Search Documents

By Animesh Jha

"Fine ceramic powders (<500 nm) exhibit exceptional physical and mechanical properties in engineered structural ceramics. The production of fine powders, in particular the non-oxide ceramics, via a cheaper route than the organic solvent route has been rather elusive. This paper examines the physical chemistry of sub-oxide vapour-phase reduction reaction for the nucleation of non-oxide ceramic phase. Well known vapour species eg SiO and BO in the production of technical ceramic powders (SiC, BN) are particularly discussed for understanding the nucleation process of SiC and BN ceramic phases respectively. The regimes of partial pressures and temperatures are particularly 'identified. The calculated nucleation rate as a function of the temperature is compared with the experimental results on powder morphology. The production of amorphous and nanocrystalline h-BN powders is discussed in the context of substrate structure and thermodynamic parameters.IntroductionThe physical and mechanical properties of ceramic components are strongly dependent on the powder particle size and morphology used for their fabrication. For example the strength (Os) of the structural ceramic components increases with decreasing average grain-size (d) in accordance with the Hall-Petch relationship: Os = 0""0 + k/(d)1/2. Here k is an empirical constant which can be established from the graphical relationship. However as the particle size approaches submicrometer-size range, the dependence of strength on the particle size becomes more complex [1]. The design of ceramic components based on nanometer-size particles have recently become an important field which can offer ceramic materials with properties comparable to their metal counterparts. Several materials based on these concepts have been developed and reported by Niihara [2]. For example, the Al2O 3-SiC nanocomposite, having average B-SiC grain size 0.3-2um with intragranular SiC particulates of 5-10 nm has unusually high strengths (1100 MN/m2) at low and elevated temperatures combined with enhanced fracture toughness (> 4 MN-ml.5) which is an unusual combination in structural ceramics. Besides mechanical properties, as the particle size of ceramic powders approaches the nanometer-size range, the charge transport properties also improve by many times. The effect of particle size on the electrical conductivity of Si3N4-TiN composites has been well documented [3.4]. The size of ceramic particulates without doubt plays a pivotal role in determining the properties of ceramic components."

Jan 1, 1996

By G. L. Fredrickson, T. A. Johnson, B. R. Westphal, J. C. Wass, S. X. Li, D. Vaden

"Recovery of uranium from the Mk-IV and Mk-V electrorefiner vessels containing a LiCl/KCl eutectic salt has been on-going during the pyrometallurgical processing of used nuclear fuel for 14 and 12 years, respectively. Although austenitic stainless steels are typically utilized for LiCl/KCl salt systems, the presence of cadmium in the Mk-IV electrorefiner dictates an alternate material. A 2.25Cr-1Mo alloy (ASME SA-387) was chosen due to the absence of nickel in the alloy which has a considerable solubility in cadmium. Using the transition metal impurities (iron, chromium, nickel, molybdenum, and manganese) in the electrorefined uranium products, an algorithm was developed to derive values for the contribution of the transition metals from the various input sources. Weight loss and corrosion rate data for the Mk-V electrorefiner vessel were then generated based on the transition metal impurities in the uranium products. To date, the corrosion rate of the 2.25Cr-1Mo alloy in LiCl/KCl eutectic is ""outstanding"" assuming uniform (i.e. non-localized) conditions.IntroductionLow-enriched uranium products are being recovered from the Experimental Breeder Reactor-II (EBR-II) and Fast Flux Test Facility (FFTF) used nuclear fuels by a pyrometallurgical treatment process at the Idaho National Laboratory (INL). The treatment process comprises a set of operations designed to neutralize bond sodium, recover uranium from radioactive fission products, and place the fission products into acceptable waste forms [1-2]. Reactive sodium metal, essential for heat transfer purposes during reactor operations, is readily converted to chloride during the process. Electrorefined uranium products are currently being stored pending a final disposition decision. Treatment of the EBR-II used driver fuel was initiated in June 1996 while blanket fuel processing started in September 1998. These treatment processes continue on the balance of the used fuels."

