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By Günter Petzow, Hans Leo Lukas, Hans Jürgen Seifert

"The CALPHAD method (CALculation of PHAse Diagrams) has been extensively developed in the last 25 years and became a useful tool in materials science. Thermodynamic descriptions for the functions of state of unary, binary and ternary phases are derived by the optimization of phase diagrams. These functions are stored in computerized thermochemical databases and can be combined to extrapolate to multi component systems. Depending on special demand, the actually most advantagous presentations of the calculated results can be chosen: tables or in a clear graphical form as phase diagrams, phase amount diagrams or volatility diagrams. The method will be desribed by the system Ti-Si-C-N-O including the ceramic subsystem Si3N4-SiC-TiCi,N1_1,-C-N-O which is very important for the development of ceramic composites. The calculations give the thermodynamic stabilities of the condensed phases as function of temperature, concentration and partial pressure of different gas species. Adjusting the sintering conditions to these results the formation of unfavourable compounds or liquid phases can be suppressed.IntroductionThe CALculation of PHAse Diagrams (CALPHAD-method) of multicomponent systems provides the possibility to plan experiments very efficiently and avoid the experimental trial and error approach for the development of materials. The main problem for best use of calculated results is their interpretation with regard to the specific applications under consideration. Tables give the exact quantitative data for the treated phenomena. However, most important to make best use of these thermodynamic data is their graphical representation especially designed for the solution of specific problems, scientific as well as application oriented. Only well chosen graphical representations support a comprehensive understanding of the thermodynamic interrelationships and the transfer to the problem."

Jan 1, 1996

By H. P. Wang, E. M. Perry

"Analytical solutions for investigating the solidification of casting problems with initial superheat and natural boundary conditions have been derived using an integral method. There are two moving interfaces in the solution field, one for the phase change line and the other for the superheat line. Two coupled nonlinear differential equations, representing two moving layers, were calculated by the Runge-Kutta numerical integration scheme. The solutions are in terms of six dimensionless parameters: phase change number, two Biot numbers for interfaces, diffusivity ratio, and dimensionless superheat temperature and time. Parametric studies on these parameters have been conducted to provide generic information about this phase change problem. This analytical information is extremely useful for validating numerical solutions. A simplified I-D finite element model was constructed for the purpose of comparison. The excellent agreement between the analytical and finite element solutions has proven that they are mutually validated.This validated finite element modeling tool was then used for modeling an investment casting process of a super-alloy with a simple geometry: a two-step plate. The nonlinear latent heat release, a common property of alloy materials, was approximated by several piecewise linear segments. The transient temperature response of this 2-D finite element solution, including a metal/mold gap resistance, shows excellent agreement with experimental data.This fundamental work provides a solid basis for further work on the development of a process modeling tool for the complex investment casting process.IntroductionAt present, the investment casting process is used in a variety of industries. In the aircraft engine industry, in particular, investment casting is used to produce parts ranging from turbine blades to engine frames. Because a large single casting can replace many component parts that require machining, fabrication, and assembly, this one-piece casting approach becomes a very cost-effective manufacturing process.The main constraint in using this process for mass production is the long design-to-production lead time. The standard rigging design is still an art, based on the experience of casting experts, rather than on scientific methods. Many trials are often required before making a sound final casting. In order to .reduce the number of expensive casting trials, the development of computer-aided tooling technology is needed.The fundamental physics describing this manufacturing process can be simply described. They reduce to a solid/liquid phase change problem, with two parts - first, the thermal balance of the initial superheat temperature of the molten metal and the preheat temperature of the ceramic shell through heat conduction, and second, the energy release from the mold surface to the ambient by radiation."

