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By Adolfo Pillihuaman Zambrano

Fe-Cr-C production is a very high electrical energy consuming process. Decrease up to 10% of this electrical energy is expected when self-reducing agglomerates are used. This research aims to understand how the synergetic effects are when stronger reductant, like Fe-Si, is substituted for coke in self reducing pellets. Brazilian chromites containing 41.2%Cr2O3 were mixed with petroleum coke and agglomerated with cement as the binder. Small amounts of 1%, 2% and 4% of Fe-75%Si were substituted for the equivalent petroleum coke, and pure silica plus hydrated lime were added for adjusting the slag composition. The mixture was pelletized, dried and submitted at 1773K up to complete the reactions. The results showed that the reduction reactions were 1.4 and 2 times faster with 1% and 2%Fe-Si addition, respectively, than with no addition. The microscopic analysis showed that it was formed a liquid phase, but the pellet did not collapse what indicates that the coalescence of the metallic phase depends on the dissolution of the pre-reduced particles of the chromites into slag.

Jan 1, 2008

By Jasper Kwong

The recycling of MgO-C refractories as a slag conditioner in EAF (electrical arc furnace) foaming slags have been evaluated by the Albany Research Center. The amount of MgO in the slags is critical for the foaming quality. Good foaming slags provide the benefits of high energy efficiency and low refractory consumption and require saturation with MgO. A computer model predicting the chemistry of MgO saturated foaming slags was designed to predict suitable amounts of MgO additives from MgO-C spent refractories. This model can also help to reduce the amount of slags and to improve the economics of producing steel. The implementation of this recycling program is underway at steel plants and the experience of recycling spent refractories will be discussed.

Jan 1, 2002

By Guy L. Fredrickson

A modified transpiration reactor was used to measure the composition of the equilibrium gas phase formed above compounds in the Hg-O-S system at high temperatures (600 to 900K). A thermodynamic database {(AGo°f AH°t. AS°t)} for-HgO, HgS, HgSO4, Hg2SO4, HgSO4?HgO, and HgSO4?2HgO was developed based on the experimental results. Prior to this study, only estimated data were available in the literature for the sulfates and oxysulfates at temperatures above 298K. A series of vapor pressure' stability diagrams were constructed from 473 to 973K with isobars of Hg(g), HgO(g), S2(g), and SO3(g). These diagrams were found to be significantly different than those available previously and do provide insight to the phase relations of importance during the thermal processing of Hg-containing wastes. The thermodynamic results were used to conduct a series of Gibbs energy minimization calculations for a thermal processor' afterburner system for the treatment of HgS-containing wastes. The retention of Hg in the discharge calcine was examined as a function of temperature and excess air. Hg was found to report to the calcine as HgSO4, Hg2SO4, or HgSO4 HgO depending on the process conditions, and Hg retention occurs at temperatures as high as 930K. The precipitation of Hg-containing phases from cooled afterburner discharge gas starts at approximately 900K and the cooling of the gas an additional 30K (to 870K) results in over 50% of the Hg being preCipitated as HgS04?HgO. It was also determined that for small amounts of Hg present in sulfide concentrates during roasting, the Hg will be retained as HgSO4 or HgSO4?HgO at temperatures as high as 870K.

