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By D. Neuschiltz, M. Witthaut, R. Cremer

"Metastable (Ti,Al)N coatings with fee structure have been shown to exhibit superior performance as compared to TiN under conditions of wear at elevated temperatures due to their better oxidation resistance and hardness. The oxidation resistance of these coatings increases significantly with increasing Al-content. However, the deposition of (Ti,Al)N films with Ti/ Al ratios below about 30/70 leads to a hexagonal structure which is not suitable for tribological coatings. Only little is known about the location of the cubic to hexagonal phase transition and hence about the optimum composition of (Ti,Al)N hard coatings.To determine the position of this transition, Tii-xAlxN films with different Ti/Al ratios were deposited on high speed steel at substrate temperatures between 100 and 700 °C by means of reactive MSIP. The composition of the films was determined by electron probe microanalysis (EPMA) and X-ray photoelectron spectroscopy (XPS), the crystallographic structure by thin film X-ray diffraction (XRD).It could be shown that in case of deposition temperatures of 300-700 °C a two-phase region exists in the metastable TiN-AlN phase diagram, which expands with increasing temperature, wheras at 100 °C substrate temperature no two-phase region was observed. But in opposition to the phase diagram known from literature, which is based on thermodynamic estimations, the detected two-phase region is narrow for typical PVD temperatures, thus allowing the deposition of cubic single-phase Al-rich (Ti,Al)N hardcoatings for tribological applications. Based on these results, a new Ti1-xAlxN film with x = 0.62 has been developed, which showed an increase of oxidation resistance by a factor of 4."

Jan 1, 1998

By G. Kyle Green

Zirconium chlorinator residues contain an array of rare earths, scandium, unreacted coke, and radioactive thorium and radium. Because of the radioactivity, the residues must be disposed in special waste containment facilities. As these sites become more congested, and with stricter environmental regulations, disposal of large volumes of wastes may become more difficult. To reduce the mass of disposed material, the U.S. Bureau of Mines (USBM) developed technology to recover rare earths, thorium and radium, and unreacted coke from these residues. This technology employs an HCl leach to solubilize over 99% of the scandium and thorium, and over 90% of the rare earths. The leach liquor is processed through several solvent extraction stages to selectively recover scandium, thorium, and rare earths. The leach residue is further leached with an organic acid to solubilize radium, thus allowing unreacted coke to be recycled to the chlorinator. The thorium and radium waste products, which comprise only 2.1% of the original residue mass, can then be sent to the radioactive waste facility.

Jan 1, 1995

By Sylwia Zymankowska-Kumon, Rafal Danko, Mariusz Holtzer, Artur Bobrowski, Michal Kubecki

"Moulding sands with furan resin constitute constantly growing part in technologies of producing castings from iron alloys. Due to the presence of harmful substances in resins such as furfuryl alcohol, phenol and formaldehyde, using those mould sands may be hazardous to the natural environment and workers. The general assessment of harmfulness of sands used for molds and cores encompasses 2 basic points: emission of hazardous substances during processes of preparing sands, pouring mold with liquid metals (high temperatures), cooling and shaking-out; possibility of washing out hazardous substances from used sands to the environment, during storage or economic use outside foundries. We present the results of research on the assessment of harmfulness of mould sands with furan resin in the scope of the above points. The research was conducted according to the original method prepared by the authors, which has been used for years in cooperation with various foundries (Poland, abroad).IntroductionSands are used by the foundry industry to create metalcasting moulds, where the individual sand grains are typically bound using bentonite clay and carbonaceous additives or resins. During the casting process, the moulds can be exposed to temperatures as high as 1500°C depending upon the metal being poured. The molten metal causes thermal decomposition of carbonaceous additives or resins, which results in the formation of potentially hazardous organics that are emitted to the atmosphere and condense in the moulding sand [1]. The moulding sands are reclaimed within the foundry, but part of them are eventually discarded in landfills, because it is not longer suitable to make metalcasting molds [2, 3]."

