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By T. J. White

Each year, thousands of tons of toxic concentrates are produced as the unwanted byproducts of industrial operations and smelting activities. The fate of these materials remains open, as in general their consumption is limited and potential markets contracting. Xtaltite (pronounced crystal-tight) is a Synthetic Mineral Immobilization Technology (SMITE) optimized for the concentration, detoxification and consolidation of toxic metal wastes. In this approach, we seek to mimic nature to produce durable synthetic minerals that survive for aeons in well characterized geological settings. This approach has high public acceptability because the concept is easily understood by the layperson and the long term stability of the waste form may be predicted with confidence. In addition, where Xtaltite is used for mine backfill, a system of ecologically sustainable mining development is established. This paper details the design and fabrication of Xtaltite under oxidizing and reducing conditions. To illustrate and contrast these stabilization regimes, specific reference will be made to the treatment of thallium, chrom~um and arsenic wastes. Waste form performance under TCLP, dynamic boiling water tests and in other leaching media will be compared and discussed with respect to their relevance to different disposal options.

Jan 1, 1995

By J. W. Lyman

The U.S. Department of the Interior, Bureau of Mines, investigated methods to recover valuable rare-earth materials from NdFeB magnet scrap. Although several processing techniques were evaluated" the best separation of rare earths from the NdFeB magnet ,scrap was obtained by sulfuric acid dissolution followed by precipitation of recyclable rare-earth salts. Both sodium and ammonium intermediate double-salt precipitates' that can be converted to a variety of useful neodymium products were investigated. The sodium system showed a neodymium recovery of 98 pct, while the ammonium system yielded 70 pct during double-salt precipitation. The iron-rich effluent following the rare-earth recovery was treated to produce sodium and ammonium iron jarosites that can be disposed of or converted to hematite. By following this new procedure, many materials handling and economic disadvantages found with fluoride or oxalate direct precipitation were avoided.

Jan 1, 1992

By L. W. Beckstead

In a conventional zinc refinery plant, zinc concentrates were roasted at 950°C. The calcine was ground and leached in a series of leaching vessels using sulfuric acid. The pH in the first leaching vessel was maintained at 2.5, while the pH of the solution exiting the last vessel was about 5.4. The leached residue typically contained (in percent) 0.1 Ag, 0.2 As, 0.7 Cd, 2 Cu, 15 Fe, 10 Pb, and 15 Zn, and it was classified as hazardous material according to the EP-toxicity test. In order to make the residue non-hazardous, and to recover most of the metal values from the residue, a brine leach process was developed. The process consisted of leaching the zinc leach residue in CaCI, brine solution at pH 2 for 1 hour at 90°C. Silver extraction was about 95 percent, while lead, copper, cadmium, zinc, and iron extractions were about 80, 50, 50, 30, and less than 0.5 percent, respectively. More extreme conditions of acidity could have been used in the leaching stage to increase zinc dissolution, but iron dissolution would have significantly increased which would have complicated subsequent recovery steps. The leached and washed residue passed the EP-toxicity leach test and could be disposed as non-hazardous. Silver, copper, and lead in the leach solution were recovered by zinc cementation, while zinc and cadmium were recovered by sulfide precipitation. The resulting solution can be recycled in the process after magnesium precipitation.

Jan 1, 1993

By Arsenio Enriquez, Adrian Deneys

"Rio Tinto through its subsidiary Kennecott Utah Copper Corporation (KUC) and Praxair have implemented the CoJet® gas injection system for copper anode refining. The system provides the capability to melt on average 60 to 70 tons of scrap copper per heat (with acceptable NOx emissions). The system has demonstrated the potential for tuyere-less sulfur and oxygen removal using coherent jet technology.This paper describes the process concept, system development, laboratory testing, implementation, current operation and ongoing developments."

Jan 1, 2009

By Alan M. Russell

In recent years, several rare earth intermetallic compounds with the B2-type structure have been reported to exhibit high tensile ductility and high KIC fracture toughness at room temperature. These materials retain considerable ductility even at 77K. These are noteworthy findings because most intermetallics possess poor room temperature ductility and low fracture toughness unless one or more special contrivances are applied (e.g., doping with small additions of interstitial elements, offstoichiometric compositions, testing in ultra-dry atmospheres, etc.). This paper summarizes recent findings on rare earth B2 intermetallics. These include the determination of the active slip systems; the strain rate sensitivities; yield strength maxima at elevated temperatures; the search for possible twinning and stress-induced phase transformations; ab initio calculations of their defect energies and the anisotropy of dislocation line tension. Potential applications of these materials and the possibilities that this study may suggest strategies for increasing ductility in other intermetallic compounds are discussed.

