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By Jason M. Porter, Douglas L. Porter, David L. Olson, Travis W. Koenig, Van S. Blackwood, Brajendra Mishra, Robert D. Mariani

"Traditional alloy theory models have been applied relative to the three solid phases of uranium: alpha (orthorhombic), beta (tetragonal), and mainly gamma (body centered cubic)[l]. The Darken-Gurry and Miedema models, with modifications based on concepts of Waber, Gschneidner, and Brewer have been used to predict the behavior of four types of solutes: 1) Transition associated with alloying in and containment of the uranium fuel 2) Transuranic elements in the uranium 3) Rare earth fragmentation elements (lanthanides) 4) Transition metals and other fragmentation elements. Using these solute map criteria, elemental behavior have been predicted as highly soluble, marginally soluble, or immiscible (intermetallic phase formers) and have been used to compare solute effects during uranium phase transformations. The overlapping of these solute maps are convenient first approximation tools for predicting alloy behavior.IntroductionAn investigation is in progress to determine the role of various solute elements on size and shape of the 'Y phase field range for uranium to optimize the burning and material processing of nuclear fuel is in progress. Traditional alloy theory models based on correlations to elemental electronic and crystal properties are used to predict solubility and micro structural formation. The effectiveness of this model is based on microstructure property correlations. Darken and Gurry, and Miedema models, with modifications based on concepts of Waber, Gschneidner, and Brewer, models have been used to describe solute solubility with respect to uranium based the on correlation between elemental electronic structure and uranium phases. The alpha (orthorhombic), beta (tetragonal), and gamma (body centered cubic) phases have different solubilities for specific alloy additions as a function of temperature. Using the method of Waber, ellipse diagrams classified those solutes that should have broad solubility in the allotropes of uranium[2]. The predictive diagrams are made from four different correlations:"

Jan 1, 2012

By John A. Mavrogenes

The Texaco gasification system developed at the Monte Bello pilot plant efficiently bums petroleum-coke thereby producing syn-gas and electricity. This system produces more electricity than conventional burners, yet the only by-products are pharmaceutical grade sulfur and V -rich slag. Vanadium is known to exist in multiple valence states in compounds which possess a wide range of melting points and physical properties. Consequently, it becomes important to carefully regulate oxygen fugacity throughout the system in order to control vanadium valence state. Vanadium phase equilibria is presently poorly understood, in large part because of the multiple oxidation states of vanadium (-I, 0, +2, +3, +4, and +5) and the difficulty of unequivocally identifying the valence state(s) in many compounds. The operation of these gasifiers at approximately 1400°C is well above the melting point of V20S but considerably below the melting temperature of V02 and V 203. If J02 can be regulated to keep the burner within the V 205 field, slag material would more likely remain molten and more easily flow out of the bottom of the burner. In pure V oxides. the oxidation state is readily determined by microprobe analysis. where V20S (V+5) is 56% V, V02 (V+4) is 61.4% V, and V203 (V+3) is 68% V. However, V valence in multi-element phases (especially phases containing other elements of variable valence) cannot be resolved by microprobe analysis alone. Petroleum-coke gasification slags collected from within the gasifier under different oxidation conditions were studied by electron microprobe analysis (EMPA). X-ray diffraction (XRD). X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. Raman spectrometry in conjunction with microprobe analysis was found to resolve the valence of vanadium in the phases of these slags. Raman spectra collected from homogeneous single phase V-oxide standards in vacuum at low temperatures (-150°C) yielded peaks characteristic to each valence state. Gasifier slag samples are, however, much more complicated. Oxidized samples contain: fine grained (Ca. Mg, Fe. V) oxide matrix of variable composition, (Fe. V, Ni) spinel. (Fe, AI, V, Ni, Mg) spinel, V205laths, AI-Si glass blebs and Ni sulfides. Reduced samples contain: crystalline Ca-siIicate matrix, subhedral to euhedral (V, Fe, Mg, AI) spinel, subhedral V02, Fe and Fe-Ni sulfides, Fe-Ni alloys, and complex Ca-oxide matrix. The different spinel assemblages, the characteristic V-oxides and the distinctly different character of the matrices makes the oxidized and reduced slags readily discernible.