Jan 1, 2013

By A. V. Tarasov

The proposed process is based on creating a controlled frothed layer of molten slag, in which fine particles of carbonaceous reductant and raw material to be processed are mixed with emulsified iron. Frothing of the slag layer without external blowing occurs as a result of intensive evolution of gaseous reduction products. The froth reaction process is maintained due to the heat of an electric arc in the slag layer. When the metal bath is heated by the arc to 1400- 1 500°C, the low temperature of the slag surface of about 1200-1 300°C is maintained due to low thermal conductivity of slag froth preventing heat loss. In order to maintain the required slag froth level and control the process temperature, air tuyeres are installed above the slag bath; blowing air serves also for oxidation of zinc in fumes and for its transportation. High adsorption and thermal insulating properties of slag froth ensure virtually complete elimination of dust and mist entrainment along with low heat losses. The main macrokinetic regularities of the carbon thermal reduction of zinc-containing slag melts have been studied under frothing conditions. The mechanism of formation of gas-slag emulsion has been identified under the conditions of reaction [C]+[O]=CO occurring locally at the slag-metal interface. It has been demonstrated that under the froth reduction conditions the zinc removal rate from the melt increases on the average by 3 to 5 times. Based on the physical and chemical data obtained, basic principles of the dezincing technology have been developed for different intermediate oxide iron-containing products produced in the process of ferrous and non-ferrous metals production.

Jan 1, 2002

By B. Wasmund, K. Adham, K. O'Keefe, C. Lee

"Metal chlorides (e.g. iron and nickel) can be pyrohydrolysed at elevated temperatures to yield an HCl rich off-gas and a metal oxide product. Typically, the high energy requirement for pyrohydrolysis is provided by the combustion of a hydrocarbon fuel with air. Here, it is demonstrated that the use of oxygen-enriched combustion can result in lower fuel requirements and higher HCl concentrations. In addition, the oxygen enrichment can result in a smaller volume of off-gas and thus, smaller and less expensive process equipment. This new concept can be applied to both the spray roaster (SR) and the fluidized bed reactor (FBR). Similar to the aircombustion case, the oxygen-enriched process can use a direct contact venturi scrubber, to recover energy from the roaster off gas, but at a higher efficiency. The new process also uses an absorption tower for capturing HCl from the roaster off-gas, but generates a stronger HCl solution than is possible with pyrohydrolysis in air.BackgroundIn recent years, the metallurgical industry has become increasingly involved with developing methods for extracting metals, upgrading products or cleaning metallic products by using hydrochloric acid. These applications of chloride metallurgy often result in metal chloride solutions, which should be processed to regenerate HCl for reuse, and to recover the metal value as a product or by-product oxide [2, 3, 4].The pyrohydrolysis of metal chloride solutions has been done in two types of air roasters: spray and fluidized bed. The existing roasters burn a hydrocarbon fuel in air, to provide the required energy for evaporating the feed solution and to provide an elevated temperature for the chloride pyrohydrolysis to occur, according to the following reactions:"

Jan 1, 2011

By Guo Chen, Xuefeng Liao, Tu Hu, Shengzhou Zhang, Hongying Xia, Jinhui Peng, Libo Zhang

Pine nut shell is as raw material for preparation of high surface area activated carbon (HSAAC) by microwave induced KOH activation. The effects of microwave power, activation duration and KOH/C mass rate (R) on the iodine adsorption capability and activated carbon yield were investigated. Additionally the surface characteristics of HSAAC were characterized by nitrogen adsorption isotherms and SEM. The operating variables were optimized utilizing the response surface methodology and were identified microwave power 738W, activation duration 17 min, and R 4, corresponding to a yield of 46.28 % and an iodine number of 2154 mg/g. The key pore structure parameters of HSAAC such as the Brunauer–Emmett–Teller (BET) surface area and total pore volume were estimated to be 3819 m2/g and 2.09 mL/g, respectively. The findings strongly support the feasibility of microwave heating for preparation of HSAAC from spent pine nut shell by microwave induced KOH activation.

Jan 1, 2016

By James W. Evans, Dong Xu, Jr. Jones

A physical (water) model based on particle image velocimetry (PIV) has been constructed at UC Berkeley. The PIV technique enables the use of water modeling to quantitatively characterize the fluid flow behavior in the mold during the continuous casting of steel, in a whole field sense, i.e., section by section. A method to obtain e\e time-averagevelocity (TA V) vector maps was developed by averaging 40 instant aneous vectc -r plots revealing the time average features of the flow. Another benefit of TAV vector maps is the ability to compare with present mathematical models, which are mostly based on the time-average technique. Bifurcated submerged entry nozzles (SEN) with ports inclined at various angles to the horizontal were used in the modeling to study their effects on the flow inside the caster. Argon was also introduced into the model to simulate the influence of argon injection on the metal delivery from the tundish into the caster. The bubble sizes and distribution (in specific sections) of argon were characterized, at the same time, by the imaging system of the PIV. This will allow for validation of current mathematical models that were developed to simulate argon injection in casters. Comparison with results calculated by the commercial finite element package FIDAP is also presented.