Jan 1, 1986

By Anja Pfennig, Thomas Böllinghaus, Marcus Wolf

During CCS components are exposed to a corrosive environment and mechanical stress which results in corrosion fatigue and is inevitably followed by the lifetime reduction of these components. The lifetime reduction of the cyclically loaded high alloyed stainless injectionpipe steel AISI 420C (X46Cr13, 1.4034) constantly exposed to highly corrosive CO2- saturated hot thermal water is demonstrated in in-situ-laboratory experiments (T = 60 °C, brine: Stuttgart Aquifer, flow rate: 30 l/h, CO2) in an environment similar to the on-shore CCS-site in the Northern German Bassin. In-situ tension-compression experiments were established simultaneously along with electrochemical measurements using a newly designed corrosion chamber in a resonant testing machine at a frequency as low as 30 – 40 Hz. In addition technical CO2 was introduced into the closed system at a rate close to 9 L/h. S-N plots, micrographic analysis and surface analysis of the fracture surface are demonstrated. X46Cr13 (surface roughness Rz = 4) reached the maximum number of cycles (12.5 x 106) at stress amplitude of 173 MPa producing a low scatter range of 1:3.5. Hydroxide and siderite layers were found on pits and crack surfaces. No typical fatigue limit exists. Pit corrosion prior to crack initiation may be identified as failure cause.

Jan 1, 2016

By Marco Olper

After two years of extensive research a new and innovative modification to the CX-EW process has been exploited. This process, called CX-EWS, avoids completely all the critical aspects of the previous process which affected the cost of the energy, of the chemicals and of The maintenance of the insoluble anodes. All these benefits reflect a saving of about 30% of The operating costs compared to the present traditional production and allow for a total operating costs of less than 6.5 cts/lb. lead (net of raw material cost). With this new technology it is allowed for the first time the treatment in the same plant facilities of both primary lead sulphide concentrate and spent batteries. The paper describes the technical and economical aspect of the new process with a feasibility study for 150,000 t/y spent battery facility throughput.

Jan 1, 1995

By E. J. Peterson

Oil shale retorting induces mineral and chemical reactions to occur on the macroscopic and microscopic levels in the kerogen-bearing marlstone. The nature and extent of the reactions is dependent upon process variables such as maximum temperature, time at temperature, atmosphere, and raw shale composition. This report describes the investigation of the mineral, chemical, and trace element release properties of spent shales retrieved from an experimental in situ retort at Occidental Oil Shale, Inc. 's Logan Wash site in Garfield County, Colorado. Correlation between mineralogy of the spent materials and the mobility of major, minor, and trace elements are indicated, and relationships with important process parameters are discussed. The progress .of carbonate decomposition reactions and silicat ion reactions is indicative of the processing conditions experienced by the shale materials and influences the mobility of major, minor, and trace elements when the solids are contacted by water. Shale minerals that are exposed to the extreme conditions reached in underground retorting form high temperature product phases including akermanite-gehlenite and diopside-augite solid solutions, kalsilite, monticellite, and forsterite. The persistence of relatively thermally stable phases, such as quartz, orthoclase, and albite provide insight into the extremes of processing conditions experienced by the spent shales. Leachate compositions suggest that several trace elements, including vanadium, boron, fluoride, and arsenic are not rendered immobile by the formation of the high-temperature silicate produce phase akermanite-gehlenite.

Jan 1, 1981

By William Petruk

A fully automatic image analysis system that consists of a microprobe, an energy dispersive x-ray analyzer, and an image analyzer was developed at CANME:I' to determine mineral behaviour that affects beneficiation. The interlacing between the instruments permits automatic identification and characterization of minerals in samples of unbroken ore pieces and of mill products. Different types of information are obtained for minerals in samples of unbroken ore pieces than in samples of mill products, and are used differently. For unbroken ore pieces size distributions are determined for discrete mineral grains to predict a grind at which they might be liberated, and other measurements are Irade to predict the percentage of mineral that occurs as nonrecoverable grains. For mill products the minerals are analysed to determine percentages that (1) are free, (2) are likely to be recovered in concentrates, (3) are likely to be lost to tailings, and (4) could be liberated with regrinding. The image analysis data for mill products are processed by a mineral-metals balance program to determine the distributions of free and unliberated mineral grains at each point in a concentrator, pilot plant or bench test. For samples containing trace minerals, such as gold, an automatic search technique is used to scan the entire area of the polished section for the trace mineral grains. The identified trace mineral grains are characterized with regard to size, liberation, and other properties.