Jan 1, 1995

By M. Cassir

"The unique properties of molten carbonates offer a large scope of applications in the field of energy. In effect, these molten salts are in the center of chemical and electrochemical reactions involving carbon and carbonaceous species, carbon dioxide and carbon monoxide, significant for energy generation or even for the production of fuels. Moreover, such media have also an oxidative character; they dissolve molecular oxygen and oxygen reduced species, O 2-, O22- and hypothetically o-, which may have an important role in waste treatments, homogeneous catalysis and synthesis of oxides. In this presentation, an overview will be given on the principal physicochemical properties of molten carbonates, before focusing on their main known application, the molten carbonate fuel cell (MCFC). Progress in other new fuel cells applications will also be analyzed, such as direct carbon fuel cell (DCFC), hybrid carbon fuel cell (HDCFC) and composite high-temperature fuel cells combining the features of MCFC and solid oxide fuel cell (SOFC). Afterwards, membranes for the separation and capture of C02 will be reviewed. Finally, other topics, as the oxidative coupling of methane in molten carbonates, will be briefly mentioned.IntroductionIn the thirty past years, the molten carbonate science and advances have been mainly dedicated to the understanding and optimization of the molten carbonate fuel cell (MCFC), which is still a major issue in the heart of a new vision of energy development. More recently, new topics related to other kinds of fuel cells (DCFC, composite SOFC/MCFC systems) and C02 capture have emerged and are concentrating important research and technological efforts. Moreover, new fields of implementation, related to molten carbonates, are also present: geology, glasses, production of nanocarbon particles etc. Considering other areas where this molten phase plays a major role, such as catalysis, waste destruction, surface treatment, it can be confirmed that the field of molten carbonates is very rich and offers many opportunities for fundamental science and competitive applications. Whatever their specific application, molten carbonates activity is associated to more efficient energy systems with low production of C02 and, in a prospective sense, to non-polluting energy using the value of C02. A recent event, the International Workshop on Molten Carbonates & Related Topics, IWMC201 I, held in Paris in 2011 , have put in evidence the importance to improve and exploit this investigation and technological domain."

Jan 1, 2012

By J. H. Huang

In this investigation, the selective precipitation of cobalt and molybdenum from Co-Mo aqueous solutions was studied in order to recover efficiently valuable elements from industrial effluents generated from a novel electrodeposition of nanocrystalline Co-based alloys process and reduce the effluent impact on environment. It was found that the behavior of cobalt in aqueous solutions was substantially affected by the presence of molybdenum. When adding 11.6 to 46.6g/L molybdenum to a 50g/L cobalt solution, the co-precipitation of molybdenum and cobalt started to occur at pH value of 3-4. However, without the presence of molybdenum, cobalt could only be precipitated out of the solution at about pH 6. Most of the molybdenum was found in the solid phase when the solution pH reached 5. After further increasing pH to greater than 7, the molybdenum dissolved back into the solution. Cobalt kept precipitating as the pH increased. When the pH was greater than 7, most of the cobalt was present in the solid phase. The chemical and physical characteristics of the precipitated materials were investigated by SEM, XRD, AAS and EDX. It was revealed that the precipitate was initially present as cobalt molybdate oxide hydrate and subsequently transformed as sodium cobalt molybdenum oxide. With further increasing the solution pH, the precipitate was transformed into cobalt hydroxide. Further investigation implied that most of molybdenum was chemically tied to the precipitate produced at the low pH, yet at the same time, physically entrapped at the high pH. The paper also presents the influence of reaction temperature and time on the precipitation process and kinetics.