Jan 1, 1998

By Nieves Iglesias

The removal of the refractoriness of a gold bearing pyrite- arsenopyrite ore is studied. Flotation concentrates were prepared and leached with a dilute acidic ferric sulfate solution. The elemental sulfur film which forms on arsenopyrite in the oxidation process is not responsible for the low rate of the arsenic dissolution observed. A positive effect on the leaching rate is observed when Ag' is added. This pretreatment eliminates the refractory nature of concentrates.

Jan 1, 1993

By H. C. Roland Kammel

Stannous sulfate electrolytes are widely used nowadays in electrolytic tin production. Characteristic features of this electrolysis process are that dense cathode deposits can only be obtained by additions of organic additives and that so called ?black mud is formed on the anode surface which leads to an increase in cell-voltage. In order to prevent excessive cell-voltages or oxygen evolution the black mud has to be removed periodically. Studies in laboratory scale have been performed about the effect of different organic additives on electrolytic tin deposition and the formation of surface layers on pure and industrial tin anodes. Results reveal that organic addition agents are effective in reducing cathode roughening as well as extending the covering time of the anode ?by black muds.

Jan 1, 1985

By Guanghui Li, Xuling Chen, Zhiyun Ji, Min Gan, Tao Jiang, Xiaohui Fan, Zhiyuan Yu

With the increase of proportion of biochar(without modified) replacing coke breeze, the physical strength of sinter decreases due to the faster burning speed of biochar. An investigation upon passivating biochar with boric acid was then conducted to strengthen sintering in this paper. A layer of thin film of B2O3 distributed in the surface of biochar was observed, which could reduce the contact between reaction gas and biochar. So the burning speed of biochar was decreased properly after passivation, and the combustion efficiency increased due to the inhibition of carbon gasification. The comprehensive effects of above changes could increase the maximum temperature of sintering bed, which facilitated to the mineralization of sintering mixtures. Eventually sintering indices got reinforced. Thus the indices of sinter as applying 40% passivated biochar were comparable with that of 100% coke breeze.

Jan 1, 2015

By R. Hurman Eric

The dew-point technique of activity measurements take advantage of the volatility of a component in solution. The pressure of the volatile component over a sample is determined from observations of the temperature at which condensation of the vapor occurs. The method is applicable best when the vapor pressure of the components would differ by about two to three orders of magnitude. Experimentally, this is a closed system involving the use of evacuated and sealed transparent quartz sample probes. Furthermore reliable vapor pressure data of the volatile component is essential along with a specialized high temperature furnace capable of giving reproducible results. In this context, the vertical Dew-Point Furnace (DPF) was designed and built after elaborate trails until enough proficiency was gained for reproducible results. Over the years the DPF was modified and improved. The DPF developed was versatile and could easily be used for activity measurements in the isopiestic mode (another method of measuring activities of a volatile component in a solution). The necessary ancillary systems; namely evacuation-flushing-evacuation followed by sealing of quartz sample probes under vacuum were also perfected over the years. As and when necessary the dew-point technique was supplemented by classical equilibration-quenching method employed on the sealed quartz sample probes to reveal necessary phase equilibrium information. The following were studied utilizing the above technique: (i) Activities in CU2S-PbS and FeS-PbS binaries and CU2S-FeS- PbS ternary at 1200°C; (ii) Activities in Cu2S-SnS and FeS-SnS binaries and Cu2S-FeS-SnS ternary at I200°C; (iii) Phase equilibria and thermodynamic in Cu-Pb-S, Fe-Pb-S, Fe-Sn-S, Cu-Sn-S and Ag-Sn-S systems. Most recently the following systems have been tackled: (i) Phase equilibria and thermodynamics in the Ag-Pb-S and Sn-Pb-S systems; and (ii) Activities in Ag2S-FeS-CuzS-PbS quaternary at 1200°C.