Jan 1, 1988

By José Luiz Rodrigues Bravo

The production of electrolytic copper with assured quality corresponding to international standards, in a conventional electrorefkery of a custom smelter, is a hard and cautious task, if no advanced technologies for selective control of electrolyte impurities are available. The improper control of the amount of As , Sb and Bi in the anode that enter the tankhouse , attributable either to a bad schedule of concentrate input or to the unavailability of clean concentrates in the international market , as well as the lack of means to maintain the suitable level of these elements in the electrolyte together with other operational circumstances, can result in off-grade copper, as well as affect the starting sheet chemically and physically. This paper presents in a practical way the relationship between the operational conditions and the cathode and starting sheet quality produced at CMSA, covering the period of the last five years of operation, discusses the technologies available in the market for antimony and bismuth removal and compare the results of testwork, achieved in the laboratories of CMSA, using two resins not associated with patented technologies.

Jan 1, 1997

By Jilai Xue, Jun Zhu, Baisong Li

"TiB2-C/C Function Gradient Materials (FGM) is used in cathode materials to improve aluminum wettability and melt penetration in aluminum electrolysis. In this investigation, FGM was tested for use as part of the cathode materials, where a 10 mm thick TiB2-rich layer was on the top as an Al-wettable surface, the TiB2-C layers in the middle as a gradient layer and the carbon on the bottom as a base. Electrical resistances ofFGM were determined in the temperature range of25- 9600C in argon atmosphere. The results show that the present of TiB2-C gradient layer can reduce the open porosity and the electrical resistance of the cathodes materials at elevated temperatures. The cathode samples after aluminum electrolysis usually demonstrates an increase in electrical resistance, but the application of FGM layer can compensate such an increase for certain extend due to less variation in porosity and lower the level of melts penetration.IntroductionCarbon is still used for aluminum reduction cathodes dominantly, but it has a poor wetting properties by liquid aluminum and the anode-cathode distance has to be kept about 4-5cm with an additional 1.3-2.0 V voltage drop [l]. TiB2 has better wettability by liquid aluminum with higher electrical conductivity and stronger chemical resistance to the electrolyte attack. And the wettability ofTiB2-C composites cathode on liquid aluminum can be also improved, while liquid aluminum can completely wet the cathode surface ifTiB2 content exceeds 27% [2-4]. However, during the process of TiB2-C composites cathodes preparation and aluminum electrolysis, the deformation by temperature variation or sodium penetration are great disparity between TiB2 and carbon due to their physical properties difference. This will accelerate the cathodes cracking and deterioration."

Jan 1, 2013

By B. Zeytuncu, O. Yucel, O. H. Celik, M. H. Morcali

"The Taguchi method was used as the experimental design to determine the optimum conditions of cementation behavior of the ruthenium chloride solution. Cementation was carried out using metallic zinc powder. The experimental conditions were studied in the range of 25-45°C for reaction temperature (A), 30--60 min for reaction time (B), 0.5-1.5 for pH of solution (C), and 30--50 mg for zinc powder (D). Experimental parameters and their levels were determined in the light of preliminary tests. Orthogonal array (OA) L9(34) consisting of four parameters each with three levels, was chosen. The optimal conditions found for ruthenium, such as a reaction temperature, reaction time, pH of the solution and mass of zinc, are respectively: 45°C, 45 min, 1.5 and 50 mg. Under these conditions, the ruthenium cementation efficiency obtained by theoretically and experimentally was in good agreement, which were 99.8% and 99.7% respectively."

Jan 1, 2013

By Baozhong Zhao

Experimental results have shown that fluxing with soda ash (Na:zC03) can remove As and Sb from molten copper at the rate of As>Sb, but is relatively ineffective in removing Hi. The rate of impurity removal is controlled by impurity mass transfer in the metal phase. In this paper, a mathematical model was developed to describe the impurity removal phenomena. The model incorporates the effects of molten bath mixing intensity, soda ash feeding rate, oxygen content in the molten copper and soda ash fluxing by surface addition and injection. The model predictions are in good agreement with experimental results and may be used in designing large scale tests.

