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By Alan J. Hurd

"New insights into the development of microstructure in sol-gel films have recently been revealed by several diagnostic techniques, including imaging ellipsometry, ""chemical imaging"" by fluorescent tracers, light scattering from capillary waves, and finite-element modeling. The evolution of porosity during the continuous transition from dilute sol to porous solid in restricted geometries such as films and fibers is becoming clearer through fundamental understanding of evaporation dynamics and capillarity.IntroductionWith sol-gel processing, the full flexibility of solution chemistry can be exploited to make ceramic films and fibers with well controlled compositional characteristics. No less important is the ability to tune porosity and connectivity for specific applications such as optical and electrical coatings and membranes. Since the chemical and physical factors that determine the microstructure are not entirely understood, new diagnostics applied to sol-gel processing are welcome.Sol-gel films and fibers are distinguished by processing that takes a sol through continuous stages of increasing concentration and connectivity of a solid precursor. The liquid carrier is usually volatile or, at least, volatilizable through heat treatment. During deposition through states of increasing solids concentration, this sol might gel, as in bulk sol-gel processing, however, the gel state may be a fleeting transient that quickly empties of liquid. Nevertheless, the structures formed in solution during this stage influence the structure of the final solid. In particular, porosity is likely to be a remnant of networks formed in the sol-to-gel transition. Here we report on experiments whose goal is to discover the factors involved with porosity development."

Jan 1, 1994

By Ralph H. Nafziger

The Bureau of Mines, in cooperation with the Idaho National Engineering Laboratory, has electroslag melted a V-5Ti-5Cr alloy using a fused CaF2, flux. The alloy is a candidate for use in future fusion reactors. One objective of this research was to evaluate the feasibility of the electroslag melting process in separating simulated radioactive isotopes from the V alloy to demonstrate recyclability. Small amounts of Ca, Y, and Mn were added as surrogates for radioactive isotopes. Results showed that this vanadium alloy can be electroslag melted satisfactorily. The impurities added intentionally were removed or decreased successfully. Among the major alloying constituents, Cr was retained but there were some Ti losses. The latter may be controlled with process refinements. This research suggests that the electroslag melting process could be a suitable method for recycling V alloys after use in future fusion reactors, or for processing other reactive metal alloys with more immediate applications.

Jan 1, 1996

By J. Brent Hiskey, Rebecca Grace Copp

The solvent extraction of yttrium and neodymium from copper pregnant leach solutions (PLS) using Primene JM-T, a primary aliphatic amine, has been studied. Effect of contact time, pH, sulfate concentration, and extractant concentration were investigated using synthetic and actual PLS systems. Standard experimental conditions were 5 minute contact time, pH ~2.5, and 10 % v/v Primene JM-T concentration. Distribution isotherms were constructed for the pure systems and for actual copper leach solutions. Synthetic solutions contained 100 ppm Y and ~75 ppm Nd. Samples of PLS contained 2 - 10 ppm Nd and 14 - 30 ppm Y. Results showed that complete extraction of both yttrium and neodymium occurred within five minutes and at pH values greater than 1. It was also found that sulfate concentration does not inhibit extraction at any concentration. Additionally, the distribution isotherms created show that extraction for these metals can operationally take place in one stage.

Jan 1, 2016

By F. Patisson

One of the major issues with multiparticle reactors is to handle their multiscale aspect. For modeling, it usually comes to coupling a reactor model (describing the phenomena at the macroscopic scale) with a so-called grain model (simulating the behavior of a single grain or a particle). An interesting approach proposed by H.Y. Sohn (1978) is to use the law of additive reaction times in order to calculate, approximately but analytically, the reaction rate of a particle in the reactor model. Its great advantage, compared to a numerical grain model, is to drastically reduce the computation time, particularly in the case of complex reactor models. This is the approach we retained for modeling the moving bed furnace, a counter-current gas-solid reactor used in the nuclear fuel-making route for producing uranium tetrafluoride from uranium trioxide. The numerical model we developed is 2-dimensional, steady-state and based on the finite volume method. It describes solid and gas flow, convective, conductive and radiative heat transfers, and six chemical reactions involved in the process. The law of additive reaction times is used to calculate analytically the rate of the three principal gas-solid reactions at every discrete point in the reactor. We have demonstrated the validity of this approach by comparing its results with those calculated from a numerical grain model. Also detailed in the paper are the main results of the moving bed furnace model itself and the possibilities of optimizing the process revealed by the calculations.