Jan 1, 1996

By Sheng Dai, Yuan Lee, Haiming Xiao, J. P. Young

"There are numerous analytical applications of scatter-emission and/or absorption spectroscopy applied to liquids and solids in the temperature range of 0 to 350°C. In this paper an all-silica fiberoptic probe is described which is useful for spectral analyses from 0 to 1600 K and can be used in harsh chemical environments. The probe has been used for Raman spectral analyses of many molten salt and solid material systems to 1000°C. It has applications for such studies at higher temperature ranges. The instrumentation required along with the demonstrated and proposed applications of the all-silica probe are presented and discussed.IntroductionThere are many kinds of scatter-emission spectroscopies that are of value for analytical measurements. Fluorescence, reflectance, arc or spark emission are descriptors for some of these. Raman scatter spectroscopy is also quite a useful technique for analytical measurements.In Figure 1, we give a simplified explanation of the Raman effect. If one shines monochromatic light into a sample, light may be absorbed, exciting the sample to some virtual state. We know from experience that almost all of the light is re-emitted in the same wavelength range. This is called Rayleigh or Mei scattering and is designated in the figure by the arrows in both examples that point up and down from the same lower energy state. A very small percentage (the order of 10-4%) of the monochromatic light is re-emitted leaving the sample at a vibrationally-excited state. Thus, this light is at a distinctly lower energy compared to the exciting radiation. This is called a Stokes shift and is represented in the left-hand example by an arrow descending to a more energetic vibrational state. If the sample is not at a temperature of absolute zero, some of this vibrationally excited state will be thermally populated. That portion of the sample still absorbs and re-emits exciting radiation as Rayleigh scattered light, but a small percentage of the exciting light is re-emitted as the sample relaxes to the lower vibrational state. The energy of this light is of higher energy and is called an anti-Stokes shift, depicted in the example to the right. Notice that the energy separation of the Stokes or anti-Stokes shifted emission from that of the exciting radiation is the same, and expressed in ~cm-I. The intensity of either shifted emission is a function of the population of the vibrational energy states; therefore, the ratio of the intensity of Stokes to anti-Stokes signal varies with absolute temperature. We will come back to this point later."

Jan 1, 1997

By M. Pakala, Z. Fan, Ray Y. Lin

Deposition of hard chromium coatings using electrodeposition is accompanied by emission of hexavalent chromium mists which is a carcinogenic. Hence alternative chromium deposition technologies are being investigated. Sputter deposition is a strong candidate to economically deposit hard chromium coatings in an environmentally friendly way. Chromium coatings of 2-3 µ m thickness were deposited on plain carbon steel coupons using RF magnetron sputter deposition. Depositions were carried out with 0 to 22 vol% nitrogen in the plasma. Structure of the coatings was studied using x-ray diffraction analysis With increasing nitrogen contents, formation of the two nitride phases was observed. The pure chromium phase was detected in coatings with up to 7% nitrogen in the sputtering gas. The solid solution of nitrogen in the pure Cr phase coating was identified by shifts of Cr x-ray diffraction peaks to higher d-spacing. The microhardness of the coatings deposited at a substrate temperature of 200°C showed an increase in hardness with increasing nitrogen content from 600 kgf/mm2 (5.9 GPa) at 0% nitrogen to I250 kgf/mm2 (I2.25 GPa) at 9.5 % nitrogen and a subsequent decrease in hardness to I 100 kgf/mm2 (11 GPa) beyond 9.5 % nitrogen in the sputtering gas. This corresponds to the formation of the hard Cr2N phase, at 9.5 % nitrogen, and CrN phase, at I5.7 % nitrogen. The reported bulk hardness values of Cr2N and CrN are I600 kgf/mm2 (I5.7 GPa) and I 100 kgf/mm2 (11 GPa) respectively. For pure Cr phase coatings, there is a slight increase in hardness for coatings deposited at 7. I % nitrogen from that without nitrogen in the sputtering gas. This could possibly result from the solid solution strengthening of the Cr lattice by nitrogen. For films deposited at 200°C, phases of the deposited films seem to be the overwhelming factor in controlling the microhardness.

Jan 1, 1998

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 Yimin Ruan

"An inverse design method is developed to obtain the optimal cooling conditions for the continuous quenching of precipitation hardenable sheet alloys to achieve the required yield strength. The yield strength of a precipitation hardenable alloy is obtained by allowing solute to enter into solid solution at a proper temperature and rapidly cooling the alloy to retain the solute in the solid solution. An aging process may be needed for the alloy to develop the final mechanical properties.The objective of the design is to optimize the quenching process so that the required yield strength can be achieved. With the inverse design method, the required yield strength is specified and the sheet thermal profile at the exit of the quenching chamber can also be specified. The conjugate gradient method is used to optimize the cooling boundary condition during quenching. The adjoint system is developed to compute the gradient of the objective functional. An aluminum sheet quenching problem is presented to demonstrate feasibility of the inverse design method.IntroductionQuenching is a critical step in metal production to achieve desired material properties, such as yield strength, hardness, etc., for precipitation hardenable alloys. In most cases, rapid quenching from the solution heat treatment temperature is necessary to obtain the required material properties, but rapid quenching may cause other problems such as excessive distortions of the quenched materials.In a solution heat treatment, the alloy is heated to a suitable temperature, held at that temperature to allow the soluble alloying elements to enter into the solid solution, and cooled rapidly (quenching) to retain the alloy elements in the solid solution. An aging process, which controls precipitation of fine particles at room (natural aging) or elevated temperatures (artificial aging), is generally followed after the quenching process to develop the final mechanical properties of the heat treated alloys."