Jan 1, 1996

By Wenbo Luo, Kang Liu, Fusheng Mao, Jilai Xue, Jun Zhu, Chunlei Yang

Extracting alumina from coal fly ash (CFA) is of great interest for both environmental protection and recycling valuable alumina content. In this study, ultrasonic aided leaching process as an effective method was investigated to enhance extracting Al2O3 from CFA via concentrated sulfuric acid sintering. The influence of ultrasonic power and processing time were tested under the conditions as the same as those without ultrasound. It is found that the alumina extraction rate can reach 90.5 % with ultrasound assistance, while the ultrasonic treatment can reduce almost 15 ~ 30 min in leaching time and 5 ~ 10 oC in leaching temperature than those without ultrasonic operation at the same Al2O3 extraction rate. In addition, the ultrasonic can reduce calcium content by 6 ~ 8 % dissolved into the leaching liquid. SEM analysis also shows that the residue particle size with ultrasound is smaller than that without ultrasonic treatment.

Jan 1, 2015

By Robert Mensah-Biney

The loading characteristics of gold-tetrabromide species onto a weak-base resin, PAZ-4, were evaluated using a completely mixed batch reaction system. The time. to attain equilibrium loading was substantial, on the order of several days. However, abnormally high loading capacity values of 15 to 20 meq Au/g dry resin (1000 to 1300 kgAu/tonne) were attainable in 24 hours. The loading of gold-bromo species by P AZ-4 was visualized as consisting of two processes: (i) the rapid adsorption of [AuBr4r species by simple ion exchange mechanisms and (ii) reduction of [AuBr4r to metallic gold by an electron exchange mechanism. Elution of gold from loaded resin was feasible provided the resin had not been loaded to high capacity values. If loading is carried to high levels, complete elution becomes impractical and the gold may be recovered by ashing the loaded resin. For the high loading capacities observed this option would appear to be cost effective.

Jan 1, 1991

By David G. C. Robertson

A new approach is described for the calculation of the kinetics of metal/slag, metal/slag/gas, and metal/matte/slag/gas reactions. The algorithm assumes that equilibrium is achieved at the interface between phases, and uses an equilibrium solver (such as SOLGASMIX) to compute the equilibrium state at the interface at each time step during the reaction. For multiple phase systems a number of unit operations, representing the different phases and interfaces, must be connected together in a reasonalbly complex manner, and the METSIM software package has been utilized for this purpose. The new approach is superior to the SMAK software developed by the author and his co-workers over the past decade, for the reasons discussed in this paper.

Jan 1, 1995

By J. M. Floyd

Technology in use commercially and available for commercialisation for injection processing of base and precious metals in bath reactors is surveyed and compared. Differences between bath smelting and suspension smelting systems are highlighted in relation to important smelting criteria. The factors affecting the results achievable with various tuyere and lance injection bath smelting systems are discussed in relation to the various smelting, converting and refining operations involved in copper, nickel and precious metal processing steps. Process chemistry, process dynamics and heat and mass transfer rates are discussed for the different systems.

Jan 1, 1993

By Anastasia Alksnis

Pyrrhotite is an iron deficient, low nickel content sulfide mineral that is commonly associated with pentlandite, a nickel-rich sulfide; and are both main components of the nickel ore mined in Sudbury. Pyrrhotite tailings generated in the concentration of Ni ores are stored in tailing reservoirs and presents serious environmental risks including acid mine drainage. This study investigated the potential of converting pyrrhotite into a valuable resource through the use of fluidized bed roasting, in which the mineral will be oxidized to produce iron oxide and SO2 gas. These products can then be used to create iron for high-grade steel and elemental sulfur. Thermogravimetric analysis of Sudbury pyrrhotite was performed to study the oxidation kinetics, supporting the feasibility of this process. Further, energy and materials balance was carried out to establish the basic parameters of a possible roasting process.

