolecular hydrogen bonds and salt bridges are important for maintenance of the backbone rigidity even at high temperature, and the highly solvated surface is a clear optimization in TLX compared with BCX. The main differences between these two enzymes can be found on the fingers domain, which indicates that this domain must be the target for the site-directed mutagenesis responsible for improving the temperature tolerance of this family of enzymes.

Thermal analysis, nuclear magnetic resonance spectroscopy, and impedance spectroscopy of N,N-dimethyl-pyrrolidinium iodide: An ionic solid exhibiting rotator phases

N,N-dimethyl-pyrrolidinium iodide has been investigated using differential scanning calorimetry, nuclear magnetic resonance (NMR) spectroscopy, second moment calculations, and impedance spectroscopy. This pyrrolidinium salt exhibits two solid-solid phase transitions, one at 373 K having an entropy change, Delta S, of 38 J mol(-1) K-1 and one at 478 K having Delta S of 5.7 J mol(-1) K-1. The second moment calculations relate the lower temperature transition to a homogenization of the sample in terms of the mobility of the cations, while the high temperature phase transition is within the temperature region of isotropic tumbling of the cations. At higher temperatures a further decrease in the H-1 NMR linewidth is observed which is suggested to be due to diffusion of the cations. (C) 2005 American Institute of Physics.

The microstructure of mechanically alloyed MoSi2 with Ni and Al additions

The effect of Ni and Al additions on grain boundary silica in mechanically alloyed and hot isostatically pressed (HTPed) MoSi2 was investigated. Mechanical alloying Mo and Si in the absence of Al produced finely dispersed silica within a fine grained structure. Mechanically alloyed and HIPed Mo and Si with Ni and Al partially transformed the silica to crystalline oxide phases, including Al2O3. An improvement in high temperature properties is not expected due to the retention of a grain boundary silica film. Rapid grain growth resulted during HIPing, possibly due to the formation of a Ni/Fe/Al liquid phase.

Electron paramagnetic resonance of Ni(II) doped tris(ethylenediamine)zinc(II) dinitrate

Variable temperature electron paramagnetic resonance spectra of tris(ethylenediamine)zinc(II) dinitrate single crystals doped with NI(II) have been measured. The host crystal undergoes a trigonal to monoclinic phase transition at 146 K. Above the transition temperature the zero field splitting tensor is axially symmetric with D = -0.831 cm(-1) and below it becomes rhombic with D = -0.785 cm(-1), E = -0.088 cm(-1). The low temperature spectrum is characterised by the pattern repeating every 60 degrees when the crystal is rotated about the high temperature c axis. The analysis shows that the Zn(II) site retains a C-2 symmetry axis and that the distortion away from the D-3 site symmetry observed for high temperatures is small, the principal axes being tilted by 2.6 degrees. This implies that the phase transition involves the flipping of the C-C backbone in one of the ethylenediamine ligands of the complex, resulting in a A delta delta delta to Lambda delta delta lambda type conformational change.

Studies on the gelation of photocatalysed dicyanate ester resins

The gel point of a dicyanate ester resin (Arocy B-10 (4-4'-dicyanato-2,2'-diphenylpropane)) heated following irradiation in the presence of the catalyst tricarbonyl cyclopentadienyl manganese (CpMn(CO)(3)) was studied using differential scanning calorimetry (d.s.c.) and dynamic rheological techniques over the temperature range 110-140 degrees C. The gel times of another commercial cyanate ester (RTX366) were also studied using independent rheological techniques, and the results agreed within experimental error. Gel times decreased linearly with increasing catalyst level and with increasing temperature according to an Arrhenius relation with activation energy of 68 +/- 6 kJmol(-1). The gel conversion was calculated by correlation of the rheological gel data to d.s.c. data to be 0.57 +/- 0.02, and differences between techniques, and between theoretical predictions, are discussed. Evidence is produced that the photocatalysed polymerization results in a greater rate of cyclotrimerization, less intramolecular cyclization and a more rigid network than the uncatalysed or metal salt-catalysed high-temperature polymerization. (C) 1997 Elsevier Science Ltd.