Jan 1, 2003

By B. Q. Li

A numerical study of the developing fluid flow and thermal aspects during the staning phase of aluminum continuous casting processes is presented. The deforming finite element method, coupled with a quasi-Lagrangian formulation, is used to represent the growth of an ingot and the dynamic fluid flow and thermal behavior that evolves in the growing ingot. The mathematical formulation of the problem and the numerical treatment are discussed. The algorithm solves the free moving nodes as part of total unknowns with an automatic time step control for time integration. This permits an optimal computing efficiency while still keeping the computational errors under control. A selection of the results obtained using the algorithm is presented. The results are concerned with the evolution of fluid flow, temperature and solidification phenomena during a DC round ingot casting process, as it evolves from the beginning of casting operation to a steady state. These results show that the time-varying, complex fluid flow and thermal phenomena during continuous casting processes can be very well represented by the computational algorithm. The results also illustrate that, during the casting process, ~e fluid flow and temperature fields change drastically at the initial stage but evolve slowly afterwards

Jan 1, 1993

By May Nyman

Due to the vast diversity of chemical media in which metal separations are executed, a wide range of ion separation materials are employed, This ,results in an ongoing effort to discover new phases with novel ion exchange properties. We present here the synthesis of a novel class at, thermally and chemically stable microporous, niobate-based materials. Ion exchange studies show these new phases are highly selective for Sr2+ and other bivalent metals.

Jan 1, 1999

By R. Hurman Eric

The dew-point technique of activity measurements take advantage of the volatility of a component in solution. The pressure of the volatile component over a sample is determined from observations of the temperature at which condensation of the vapor occurs. The method is applicable best when the vapor pressure of the components would differ by about two to three orders of magnitude. Experimentally, this is a closed system involving the use of evacuated and sealed transparent quartz sample probes. Furthermore reliable vapor pressure data of the volatile component is essential along with a specialized high temperature furnace capable of giving reproducible results. In this context, the vertical Dew-Point Furnace (DPF) was designed and built after elaborate trails until enough proficiency was gained for reprodueible results. Over the years the DPF was modified and improved. The DPF developed was versatile and could easily be used for activity measurements in the isopiestic mode (another method of measuring activities of a volatile component in a solution). The necessary ancillary systems; namely evacuation-flushing-evacuation followed by sealing of quartz sample probes under vacuum were also perfected over the years. As and when necessary the dew-point technique was supplemented by classical equilibration-quenching method employed on the sealed quartz sample probes to reveal necessary phase equilibrium information. The following were studied utilizing the above technique: (i) Activities in CuzS-PbS and FeS-PbS binaries and CU2S-FeS- PbS ternary at 1200°C; (ii) Activities in CuzS-SnS and FeS-SnS binaries and Cu2S-FeS-SnS ternary at 1200°C; (iii) Phase equilibria and thennodynamic in Cu-Pb-S, Fe-Pb-S, Fe-Sn-S, Cu-Sn-S and Ag-Sn-S systems. Most recently the following systems have been tackled: (i) Phase equilibria and thennodynamics in the Ag-Pb-S and Sn-Pb-S systems; and (ii) Activities in Ag2S-FeS-CuzS-PbS quaternary at 1200°C.

Jan 1, 2003

By Yasumasa Hattori

Fluid flow in a flash furnace concentrate burner was investigated quantitatively in order to improve burner performance. Computational fluid dynamics was utilized for researching fluid flow in a burner port mathematically then its results were reviewed in the commercial flash furnace burner and its calculation results were found to be in good agreement with the actual measurement results. Based on those results, a mathematical fluid flow model for the Sumitomo flash furnace concentrate burner has been developed so as, to improve premixing and combustion efficiency of concentrate in the reaction shaft.

Jan 1, 2002

By Adrian C. Deneys, David G. C. Robertson

"Fluid flow phenomena on the surface of a molten slag have been documented using video photography in a laboratory scale D.C. arc furnace. The flow on the surface of the slag appeared to be electromagnetically influenced. This was confirmed by varying the position of the anode, which changed the direction of flow on the surface of the slag. Temperature measurements in the bath also confirmed the change in the directional nature of the fluid flow induced by the arc.During some periods, solids were fed into the arc attachment zone (AAZ) down the center of the hollow graphite electrode. Significant movement of the arc around the basal annular surface of the hollow electrode takes place. The point of attachment of an arc on a hollow electrode was more variable than an arc attached to a solid graphite electrode. Video images showed that the solids were rapidly incorporated into the bulk of the slag. Temperature measurements confirmed the existence of a superheated slag layer at the slag-gas interface, which allowed the solids to be rapidly incorporated into the melt.This work has been conducted to study fluid flow, temperatures, and solid behavior during feeding, in the arc attachment zone of a D.C. arc furnace. The work also has relevance to optimizing furnace design for pyrometallurgical slag cleaning processes."

