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By Wade L. Karlsen

"Revision surgery to replace joints in the human body requires materials that are strong, long-lasting, and biocompatible. Metallic implants made of cobalt-chromium-molybdenum alloys are already popular because of their proven corrosion and wear resistance properties, but there is an on-going effort to economically improve their performance. Alloying with inert nitrogen can enhance the mechanical properties of the alloy, enhance its corrosion resistance, and elevate the temperature at which the metallic implants can be thermally treated, without increasing the threat to the human body. The current work has produced a high-nitrogen Co-Cr-Mo alloy through HIP consolidation of metal powders that have undergone nitriding in a mechanically fluidized bed. The already fine microstructure of the powders combined with the increased nitrogen content resulted in significant property gains in the consolidated materials.IntroductionMetallic implants made of cobalt-chromium-molybdenum alloys are already popular because of their proven corrosion and wear resistance properties, but there is an ongoing effort to improve their performance. Research on a Stellite 21 cobalt-chromiummolybdenum alloy has shown that nitrogen alloying can be desirable from several standpoints [l]. Firstly, it has indicated that nitrogen can enhance the mechanical properties of the alloy, which could allow more demanding implant designs. The same work also demonstrated that nitrogen can elevate the temperature at which the metallic implants can be thermally treated, which is desirable in situations in which surface textures are to be sintered to the implant to enhance its fixation properties. Finally, that research work discovered that, not only does nitrogen not harm the corrosion resistance of the cobalt-chromium-molybdenum alloys, but it may in fact enhance it. Combining this with the fact that small amounts of nitrogen are not considered a threat to the human body, makes nitrogen alloying an attractive alternative for enhancing the properties of Co-Cr-Mo."

Jan 1, 2000

By Avijit Moitra

The behavior of the solidifying shell in the early stages of solidification has an important influence on the final quality of continuously-cast steel slabs. In order to understand the thermal and mechanical behavior of the shell, a two-dimensional transient piecewise-coupled finite-element model has been developed. The model simulates a transverse section of the slab as it moves down through the mold and incorporates the effects of heat conduction, solidification, shrinkage, turbulent fluid flow, thermal distortion of the mold and the visco-plastic behavior of the steel. Coupling between the thermal and the mechanical model is based on the mutual dependence of heat transfer across the interface between the shell and the mold and the size of the gap. The effects of mold distortion and taper on the gap size are also included. The effect of fluid flow has been incorporated via a heat flux imposed at the solid-liquid interface, which is obtained from a separate fluid flow model. The high temperature creep and plasticity of the steel is incorporated through a unified constitutive law defining the inelastic strain rates as a function of temperature, time and stress state. The model can be applied to various problems in continuous casting, such as the formation of surface defects and the design of mold taper.

Jan 1, 1992

By J. Wong

We report a successful use of x-ray absorption spectroscopy to probe the chemical and structural environment of trace elements in coal. When applied to vanadium in coal, it was found that vanadium exists in at least two environments: a trivalent site 6-fold coordinated by oxygens at ca. 2.0~ and a tetravalent site 5-or 6-fold coordinated also by oxygens, one of which forms a short V=O bond at ca. 1.6a. No evidence of nitrogen (porphyrin)1'or sulfide environment was found. It was also found that the vanadium environ-ments in the raw coal did not survive unchanged in a liquefaction process. These findings have implications for coal cleaning processes and for trace element release into liquefaction process streams.

Jan 1, 1982

By C. Flores

A novel process using solid metals for the direct reduction of more noble metal ions from solvent extraction organics has been developed. Base metals recovery has been the principal focus of investigations to date but feasibility tests have now also been made on galvanically stripping selected precious metals. In this study gold (III) was loaded from an aqueous HAuCI4 .3H20 solution into a mixed organic 40 vol.% TBP, 10 vol. % D2EHPA in kerosene. The direct precipitation of metallic gold from the loaded organic phase using zinc powder and iron, aluminum and copper slabs at 70 °C was successfully demonstrated. The gold reduction rates were relatively fast even though the conductivity of the organic solutions is very low. The reaction rates were studied as a function of the variables zinc particulate size, oxygen and nitrogen atmosphere, water content in the organic phase, organic ratios and temperature. The gold morphology was usually powdery or dendritic in nature but continuous films were obtained in some instances. Activation energies were calculated and possible reaction mechanisms are discussed. In general, the results obtained were very promising and showed that gold can be successfully cemented from selected organic solvents by galvanic stripping using less noble solid metal reductants.

