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By Yiling Zhang, Paul A. Salvador, Gregory S. Rohrer

"Photocatalysis utilizes solar energy to produce hydrogen by splitting H2O. When a thin film of photocatalyst TiO2 is supported on a ferroelectric BiFeO3 substrate (band gap ~2.5 eV), the TiO2/BiFeO3 heterostructure is capable of photochemically reducing Ag+ to Ag0 in aqueous solutions under blue light with enhanced efficiency. The observation of spatially selective silver patterns on surface of the heterostructure after reaction suggests that photogenerated electrons and holes in ferroelectric BiFeO3 are driven in opposite directions to reduce their chance of recombination. Comparisons of the amounts of reduced silver on TiO2 film grains with distinct phases/orientations show that the reactivity is mildly preferential on anatase TiO2 phase and does not strongly depend on crystallographic orientation of BiFeO3.IntroductionTitania (TiO2) is capable of photocatalytically converting H2O to hydrogen and oxygen under the irradiation of ultraviolet light. [1, 2] One of the limiting factors for titania to be used as an effective photocatalyst is its band gap. Because the absorption edges of rutile and anatase titania are at 3.0 eV and 3.2 eV, respectively, they can only absorb light in the UV portion of the spectrum, which is about 3% of the available solar energy. [3-5] This limitation has motivated attempts to modify the absorption edge of titania so that it can absorb visible light.One strategy is to substitute a portion of the titanium and/or the oxygen with other atoms. There are numerous reports on visible light absorption of titania by doping and co-doping of Cr, V, Mo, Sb, Fe, N, S, C, and F. [6-34] Another strategy is to add an adsorbed molecular species that absorb visible light and donate an electron or hole to the titania, such as organic dyes [33, 35, 36] and Ce3+/Ce4+. [37, 38]The strategy in the present work takes the approach of depositing a pure titania thin film on a visible light absorbing substrate BiFeO3 to induce visible light activity of the heterostructure. BiFeO3 is a semiconductor with a band gap of about 2.5 eV [39-41] and is photocatalytically active in visible light. [42, 43] It is also ferroelectric with spontaneous polarization along pseudo-cubic <111> directions of 6.1 µC cm-2. [44] The spontaneous polarization gives rise to internal electric fields that drive photogenerated charge carriers, namely electrons and holes, in opposite directions to reduce their chance of recombination. [45-47] Additionally, the separation of electrons and holes leads to the spatial separation of reduction and oxidation half reactions so that the back reaction of intermediates is also suppressed. Such charge carrier separation has been reported in TiO2/BaTiO3 heterostructures with UV light illumination. [48-51] The TiO2/BiFeO3 heterostructures in this work combine both advantages of the relatively narrow band gap and the internal fields in BiFeO3 to enhance the overall photocatalytic activity."

Jan 1, 2014

By Qinmeng Wang

The oxygen bottom blown copper smelting process is a new technology which has been widely applied to the copper production in China. In this work, a computational thermodynamics model for this technology has been established, based on smelting mechanism and theory of Gibbs free energy minimization. The calculated results from the model agree well with the actual industrial data, indicating that the model can be used for the predictions under different operating conditions. The tendencies of the key parameters (such as Cu losses and Fe3O4 content in slag) and the distribution ratios of the minor elements (such as Pb, Zn, As, Sb and Bi) can be predicted by adjusting the oxygen/ore ratio charged into the bottom blown copper smelting furnace. The model can be used to monitor and optimize the industrial operations of the oxygen bottom blown copper smelting process.

The high pressure acid leach process (HPAL) is being commercially used in four plants around the world to treat limonitic laterites. The two major operating costs of the HPAL process are the sulphuric acid and the energy required to heat the pulp to the desired temperature (>240°C). As an alternative to acid injection and steam heating, the in-situ generation of sulphuric acid and heat, produced during the high temperature pressure oxidation of sulphur-bearing materials blended with laterites, has been investigated at the laboratory scale. Various sources of sulphur have been examined, in particular, elemental sulphur, pyrrhotite and a Cu-Ni low-grade bulk concentrate. Under the proper blend ratios, all sulphur sources tested generated sufficient acid to result in equivalent nickel and cobalt dissolutions. A significant improvement to the process economics can result from the addition of sulphur sources containing valuable by-products, such as nickellcobalt andlor precious metals (gold and PGMs). This is especially true in the latter case, when the HPAL can be operated under Platsol conditions (i.e. with the addition of 5-10g/L of chloride), to dissolve the base metals and precious metals simultaneously in the autoclave. Various examples of the application of this concept are presented, together with a brief discussion of its implication on the autoclave design and the downstream processes to recover the values from the leach solutions. Keywords: limonite, co-treatment, acid consumption, sulphur, sulphur compounds, pressure acid leach (HPAL, PAL), Platsol process