Jan 1, 2006

By Jinqian Zhao, Jiarong Li, Shizhong Liu

"Creep cavitation of in single crystal (SX) superalloy was investigated. The constant load creep tests, in single crystal superalloys DD6, were conducted at the conditions of 800°C/700MPa, 850°C/550MPa and 900°C/450MPa, respectively. It was found that there were square facets on the stress fracture surface, and microscopic cavities in the ruptured specimens in the vicinity of the fracture surface. Both the square facets on the fracture surface and microscopic cavities in the section of the ruptured specimens show the morphology of the same thing at the different views, namely creep cavities, which are take the form of flatten cuboid. In fact, creep cavities are the longitudinally tensiled creep cracks slowly growing during the stress tensiling. The factors of creep cracks nucleation and growth conditions include: (a) enough high temperature to activate diffusion (b) casting pores as nucleation origination (c) high strains and strain rates. Eventually, the instantaneous fracture mechanism of creep specimen is cleavage fracture.IntroductionFor the materials used in elevated temperature service, creep behavior has to be accounted for. It is well recognized that creep rupture in polycrystalline materials at high temperature occurs principally by the nucleation and growth of microscopic cavities at grain boundaries, followed by microscopic cavities linkage to form micro- and eventually macro-intergranular cracks[l,2]. Without the usual grain boundaries, SX superalloys have superior capabilities at high temperatures to polycrystalline superalloys, and have become an established feature of gas turbine technology where they are commonly employed in the manufacture of high performance blades[3]. A considerable amount of work has been done over the past tens of years, and many models for nucleation and growth of creep cavities have been proposed, however, those are mainly for polycrystalline materials.In order to improve creep resistance that single crystal superalloys, in which grain boundaries are removed, have been developed. Because there don't exist grain boundaries in SX superalloy, the mechanism of nucleation and growth of creep cavities must be different from that in polycrystalline materials.Understanding the formation and characteristics of creep cavitation is crucial to model the lives of single crystal superalloys.M. Marchionni and L.G. Zhao et al. found that there were square facets on the stress fracture surface [4,5]. Roger C. Reed pointed out creep cavities lie in the necked region[6]. In this paper, the effects on the formation of creep cavities are discussed, as well as the morphology of creep cavities and fracture mechanism of SX superalloys."

Jan 1, 2013

By F. Mucciardi

With the increasing trend to continuous smelting and converting, granulation of copper matte is gaining prominence as a means of decoupling the smelting and converting operations. Moreover, granulation is also being seen as a possible avenue to using higher grade oxygen in converters. By feeding cold solid matte, the oxygen concentration can be increased to compensate for the lower enthalpy feed. This leads to a higher grade of SO2 in the off gas and a lower total flow rate. Current granulation technology relies on the cooling of a falling matte film by water jets. This technology while effective has several drawbacks including those related to safety. Noranda and McGill University have developed a new process (patent pending) for solidifying copper matte (or slag). It overcomes many of the negatives of current technology. The system is based on an air cooled twin roll caster. This: new system uses no water and instead incorporates heat pipe technology to transfer the heat from the solidifying matte to the cooling air to produce a thin strip of 1 to 2 mm in thickness. Testing of a prototype unit demonstrated its viability. This paper describes this newly developed, twin roll casting system that is completely waterless. The advantages of this process as well as the findings from several tests are also detailed.