Jan 1, 2003

By Jr. Napolitano, Jr. Sanders

"Morphological evolution of a dendritic growth front in a binary alloy is simulated using a cellular automaton approach to establish the feasibility of modeling such growth with a local rule-based scheme. The motivation for this work is derived from the need to predict the development of solidification structures within real components of complex geometry, where significant constraint of the thermal and solutal fields may exist. Such cases present complex boundaries and large domain sizes, which may preclude the effective use of more conventional methods. In this work, a model is presented which couples a two-dimensional alternate-direction-implicit finite-difference diffusion solution with a cellular automaton growth algorithm to simulate morphological evolution in alloys solidifying under directional growth conditions. Temperature, composition, and interface curvature are incorporated into a local growth potential which is used by the automaton, allowing the interface to evolve. Alloy solidification is simulated over a range of experimental conditions, producing various structures. Issues addressed include morphological instability, primary spacing selection, interface curvature, microsegregation, and tip conditions.IntroductionThe development of dendritic structure plays an essential role in alloy solidification. Virtually every microstructural feature, within a cast alloy component, is related to the interface morphology present during solidification. Conventional solidification theory, describing dendrite tip kinetics and mushy zone phenomena, provides a means for estimating overall microstructural parameters for an alloy solidified under steady-state conditions. Microstructural prediction for actual components, which are finite in size and complex in geometry, requires a description of the evolution of the interface morphology under transient conditions and geometrical constraint and an understanding of how the structure propagates through the mold. Any useful simulation tool must be equipped to handle these circumstances within the limits of computational feasibility."

Jan 1, 1998

By Xingye Guo, Yeon-Gil Jung, James Knapp, Zhe Lu, Jing Zhang, Li Li

La2Zr2O7 is a promising thermal barrier coating material due to its low thermal conductivity and superior high temperature stability. In this work, Bilayer La2Zr2O7 and conventional 8 wt% yttria stabilized zirconia (8YSZ) coatings were deposited using plasma spray technique. Both singlelayer La2Zr2O7 and double-layer 8YSZ/La2Zr2O7 coating architectures were designed. Thermal cycling and thermal shock tests were used to evaluate coatings’ thermomechanical properties. All La2Zr2O7 coats were delaminated in the furnace cycle test in less than 20 cycles. This is because residual thermal stresses accumulated during thermal cycling. In the jet engine thermal shock (JETS) tests, the SCL La2Zr2O7 and DCL dense 8YSZ/La2Zr2O7 coatings were fully delaminated. In contrast, the DCL porous 8YSZ/La2Zr2O7 coating sample only partially delaminated on the edge. This is because of the porous 8YSZ layer provides strain compliance. The findings will help to propose efficient thermal barrier coating systems.

Jan 1, 2016

By Cong Wang, Kexin Jiao, Yongan Zhao, Haibin Zuo, Jianliang Zhang

The carbon composite brick is a new refractory used in blast furnace hearth and bottom. It caused wide attention due to its high thermal conductivity and low erosion by molten iron. In this paper, chemical constituents, SEM-EDS and X-ray diffraction were carried out in order to understand reaction mechanisms. A series of experiments of oxidation resistance characteristics were made. The oxidation mechanisms of carbon composite bricks in the presence of air were analyzed. According to the analysis on many experimental results, the oxidation process of carbon composite bricks under different temperatures were controlled by different mechanisms. In the condition of high temperature, SiO2 as oxidation product hindered the diffusion of O2, and reduced the oxidation loss of graphite in the internal.

Jan 1, 2015

By Gaifeng Xue, Xiaohong Xu, Meng Liu, Yijie Song, Guotao Xu, Jixiong Liu

BN (Boron Nitride) based composites were prepared with hot-pressing by using h-BN as main material in ceramic preparation process. The relative density, bending strength, vickers’ hardness, thermal shock resistance, thermal expansion coefficient, thermal conductivity, phase composition and microstructure were tested and analyzed by using modern testing technology. The results indicate that the best formula is B, the relative density is 97%, the bending strength is 260 MPa, the hardness is HV5 343kg/mm2, the thermal expansion coefficient is 2.8×10-6℃-1, the thermal conductivity is 22 W/(m.K) and have no crack after thermal shock for 20 times by water cool. XRD analysis indicates that the main phase compositions are h-BN, β-Si3N4 and sialon. SEM studies show that the grains wrapped up by solid solution.