Jan 1, 2011

By Steven Wright

The reduction of a slag produced 6om the recycling of lead batteries was studied in a kilogram scale laboratory investigation by reacting with graphite at temperatures of 1180 and 1200°C. Simultaneous reduction of PbO, Fe203, Sb203 and As203 occurred with the Sb and As reporting to the metal while the lead content in the slag was above 2 wt%. The Sb and As distributions between metal and slag were strongly affected by temperature and slag oxidation state. The rates of reduction of PbO and Sb203 increased with increasing slag basicity and temperature and decreased as the PbO content in the slag decreased. The reduction rate of PbO from these slags was similar to other industrial lead slags at the same CaO/SiO2 ratio and temperature. The implications of the behavioural similarities of the antimonous slags during reduction with carbonaceous reductants and other lead slags are briefly discussed.

Jan 1, 1994

By Pesic. Batric

A novel chitosan-pyridoxal-epichlorohydrin was synthesized and evaluated in our laboratories. The evaluation was achieved by performing kinetic and equilibrium studies of copper sorption. The parameters examined were pH, temperature, concentration of copper, particle size and selectivity of copper sorption against iron, zinc, cadmium and cobalt. It was found that pH was the most important parameter, and sorption of copper increased with pH increase in the range pH 2.5-6.0. The low activation energy of the sorption reaction, 1 1.13 kJ/mole (2.66 Kcal/mole), showed that temperature was not an important parameter. The synthesized chitosan was selective against iron, zinc, cadmium and cobalt. The selectivity with respect to last three metals was achieved by the kinetic difference of sorption, as sorption of copper was much faster than for other metals. Iron (Fe2+) does not adsorb on chitosan. The mechanism governing the sorption of copper is intraparticle diffusion. This finding was supported by the dependance of copper sorption on the square root of time, the low activation energy, and the fit of experimental data in the diffusion through the product layer equation.

Jan 1, 1994

By A. Deneys

An experimental technique has been devised for studying the reaction kinetics of the reaction: ZnO + 2Fe0 = Zn(g) + Fe203, by which zinc evolution can occur from a molten slag bath in the absence of a carbonaceous reductant. When studying the reaction kinetics by heating from room temperature, solid state reactions and poorly defined melting points may obscure the starting point of the reaction. In order to eliminate this problem, an experimental technique was devised whereby two molten slags could be melted independently, and then mixed, to provide a well defined starting point from which to begin taking measurements. Two crucibles were mounted in a vertical reaction cylinder. The upper, mild steel, crucible had a bottom pouring plug which was sealed by a steel stopper rod. A fayalite mixture was contained in this crucible. The lower crucible contained an A12O3-CaO-SiO2-ZnO solution. Once the two slags had been melted, the steel stopper rod was removed from the upper crucible. The upper, reduced slag (fayalite in equilibrium with the upper steel crucible), drained into the lower crucible where the two slags were mixed by submerged argon stirring. Dip samples were taken to measure the zinc content of the final mixture as a function of time. The experimental procedure will be described, as well as results of experiments which were conducted on synthetic slags. The system investigated was similar to the lead blast furnace slag which is produced by the primary lead smelters of Missouri, USA.

Jan 1, 1997

By Yang Tian-zu

The separation of precious metals from base metals containing in gold-antimony alloys by selective chlorination leaching under controlling potential was studied in this work. The effects of the consumption of hydrogen peroxide, the concentration of hydrochloric acid, the concentration of sulfuric acid, leaching temperature, leaching time and the liquid-solid ratio in hydrochloric acid system on the leaching efficiencies of the base metals have been investigated. The optimal leaching conditions of the gold-antimony alloys are as follows: hydrochloric acid concentration 4.0mol?L-1, sulfuric acid concentration 1.2mol?L-1, liquid-solid ratio L:S=7.5:1, the leaching temperature 80 0C, leaching time 2h, and the oxidation potential of the leaching system 400±20mV( vs SCE).The leaching efficiencies of copper, nickel and antimony are more than 99% and the gold leaching efficiency is about 0.042% under the above leaching conditions. The base metals containing in the gold-antimony alloy are separated from the precious metals thoroughly.