Jan 1, 2008

By Stavros A. Argyropoulos, Michael Trovant, Norman J. Goudie

"Two studies were carried out to estimate the thermal resistance of various interfaces using experimental and computational techniques. Three types of interfaces were examined. The first study investigated metal-mold interfaces, and the second study focused on metal-metal and metal-oxide interfaces.For the metal-mold interface, the air gap size was measured and subsequently correlated with the interface thermal resistance. The procedural details are outlined for the development of a correlation which predicts thermal resistance as a function of air gap size.Investigation of the metal-metal and metal-oxide interfaces employed data from a series of experiments as input into a model, which solved the inverse heat conduction problem in terms of a resistance estimate. These experiments, involved dipping a cold cylindrical metal into a liquid metal or liquid oxide, respectively. Under these conditions, a shell freezes around the cylindrical addition and a thermal resistance develops during the time period which shell exists . The Heat Transfer Coefficient (HTC) at the addition shell interface differs significantly among the various types of metals and oxides used. In the case of an oxide shell, the (HTC) is about an order of magnitude lower than the (HTC) of the metal shell.INTRODUCTIONIn many metals processing operations there is a need to estimate the thermal resistance at metal-metal, metal-oxide, metal-mold interfaces. This need was further intensified with the recent proliferation of mathematical models, which predict various transport phenomena events. There are many factors which can influence the magnitude of the interfacial thermal resistance. Some of the factors, among others, are as follows: contact temperature, metal thermal conductivity, apparent contact pressure, surface roughness, interstitial gas conductivity, and interstitial gas pressure.In this paper, two studies are reported on the estimation of thermal resistance. The first involves, the development of heat transfer coefficient-air gap relationships at the metal-mold interfaces. The second includes, estimations of thermal resistance at the addition-shell interface. The former case is encountered in the metals solidification and the latter during the melting and/or dissolution of additions to liquid metals or slags."

Jan 1, 1999

By Ann E. Visser

Aqueous Biphasic Systems (ABS) form upon the admixture of certain water-soluble polymers or polymers and salts above critical concentrations, and thus represent liquid/liquid extraction systems whose nature is entirely aqueous. We are currently investigating the utility of ABS (and its solid phase analogs) as "green" alternatives to the use of volatile organic diluents in separations of metal ions. Chaotropic (water-destructuring) metal ions with small negative AGhyd (e.g., Tc04) tend to partition quantitatively to the PEG-rich phase of an ABS, but even hydrated metal cations can be partitioned to the PEG-rich phase if a suitable extractant (e.g., halide, dye, crown ether, etc.) is used to produce a more chaotropic ion-complex.

Jan 1, 1999

By A. E. Isaacson

The U.S. Bureau of Mines is studying the effect of supercritical water, at 400' C and 3,500 psi, and subcritical water, at lower temperatures and pressures, on mixtures of minerals and metals to determine the possible applications of water at high temperature and pressure for processing these materials. This research was conducted using a flow-through bench-scale system. Copper-bearing minerals studied were chalcocite, chalcopyrite, covellite, and cuprite. In general, mixtures of copper minerals and pyrite reacted to form bornite. Intermediate phases formed were chalcopyrite and digenite. Similar reactions occurred between pyrite and metallic copper. A mixture of chalcopyrite and pyrite was inert in supercritical water'. The reaction between cuprite and metallic zinc yielded metallic copper. The cuprite was reduced by hydrogen generated by the reaction between metallic zinc and water. None of the reactions occurred exclusively in supercritical water, but also occurred in water at high temperature and pressure below the critical point. 'Experimental results did show that a dual-reaction process, consisting of solid-state diffusion and fluid transport, was occurring.

Jan 1, 1989

By Chuan-fu Zhang

Li(Nil/3Col/3- xMnl/3)MxO2(M=Ti, Mg) cathode materials were prepared from LiOH?H2O and oxalate precursor. The physical and electrochemical properties were studied by XRD, SEM, cyclic volt-ampere (CV), AC impedance and constant current charge-discharge. The results show that crystal volume of Ti4+ or Mg2+ doped sample is increasing and the electrochemical reaction resistant Rct is decreased at high rate, improving the cyclic performance and rate capability. The effect of Ti4+ doped is better than Mg2+. The sample is well crystallized and simple pure phase with a-NaFeO2 layered structure when doping quantity x=0.025. The second specific discharge capacity of Li(Nil/3Col/3- 0.025Mnl/3)Ti0.025O2 is 143.2mAh/g at 1C,128.0mAh/g at 2C in the voltage of 2.75-4.3V,and still has 140.7mAh/g and 121.7mAh/g after 20 cycles, respectively, keeping 98.25%, 95.07% capacity.