Jan 1, 1995

By Zhao wen Wang, Ramana G. Reddy, Min Li

"The electroreduction of Co(II) in l-butyl-3-methylimidazolium tetrafluoroborate (BMlMBF4) ionic liquid was investigated by cyclic volatrnmetry at 353 K. The results show that the reaction of Co(II) to Co is irreversible in one step with two electrons transferred. The diffusion coefficient of Co(II) was estimated to be 7.6 x 10-8 cm2 s·1 at 353 K. Then the electrodeposition of cobalt was studied at different cathodic potentials (-0.80 to -0.95 V) and different temperatures (333 to 363 K) in BMIMBF 4 containing 0.20 mol L-1 Co(BF4)z. The deposits were characterized using scanning electron microscope (SEM), energy-dispersive spectroscopy (EDS), and X-ray diffraction (XRD). SEM images show that a uniform, dense, and compact deposit was obtained at -0.80 V and 333 K. The deposits were identified as high-purity metallic Co for all experiments by EDS and XRD.IntroductionCobalt is known as a hard magnetic material and cobalt alloys have been shown to have excellent magnetic properties with adequate mechanical durability and corrosion resistance, which are needed for high performance magnetic recording applications [1-4]. The electrodeposition of Co alloy in the aqueous solution is generally difficult because of the narrow electrochemical potential window of water, which leads to the low current efficiency and worse quality of deposits due to the hydrogen embrittlement. Thus, aprotic ionic liquids (ILs) are expected to be the ideal alternative media for electrodeposition of cobalt or its alloy since ILs usually provide a wide working potential windows, negligible vapor pressure, and acceptable conductivity for electrolysis without the occurring of hydrogen evolution [5, 6]."

Jan 1, 2014

By Marco Zurco, Claudia M. Mendez, Alicia E. Ares, Carlos E. Schvezov, Carlos M. Rodriguez

"Zinc-Tin alloys were solidified in horizontal form and the obtained results were analyzed. During solidification the distribution of temperatures were measured by using thermocouples located strategically along the length of the samples. From the measured temperatures the following parameters were derived; the local temperature gradient, the cooling rate and the velocities of the liquid and solids fronts. Comparing the structure of the samples and the values of these parameters it was found that the temperature gradient reaches minimum values of as low as - 0.6 °C/cm, and velocities of the fronts of around 0.1 cm/s. In addition, the grain size was measured along the samples. The results are presented and discussed in the frame of the results previously obtained for other alloys.IntroductionGenerally solidification leads to two types of grain morphologies: columnar and equiaxed. The origin of each one has been the subject of numerous theoretical and experimental researches in the field of metallurgy for many years [1-7]. The columnar-to-equiaxed transition, CET, is considered as an object of high technological relevance with respect to the directional solidification of metallic alloys. This structure transition may be sharp or gradual and it has been reported to be dependent on thermal conditions associated with the casting process, including melt convection, heat transfer coefficients at the metal-mold interface, growth rates, thermal gradients, cooling rates, transport of solute, alloy composition, melt superheat, mold temperature, mold design, casting size, casting geometry, and the concentration of nucleating particles. As a consequence, it is critical for industrial applications to understand the physical mechanisms which control this transition during solidification. Many studies highlight the importance of the relative growth of the equiaxed and columnar grains and develop expressions or numerical procedures to describe a criterion for the CET. A number of experimental investigations reported in the literature suggest that the CET occurs when GL in the melt reaches a minimum critical value [5-7]."