Jan 1, 2015

By V. I. Lakshmanan

Whilst the prices of metals in nominal terms have largely remained static over the past forty years, in real terms, the primary metals industry receives very much less today for its products than in the past. Yet, it has largely managed to remain competitive, despite the fact that ore reserves are not only diminishing, but are of lower grade and higher complexity, and that there are much greater pressures on companies to be good environmental stewards. This paper examines how hydrometallurgical processing has shown itself to be highly innovative in order to remain viable both economically and environmentally. Aspects of process chemistry are discussed, and the lessons to be learned from having a good understanding of this chemistry are highlighted with reference to a number of case histories such as HPAL for nickel laterites, the Avmin/Chambishi Cosac Project, use of chloride chemistry for titanium extraction, and plant effluent treatment and recycle.

Jan 1, 2003

By P. D. Ferro

The direct oxide reduction (DOR) of plutonium oxide generates significant amounts of contaminated waste. This waste primarily consists of calcium oxide-saturated calcium chloride salt. This investigation explores the possibility of recycling the salt, by the electroreduction of the calcium oxide. Fused salt electrolysis of a simulated salt mix (CaC12 + ~10 wt. pct. CaO) is being carried out to electrowin calcium, and the process is being optimized in terms of the calcium solubility, cell temperature, current density and cell design to maximize the current efficiency. This work identifies the major concerns in the development of a process to electrowin calcium from this simulated salt mix.

Jan 1, 1992

By V. V. Khristenko, V. I. Dubodelov, V. A. Seredenko, B. A. Kyryyevsky, H. V. Seredenko

"During the last decades investigators of many countries shows an increased interest to alloys which are characterized by miscibility gap in a liquid state. It is connected with essential possibilities of control of structurization in such alloys because of the melt at certain temperature parameters is · emulsion with disperse phase inclusions. These ensure essential influence ·on structurizations.The certain inclusions can play a role of lubrication ensuring ""wearless"" process. The sizes of inclusions of this phase can be rather large proportional to sizes of strengthening phase (up to 1000 nm). Other inclusions ensure process of strengthening of a main material. In this case requests to a dispersibility character of distribution and structure of such inclusions are much higher.The multicomponent alloys of system of copper - (Fe - Cr - C)- alloy concern to the number of advanced compositions. The copper alloys with structure of a type of a ""frozen emulsion"" in which strengthening phase· is a chromium pig-iron are characterized by high thermal stability in the extreme operating conditions. The mechanism of inclusions forming is emulsifying of a melt in miscibility gap at temperatures close to temperature of binodal under superimposition of external effects.The main complexity of producing of ware from such alloys is .a providing in their structure of necessary dispersible inclusions uniformly distributed all over the volume. Thanks to a selective action of electromagnetic fields on liquid phases with various electroconductivity relative velocity of phases is created and is regulated the ratio of their ""apparent"" specific gravity is changed. Excitation of pulsing force effects with the certain frequency on interphase surface allow actively to influence on process of a dispersion of a liquid metal medium."

Jan 1, 2000

By David J. Roha

"The harsh environment of the Carbothermic Aluminum process makes necessary numerical modeling as a means of process visualization and understanding. A brief survey of the various numerical models, with emphasis on CFD, applied in the development of the process is presented.IntroductionThe environment of the Alcoa Carbothermic reactor is necessarily a harsh one, with temperatures approaching 2100 °C and plenty of reactive dust and vapors. As such, it is difficult to directly observe what is actually taking place. Thermocouples can last for a few minutes but are eventually destroyed. The openings to optical pyrometers become occluded with dust and condensation. Graphite sheathing embrittles, reacts away or becomes clogged with condensate. Dip-samples on steel rods are routinely taken, but their interpretation is often unclear.Those measurements that can be reliably taken are invaluable, but often do not provide a complete picture. Therefore from the very inception of the project both physical and computer based models have played an important role. Modeling provides an intuitive understanding of the processes that might be taking place and in very many cases approach quantitative prediction. I will briefly touch upon computer-based modeling performed at Alcoa over 12 years of the Carbothermic project, with special emphasis on CFD. The explanation of physical models is perhaps best left for those with the greatest familiarity with them"