Coupled experimental and thermodynamic study of the Zn-Fe-Si-O system

Experimental and thermodynamic modeling studies have been carried out on the Zn-Fe-Si-O system. This research is part of a wider program to characterize zinc/lead industrial slags and sinters in the PbO-ZnO-SiO2-CaO-FeO-Fe2O3 system. Experimental investigations involve high-temperature equilibration and quenching techniques followed by electron probe X-ray microanalysis (EPMA). Liquidus temperatures and solid solubilities of the crystalline phases were measured in the temperature range from 1200 °C to 1450 °C (1473 to 1723 K) in the zinc ferrite, zincite, willemite, and tridymite primary-phase fields in the Zn-Fe-Si-O system in air. These equilibrium data for the Zn-Fe-Si-O system in air, combined with previously reported data for this system, were used to obtain an optimized self-consistent set of parameters of thermodynamic models for all phases.

Development and survival of the diamondback moth (Lepidoptera : Plutellidae) at constant and alternating temperatures

Survival and development time from egg to adult emergence of the diamondback moth, Plutella xylostella (L.), were determined at 19 constant and 14 alternating temperature regimes from 4 to 40degreesC. Plutella xylostella developed successfully front egg to adult emergence at constant temperatures from 8 to 32degreesC. At temperatures from 4 to 6degreesC or from 34 to 40degreesC, partial or complete development of individual stages or instars was possible, with third and fourth instars having the widest temperature limits. The insect developed successfully from egg to adult emergence under alternating regimes including temperatures as low as 4degreesC or as high as 38degreesC. The degree-day model, the logistic equation, and the Wang model were used to describe the relationships between temperature and development rate at both constant and alternating temperatures. The degree-day model described the relationships well from 10 to 30degreesC. The logistic equation and the Wang model fit the data well at temperatures 32degreesC. Under alternating regimes, all three models gave good simulations of development in the mid-temperature range, but only the logistic equation gave close simulations in the low temperature range, and none gave close or consistent simulations in the high temperature range. The distribution of development time was described satisfactorily by a Weibull function. These rate and time distribution functions provide tools for simulating population development of P. xylostella over a wide range of temperature conditions.

Prediction of coal ash fusion temperatures with the F*A*C*T thermodynamic computer package

This paper outlines research on the processes taking place within the coal mineral matter at high temperatures and development of the relationship between ash fusion temperatures (AFT) and phase equilibria of the coal ash slags. A new thermodynamic database for the Al-Ca-Fe-O-Si system developed by the author was used in conjunction with the thermodynamic computer package F*A*C*T for these purposes. In addition, high temperature experimental studies were undertaken that involved heat treatment and quenching of the ash cones followed by the analyses using different techniques. The study provided new information on the processes taking place during AFT test and demonstrated the validity of the AFTs predictions with F*A*C*T. Examples of practical applications of the AFT prediction method are given in the paper. The results of this study are important not only for the AFT predictions, but also in general for the application of phase equilibrium science to the characterisation of the coal mineral matter interactions at high temperature. (C) 2002 Elsevier Science Ltd. All rights reserved.

Starch degradation in 'Kensington' mango fruit following heat treatments

Changes in carbohydrate metabolism of 'Kensington' mango fruit from 2 major production regions in Queensland were measured after conditioning fruit with hot air at 40degreesC for 0, 2, 4, 8 and 16 h or at 22degreesC for 16 h (control) followed by hot-water treatment at either 45degreesC fruit-core temperature for 30 min or 47degreesC fruit-core temperature held for 15 min. Advancing physiological maturity of 'Kensington' mango fruit was correlated with increased starch concentration within the mesocarp. An alpha-amylase inhibitor was present in unripe 'Kensington' mesocarp. alpha-Amylase activity was promoted by conditioning fruit at 40degreesC for 8 h, and this enhanced enzyme activity persisted until the fruit were ripe. Consequently, starch degradation was accelerated and the concentration of total soluble solids was higher in fruit conditioned at 40degreesC for 8 h than in fruit left at the lower temperature of 22degreesC for 16 h or not conditioned. Immediately on removal of fruit from hot-water treatment, activities of alpha-amylase and phosphorylase were inhibited. This inhibition was correlated with higher starch concentration and starch layer and starch spot injuries in these fruit. A positive correlation was also found between increased sucrose concentration and greater starch loss in 40degreesC conditioned 'Kensington' fruit. It is proposed that increased sugar concentration in the mesocarp increased the level of fruit heat tolerance.