Jan 1, 2004

By Randall M. Gennan

Generally sintering is focused on the bonding of particles at high temperatures; possibly with simultaneous densification. However, an important aspect of sintering occurs during heating at relatively low temperatures where polymer processing aids are removed via control of the atmosphere, heating rate, or hold time at intennediate temperatures. New insights into burnout processes show impact from the polymenype, particle size, amount of polymer, atmosphere, part geometry, and thermal profile. This presentation focuses on the key parameters to demonstrate improved mechanical property levels are available in traditional powder metallurgy alloys by proper selection of the processing polymer and proper care in its thermal extraction. The focus is on mechanical property, where gains up to 40% are demonstrated due 10 changes in the processing polymer. Further, atmosphere control during polymer burnout provides a benefit by allowing formation of desirable carbonitrides, giving strength levels over 3 GPa (over 400 kpsi). Insight is? gleaned from powder injection molding, where high polymer contents mandate proper processing control.

Jan 1, 1996

By J. D. Law

The presence of long-lived radionuclides presents a challenge to the management of radioactive wastes. Separation of the radionuclides from the waste solutions has the potential of significantly decreasing the costs associated with the immobilization and disposal of the waste by minimizing waste volumes. Several solvent extraction processes have been developed at the Idaho National Engineering and Environmental Laboratory for the separation of transuranic elements (TRUs), 90 Sr, and/or 137 Cs from acidic radioactive waste solutions. The TRUEX and POR processes for the separation of TRUs, the SREX process for the separation of 90Sr, the cobalt dicarbollide process for the separation of 137Cs and and a universal solvent extraction process for the simultaneous separation of TRUs, 90Sr, and 137Cs have all been developed in centrifugal contactors using actual liquid radioactive waste solutions and simulated dissolved calcine waste solution. In addition, the behavior of metals with each of the solvent extraction processes was evaluated. This article summarizes the most recent results of the each of the flowsheet demonstrations and provides Information on the centrifugal contactor equipment used for the testing.

Jan 1, 1999

Cuspidine (3CaO?2SiO2?CaF2) is one of the most important compounds crystallized in mold flux films during casting in the continuous casting process of steel. The primary crystallization field of cuspidine has been experimentally developed in the CaO-SiOrCaF2-SiF4 system. The cuspidine-NaF binary and cuspidine-CaF2-NaF ternary systems have been also experimentally determined to study effects of addition of NaF on the primary field of cuspidine. In order to discuss its thermodynamic stability the standard Gibbs energy of formation of cuspidine has been determined by an electromotive force method using CaF2 as solid electrolyte and a transpiration method as follows: The chemical potential diagram and constituent activities for the CaO-Si02-CaF2 system have been evaluated based on the obtained thermodynamic data.

Jan 1, 2003

By Eddie C. Chou

Phelps Dodge, Inc. (PD) is currently developing a lateritic nicke/Vcobalt deposit in Madagascar. Hazen Research, Inc. provides technical assistance to PD to investigate recovery processes for nickel and cobalt. Various process options were evaluated in laboratory experiments and pilot plant operations. The process selected for the feasibility study consists of feed preparation, high-pressure acid leach, countercurrent decantation wash, sulfide precipitation, sulfide dissolution, solvent extraction, ion exchange, and electrowinning. Among these unit processes, high-pressure acid leach, sulfide precipitation, and sulfide dissolution are applications of pressure technologies. Process development work and design criteria for commercial operations of these unit processes are presented in this paper. Concerns related to scaling in the high-pressure acid leach and the sulfide precipitation processes are discussed. Corrosion of various metal coupons under these environments was examined.