Jan 1, 2012

By Thomas Niehoff

Many industrial processes require energy. Energy is required for melting or heating purposes. The heat can be generated by electrical heating or combustion/oxidation of hydrocarbons. Oxygen supports the combustion process. Oxygen is naturally contained in air with about 21 vol.-percent. The use of technical oxygen will allow an increase to the natural oxygen concentration of combustion air. Altering the combustion process by increasing the oxygen content has various effects. These effects are described and analyzed with regard to heat transfer, emissions and energy consumption. Industrial processes requiring oxyfuel are described and discussed regarding energy aspects.

Jan 1, 2008

By S. V. Subramanian

The tool material and the machine design for high speed machining are well advanced over the last decade but the steel design has lagged behind. The paper examines the design of steel in order to control the sliding tribology for high speed machining under dry machining conditions. In high speed machining of steel, accelerated chemical wear of the tool occurs once atomic contact is established at the tool-chip interface, resulting in poor tool life even with high performance tools such as cubic boron nitride. Recent research has confirmed the occurrence of nanocrystalline grains in the interfacial layer of the chip at the tool-chip contact. The volume percentage of grain boundary is increased significantly (10 to 30%) as the nanocrystalline grain size is decreased well below 30 nm. The solubility of tool material into the nanocrystalline grain boundary is two or three orders of magnitude greater than in the crystal lattice. Further the kinetics of diffusion in the grain boundary is seven or eight orders of magnitude greater than in the crystal lattice. Enhanced nanocrystalline grain boundary diffusion occurring in the interfacial layer at the tool-chip contact causes the accelerated chemical wear. Significant improvement in tool life could be achieved by engineering glassy oxide inclusions in steel, designed to self-lubricate the tool-chip interface in-situ at higher cutting speeds. Thus the control of sliding tribological condition at the tool-chip interface is key to suppress nanocrystalline layer formation at the tool-chip contact and hence prevent accelerated chemical tool wear. Sulfide inclusions are designed essentially to promote chip fracture. In addition, sulfide inclusions are designed to act as a diffusion barrier at the tool-chip interface. The application of inclusion engineering concepts to enhance the tool life in high speed machining will be demonstrated with a suitable case history.

Jan 1, 2006

By Hal dun Kurama

In thus-study, Bigadic upper zone zeolitic tuff, which contains about 87% clinoptilolite was used as an ion exchanger for removal of Pb++, Cu++, Cd++ and Hg++ ions from wastewater. Bench scale experiments with two different glass columns, were carried out continuously under the closed/ open circuit conditions. Before ion exchange tests, zeolite samples were treated with NaCI (6ml/ min. and 42BV). The effects of particle size, bed volume, pH and flow rate on the ion exchange capacity were determined. Under the best operation conditions, the effect of initial influent solution concentration on ion exchange selectivity was tested. As a-result, it was found that the Bigadiç clinoptilolite had the following ion exchange capacities;

Jan 1, 1995

By J. Riccardi

Copper refineries use massive copper castings as moulds into which impure molten copper from the reverberatory furnace is poured to form anodes for further electrolytic refining. To facilitate removal of the copper anodes from the mould and to prolong the life of the mould itself, it is traditional to spray the mould surface prior to each use with a slurry of baryte in water. This slurry application leads to poor housekeeping, operating costs are escalated by the cost of the slurry, and additional problems in the subsequent refining process are experienced due to carry-over of excess undesirable baryte powder. A one-time application of a diffused layer of aluminum to the surface of the copper mould prior to putting the mould into service has been found to provide extended mould life and facilitate anode removal, as well as reducing baryte consumption; thereby reducing operating costs at both the anode manufacturing and refining stages.