Jan 1, 2009

By Y. W. Chung, W. I. Chia

"The interaction of water vapor with single crystal Ni3(Al,Ti) and polycrystalline Ni3Fe, with and without the presence of oxygen, has been studied with Auger electron spectroscopy, photoemission spectroscopy, thermal desorption and isotope exchange. Water dissociates to produce atomic hydrogen above 200 K on both Ni3(Al,Ti) and Ni3Fe surfaces. For Ni3(Al, Ti), the reaction is structure-sensitive. Pre-adsorbed or co-adsorbed oxygen on Ni3(Al,Ti) and Ni3Fe significantly suppresses hydrogen production due to water dissociation. This suppression process occurs more efficiently on Ni3Fe than Ni3(Al, Ti).IntroductionOrdered intermetallic compounds such as aluminides, silicides and titanides are very attractive for structural applications at high temperatures. This is because these intermetallics tend to form adherent oxides in oxidizing environments which protect the base materials from excessive oxidation and corrosion. In addition, they have low density, relatively high melting points and good high-temperature strength. However, the moisture in air severely embrittles many ordered intermetallics such as FeAl [1-3], Fe3A1 [4,5], C03Ti [6,7], (Co,Fe)) V [8], Ni3Si [9], Ni3(Si,Ti) [10], Ni3(AI,Mn) [Ill, and Ni3A1 [12-14], resulting in low 'ductility and brittle fracture at room temperature. Recent studies by Liu and coworkers (see review by George and Liu [15]) provide a qualitative description of the mechanism for this moisture-induced embrittlement. During elongation testing, cracks are formed, thus exposing fresh alloy surfaces. One or more active components of the alloy react with water vapor in the environment to produce atomic hydrogen which penetrates into crack tips and causes hydrogen embrittlement. This is similar to that proposed for moisture-induced embrittlement of aluminum alloys [16]."

Jan 1, 1996

By Gordon Lewis

A complex mixture of hydrated reaction products is obtained from hydrothermally treated refractory cements and castable concretes. TGA can be used both to identify the product phases in the mixture and to determine a quantitative relationship among the phases. When reacted mixtures contain compounds that decompose simultaneously, or nearly so, additional assumptions must be introduced in order to develop a quantitative phase analysis. It is the purpose of this paper to examine some of these assumptions and to demonstrate their application, particularly to refractory cement systems.

Jan 1, 1982

By Rainer Schmid-Fetzer

"Isothermal solidification can be used to form strong bonds at low temperature which remain solid at much higher temperatures. The exploitation of this principally known technique for new high temperature processing steps and applications in electronic assemblies is the aim of this study. Three basically different variants of this bonding process are given. A comprehensive metallurgical screening is performed and the feasibility of binary material systems is given on a quantitative scale. Very attractive systems are spotted that have never been studied before. Detailed examples for the realization of bonding with complex ternary and multilayer systems are given. A highly innovative example is the chip stack or wafer to wafer bonding of unmetallized Si or SiC at 250°C. The proposed bond remains stable above the melting point of Si and enables entirely new semiconductor manufacturing steps. An improved die bonding process was proposed and verified experimentally.1. IntroductionIsothermal solidification can be applied to form strong bonds at relatively low temperature which remain solid at higher temperatures. The general principle of this type of joining processes is illustrated in Fig. 1. An interlayer of a low melting component, Lo, is provided as a foil or a thin film coating between the high melting joint components, Hi. The assembly is heated under moderate pressure to the bonding temperature, T 8 , and a liquid filler forms, either because the melting point of Lo is exceeded or due to a eutectic reaction between Lo and Hi. This molten filler initiates a rapid interdiffusion or reaction diffusion between Lo and Hi and the subsequent approach to an equilibrium state results in isothermal solidification. The solid phases formed at T 8 in the joint region exhibit a remelt temperature above T8 •"