Jan 1, 2000

By E. T. White, Dean Ilievski

"Mathematical modelling of the precipitation process requires that the kinetics of crystal growth, nucleation and agglomeration be known. This paper reviews the current state of knowledge on these precipitation sub-processes (ie. growth, nucleation and agglomeration) and describes a number of experimental techniques for estimating their kinetics. The experimental methods used to generate the precipitation data and the data analysis techniques used to extract the kinetics information from the data are discussed separately. There is no universal ""best"" technique for determining the kinetics. However, studies on multi-crystal systems are more reliable for modelling purposes than are single crystal studies. The selection of a technique will depend on which sub-processes are present. A problem with all kinetics studies is that there is generally a large uncertainty in the estimated kinetic parameters. This stems from the scatter in the experimental data being further propagated by the mathematical techniques used to extract the kinetic parameters.IntroductionCrystallisation operations, including precipitation, are widely used in a number of hydrometallurgical processes to recover a desired component or to remove an undesired impurity. The goals of industrial precipitation processes are to maximise the recovery while maintaining product quality (generally product crystal size distribution, purity and morphology and product handling properties). Knowledge of the precipitation mechanisms and kinetics is invaluable for designing new precipitators or for improving existing units. The mechanistic and kinetic information is generally incorporated into mathematical precipitator models, which are then used for process design and optimisation."

Jan 1, 1996

By Christopher Gammons

In developing countries throughout the world, gold ores are being processed by mercury amal-gamation, a technique long banned in the U.S. - unless a retort operation is used for mercury recovery - due to mercury toxicity and its effects on the environment. Amalgamation is a simple process that involves contacting a ground, slurried concentrate or ore with mercury in a slightly agitated vessel, usually for several hours, The amalgamated mercury is separated by gravity and then filtered through a fine cloth to collect the gold amalgam as a sponge, which is then fired to remove the final remnants of mercury and produce high quality gold. However, in Peru and other developing countries in South America and throughout the world, tailings are simply discarded into uncontrolled drainages and ponds and the sponge is fired in the open air. Clearly, in this case, environmental friendly and, to make matters worse, is typically conducted by family members of all ages without proper protection. Furthermore, the technique is inefficient, yielding approximately 50% gold recovery. For the past two years, faculty members from Montana Tech in Butte, MT, USA and the Universidad Nactonal del Altiplano in Puno, Peru have teamed to study the La Rinconada Mine Complex located in southern Peru approximately 100 kilometers north of Lake Titicaca and 25 kilometers west of Bolivia. The mining complex is over 5,000 meters above sea level and exists at the foot of a receding glacier in the Andes Mountains. A suite of soil and water samples collected in 2001 documented extensive Hg contamination in the Rinconada area [1]. The present paper summa¬rizes a follow-up investigation in July-2002, in which water samples were collected at numerous locations along the 200 km length of the Rio Ramis, from the Rinconada mine com¬plex to Lake Titicaca, In addition, we report new results of Hg analyses of fish from Lake Titi¬caca, The results of this study have relevance to safety and health concerns for the miners as well as people in downstream communities.

Jan 1, 2003

By Neng-Wen Yu, Miao Wang, Ji-He Wei

The mass transfer characteristic between powder particles and liquid steel in the RH-PTB (Powder Top Blowing) refining has been investigated in a water model of 1/5 scale for a 90t RH degasser. The sodium chloride powder with analytical purity has been used as the flux for blowing. The mass transfer coefficient of the liquid side has been determined under the conditions of RH-PTB process. The influences of the main technological and structural parameters on the mass transfer rate have been examined. The results indicated that under the conditions of the present work, the mass transfer coefficient on the liquid side increases with raising the lifting gas blowing rate, inner diameter of the up-snorkel, circulation rate of the liquid and particle size of powder flux. And it decreases with an increase in the inner diameter of the down-snorkel. It is in the range of (l.36-7.30) x 10·4 mis, the appropriate dimensionless relationships have been obtained as follows:

Jan 1, 2000

By F. F. Lins

There is a large use of mercury in Brazil by the gold miners in the so called "garimpos" (non registered mining operations), where it is usual to recover the gold contained in the gravity concentrates by amalgamation, which is highly deleterious to environment if not conducted properly. Unfortunately, this is a common practice there. After presenting in brief the modus operandi generally practiced in the garimpos and the environmental problems, this work reviews some of the research conducted in CETEM according to two approaches: (i) replace amalgamation by other processes and (ii) develop technology to treat mercury-contaminated soils and effluents. Conventional processes like froth flotation, to recover gold from gravity concentrates, and centrifuges were considered. Also as alternatives to amalgamation, innovative process like the recovery of gold by coal-oil agglomerates and a technology that is currently under development in our laboratory, called gold-paraffin process, are described in brief, some results presented and their potential use assessed. To reclaim sites already polluted a technology was developed to float mercury selectively from contaminated soils. The potential use of centrifuges to pre-concentrate the mercury is also discussed. The scope for applying the last techniques is to concentrate the pollutants in a small volume of mass which would be suitable for recycling or isolation from the environment. A prospective technology to treat contaminated soils, or mercury concentrates, is the immobilization of mercury by adding inorganics. Concerning the ionic mercury which may be present in effluents, precipitation of the ions and flotation of the precipitates are being studied.