Jan 1, 1999

By T. Ueno

Naoshima Smelter & Refinery of Mitsubishi Materials Crop. commissioned a new Mitsubishi continuous copper smelter in May 1991. Process offgas volume of the conventional reverberatory furnace line, one of the previous smelters having been shut down, was very large and thus two acid plants had been operated. It was expected that the offgas volume would be reduced at the new smelter to about a half of the sum of those from previous two 1 smelters and the sulfur dioxide strength would be increased. So various alternatives were studied to minimize the operation cost. And it was decided to utilize both of the plants with minor modifications by diluting the gas either with air or with dilute gases. The acid plants now receive offgases from the new copper smelter, a sintering machine of a lead smelter and a decomposer of waste acid. The paper discusses plant design, operation, improvements and modifications realized in relation with the retrofitting of the copper smelter.

Jan 1, 1992

By Ryokichi Shimpo

Much amount of sludge is produced from the wastewater treatments in surface finishing industry. There are many problems for the abandonment of the sludge because of the high water content and heavy metals included. It is often observed that hexavalent chromium, which is toxic, is generated in the course of heat treatments of the sludge for reducing its amount by dispersing water. In this study, conditions of the sludge calcinations for reducing water contents have been examined. Maximum hexavalent chromium generation was observed in the temperature range around 773 K, at which most of the crystallization water decomposed from the sludge. When the heating temperature became higher than 1173 K, the amount of the hexavalent chromium extracted from the calcined sludge became as low as 10 mg/kg sludge. When the sludge was heated with iron oxides, FeO or Fe203, iron ferrite has been synthesized which may be used as a magnetic material. The amounts of hexavalent chromium generated in the heat treatment with iron oxides were not much different from those without iron oxides.

Jan 1, 2003

By W. D. Riley

Engineered Scavenger Compounds (ESCs), developed by the U. S. Bureau of Mines I are a novel class of compounds that can selectively recover a desired element from 'a solid or molten alloy. Lithium titanate (Li2Tip7 or Li20' 3TiO.) is being used as an ESC to recover lithium (Li) from Aluminum-Lithium (AI-Li) alloys. X-ray diffraction measurements have shown that lithium titanate undergoes a phase change from an orthorhombic structure to a hexagonal structure. This change is due to the incorporation of Li in the matrix of the material and the effect of temperature. Although both of the structures are metastable, the hexagonal phase that forms during the scavenging of Li from AI-Li alloys appears to be the more stable phase. Recovering Li from the ESC by electtodeposition does not cause the structure to revert to the orthorhombic phase. Both the orthorhombic and the hexagonal structures of Li.Til07 have similar scavenging capacities for Li. This paper proposes a new mechanism for the phase transformation.

Jan 1, 1991

By F. J. J. van Loo, J. K. Kivilahti, M. Paulasto

"Activation mechanism and interfacial reactions in brazing of ShN4 with different AgCuTi filler alloys has been investigated thermodynamically and experimentally. During brazing the AgCuTi filler alloy is divided into two liquids Ll and L2, where the (Cu,Ti)-rich liquid L2 gathers at the ShN4 interface and reacts with it. The concentration of Ti in L2 is high, but due to the strong attractive interaction between Cu and Ti, the activity of Ti in L2 is considerably low. In reaction between ShN4 and Cu-containing brazes a Ti-Cu-Si-N compound is typically formed at the interface. In absence of Cu, in joints brazed with AgTi based filler alloys, extremely Ti-rich solution reacts with ShN4 and as reaction products TiN and TisSh[N] are formed. IntroductionAdvanced ceramics like silicon nitride are increasingly used as structural components in demanding applications as well as in electronics industry. Complex, multicomponent structures for engineering applications generally require interconnections and therefore joinability of ceramics largely determines the possibilities of metal-ceramic structures to enable demanding functions. Brazing with active filler metals, most of which are based on the Ag-Cu-Ti system, has been commonly employed for joining of ShN4 to other ceramics and metals. The interfacial microstructures formed when ShN4 is brazed with Ag-Cu-Ti braze alloys have been discussed in several recent studies [1-7]. However, some inconsistencies exist in the reported results. The formation of layers of TiN and titanium silicides, possibly TisSh, next to the ShN4 has been reported in several studies [1-5], while in another investigation, a layer of an orthorhombic TiSi- Cu-N phase was found beyond the TiN layer [6]. In few investigations the thermodynamics of the ShN4-Ti system has been considered, but no detailed thermodynamic analysis of the chemical interactions between the braze and ShN4 has been provided. In order to resolve which chemical reactions are possible under various joining conditions and thereby to be able to control the brazing of ShN4 the reactions in brazing has to be studied using both microstructural and thermodynamic analysis."

Jan 1, 1996