Characterization of heat tolerance in wheat cultivars and effects on production components

Abstract: There is a need for heat tolerant wheat cultivars adapted to the expansion of cultivation areas in warmer regions due to the high demand of this cereal for human consumption. The objective of this study was to evaluate the effect of high temperatures on grain yield and yield components of wheat and characterize heat tolerant wheat genotypes at different development stages. The genotypes were evaluated in the field with and without heat stress. High temperatures reduced the number of spikelets per spike (21%), number of grains per spike (39%), number of grains per spikelet (23%), 1000-grain weight (27%) and grain yield (79%). Cultivars MGS 1 Aliança, Embrapa 42, IAC 24-Tucuruí and IAC 364-Tucuruí III are the most tolerant to heat stress between the stages double ridge and terminal spikelet; MGS 1 Aliança, BRS 264, IAC 24-Tucuruí, IAC 364-Tucuruí III and VI 98053, between meiosis and anthesis; and BRS 254, IAC-24-Tucuruí, IAC-364-Tucuruí III and VI 98053, between anthesis and physiological maturity. High temperatures reduce grain yield and yield components. The number of grains per spike is the most reduced component under heat stress. The genotypes differed in tolerance to heat stress in different developmental stages.

New Steel Alloys for the Design of Heat Recovery Steam Generator Components of Combined Cycle Gas Plants

Demand for power is growing every day, mainly due to emerging economies in countries such as China, Russia, India, and Brazil. During the last 50 years steam pressure and temperature in power plants have been continuously raised to improve thermal efficiency. Recent efforts to improve efficiency leads to the development of a new generation of heat recovery steam generator, where the Benson once-through technology is applied to improve the thermal efficiency. The main purpose of this paper is to analyze the mechanical behavior of a high pressure superheater manifold by applying finite element modeling and a finite element analysis with the objective of analyzing stress propagation, leading to the study of damage mechanism, e.g., uniaxial fatigue, uniaxial creep for life prediction. The objective of this paper is also to analyze the mechanical properties of the new high temperature resistant materials in the market such as 2Cr Bainitic steels (T/P23 and T/P24) and also the 9-12Cr Martensitic steels (T/P91, T/P92, E911, and P/T122). For this study the design rules for construction of power boilers to define the geometry of the HPSH manifold were applied.

Magma flow, exsolution processes and rock metasomatism in the Great Messejana-Plasencia dyke (Iberian Peninsula)

Magma flow in dykes is still not well understood; some reported magnetic fabrics are contradictory and the potential effects of exsolution and metasomatism processes on the magnetic properties are issues open to debate. Therefore, a long dyke made of segments with different thickness, which record distinct degrees of metasomatism, the Messejana-Plasencia dyke (MPD), was studied. Oriented dolerite samples were collected along several cross-sections and characterized by means of microscopy and magnetic analyses. The results obtained show that the effects of metasomatism on rock mineralogy are important, and that the metasomatic processes can greatly influence anisotropy degree and mean susceptibility only when rocks are strongly affected by metasomatism. Petrography, scanning electron microscopy (SEM) and bulk magnetic analyses show a high-temperature oxidation-exsolution event, experienced by the very early Ti-spinels, during the early stages of magma cooling, which was mostly observed in central domains of the thick dyke segments. Exsolution reduced the grain size of the magnetic carrier (multidomain to single domain transformation), thus producing composite fabrics involving inverse fabrics. These are likely responsible for a significant number of the 'abnormal' fabrics, which make the interpretation of magma flow much more complex. By choosing to use only the 'normal' fabric for magma flow determination, we have reduced by 50 per cent the number of relevant sites. In these sites, the imbrication angle of the magnetic foliation relative to dyke wall strongly suggests flow with end-members indicating vertical-dominated flow (seven sites) and horizontal-dominated flow (three sites).