Jan 1, 1994

By D. Bruce Wilson

The reaction of oxygen and solid aluminum produces the well-known surface coating of aluminum oxide, Al2O3. Thermodynamic properties and kinetic mechanisms of this reaction are extensively documented. Less well-defined are the corresponding liquid phase reaction and reactions which would be characterized. as &apos;burning&apos; of aluminum. This paper reviews the solid aluminum-oxygen reaction as a foundation for discussing the flammability of aluminum in oxygen-enriched atmospheres. Appropriate thermodYDan3ic analysis and kinetic reaction mechanisms are developed. Available models of aluminum burning are reviewed and evaluated, The appropriate information for design of engineering applications of aluminum in oxygen atmospheres? is summarized.

Jan 1, 1996

By P. N. Anyalebechi

The effects of application of steady and pulsed electric current on the cast microstructures of ingots of a 7050 type aluminum alloy have been experimentally investigated over a solidification rate range of 0.1-10 K/s. This involved the application of an electric current of 465-930 mA/cm2 of melt surface area to laboratory-size ingots solidified in a unidirectional manner. Within the ranges of electric current density and solidification rate investigated, the applied electric current reduced the average dendrite, grain, and second-phase particle size. It also made the size distribution of the second-phase particles more uniform. The mechanism for the observed refinement of the cast microstructure by the applied electric current is not well understood. The potential effects of heat-induced local convections, shear stress-induced fragmentation of dendrites, increased temperature gradient due to Joule heating and the thermal and constitutional supercooling engendered by Peltier, Thompson, and Joule heating are discussed.

Jan 1, 2009

By Omid Marzoughi

Chromium has a wide range of applications, including as an alloy addition in various steels and also as a corrosion resistance coating. Carbothermal reduction of chromite ore (FeCr2O4) in a submerged arc furnace is an important industrial process for extracting chromium, but the energy consumption is excessive. It is suggested that one area for future research is the low temperature carbothermic solid state reduction of chromite to produce an intermediate product, which can subsequently be upgraded to ferrochromium. In this regard, a thermodynamic model has been developed to investigate this process and the effects of temperature, carbon additions and ore composition on the recovery of chromium and the grade of the ferrochromium, have been studied. Further development of the model may allow it to be applied to the simulation of other processes for the recovery of chromium from chromite ores.

By M. C. Esposito

Seven pyrite samples purified from coal sources and one ore source pyrite (for comparative purposes) have been characterized by chemical and mineralogical analyses, inherent floatability, apparent specific gravity, surface area, semiconductor type, optical anisotropy, dissolution and oxidation rate. The data clearly demonstrate that pyrites from various coal sources differ not only from ore pyrite but from each other as well.

Jan 1, 1987

By Y. Z. Zhang

Cyanide has generated environmental concerns because of its toxicity, and it may not respond to the treatment of complex and refractory gold ores. Gold leaching by thiourea is one of the most promising substitutes of cyanide. However, the high reagent consumption has hindered thiourea from its commercial application in gold extraction. The process chemistry and mechanism of thiourea degradation has been discussed on the basis of chemical bonding theory, thermodynamics and electrochemistry in this paper. Progresses on the decreasing of thiourea consumption have been summarised. The potential application of thiourea in gold extraction has been evaluated.

Jan 1, 1996

By E. Dendy Sloan

An overview of hydrate properties is given, with emphasis on unusual deviations from ice, the most common solid water form. Reliable sample preparation and reproduction of in situ hydrates provide the foundation for all hydrate science and engineering. Relations are given to connect the three domains in the title: (1) micro-scopic properties measured with Raman, NMR, and diffraction spectroscopy, (2) meso-scopic properties measured with single crystals, and (3) macro-scopic properties measured with pressures, temperatures, volumes, etc. A principal illustration relates micro-scopic and macro-scopic domains. Experiments provides the basis for improving statistical thermodynamics model for these compounds. To date, this model is one of the most commonly used industrial statistical thermodynamics applications, based upon the classical model of van der Waals and Platteeuw (1959). Microscopic measurements and simulations indicate model assumption improvements, resulting in the next generation of the statistical thermodynamics for improved macroscopic property prediction.