Jan 1, 1999

By A. Filzwieser

The highest current density suitable for the electrowinning process is between 50 to 60 % of its limiting current density. One of the most important influences on the limiting current density is the thickness of the hydrodynamic boundary layer near the electrode surface. Therefore, the fluid flow in a copper electrowinning cell is calculated. The numerical simulation - using the CFD-software package FIRE® - considers all three different types of the fluid flow, namely, the natural convection, the forced convection by electrolyte circulation and the forced convection by electrochemically induced gas stirring. The simulation of natural convection is based on the different density values in the boundary layer at the electrode surface given by a density/concentration correlation. The copper concentration - linked with the current density by Faraday law - is solved by an additional transport equation. The simulation of the forced convection by the electrochemically-induced gas stirring is done by using a real two-phase calculation. That means that all differential equations are solved again for the second phase. The numerical solution of the fluid flow field is compared with the results of LDA- measurements, which were done in a special cell. The software for the LDA enabled a calculation of the void fraction possible and therefore a rough estimate of the mass transfer coefficient through the prevailing gas bubble induced convection can be made by assuming the influence of relative bubble volume.

Jan 1, 1999

By Lanre Oshinowo

The trend in process engineering is to design compact, more efficient processes, there is the paramount requirement to get the job done right the first time going from the drawing board to full-scale commercial operation. To accomplish this goal, there is also the need for tools beyond the traditional engineering toolkit to evaluate designs through virtual prototyping, thereby reducing the risks associated with making design decisions. One of the most important tools that has recently come to the forefront of process design and development is Computational Fluid Dynamics (CFD). CFD has been used at HATCH to address the key process parameters that drive the design of hydrometallurgical unit operations. This paper will detail the role of CFD at HATCH in achieving a superior level of confidence in the process design of autoclave circuits. Specifically, the optimum application of multiphase modeling including hydrodynamic, heat and mass transfer to hydrometallurgy operations, the impact of non-Newtonian slurry rheology on autoclave performance, and the challenges of optimizing the mixing of key reactants into slurries in autoclave reactors, is discussed.

Jan 1, 2003

By S. Yokoya

With increasing requirement of steel productivity and quality in continuous casting in the conventional casting system using an immersion nozzle, it is very difficult to establish a reasonable molten flow pattern. In order to overcome this difficulty, we propose a new method of imparting swirling motion onto the flow in the immersion nozzle and to control the flow pattern in the mold. Following results have been obtained during the studies. For the case of slab continuous casting mold: High amplitudes of oscillation with a period of 10 to 15 seconds are observed in the outlet flow of the immersion nozzle and meniscus flow in the conventional casting system, while these phenomena are remarkably suppressed using swirling motion in the immersion nozzle, which leads to very calm and uniform flow pattern at the outlets of the immersion nozzle, in the mold and on the meniscus in the mold; For the case of billet continuous casting mold: (1) heat and mass transfer near the meniscus can be remarkably activated compared with a conventional straight type immersion nozzle without swirl, and (2) Quite different mold flow patterns are observed between the divergent and straight immersion nozzles. Heat and mass transport in the mold using the divergent nozzle is much more reasonable compared to that of straight nozzle. The findings, mentioned above, are very useful to control the flow pattern in the slab, and billet continuous casters. Such effectiveness of swirling flow in the SEN on the mold flow has been put into practical use. As a result, remarkable progress on the quality and production of continuous casting products has been observed in practical application.

Jan 1, 2006

By Kent D. Peaslee, Lifeng Zhang, Edith Martinez, Yufeng Wang

The current study investigated the multiphase fluid flow, heat transfer, solidification of the steel, and the motion and entrapment of inclusions during the centrifugal casting process using FLUENT software. User-defined functions (UDFs) were developed to add velocity with a value related to the rotation speed and radial distance to the solidified steel, to exert a centrifugal force to the motion of inclusions, and to add the entrapment condition of inclusions at the solidifying shell and export the entrapment locations of the inclusion. The calculation shows that there are two peaks of inclusions along the thickness of the produced tube: one at close to outer surface and another one close to the inner surface of the tube. With a larger rotation speed, inclusions tend to be entrapped more towards the inner surface. The calculation agrees well with the industrial measurements.