Jan 1, 1999

By Nils Lippmann, Ulrich Weber, Siegfried Schmauder, Jr. Mishnaevsky

"A computational approach to the optimization of fracture resistance of multiphase materials (here - high speed steels) by varying their microstructure is presented. The main points of the optimization of steels are as follows: (1) development and verification of the model: numerical simulation of crack initiation and growth in real microstructures of steels, (2) computational experiment: simulation of crack growth in different idealized quasi-real microstructures and (3) the comparison of fracture resistances of different microstructures and the development of recommendations to the improvement of the fracture toughness of steels. Numerical simulations of crack growth in real microstructures of steels and different idealized carbide distributions are carried out. On the basis of the simulations, recommendations for the improvement of high speed steel microstructures are given. It is shown that the fracture resistance of the steels is much higher for the fine than for the coarse version of the same type of microstructures.IntroductionThe purpose of this work is to develop an approach to the optimal design of multiphase materials on the basis of numerical simulation of their behaviour under mechanical loading. We suggest here the following strategy:1. Collecting input data for the simulations: taking a micrograph of a microstructure, and determining mechanical properties and failure conditions of the material constituents [1, 2],2. Simulation techniques and assumptions are tested for a real microstructure of the material: crack growth in a real microstructure is simulated and then compared with the experimental data,3. Computational experiments: different microstructures of materials are tested in the numerical model under the same loading conditions. The calculated service properties of the different microstructures are compared, and recommendations are developed. As differentiated from the ""real"" experimental techniques, the computational experiment is much cheaper and not labor- and time-consuming."

Jan 1, 2001

By Brian G. Thomas

Quality problems in continuous casting of steel can be identified as they occur by monitoring mold signals (level sensor, thermocouples in the mold walls, friction etc.) and taking appropriate action (such as slowing casting speed, changing taper, changing a clogged nozzle, or later visual inspection of the surface for possible downgrading. Surface depressions and groups of deep oscillation marks form at meniscus and reduce local heat transfer as they move down the mold at the casting speed. This slows shell growth, increases shell surface temperature, and causes characteristic dips in mold thermocouple signals. More importantly, they are also associated with longitudinal cracks. Characteristic thermocouple signatures have been identified for many defects, including sticker breakouts, transverse depressions and deep oscillation marks, narrow-face bleeds, transverse comer cracks, longitudinal cracks, mold level fluctuation defects, and other problems. With the help of computational models, these mold signals should be used to troubleshoot defects, and to take appropriate corrective action. Keywords: Continuous casting, defect detection, thermocouple signals, on-line control

Jan 1, 2003

By Alan Branham

The Mike deposit is a large, low grade, oxide, gold-copper system found at the intersection of two major faults that bound the Carlin Window, Eureka County, Nevada. Disseminated gold occurs within metamorphosed and hydrothermally altered silty limestone (Silurian-Devonian Roberts Mountains Formation), beneath 182 m (600 feet) of barren Tertiary sediments and tuffs. A supergene copper oxide blanket occurs beneath and locally overlaps the lower portion of the gold zone. Decalcification argillization, silicification, and brecciation are superimposed on earlier calcsilicate hornfels and marbles. Altered dikes and sills intrude the gold zone and are locally auriferous.

Jan 1, 1995

By N. J. Tannyan

Laboratory bath smelting tests were conducted to determine the feasibility of smelting nickel- copper concentrate directly to a low iron matte in one step. Concentrate, air/oxygen and a silica flux were fed to a matte-slag bath kept in MgO crucibles at 1300°C. Various oxygen enrichments and smelting rates were used to maintain 0.5 to 2 wt"10 iron in the product matte. The slag losses are comparable to those obtained under similar industrial conditions. Due to the highly oxidizing conditions required to produce mattes with low iron contents, it is not recommended to target iron contents below about 2% in the matte. The specific bath smelting rates were equal to or higher than those in various industrial bath smelting processes.

Jan 1, 2003