Jan 1, 1998

By Takuya Shinagawa

After vitrification of the residues from a municipal solid waste incinerator, the vitrified products can be used as a construction material, and the dust can be used as raw materials for the non- ferrous industry. The NKK electric-resistance furnace is operated under a reducing atmosphere, and heavy metals such as zinc and lead in the ash vaporize to form dust. Also, dust from the NKK electric-resistance ash melting furnace is composed of water insoluble zinc and lead components and water soluble NaCl and KCI. This is why, The concentration of zinc and lead in the dust after washing is sufficiently high for the dust to be used as a raw material for the zinc and lead industry. NKK developed a heavy metal recovery process in which zinc and lead in the dust are reclaimed as a raw material for smelting by making the best use of the characteristics of the dust.

Jan 1, 2002

By Zhang Chuanfu, Tan Pengfu

"A thermodynamic model is developed to simulate nickel flash smelting process. In the nickel flash furnace, oxidation of concentrate occurs at one end, and reduction of slag occurs at the other. The model makes use two zones, namely the reaction shaft/settler zone and the appendage zone and accounts for 6 phases (matte, slag, silica, magnetite, Cu-Ni alloy and gaseous phase), 13 elements (Ni, Co, Cu, Fe, S, 0, N, C, H, Si, Al, Mg and Ca) and 33 chemical components in nickel flash smelting system. The compositions of matte, slag and gaseous phases in equilibrium are calculated by using the data of free energies of formation and activity coefficients of components. Two nickel sulfide species are used to allow for the modeling of sulfur-deficient mattes. The model predictions are compared with the known industrail data from Kalgoorlie Nickel Smelter, and excellent agreement is obtained. The model can be a very useful tool for monitoring and optimizing the actual industrial operations of nickel smelting process. The distribution behaviors of Ni, Co, Cu, Fe, S and 0 in the nickel smelting furnace depend on the process parameters such as smelting temperature, volumes of air, the content of the elements~ charge and oil.1. IntroductionThe nickel flash smelting furnace essentially consists of a reaction shaft where nickel sulfide concentrate is partially oxidized with air, a settle zone where matte and slag are allowed to separate, and a slag cleaning end where coke is added to provide for the reduction of the oxidized nickel from slag, and electrodes are used to provide heat.The theoretical model to consider a mass balance for copper flash furnace is developed by S. Goto and R. Shimpo[1][2J. However, this can not be true for nickel flash furnace as a whole since oxidation of concentrate occurs at one end (in the reaction shaft/settler), and reduction of slag occurs at the other (in the appendage). Despite these limitations, an acceptable pseudo-thermodynamic description of the furnace can be achieved using essentially two zones, namely the reaction shaft/settler zone and the appendage zone. Compositions of gas, slag and matte in two zones are calculated."

Jan 1, 1998

By Charles H. Rawlins

Reported is work done on processing of steel mill effluents in the areas of dewatering and separation. Much of the waste from these operations is in the form of sludges from scrubbers, in which the primary constituent is iron oxide. Recycling of the sludge&apos;s magnetic fraction has become economically attractive in order to reduce the overall volume placed in landfills. The objective of this research is to determine the effectiveness of combining magnetic and cyclonic forces, to recover iron oxide particles from waste water stream, while decreasing the volume to be disposed. Three different size hydrocyclones, operating within the field of a quadripole magnet, were tested using varying feed pulp densities of magnetite, magnetite/dolomite, blast furnace (BF), and basic oxygen furnace (BOF) slurries. In the first three cases, the percentage of magnetics recovered increased to greater than 95%. The limiting operational factors are; high pulp density for small cyclones, which can cause flow blockage within the magnet field, and extremely fine particle sizes (<2 microns), which cannot be recovered. The results indicate this technique can remove virtually all the magnetic particles from some steel effluents to a 40-50% weight percent solids pulp, on an in line continuous basis.