Jan 1, 2006

By Marietta Canty

A paper is presented in which an innovative biological process is described for the treatment of cyanide-, metals-, and nitrate-contaminated mine process water. The technology was tested for its ability to detoxify cyanide and nitrate and immobilize metals in wastewater from agitation cyanide leaching. A pilot-scale demonstration is described in which a pilot plant was constructed to demonstrate the technology on a mine process waste stream at a mine in Nevada. The demonstration was performed Jointly under the Mine Waste Technology Program (MWTP), which is funded by the U.S. Environmental Protection Agency (EPA) and is jointly administered by the U.S. Department of Energy&apos;s (DOE) Western Environmental Technology Office (WETO) and the Superfund Innovative Technology Evaluation (SITE) Demonstration Program under Interagency Agreement Number DW89938513-0 I-0. MSE Technology Applications, Inc. (MSE) located in Butte. Montana, was the contractor responsible for conducting the project, and Pintail Systems, Inc., of Aurora. Colorado, was the technology provider. The pilot-scale unit was field-tested at the Echo Bay McCoy/Cove Mine southwest of Battle Mountain, Nevada. The biotreatment process was considered to be successful in destroying cyanide in the mine process water. The process was also determined to be effective in removing metals. The pH was consistently neutralized, and nitrates were successfully removed from the mine process water. As a result of conducting these pilot-scale tests, the biotreatment process was concluded to be an innovative, cost-effective alternative for the treatment of mining wastewaters.

Jan 1, 1998

Numerical simulation of the fluid flow and heat transfer has been carried out for a waste-heat boiler in an Outokumpu type copper flash smelter. In this boiler, SO2-containing off-gas flows into the waste-heat boiler radiation section at about 1350°C. A fraction of cooler off-gas from the electrostatic precipitator at about 200°C was recirculated into the radiation section, and a small amount of ambient air was leaked into the boiler from the bottom. The computational results show that the flow is strongly recirculating and distinctly three dimensional in most of the boiler, particularly in the radiation section. The hot off-gas cooled down rapidly after entering the radiation section due to radiation. The predicted flow pattern and temperature distribution were in a good agreement with laboratory models and industrial measurements.

Jan 1, 1995

By H. Y. Sohn

The purpose of this article is to analyze critically and quantitatively the effect of chemical equilibrium on the overall rates of fluid-solid reactions. It is shown through a mathematical analysis that a reaction with a small equilibrium constant (a positive standard free energy of reaction) is more likely to be rate-controlled by pore diffusion or mass transfer than a reaction with a large equilibrium constant. The overall reaction rate of the former also tends to be slow. Furthermore, the apparent activation energy of such a reaction approaches the standard enthalpy of reaction (M-f&apos;), rather than the true activation energy of the chemical reaction. The Law of Additive Reaction Times developed by the author is shown to apply to equilibrium-limited fluid-solid reactions and to be useful in quantitatively analyzing the behavior of such reactions.

Jan 1, 2003

By Cesimiro Fabian

The crystallite size of copper electrodeposits was determined by X-Ray powder diffraction analysis using a General Area Detector Diffraction Solution (GADDS) diffractometer. Crystallite size was calculated for copper thin films which were deposited on a 316 stainless steel rotating cylinder electrode (RCE) in the presence and absence of additive ?A?. The crystallite size was calculated from a corrected full width at half maximum (FWHM) of the [110] peak profile using the Scherrer equation. The test of significant difference on crystallite size was derived using Kruskal-Wallis method. It was found that in the absence of the additive the median crystallite size was 426, which decreased to 364 in the presence of the additive. As the additive degraded, the crystallite size increased to a size similar to that observed in the absence of additive.

Jan 1, 2003

By Carl C. Nesbitt

A study was conducted to examine the treatment of metal-bearing effluents by precipitating the metals as sulfides and simultaneously collecting the particles by flotation. The precipitant was hydrogen sulfide gas which was introduced into a bench-scale column cell with air. The study included experiments of various flotation reagents and column configurations in treating solutions containing dissolved copper, lead, mercury, iron, zinc and cadmium. An acidic laboratory waste from a local copper operation was used to test the column with a solution containing several metals and arsenic. Precipitates were observed to form at the gas/liquid interface when the gas mixtures were rich in H2S. Copper, mercury, lead, and cadmium were precipitated from solution as sulfides to concentrations near detection limits. The flotation of these precipitates was enhanced with small amounts of S-7151 promoter from American Cyanamide Company and Dowfroth 1263 mixed with the feed. The recovery of the precipitates in this manner produced a smaller volume slurry which was easier to dewatering than a slurry produced by conventional precipitation techniques. The low pH and high oxidation-reduction potential in the cell from H2S addition was not conducive to form precipitates of iron, zinc or arsenic. However, these ions were precipitated as sulfides by raising the pH of the column discharge.