Jan 1, 2002

By Ramana G. Reddy

Thermodynamic modeling and experimental study on impurity capacities and their distribution between mattes or metal and slags in smelting, converting and refining of non-ferrous metals was discussed. A brief review on the recent developments in copper smelting and converting is presented. The analysis showed that, copper smelting capacity increased by a factor of 10 since 60&apos;s, smelting rate increased by a factor of more than 5 and process fuel equivalent decreased by a factor of 2. A thermodynamic model for prediction of impurities capacities in slags and their distribution in mattes and slags was developed. The impurities capacities (i.e. sulfur and arsenic) of slags were calculated a priori with no adjustable parameters using the Reddy-Blander model. The capacities predictions were made in a wide range of matte and slag compositions, Pso, and temperatures in conditions pertaining to copper and lead industrial slags. The calculated results for sulfide and arsenate capacities are in good agreement with the available experimental and industrial copper and lead industrial slags data. The sulfide and arsenate capacities in copper slags (fayalite, ferrite and olivine) and lead slags are reviewed. The application of RB model predicted ratios of 02 and S2 partial pressures in industrial copper smelting processes are discussed. Application of this model for the prediction of Sb, Bi and other impurity capacities and their distribution ratios in mattes or metal and slags, in industrial smelting and refining processes is discussed.

Jan 1, 2003

By P. N. Anyalebechi

"The effects of solidification rate, initial melt hydrogen concentration, and grain refining on porosity formation in aluminum alloy 2024 have been investigated with unidirectionally cooled laboratory-size ingots. The ingots were prepared from melts containing hydrogen concentration of 0.059-0.27 cm3/100 g and solidified at 0.2-37 °C/s. As expected, the amount of porosity, average pore size, and pore number density increased with increase in melt hydrogen concentration and decrease in solidification rate. However, the effect of solidification rate was greater at the very low melt hydrogen concentration (0.059 cm3/100 g). These results are consistent with reported effects of solidification rate and melt hydrogen content on porosity formation in other aluminum alloys. Interestingly, addition of grain refiner slightly increased the amount of porosity and the average pore size, especially at solidification rates above 1°C/s. IntroductionIn shaped castings and wrought products fabricated from ingots, billets, bars, or slabs of aluminum and its alloys porosity formation is a problem. This is because it compromises their tensile strength, fracture toughness, and fatigue properties [ 1-18]. The pores are usually the crack initiation and propagation sites [6,8,9] and the largest pores tend to dictate the fatigue life of the aluminum products [9,10,14]. Porous regions within an aluminum product probably yield first due to the reduced tensile load bearing capacity, causing the concentration of the strain near the voids which subsequently results in premature fracture. In aluminum alloy ingots, billets, bars and slabs porosity formation is particularly problematic because of its persistence through fabrication and potential for reappearance or exacerbation during subsequent thermal treatment processes before and/or after fabrication [19]. In fact, persistence of microporosity is a serious problem in large thick plates of wrought aluminum alloy products that must be rolled from correspondingly large direct-chill or electromagnetic cast ingots. Some of these thick plate products are machined into large aircraft components that are required in service to withstand multi-directional stresses and to possess high fatigue strength, fracture toughness, resistance to stress corrosion cracking, and strength in the short-transverse direction [1,20]."

Jan 1, 2011

By Kenneth N. Han

Thermodynamic and kinetic aspects of nickel and cobalt leaching from metals. minerals and ores in various media have been reviewed and discussed in this paper. A kinetic model developed to delineate the leaching mechanisms for these metals has been discussed in view of experimental observations. The current review also includes the dissolution behavior of nickel and cobalt from various minerals such as oxides, sulrides. ocean floor manganese nodules, and laterites. A particular emphasis has been extended to similarities and differences of the dissolution behavior of these two metals in various media. The leaching of nickel as well as cobalt metal in acidic solutions and arnmoniacal solutions exhibits in most part mass transfer controlling. although at some pH&apos;s, chemical controlling or mixed controlling mechanisms seem to prevail. The leaching of nickel and cobalt from oxides in acids and ammoniacal solutions. on the other hand, can be described best by chemical controlling mechanisms.

Jan 1, 1993