Jan 1, 1996

By Qingchun Yu, Bin Yang, Yong Deng, Heng Xiong, Fei Wang, Minxiu Chen

"Metal aluminum produced by non-electrolysis process received much attention due to its lower energy consumption. In this paper, carbothermic reduction and carbothermic-chlorination of alumina in normal pressure and vacuum were studied. The products were examined by means of XRD, EDS and SEM. During the carbothermic reduction process using carbon reductant in normal pressure, no metal aluminum was found. However, when coal was used as reductant, a mixture containing metallic aluminum, A14C3, and silicon was obtained, but metallic aluminum couldn't be separated from the mixture. During the carbothermic-chlorination process in vacuum, Al404C and Al4C3 were produced by the reaction between alumina and carbon, and Al Ch gas reacted with Al404C and Al4C3 to produce Al Cl gas. Metallic aluminum was produced due to the disproportionation of A!Cl gas and condensed on the collecting plate. Meanwhile, the initial temperature of carbothermic reduction of alumina reduced in vacuum compared with that in normal pressure.IntroductionIndustrial production of primary aluminum is carried out in alumina cell by the so-called Hall- Heroult process, necessitating the use of very high currents of low voltage. The alumina from which metallic aluminum is gained must be chemically pure, otherwise impure metal results. The main drawbacks of the electrolytic production are its very high energy consumption, the release ofperfluorocarbons, and the high specific C02 emissions [1]. During the past years, there were a lot of attempts to produce metallic aluminum by carbothermic reduction of A1203 [2, 3]. Cox [4] determined the vapor pressure over the A1203-C system and performed X-ray diffraction analysis of condensed products. It was demonstrated that an increase in the carbon content in the system leaded to the sequence of transitions: A1203~Al404C~A1zoc~A14C3 ~AI [5]. In any carbothermic reduction process for aluminum, extremely high temperatures (2000 °C ) were required [6]. In spite of considerable effort, the carbothermic reduction of alumina to aluminum remains a formidable technical challenge, due to the high temperatures required, and to the formation of aluminum carbide and oxycarbide byproducts [7]."

Jan 1, 2013

By L. J. Davies

Refractories usage in furnaces for the extraction of nickel from both sulphides and lateritic ores is reviewed. Recent changes in raw materials and basic brick qualities developed to meet the increasing demands of existing and new processes are outlined. Examples of used brick examinations to establish mechanisms of wear are given. The importance of physical and chemical properties are discussed. The use of simulative laboratory testing to aid in refractories development and selection is described.

Jan 1, 1988

By J. L. Jambor, H. W. Nesbitt

Oxidative dissolution of pyrrhotite and pyrite is largely responsible for the sulfate-rich waters of the vadose zone in the Waite Amulet tailings. Although the shallowest of the sulfate-rich waters are of the Fe-SO4 type, they change to Mg-SO4-type, near-neutral waters within 1-2 m of the tailings surface. Phyllosilicates and amphiboles are the only minerals present in sufficient quantity to ameliorate the amount of acidity produced. X-ray diffraction and microscopic studies of bulk sample indicate that quartz, chlorite, talc, amphiboles, magnetite, albite, and micas are the major and minor non-sulfide minerals, but their variations with depth do not give clear indications of depletion in the vadose zone. Mineralogical and bulk chemical compositions of the tailings confirm that Fe2O 3 has accumulated in large quantity in the vadose zone, with the Fe having been derived from Fe sulfides. When the effect of Fe2O3 is accounted for, the bulk compositions suggest that SiO2 is slightly more abundant in the vadose zone than in the saturated zone. This may be the result of residual enrichment of siliceous minerals such as quartz and albite in the vadose zone. Weathering of the tailings since the cessation of deposition in 1962 has resulted in a well-defined zone of sulfide depletion and secondary sulfate-mineral development. Although some silicate dissolution is indicated by pore-water compositions, the role of silicates in providing neutralization seems to have been minimal. The contribution by silicate minerals in laboratory tests of neutralization potential may be excessive relative to that in natural settings.

Jan 1, 1999

By Grégory Miette

The paper deals with a process that allows the recycling in a cupola of EAF dusts with 18 % Zn. It produces dusts with zinc grade higher than 50 - 55 % and commercial cast iron with less than 200 ppm Zn, 50 ppm Pb, 0.15 % S. The paper focuses mainly on lab tests made with the aim to develop an effective formulation of self reducing - melting pellets. With such a formulation, agglomerates develop a breaking load higher than 125 - 150 kg without any thermal treatment. Zinc and lead are volatilized in the cupola with yields higher than 95 % at 1200 OC, before any melting. Sulphur is transfemed into gas and slag. All these conditions allow to lower zinc, lead and sulphur grades below the cast iron specifications. Results of first bench scale tests performed at Fonderie Piret to validate the process will be presented.