Jan 1, 1994

By Jennifer Murphy, Brad S. Schake, Karol Holmes, John R. FitzPatrick, Mike H. West

"The separation and purification of uranium from either nitric acid or hydrochloric acid media can be accomplished by using either solvent extraction or ion-exchange. Over the past two years at Los Alamos, emerging programs are focused on recapturing the expertise required to do limited, small-quantity processing of enriched uranium. During this period of time, we have been investigating ion-exchange as a method for extraction/purification of uranium from acidic media. In addition, waste stream polishing is associated with this effort in order to achieve more complete removal of the uranium prior to recycle of the acid. Extraction chromatography has been demonstrated to further polish the uranium from both nitric and hydrochloric acid media thus allowing for a more complete recovery of the actinide material and creation of less waste during the processing steps.We will discuss contact experiments for evaluation of eleven different resins for uranium removal from nitric acid, the evaluation (again by contact experiments) of uranium elution from the ion-exchange media by various chemicals, and small-scale experiments for the removal of 235U from nitric acid. Larger-scale (1 DO-gram) flow experiments, using depleted uranium, were done after the small-scale evaluation of the selected resin. A discussion is also included concerning the shortcomings of the contact experiments and how the flow experiments were modified in order to overcome these problems. We will also discuss the application of ion-exchange for some specific process needs at Los Alamos.Contact experiments were used to evaluate some commercially available solvent-impregnated resins in addition to evaluation of several resins of this type synthesized in our laboratory. These experiments involved both nitric and hydrochloric acid media. The data from these experiments will be used to determine the column size and amount of resin required to polish the waste stream produced by the ion-exchange process described above. Small-scale flow experiments will be described and data given on the mass balances achieved using this two step process.Future work for evaluation of new ion-exchange and solvent-impregnated resins as well as the search for new eluants will be discussed. Other future experiments for both processes, including large-scale experiments, will be discussed in detail."

Jan 1, 1996

By Nobuhiro Oguma, Yuji Mizuta, Hideya Sato, Shigehiko Iwahori

"Recyclable materials containing copper and precious metals have been treated at the Mitsubishi Process in Naoshima. In 2003, a new incinerating and melting plant (pre-treatment plant) for waste materials, such as shredder residue of automobile and scrapped appliance, was constructed. All of produced slag/metal mixture is treated at the Mitsubishi Process, and which results in the significant increase of recyclable materials treatment. The combination of two processes has realized a highly efficient and environmentally friendly system for recycling valuable metals in the waste which used to be sent to a landfill. Naoshima continues to make efforts to achieve the highly efficient operations of the two processes, and plans to increase the treatment of recyclable materials further. This paper summarizes the recent operations and the various improvements implemented in the pre-treatment plant.IntroductionRecyclable materials containing valuable metals such as copper and precious metals have been treated at the Mitsubishi Continuous Copper Smelting and Converting Process (Mitsubishi Process) since the start-up in 1991. In the early stages, recyclable materials consisting mainly of metal scrap were charged into the process and the treatment had been increased steadily. In order to promote the recycling business, treatment of various kinds of materials including printed circuit boards was started. However, the treatment hit the ceiling due to a limitation of furnace boiler capacity, since they contained large amounts of combustible materials. In addition, severe corrosion of boiler tubes was caused by halogen contained in recyclable materials."

Jan 1, 2012

By Jose Castro

The growing demand of scrap to supply the electric arc furnace has driven to search for new alternatives of raw material. The DRI produced using self-reducing pellets has become competitive due to the potential use of a wide range of carbonaceous materials such as coal, charcoal, biomass etc. In this context, the rotary kiln process using improved technologies such as post-combustion and self-reducing burden is a promising source of high quality raw materials. This paper presents a mathematical model of the rotary kiln process designed for self-reducing pellets and post-combustion. The model is based on the transport equation of two-phase flow, energy and mass transfer. The solid material is composed of a typical self-reducing pellet. The model considers the solid phase (C, volatiles, Fe2O3, Fe3O4, FeO, Fe, H2O, SiO2, Al2O3, MgO, P2O5, K2O, Na2O, FeS, CaO and gangue) and the gas phase (N2, O2, CO, CO2, H2, H2O, SO, SO2 and SiO). For each of the above components a conservation equation is solved and the mass and energy transport is accounted. The set of differential equations are coupled by the rate equations describing the kinetics of the several reactions, which take place within the rotary kiln. All the conservation equations are solved based on the finite volume method applied for a three-dimensional cylindrical coordinate system. Simulation results are presented for global parameters such as metallization degree, productivity, gas utilization ratio and calorific value. Inner conditions such as three-dimensional gas and solid temperature patter and compositions are discussed.