Jan 1, 2012

By Rodney Hundermark, July Ndlovu, Lloyd Nelson, Phillimon Mukumbe, Paul van Manen, Whitey Seyanund, Bart Pieterse, Bertus de Villiers, Diale Mokwena

The 2003 redoubling in power to 68MW on the Polokwane Smelter furnace represented a significant intensification in platinum group metal (PGM) smelting. Combined with onerous ‘green’ PGM concentrate smelting requirements, this yielded conditions unusually corrosive to copper coolers and refractories. This presented unexpected operational and design challenges to reliable crucible operation and maintenance. Combined with specific operational control intervention, development of protective coatings has led to the life of water-cooled copper components improving from 9 to 40 months. The furnace matte endwall was extended in 2010 to address accelerated wear of refractories and the potential risk for contact of copper components by superheated matte. An 18 month planned endwall rebuild cycle has been demonstrated (versus catastrophic failure within 9 months). Finally, benefits including lower energy consumption, improved metal recoveries and higher productivity resulting from operational and in-house design developments will be described, that justify “Celebrating the Mega-scale” in PGM smelting.

Jan 1, 2014

By Charles L. Richman

The effect of the addition of Silver Sulfide on the rate of Chalcopyrite (CP) of Sulfuric acid (H2SD4 leaching is discussed, Although Ag2S in an expensive addition, a theoretical explanation of it's use will aid in the development of a economic substitution. We have used cyclic voltammography to show the presence reaction species at different potentials. Cyclic Voltammography maps the surface reaction current peaks on CP, to regions on the CP Phorbaix diagram. AC Electro-lmpedance spectroscopy (EIS) models the surface impedance properties, which control the rate of electron and ion transfer, and the surface kinetic reactions, with and with out light. EIS and other measurements show that AgCuS u Photo-reactive material- The EIS results are compared with the SEM and EDXA results to show the presence of diffusion pores, and diffusion controlled reactions during CP leaching without the addition of silver sulfate. We hypothesize that AgCuS is an ionic conductor like Ag2S. EIS shows an imposed negative leaching rate greatly. Our theory shows how the formation of Silver Copper (1) sulfide layer at open circuit potential gives an effect similar to negative potential, that is enhanced with illumination. We verify that AgCuAS is an N-type semiconductor that forms a diode type junction with the electrolyte with the Mott-Schoottly relation.

Jan 1, 2001

By R. L. Nyirenda

One of the problems with ammoniacal-ammonium carbonate leaching of EAF carbon steelmaking flue dust is that zinc present in spinel phases is not leached. This paper presents results of test work in which prior to leaching, EAF dust was reduced with CO containing gas to decompose the spinels into zinc oxide and iron bearing phases, mainly metallic iron and wustite. From such reduction products, the amount of zinc leached increases but the iron co-leached becomes extensive. The effect of various leaching parameters such as liquor concentration and redox potential on zinc and iron dissolution has been investigated. Supplementary experiments utilizing pure zinc oxide and pure iron phases were also carried out. Results show that the co-dissolution of iron from severely reduced EAF dust cannot be prevented. This is because the wustite phase contains zinc which can only be leached when iron also dissolves. Further, the zinc bearing wustite phase is not totally soluble so that the residue cannot be made zinc free. In the absence of air, dissolution of metallic iron hardly occurred, though in leaching experiments of a long duration its transformation to a spinel structure was observed.