Jan 1, 1994

By O. Forsén

A new cell construction was designed for the study of the electrochemical behaviour of additives in conditions that simulate real copper, electrorefining. The behaviour of gelatine and thiourea was studied by applying different electrochemical methods, i.e. polarization resistance and voltametric measurements. In this study, individual galvanostatic electrolysis experiments were carried out for 120 hours. The organic additives were introduced to the electrolyte at certain intervals and their concentration was varied in the range &om zero to four ppm. An optical microscope was applied for the examination of copper cathode deposit microstructures. The results show that gelatine has a polarizing effect on the deposition potential of copper whereas even small amounts of thiourea depolarize the electrodeposition of copper. The maximum inhibitor efficiency of gelatine was obtained at a gelatine concentration of slightly lower than two ppm. When both gelatine and thiourea were present in the electrolyte, the depolarizing effect of thiourea exceeded completely the polarizing effect of gelatine. If chloride ions were added to gelatine and thiourea containing electrolyte, the electrochemical behaviour of the system was altered drastically. Chloride ions resulted in the prevailing of polarization effect caused by gelatine while the depolarizing effect of thiourea disappeared in this system. The polarizing effect of gelatine increased until chloride ion concentration of 30 ppm was reached. Also, the above electrochemical phenomena could be detected in the optical examination of copper deposit microstructure.

Jan 1, 1995

By Ravi Vancheeswaran

The consolidation of ceramic fiber reinforced metal matrix composites is a key process step in the synthesis of high performance composite systems. A simulation tool has recently been developed for predicting the evolution of the composites internal state microstructural variables (eg. relative density, fiber microbendinglfracture, and chemical reaction layer thickness at the fiber-matrix interface) during the consolidation processing of spray deposited composite mono-tapes. A Generalized Predictive Control (GPC) scheme is used in conjunction with the simula-tion tool to design near optimal process paths that minimize fiber damage and reaction product thickness while simultaneously maximizing the composites relative density. The microstruc-tural evolution depends nonlinearly on the process conditions and therefore the scheme uses a constantly updated linearization of the model to optimize the input process variable vector. A control simulation is presented to illustrate the performance of the design scheme and to assess the feasibility of its use for the achievement of goal state microstructures at the completion of consolidation cycles.

Jan 1, 1996

By H. L. Fraser

A review of the possibilities of performing microchemical analysis in thin sections using a combination of scanning transmission electron microscopy and energy dispersive spectroscopy of x-rays is given. Particular attention is paid to the factors that limit accurate analysis at the highest spatial resolution. As an example of the use of these techniques applied to a potential problem in minerals processing, the identification of iron pyrite and pyrrhotite particles in Illinois, Herrin #6 coal is presented.

Jan 1, 1981

By Jie Li, Zhongliang Tian, Xun Hu, Kai Zhang, Yanqing Lai, Hongliang Zhang

The Al-Sc Alloys show many advanced properties for a wide range of engineering applications. But the metal Sc must be added into the metal Al in the form of the Al-Sc master alloy, which is usually produced by the thermal reduction process. In this paper, the decomposition voltages of Sc2O3 and Al2O3 in Na3AlF6-K3AlF6-AlF3 melt were calculated based on the Nernst equation. And the Al-Sc master alloy was prepared in the melt at 950°C by electrolysis. The results show that the Al-Sc master alloy can be prepared by the co-deposition of Sc3+ and Al3+ at the cathode if the concentration ratio of Sc2O3 to Al2O3 in the melt is more than 2:1 under the condition of the aluminum electrolysis. SEM and ICP analysis of the product indicates that the Al-Sc master alloy is made of the phase Al and the phase Al3Sc.

Jan 1, 2016

By Gervais Soucy, François Quesnel, Pierre Hovington, Wen Zhu, Karim Zaghib, Jocelyn Veilleux

The properties of lithium titanates anodes in Li-ion batteries are highly dependent on their secondary constituents. While their main phase is usually constituted of Li4Ti5O12, significant quantity of lithium titanates compounds of various stoichiometry are often present, due to either the processing, usage or aging of the material. These may go underreported, as many of these spectrums overlap or display low signal in X-ray diffraction (XRD). Samples of nanosized lithium titanates synthetized by inductive plasma were characterized by XRD and scanning electron microscopy (SEM), as they provide a regular yet typical crystallite size and shape including multiple phases. A Rietveld refinement was developed to extract the composition of these samples. Mass balance through further annealing and differential scanning calorimetry (DSC) enthalpy measurements from phase transformations were also used as identification and validation techniques.