Jan 1, 2006

By Onder Guney, Erdem Demirkesenm

"In this study, the crystallization behavior and thermal expansion coefficient of a lithium disilicate (LS2) based glass-ceramic derived from SiO2-Li02-AhO3-K2O-ZrO2 system was investigated by using x-ray diffraction (XRD), high temperature x-ray diffraction (HTXRD), differential thermal analysis (DTA) and dilatometer techniques. Analytical reagent grade chemicals were chosen as raw materials for preparing glass batches. Nucleation and crystal growth heat treatments were planned according to DTA results. The amounts of the amorphous and crystalline phases developed during the heat treatments were determined by quantitative XRD. XRD results of crystallized samples showed simultaneous formation of lithium silicate (LS) and quartz in the early stage of the crystallization followed by formation of lithium disilicate (LS2) at higher temperatures. The thermal expansion coefficients of glassceramics were also measured depending on the applied heat treatments.IntroductionSignificant developments occurred in all ceramic materials provide the fabrication of high quality dental implants [1]. Glass ceramic based dental restorations like dental inlays, crowns, bridges and veneers are becoming increasingly popular with their reliable and durable performance [2,3]. In addition to their advanced functional properties, glass ceramic implants especially lithium disilicate glass ceramics also face the esthetics expectations of patients and dentists and in this way they are starting to take the place of metal based restorations today [1,3,4,5]. Lithium disilicate glass-ceramics derived from multicomponent glass systems have some superior mechanical and optical properties comparable to natural teeth [ 6]. In restorative dentistry, mechanical characteristics of biomaterials play very crucial role in order to resist the masticatory forces occurred during biting and chewing [7] According to three point bending test results of Roland, flexural strength of the lithium disilicate glass-ceramics were 400±40 MPa and their fracture toughness (K1c) are approximately 3,3 MPa m112 [2,6]. In addition to high mechanical strength, aesthetic appearance is another important prerequisite as material for dental restorative applications. Translucency and light transmission of the LS2 glass ceramics mimic enamel. Moreover, opacity of the material can also be adjusted depending on the restoration types [2,6, 7]. These superior properties of the LS2 glass ceramics are directly related with chemical composition of the base glasses and controlled crystallization heat treatments [ 4, 7]. The aim of the present work is to determine the effect of heat treatment schedules on the crystallization behavior and thermal expansion of the LS2 glass-ceramics."

Jan 1, 2011

By R. T. Jr. Faria, H. Vargas, R. Toledo, S. Cosin, V. P. Souza

"With the purpose of decrease environmental impact, caused by industrial residues (just discarded in the environment) and clay extraction in the ceramic industry, sanitary ware wastes were incorporated into clay. In contrast, it is important to evaluate not only the technological essays but also gases emissions in the ceramic firing process. The pollutant gases emitted in ceramic with residues can be in much larger concentrations than that in a pure clay ceramic firing or, on the other hand, can decrease the pollutant gas concentrations. With the aid of thermal analyses and photo acoustical techniques it was observed that sanitary ware waste can reduce the C02 emission. The gas emissions were shown as in function of firing temperature from 300 DC to 1100 DC. In order to analyze phase transformations during the firing process, clay samples and wastes were both analyzed by x-rays fluorescent chemical analysis and x-rays diffraction.IntroductionResearch works on the structural and physical changes that wastes, mainly industrially produced, cause to the final ceramic product has been rapidly expanding in these last two decades. See, for instance references in [1]. In spite of these examples of a continuous effort to incorporate wastes into clay ceramic motivated by technical and economical advantages, environmental issues are still a matter of concern. However, the gas emission due to the clay firing process and its related atmospheric pollution may be enhanced as a consequence of an incorporated waste [2]. It is known that the firing of clay ceramics in conventional furnaces using fuels such as wood, charcoal, heavy oil and natural gas generates appreciable amounts of gaseous components, mainly carbon dioxide (CO2), carbon monoxide (CO) and methane (CH4). Additionally to the atmospheric pollution, these gas sets could be harmful to the human health and can corrode equipments [3,4]."