Jan 1, 2012

By Atsushi Shibayama

The aim of this research was to develop a copper recovery process from mine tailings (0.34%Cu) using flotation followed by high-pressure oxidative leaching (HPOL) and solvent extraction. The results of HPOL using the concentrate of mine tailings obtained by flotation under the optimal conditions of the previous study shown that an efficient copper dissolution of 94.4% was achieved in an H2O media, while the copper concentration of PLS reached to be 2.9 g/L. The solvent extraction of PLS obtained from the optimal HPOL showed that 91.3% copper was recovered in stripped solution under the determined optimum conditions, in which the copper concentration achieved to be 44.8 g/L. Finally, a proposed copper recovery process from the concentrate of mine tailings was developed by combination of HPOL and solvent extraction, while a total copper recovery of 86% was achieved.

By E. A. Román

An ion exchange pilot plant, provided by Mesco Inc., was tested for antimony control in the electrolyte at three Chilean tankhouses for copper electrorefining: Chuquicamata, Potrerillos and Enami -Ventanas. The pilot plant, with a nominal extraction capacity of 1.2 kg Sb/day, worked connected to both experimental and commercial circuits, performing a total of 310 loading and elution cycles. An innovation in this process is the use of a chelating organic elution reagent, which presents some advantages over the traditional 6N HCI. This new eluent is amenable to continuous regeneration and recycling with high recovery efficiency. Antimony removal starting at initial, concentrations of 0.5 to 0.6 g/l of Sb down to steady concentrations of 0.1 to 0.0.6 g/l Sb, resulted in the production of High Grade copper cathodes with Sb contents below 0.1 ppm. Anodic slimes showed Sb contents below 1%.

Jan 1, 1999

By Cyro Takano

This paper is a contribution to fundamentals data on the equilibrium metal/slag for refining silicon in relation to Ca and Al as impurities. Silicon containing 0.1% Al and no Ca was placed in contact with a slag of various contents of CaO, SiO2 and Al2O3. Slag Al2O3 contents were 11.4%, 25.1% and 29.6%, keeping the ratio %CaO/%SiO2 constant and equal to ~0.53. The experiments were conducted at 1550oC, in a graphite crucible with argon atmosphere. The equilibrium was observed with low and medium content of Al2O3. The derived activities coefficients of Ca and Al in dilute solution of Si presented good correlation with those of the literature. Parallel reactions with formations of SiO(g) and CO (g) were also observed.

Jan 1, 2006

By A. Buzaianu, P. Motoiu, G. Popescu, C. A. Popescu, I. Rusu, A. F. Olteanu

"In recent years, the recycling magnesium metallurgy has developed new types of alloys, some of which exhibiting special electrochemical characteristics. Their application has found a fertile field in the energy conversion technologies. The paper introduces some technologic data on the recycling of aeronautical parts and scrap materials generated from the disassembling of magnesium alloy components, attempting to also solve the recycling of magnesium painted parts. The approach is meant to establish a superior quality method for recycling discarded parts or the excess of re-melting material in order to reduce environmental impact and costs. Magnesium-base alloys used as anodic materials are characterized by a high uniformity of the structural properties as well as by superior electrochemical performances, as compared to the ""classically"" used materials: Zn, Pb, etc. In nonconventional applications of magnesium alloys used as sacrificial anodes working in seawater, special alloying elements contribute to improving anodic processes. The influence of these alloying elements on magnesium sacrificial anodes was studied. It was found that the use of recycled materials in anode manufacture could reduce the Mg alloy cost by as much as up to 75% of the cost for virgin material, including the costs for the entire sequence of collection and transportation from a molding factory to a refinery, re-melting and composition adjustment.1. IntroductionMagnesium alloys are valuable materials because they exhibit low density, good forming and machining qualities, particular electrochemical properties and have a high recycling potential. There exists a false idea about the high costs of the use of magnesium alloys, partly justified by the lack of secondary materials suppliers and the insufficient knowhow in the diverse user industries to provide for an efficient substitution of conventional magnesium alloys for multipurpose applications. These circumstances have lately spurred the magnesium industry to develop new alloys and coatings and to improve processing techniques [1]. As a result, magnesium supply has greatly expanded and so have the research and development efforts to achieve complete recycling of Mg alloys.In consumer markets, magnesium is frequently selected because it helps reduce enery consumption. For example, an equal volume part made of magnesium is 23% the weight of a steel part and 64% the weight of an aluminium part."