Jan 1, 2002

By T. Wang, R. G. Reddy

"A new eutectic of LiNO3-NaNO3-KNO3 ternary system was calculated by using thermodynamic modeling and the eutectic temperature was predicted to be 389.15K. The melting point was determined using Differential Scanning Calorimetry (DSC). On repeated measurements, it was found that the melting point of the eutectic composition showed excellent reproducibility with the predicted value. The heat capacity was also measured using DSC and the data as function of temperature were fit to polynomial functions. Subsequently, the thermodynamic properties such as enthalpy, entropy and Gibbs energies of this novel ternary eutectic salt mixture were deduced as function of temperature.IntroductionIn these days, the provision of the large amount of energy required in the peak period relies more and more on the parabolic trough solar power plant and it works by utilizing the thermal transfer fluid. Consequently, the development of inoovative thermal transfer fluid with higher energy storage density is paramount to lower the expense for generating energy [1-4]."

Jan 1, 2013

By Tom Lewis

The metal finishing and electronic industries are searching for ways to recycle materials · and reduce costs. The areas of heavy metal waste and water recycling has gained new interests with the potential of impacting the operation's bottom line. Lewis Environmental Services, Inc. has completed numerous heavy metal recovery and effluent recycling projects with its ENVIRO-CLEAN PROCESS for government and private sector clients. This patented process utilizes a proprietary chemically treated granular activated carbon with enhanced heavy metal adsorption capabilities combined with electrolytic metal recovery to produce a saleable metallic product. The process generates no sludge or hazardous waste and the effluent meets EPA .limits. This paper covers several heavy metal removal projects, two fullcscale commercial installations, and one treatability case study.

Jan 1, 2000

By E. Allain

Extraction of basic metals from sulfides by conventional pyrometallurgical processing leads to the emission of SO2. To avoid this inconvenient, low temperature selective chlorination of sulfide concentrates could be an alternative. However, such process generates hazardous chlorides SxCly. A part of sulfur chlorides such as SCI2 can be recycled as a chlorinating agent of metal sulfides. Hydrolysis of sulfur chlorides, using a solution containing Na2S.9H2O, led to the recovery of more than 90 pct of elemental sulfur. Reduction of SxCly by hydrogen was investigated between 300 °C and 800 °C. About 70 and 90 pct of elemental sulfur were recovered from SC12 and S2C12, respectively. A flow sheet for the chlorination of metal sulfides and the treatment of sulfur chlorides was suggested.

Jan 1, 1998

By Masahiro Hirasawa

"As a fundamental study on pyrometallurgical process that involves recycling steel-making dusts, of which major components are oxides of Zn and Fe, and waste polyvinyl chloride simultaneously ·at. a temperature below 1273 K, the reactions between the mixture of ZnO + Fe20 3 and PVC or the compound ZnFez04 and PVC are investigated in a series of thermogravimetric and small scale reactor experiments under inert atmosphere at below 1273 K. The reaction mechanisms are discussed· on the .basis of the thermogravimetric data. From the results of reactor experiments, it is shown that the chlorination of Zn in the oxides by Cl in PVC, the vaporization of ZnC12, the reduction of iron oxide to metal Fe by C and H in PVC, and, thereby, the separation of Zn and Fe in the oxides take place simultaneously at the temperature ~= 1200 K.IntroductionSteelmaking dusts are metallurgical wastes consisting mainly of oxides of Zn and Fe with smaller amounts of other heavy metal elements, such as Pb. In the recent investigation, [1] the present authors have investigated the fundamental aspects of a potential pyrometallurgical process· of recycling steel-making dust with polyvinyl chloride (PVC) at temperature T < 1273 K under Ar atmosphere. The performance of a similar process, in which HCl in the combustion gas of PVC is used to chlorinate Zn in the EAF dust under oxidizing atmosphere, has been investigated by Tailoka and Fray [2] with fundamental experiments. Figure 1 shows an example of the potential ·diagram of Zrt-Cl-0 and Fe-Cl-0 systems. In the figure, we can find two regions where ZnCl2(g) can be separated from Fe containing compounds. One is ZnCiz-Fe20 3 coexistence region at higher oxygen and chlorine potentials and the other is ZnCl2-Fe coexistence region at lower oxygen and chlorine potentials. The process adopted by Fray and coworkers is aimed mainly at the performance of Zn/Fe separation in the higher oxygen potential region. In the present study, the lower oxygen potential region is focused on."

Jan 1, 2000