Jan 1, 2012

By David Ellis

The next generation of Reusable Launch Vehicle (RLV) will utilize regeneratively cooled combustion chamber liners in the engines. The current design calls for using a new Cu-8 at. % Cr-4 at. % Nb (Cu-8 Cr-4 Nb) alloy for the liners. Work is ongoing to characterize the thermophysical and mechanical properties of the alloy from - 253 to 800°C, the temperature range to which the alloy will be subjected during service. The alloy has been commercially produced in quantity for NASA. The powder size has been characterized and the microstructure examined. The powder was extruded into bar using a commercial extrusion press. In addition, samples have been hot isostatically pressed (HIPed) at NASA Glenn Research Center. Both processing methods produced fully consolidated material. Transmission electron microscopy (TEM) revealed highly faulted Cr2Nb and some elemental precipitates. Cryogenic tensile testing showed the extruded specimens had significantly higher strengths than NARloy-Z (Cu-3 wt % Ag-0.5 wt % Zr) even after being subjected to a simulated braze cycle. The Young&apos;s moduli (Cu-8 Cr-4 Nb) were lower than NARloy-Z. The lower moduli is highly beneficial for reducing thermally induced stresses in rocket engine combustion chamber liners and similar applications.

Jan 1, 1999

Lance based copper-nickel matte converters have become an established technology in the field of base metal sulphide smelting and converting. An Ausmmelt® converter is currently being constructed at Anglo Platinum in South Africa to convert a nickel-copper rich matte containing platinum group metals (PGM&apos;s). The accurate prediction of the matte chemistry is required to control the composition at the endpoint which influences segregation of PGM&apos;s during the subsequent slow cooling and magnetic separation processes. A hybrid modelling approach is introduced in this paper that incorporates both the effect of thermochemistry and system dynamics. It will be shown how the model relates to fundamental conservation laws, while still providing enough flexibility to adapt to changing operating conditions. It will also show how off-line modelling can be incorporated into a robust on-line model. Based on the data from many pilot plant trials, the model prediction performance is shown to be within the accuracy requirement set by industry and therefore constitutes a reliable basis for model based control. The final generic model structure takes on the form of an thermodynamically integrated ARMAX hybrid model. The final model has the advantages of being dynamic, adaptive, robust and it can be related to thermochemical fundamentals.

Jan 1, 2002

By W. Kasprzak

Modern light metals processing technologies are very complex and involve a diverse set of variables that must be quantitatively evaluated. The most effective way to design new casting processes that deliver specified metallurgical and mechanical properties is to develop a method of simulating the "real-time" process within a test sample of sufficient size. The results can then be analyzed and the required optimizations can be performed. This paper presents a novel method of simulating the industrial casting processes in a laboratory environment using an experimental apparatus based on the principle of high frequency induction heating. The applicability and accuracy of the proposed analytical method is demonstrated, for example, by simulation of the solidification and heat treatment of a test sample composed of two dissimilar materials. The simulation can be used to develop a stress model for an engine block made from an aluminum based alloy with iron cylinder liner inserts.

Jan 1, 2002

By Hong Yong Sohn, Miguel Olivas-Martinez, Zhixue Yuan

A novel flash ironmaking process that directly reduces iron oxide concentrate particles by gas is under development. The goal of this work was to study the possibility of reoxidation of iron particles in various gas mixtures. As the product iron cools down in the lower part of the flash reactor, conditions may become favorable for reoxidation because of equilibrium and high reactivity of iron particles. The effects of temperature (823 – 973 K) and H2O partial pressure (40 – 100 pct., Ptotal = 86.1 kPa) on the reoxidation rate were examined. The pressure dependence was first order with respect to water vapor, and the activation energy was 146 kJ/mol. A complete rate equation that adequately represents the experimental data was developed. For oxidation in O2-N2 mixtures, the effects of temperature (673 – 873 K) and O2 partial pressure (5 – 21 pct., Ptotal = 86.1 kPa) were determined. Reoxidation in pure CO2 was also investigated at 873 – 1073 K for comparison.

Jan 1, 2014