Jan 1, 2008

By Chikabumi Yamauchi, Masami Tashiro, Toshiharu Fujisawa, Hiroyuki Snano

"Rare earth metals usually contain large amount of oxygen because of their reactiveness, and therefore oxygen removal is one of the major problems on the purification of rare earth metals. In the present research work, halide flux treatment at high temperature under inert gas atmosphere was applied to the oxygen removal from neodymium. NdF3 was used as a halide flux. Deoxidation reaction and its mechanism were discussed based on the experimental results. Halide flux treatment is very effective for oxygen removal from rare earth metals.IntroductionSolid Sate Electrotransport (SSE) process has been successfully applied for the elimination of interstitial gaseous impurities from chemically active metals[l]-[5]. However, to achieve a higher effectiveness of the SSE process, it is required a very low initial impurity content in the metal. In case of rare earth metals, it is known that they usually contain large amount of oxygen that should be lowered as much as possible before applying the SSE process. In addition, if effective oxygen removal is achieved by simple process, it is significant also from the industrial viewpoint. In the present work, the application of a halide flux treatment is investigated to remove oxygen from neodymium by using NdF3 as a flux. At first, deoxidation reaction and its mechanism were discussed based on the phase diagram of the Nd-NdF3-Ndp3 quasi-ternary system. Based on the results, oxygen content in deoxidized neodymium was calculated theoretically and it was verified by deoxidation experiments."

Jan 1, 1998

By Jianxun Song, Hongmin Zhu, Qiuyu Wang, Jungang Hou, Shuqiang Jiao, Xiaobo Zhu

This work presents the results of a study on the Ti3+/Ti2+ couple redox potentials vs. Cl–/Cl2 at the temperature range (673 to 1073 K) in fused LiCl-KCl eutectic by direct potentiometric method. Initial concentrations of TiClx in solvents did not exceed 5.0 mol%. Basic thermodynamic properties of the reactions TiCl2+1/2Cl2(g)=TiCl3 were calculated using the temperature dependencies of apparent standard potentials of the couples E* Ti3+ /Ti2+.