Jan 1, 1992

By Kuniaki Murase, Tetsuji Hirato, Koji Nitta, Yasuhiro Awakura

"The redox behavior of copper species in an ""ammonium imide"" room temperature molten salt was examined in order to clarify the applicability of the salt to the electroplating media of various metals. Trimethyl-n-hexylammonium bis(trifluoromethanesulfonyl)- amide (TMHA-Tf2N), having an electrochemical window of 5.6 V (50 °C), and corresponding copper(II) salt were synthesized. In TMHA-Tf2N media monovalent copper ion, Cu(I), was stable and Cu metal was oxidized, or corroded, in the presence of Cu(II) species. Cathodic electrodeposition of copper metal and anodic dissolution of it were, thus, one-electron reaction and their current efficiencies were almost 100%.IntroductionElectrodeposition of metals from aqueous solutions is an important soft process for manufacturing thin-film materials, surface finishing, and extractive metallurgy. However, the electrodeposition of base metals, such as zinc, chromium, and nickel, from aqueous media inevitably accompanies hydrogen evolution, which lowers the cathodic current efficiency of metal deposition. Since the electrodeposition of aluminium, titanium, and rare earths from aqueous media is actually impossible due to their largely negative redox potentials, nonaqueous media such as aprotic organic solvent and high-temperature molten salts have been employed for the electrodeposition of these metals. Room temperature molten salts (RTMS),1, 2) or room temperature ionic liquids, have also been developed as a promising electrolytes for the electrodeposition of base metals. In this field, chloroaluminates of alkylpyridinium or alkylimidazolium cation have been well investigated for aluminium3) or alluminium-alloy4-5) electroplating media. On the other hand, in order to avoid high hygroscopicity arising from the use of aluminium chloride, attempts have been made to combine the alkylimidazolium cations with fluorine-containing hydrophobic anions, e.g. BF4-,6) CF3SO3- (TfO-),7) (CF3SO2)2N- (Tf2N-),8) and H(HF)n-ions,9) and investigated for electrodeposition media.'°) Recently, a new series of RTMS consisting of tetraalkylammonium cations and Tf2N- anion, sometimes abbreviated as TFSI- anion, was found independently by MacFarlane et al.11, 12) and Matsumoto et al. 13) This type of RTMS, which is commonly named ""ammoniumimide"" salt, has a wide electrochemical window of ca. 5 V and, thus, the RTMS seems to be suited for practical application as a solvent for the electrodeposition process. In this paper, we report the electrochemical behavior of copper species in an ammoniumimide RTMS, trimethyl-n-hexylammonium bis(trifluoromethanesulfonyl)amide (TMHA-Tf2N)."

Jan 1, 2000

By Magnus Ek

After the installation of three new converters as part of the recent expansion of the Rönnskär smelter completed in 2000 work continues to further improve the converter operation. The converter upgrade led to an increase in blister copper taps from 150 tons per batch to more than 300 tons. The total cathode copper production increased from 130,000 tons in 1999 to 230,000 tons in 2001, the first year in full production. In recent years focus has been to improve operating practise, maximize the blowing time, extend the converter campaigns hence to reduce the specific brick consumption and improve the converter slag composition.

Jan 1, 2005

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 S. N. Monteiro, C. M. F. Vieira, A. P. N. M. de Sa, J. P. D. Vitorino

"This work has as its objective to characterize an ash waste and to evaluate its incorporation into a clay to produce bricks and roofing tiles. The waste is a type of fly-ash resulting from the incineration of a selected part of urban garbage, which is basically constituted of organic matter and plastics. The waste was submitted to mineralogical and chemical characterization. Compositions were prepared with incorporation of the waste in amounts of up to 20wt.% into athe clay. Rectangular specimens were prepared by extrusion and fired in a laboratory furnace at 900°C. The physical and mechanical properties evaluated were: linear shrinkage, water absorption and flexural rupture strength. The results showed that the waste is predominantly composed of quartz and calcium compounds. The incorporation of the ash was deleterious to the evaluated properties of the clay. It is suggested that the incorporation should be made in amounts below 5wt. % to avoid deleterious effect in the mechanical strength and water absorption of the clayey ceramic.IntroductionThe world attention has turned to a subject of great concern today, the production and disposal of large amounts of industrial wastes as well as wastes of various sources. When deposed in an unsuitable place, these wastes can cause considerable harm to human health and to the environment. Our planet suffers with air pollution, groundwater and soil contamination as well as silting of rivers and lakes with the growing amounts of our society wastes.The recycling of waste materials is of great interest to the industries, mainly due to the environmental agencies legislation. One of the practices for correct disposal of these wastes being investigated is to incorporate into red ceramics, such as bricks and roofing tiles. The natural variability of the characteristics of the clays associated with the relatively simple processing techniques and also the low performance required for the products allow the presence of relatively high levels of impurities in clayey ceramics."