By Andrew Case

The Port Nickel facility in Braithwaite, Louisiana, is known for pioneering hydrometallurgical processes for the 'separation and recovery of nickel, cobalt and copper. Ten years ago, in 1985, a new CRI-MET process for the recovery of molybdenum, vanadium, nickel, cobalt and alumina from spent catalysts was developed and implemented. Spent- catalysts from the petroleum industry consietute the majority of feed. These are not only a valuable-source of metals, but due to EPA regulations are frequently classified as hazardous under RCRA. Molybdenum and vanadium are selectively leached in an oxidative hydrothermal step. Alumina is then extracted in a caustic digestive leach. The unique technology produces four primary commercial products l molybdenum trioxide, vanadium oxide, aluminum trihydrate and nickel-cobalt concentrate. This paper discusses the process, modifications. during ten years of operation, and the relationship of these modifications to the future of the catalyst recycling business.

Jan 1, 1995

By Patrick R. Taylor

Keywords: Thermal Plasma, Electroreduction, Electrolysis, Transition metals, Waste treatment, Molten oxides, Chromium oxide. An innovative process to treat transition metal oxide waste materials from diverse sources is presented. This technology involves using reverse-polarity DC plasma driven electrolysis in molten oxides. The process results in the recovery of the transition metal and other heavy metals from waste. By-products generated throughout the processing was converted to environmentally acceptable slag. The significance of this technology is that the treatment of the waste is accomplished in one step which in turn lowers the cost of remediation. Moreover, this process uses high temperature properties of thermal plasmas, which makes it possible to use molten oxides instead of halides as electrolytes. Chromium was successfully reduced from chromium oxide through the plasma driven electro-reduction process. It was shown that the selection of the appropriate ionic conducting oxides was critical for the formation of a slag that would enhance the reduction of chromium oxide.

Jan 1, 2004

By Demaerel. J. P.

Arsenic plays a major role during electroreflning of copper. Both the arsenic content in the anode and the arsenic concentration of the electrolyte have, in conjunction with other impurities such as lead, antimony, bismuth and oxygen, a direct influence on the quality of the cathode. The mechanisms are currently slime. inclusion and precipitation of insoluble compounds in the bulk of the electrolyte. Arsenic has also been reported to have a depassivating effect on the anode. An influence on the anode slime adhesion has also been found. A literature survey is given and these data are compared with and completed by our own results based on lab and pilot scale experiments as well as on Olen tank.house practice.

Jan 1, 1987

By Uday B. Pal

In the electrochemical vapor deposition (EVD) process, gaseous cation precursors are passed over one side of a porous substrate, and oxygen is passed on the other side of the substrate. The gases diffuse and react within the porous substrate, and the pores get filled with the desired solid oxide. Subsequent solid state electrochemical transport through the solid oxide in the pores continues the reaction, and the film grows over the porous substrate. The EVD process has been used to deposit lanthanum chromite interconnection films and yttria stabilized zirconia electrolyte films over porous air electrodes. The EVD growth of these solid oxide films is found to be parabolic in nature, which indicates that the solid state transport (diffusion) of ions through the film controls the growth. This solid state transport can be analyzed using Wagner's treatment of the electrochemical transport. Conductivity measurements and the information on the defect structure of the oxide can be combined with the EVD growth rate measurements to calculate the solid state transport properties (transport numbers and partial conductivities) of the rate-controlling minority species in the oxide. Using this approach, the EVD growth of other electronic, mixed conducting and ionic solid oxide films can also be analyzed.

Jan 1, 1992

By Xiangwen Wang

Electrochemical measurements associated with the electrowinning of lead metal from concentrated brine (NaCI) - lead chloride (PbCI,) electrolytes at temperatures in the range 328 to 353°K (55 - 80°C) were conducted. The electrodeposition of lead metal onto a lead rotating-disk electrode may be described by the electrodic reaction: {PbCl 4 2 + 2e- = Pb° + 4Cl-} The deposition-overpotential requirements are low (approximately 41mV per decade of current density - Am+), with a corresponding high exchange current (approximately 0.018 A.cm2). The diffusion coefficient of the electroactive PbC142- species in a 3.5 NaCl electrolyte at 353°K was insensitive to the total PbCI, concentration (0.01 to 0.1M), and its value was found to be (1.21*0.1)~10-5 cm2Is with a temperature-sensitivity coefficient (E,/R) of approximately 1.98x103K-1 (328OK(T<353OK).

Jan 1, 1993