Jan 1, 2014

By William J. Pardee, Michael A. Shaff

"Deeper materials science knowledge from mathematical models and in situ material property sensors will be exploited in next generation factory process controllers to improve productivity and quality. These intelligent control systems will accelerate productivity growth and materials science application through the ease with which they can be modified to accept new materials knowledge and sensors. Carbonization of resin matrix carbon fiber composites, specifically, is a violent solid state chemical reaction with large stresses due to gas pressure, matrix shrinkage, and differences in thermal expansion. The matrix strength falls sharply, then rises again during the process. At least two competing reaction paths are important; the first cleaves methylene bonds, reduces toughness, density and stiffness; the second reforms those bonds, ultimately resulting in aromatic ring condensation that increases density, strength, and modulus. Since these reactions have different temperature dependencies, one can expect to shift the process towards the second path by changing the heating rate, but that change must be accomplished without producing macroscopic interlaminar crack growth. To accomplish this, we employ gas sensors to infer matrix chemical state and acoustic emission to identify microstructural changes and to recognize brittle fracture. The latter does not prevent delamination, but is important in testing models for the causes of delamination and in improving the processing cycle. This paper describes a control strategy to accelerate the process while still lowering the risk of failure.IntroductionDeeper materials science knowledge from mathematical models and in situ material property sensors will be exploited in next generation factory process controllers to improve productivity and quality. These intelligent control systems will be more easily modified to accept new materials knowledge and sensors, thus accelerating productivity growth. Such a control strategy for carbonization control is described below.Carbon-carbon composites are time consuming and costly to manufacture. Processing methods have been developed empirically and are usually very conservative because the process often fails when any change is made. Apparently minor changes in materials or geometry can produce failures that are difficult to diagnose and correct. We will describe below several essentially unavoidable sources of variability. These are best dealt with by applying materials science to adapt (i.e., closed loop control on materials properties) the process in real time to reduce the effect of unavoidable model idealizations, material variability and environmental noise. The most critical issue in control of the carbonization process control is avoiding catastrophic delamination. The strategy developed below makes use of a priori materials knowledge and real time sensors to accelerate the now very slow process without destroying the material, and without requiring unreasonable resources to determine the statistical properties of the material."

Jan 1, 1988

By James B. Pfeiffer

TETRA Technologies, Inc., has applied its HDS? metals precipitation system to control a mine drainage problem. The effluent from the mine contains primarily zinc, manganese and iron, plus varying small amounts of cadmium, copper and lead. The flow from the mine averages 350 gpm, and varies considerably depending on season and weather conditions. The plant was designed to treat 1000 gpm of the water and generate a dense sludge suitable for recycling. The HDS? system contains a number of reactors, followed by post filtration and meets stringent metals discharge criteria as specified by New Source Performance Standards.

Jan 1, 1994

By Akira Yazawa

To realize highly efficient process in extractive metallurgy, continuous operation nearly in equilibrium is preferable, but most metallurgical processes consist of plural steps with different chemical potentials. Traditional two-step process of sintering followed by reduction is continuous in each step, but is heterogeneous reaction system far from equilibrium, and the chemical potentials are varied considerably along the distance the charge travels in a reactor. This route will become old-fasioned in next century due to the various inherent problems caused especially by sintering process. To establish reasonable new smelting processes, the important tasks of the metallurgists are how to introduce feed and reacting gas in the reactor, and also how to overcome the difference in chemical potential in the reactor system. Based on the ways to solve theses tasks, recent proposals of new smelting process for copper and lead are classified and discussed with the help of sulfur-oxygen potential diagram. On such potential diagram, each equilibrium step in continuous smelting is expressed at a fixed point, and two reactors with different chemical potentials must be connected by continuous molten flow through launder or partition wall. In the latter case, the reactor is apparently single, but some technical problems must be overcome. While, in a batch smelting like converter, potential variation is successively realized along a path on chemical potential diagram with the time elapsed. To establish immediate equilibrium, continuous steady flow of reactants into well mixed reactor is indispensable. In modern smelting process, the ore is mostly supplied in the form of powder which have huge surface area and fluid character, and consequently injection process must be very attractive. Several examples are discussed for both of copper and lead smelting, and promising future technologies are suggested.

Jan 1, 1988

By A. Niedbalska

A technique was developed for low pressure diamond synthesis using a specially prepared glassy carbon. The glassy carbon is produced in the form of solid plates by slow carbonization process of phenol formaldehyde resin interrupted at temperatures of 1273° K, 1073° K, and 923° K. The diamond synthesis is performed using cobalt plates as a catalyst-solvent. Synthesis was carried out at applied pressures of 6.0 and 3.8 GPa and a temperature of 1970° K and 2170° K. The products were analyzed by the x-ray powder dyffraction method and by microprobe to identify the diamond crystallites. The samples were taken from the place of contact between the glassy carbon and the cobalt catalyst. They were separated from the charge by a chemical method. Diamonds of the best form and the largest size were obtained at pressures that were much lower than those used in the traditional graphite method of diamond synthesis.

Jan 1, 1989