Jan 1, 2011

By Yasuhiko Ito

"This talk is concentrated on the topics of compound film formation on the substrate electrode by interdiffusion of substrate element and electrochemically deposited species and/or by direct electrochemical implantation of the component element of the film into the substrate. As a typical example, electrochemical implantation of nitrogen atom into Ti metal to form TiN surface film is described. Another example is the formation of various kinds of intermetallic compound films including Ni2Y, Ni2Dy and Pd3 Y by the electrochemical implantation of lanthanoid elements into transition metal electrodes. By combining these two methods, Sm-Fe-N ternary material film also could be formed. The principle and application of the ""electrochemical implantation"" are discussed in detail.IntroductionGenerally speaking, surface film formation by molten salt electrochemical process can be divided into the following three categories:(i) single element film formation on the electrode by electrodeposition,(ii) compound film formation on the electrode by electrocodepostion of more than two elements, and(iii) compound film formation on the substrate electrode by interdiffusion of substrate element and electrochemically deposited species and/or by direct electrochemical implantation of the component element of the film into the substrate.This talk is .concentrated on the topics of category (iii), especially on the electrochemical implantation. Typical example can be seen in the electrochemical implantation of nitrogen atom into Ti metal to form TiN surface film. Another example is the formation of various kinds of intermetallic compound films including Ni2 Y, Ni2Dy and Pd3 Y by the electrochemical implantation of lanthanoid elements into transition metal electrodes. By combining these two methods, Sm-Fe-N ternary material film also could be formed. The principle and application of the ""electrochemical implantation"" are discussed in detail with examples above as well as other experimental results also obtained very recently in the author's laboratory."

Jan 1, 2000

By Hojat Naderi

In this research assisted leaching of chalcopyrite using sodium peroxodisulfate was studied. Electrochemical techniques such as Tafel analysis and electrochemical impedance spectroscopy (EIS) were used to investigate the surface reactions of a chalcopyrite electrode in the presence and absence of Na2S2O8. According to the results, addition of sodium peroxodisulfate increases the current exchange of the corrosion process and prevents the formation of a passive layer on the surface of the electrode. EIS tests show the trans-passive dissolution of the passive layer on the chalcopyrite electrode in presence of Na2S2O8. Equivalent electrochemical circuits were modeled for Na2S2O8-free and -containing solutions and the model parameters were compared to determine the effect of S2O8 2− on chalcopyrite dissolution. Copper dissolution from pure chalcopyrite mineral and chalcopyrite concentrate was carried out using 15 g/L sulfuric acid solution with and without Na2S2O8. Simultaneous presence of 10 g/L ferric ion and 40 g/L peroxodisulfate salt results in about 40 and 18% of Cu extraction from chalcopyrite concentrate and pure chalcopyrite mineral, after 96 h, respectively.

By Gaballah I.

Elimination of arsenic, mercury and zinc from synthetic solutions containing H;\A.sD4. HgCI2 and ZnCI2 using modified barks was investigated. The pH range was varied from ?1 to 10. The initial concentrations of individual element were 10,100 and 1000 ppm. More than 99 % of mercury and 65 % of zinc cations were removed by the modified bark .. In this case, the modified bark reacts as a cation exchanger leading to the release of ' two protons for every HgII or ZnII fixed by this material. About 30 % of arsenic was eliminated from the solution. This 'low efficiency could be attributed to? the presence of arsenic ,as. anion. Decontamination of a treated industrial effluent containing 4 ppm of ion? metals was performed on a pilot plant scale by the modified bll(k. More than 70'% of these ion metals were eliminated.

Jan 1, 1995

Cuspidine (3CaO?2SiO2?CaF2) is one of the most important compounds crystallized in mold flux films during casting in the continuous casting process of steel. The primary crystallization field of cuspidine has been experimentally developed in the CaO-SiOrCaF2-SiF4 system. The cuspidine-NaF binary and cuspidine-CaF2-NaF ternary systems have been also experimentally determined to study effects of addition of NaF on the primary field of cuspidine. In order to discuss its thermodynamic stability the standard Gibbs energy of formation of cuspidine has been determined by an electromotive force method using CaF2 as solid electrolyte and a transpiration method as follows: The chemical potential diagram and constituent activities for the CaO-Si02-CaF2 system have been evaluated based on the obtained thermodynamic data.