Jan 1, 2015

By V. E. Antonov

Hydrides of iron and iron-based alloys are thermodynamically stable only at hydrogen pressures in the gigapascal range and rapidly loose hydrogen under ambient conditions. At low temperatures, however, these hydrides can be retained in a metastable state at atmospheric pressure after being cooled under the high pressure to liquid nitrogen temperature. This review will discuss the current state of studies on phase transformations in the Fe-H and related systems and also on the composition, crystal structure and physical properties of the hydrides, both under high hydrogen pressures and in the "quenched" metastable state at ambient pressure. The studies at ambient pressure include magnetization measurements, X-ray and neutron diffraction, Mossbauer spectroscopy and inelastic neutron scattering. In the sections on Mossbauer and structural investigations of hydrides of Fe-Cr and Ni-Fe alloys new experimental results will be presented.

Jan 1, 2002

By Dmitri Nassyrov, In-ho Jung

"All relevant thermodynamic and phase diagram data in the CaO-Fe10-CaF2 system were critically reviewed. One set of model parameters describing the Gibbs energy of all phases has been obtained as a result of critical evaluation of the available data and optimization of the model parameters. The Modified Quasichemical Model was used to describe the interactions in the liquid phase. All calculations were performed using the FactSage thermochemical software.IntroductionSlags contaimng CaF2 are of significant interest to the steelmaking community. Notable examples of slags containing significant amounts of CaF2 include Electro-slag Remelting (ESR) slags [1] and mould flux for continuous casting [2]. The role of these slags is, among other things, to refine steel by absorbing inclusions and dissolved impurities. During slag-steel interaction, some iron from the steel will inevitably get oxidized and form iron oxides which will dissolve into the slag. With this in mind, it is important to understand the interaction between CaF2 and Fe,0 for accurate prediction of slag composition and process optimization. A thermodynamic optimization of the CaO-FetO-CaF2 was thus undertaken."

Jan 1, 2013

By A. González

Arsenic is one of the main contaminants present in Chilean copper concentrates and its abatement represents a challenge for the process metallurgy, particularly under the strong environmental requirements in the global community. The possibility to form ferric arsenate directly from a gas phase by means of a heterogeneous reaction between an arsenic gas bearing and iron oxide was studied at laboratory scale. A thermodynamical analysis for the system Fe-As-O-S has been initially made, in order to obtain the stability conditions for the ferric arsenate or other FexAs2O2 type compounds. Experiments were made using an hematite sample suspended in a thermogravimetric device. AS4O6 gas generated from solid AS203 that was passed through the iron oxide sample and its instantaneous weight change was recorded directly. A kinetic study for the AS4O6 volatilization was made to control the gas composition. A chemical control between 300 and 600°C with an apparent activation energy of around 14 Kcal/mol As2O3 was determined. The samples after the reactions were chemically and XRD analysed. Arsenates detected corresponds to complex compounds. Results shows a dependence on temperature and oxygen content in the gas phase. The kinetics for iron arsenates formation is slow, reaching an arsenic capture of 6% after 80 minutes of reaction when an oxygen content of 50% is fed continuously at 800°C and 3,56% As in the gas. Experiences made at the same temperature but under higher oxygen content in a closed reactor, allowed arsenic capture close to 60%. For higher temperatures the capture is considerably lower.

Jan 1, 2003

By J. C. Yannopoulos

The quest for a continuous copper smelting and converting process, which has been going on for a long time, has not as yet reached its objective. The most recent efforts for the development of a continuous copper?making process started about two decades ago. Among the contending proposed processes, four have been piloted and three of them are currently in operation: the WORCRA process., the NORANDA process, the MITSUBISHI process, the OUTOKUMPU process. The WORCRA process, after some long pilot plant tests, failed to develop as an industrial process: The NORANDA process, as currently operating, is a smelting process and not a continuous copper?making reactor as initially conceived. The MITSUBISHI, although the only continuous process, has not been widely accepted. The OUTOKUMPU process can be applied only to a low iron concentrate feed and co?produces blister and high in copper slag. The thermodynamics of these "continuous" systems and the practical problems of their industrial application are reviewed and discussed. The achievement of efficient and inexpensive environmental control should&apos; be the primary objective of any new process development. A review of the environmental problems of the copper industry indicates that the quest for a continuous smelting and converting furnace should be intensified.

Jan 1, 1983

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