Jan 1, 2003

By A. V. Reddy, C. Beckermann

"The DC continuous casting of a grain refined AI-4.5%Cu round ingot with realistic boundary conditions is numerically simulated. Of particular interest are the effects of the transport of free solid in the form of equiaxed grains on the macro segregation patterns and the final grain size distribution. The study uses a previously developed two-phase model that incorporates descriptions of heat transfer, solute redistribution, melt convection, and solid transport on the system scale with microscopic models of solutal undercooling, microsegregation and grain impingement. The numerical results indicate that grain transport inhibits the formation of inverse segregation in the ingot shell and promotes negative centerline segregation. This is explained by the reduction in the solid coherency next to the mold and the advection of solute-lean grains towards the centerline. Comparisons with the experiments of Finn et al. [5] illustrate the need for considerable improvements in the model. IntroductionMacrosegregation continues to be one of the concerns in DC continuous casting of aluminum ingots. The variation in composition over the ingot cross section results in the need to adjust alloy composition in order to meet mechanical property specifications in finished products. The extent of macrosegregation is greatly affected by the casting conditions, such as casting speed, superheat, cooling rate, mold size, alloy composition, and grain refining practices. Thus, it is of great interest to develop a comprehensive mathematical model to simulate the casting process, enabling the selection of conditions that minimize macrosegregation while maintaining a high productivity."

Jan 1, 1994

By Kunwar Pal, S. K. Tyagi, A. K. Pandey

"This study deals with the performance evaluation, technical and environmental aspects of different cookstove models (NIRE-02, NIRE-03 & NIRE-04). These cookstove models were designed, fabricated and evaluated following Bureau of Indian Standards (BIS) and their performance was compared from technical and environmental points of views. The theoretical efficiencies of all the cookstove models are found to be in good agreement with the experimental one. Also, the overall performance of these models is found to be in the order of (NIRE-04 > NIRE-03 > NIRE-02) which is also observed to be much better than that of the traditional cookstoves being used by the people in most of the developing countries around the world. The CO2 emission reduction from these models is found to be between 2.0-3.0 tons per household annually which is ultimately in good agreement with the experimental values.IntroductionMore than 2.5 billion people around the world depends on the biomass based resources for cooking and heating applications which includes wood, cattle dung, charcoal and agriculture residue [1,2]. Generally, people of rural area cook their food on unvented open fire, which burn biomass fuel inefficiently besides it creates many thermal and environment pollution hazardous causing health problems in the women and girl children due to more exposure of emissions. Also the consumption of biomass is very high as compared to the fossil fuels due to the fact that the large population of the developing countries lives in the rural area than that of in the urban area. It is estimated that about 3% of the diseases are caused due to incomplete combustion of biomass, which results in the around 1.8 million premature death every year including around 0.9 million death under five year of their age [3,4].Ramanathan and Carmichael [5] recently found that the black carbon of unburned smoke is playing a major role in global warming. The emission factors for different combinations of fuel and stove tested in China for direct and indirect GHGs as well as other airborne pollutants such as, CO2, CO, CH4, TNMHC, N2O, SOx, NOx, TSP etc. for a typical set of operating parameters [6]. The improved biomass cookstove technology came into assistance which is technically feasible, socially reliable and economically viable [7, 8]. The improved biomass cookstove not only reduces pressure on the biomass resource, but also reduces the environmental pollution and also minimize the time required for collection of fuel wood [9, 10]. Sharma et al. [11] emphasized on the adoption and large-scale propagation of efficient stoves to improve the health of rural women and to reduce the consumption of firewood and environmental pollution."

Jan 1, 2014

By Thomas P. Battle

Modern-day direct reduction of iron first developed as a small-scale, low capital and operating cost alternative to the blast furnace. Since commercialization of continuous DR technology in the late 1960s, the market for the products of direct reduction has grown to more than 74 million tonnes in 2012. The initial advantages of DR plants over BF facilities have grown over the years, for several reasons, including the increased size of DR modules, lower energy and emissions (particularly CO2), along with the flexibility to use a number of different reductants. The development of DR technology over the past forty years will be emphasized in this presentation, including recent developments that allow for even more direct sustainability comparisons with the iron blast furnace – and even combine the two technologies for improved synergies. Also briefly discussed will be the possibilities of using direct reduction for non-ferrous ores.

Jan 1, 2014