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By A. D. Neuman, C. C. Davis, M. R. Lopez, A. C. Martinez, T. A. Nothwang, F. G. Hampel, S. L. Voit

"One of the thrust areas for the Global Nuclear Energy Partnership (GNEP) program is the development of actinide bearing fuels for transmutation in a fast reactor. Mixed Oxide (MOX) fuel has an extensive fast reactor irradiation history and thus is being considered for use as a baseline composition from which minor actinides can be incorporated for use as a transmutation fuel. The current study involves characterization of precursor powders and pellets destined for the Advanced Test Reactor in Idaho. These pellets will have three compositions: one standard MOX composition, (U0.80Pu0.20)O1.98, and two compositions of minor actinide mixed oxide (MAMOX) with oxygen to metal ratios (O/M) of (U0.75Pu0.20Am0.03Np0.02)O1.98 and (U0.75Pu0.20Am0.03Np0.02)O1.95. The precursor powders were characterized using a field emission gun scanning electron microscope (FEG-SEM) to determine particle morphology, size, and size distribution. An electron probe microanalyzer (EPMA) was used to characterize element distributions in the pellets.IntroductionThe fundamental purpose of GNEP is to enable a fuel recycling partnership between member nations. The customer nations utilize the fuel for electricity generation provided by and subsequently recycled by the supplier nation. The supplier nation recycles the actinide constituents, mainly uranium and plutonium, in advanced nuclear power reactors, and thus reducing waste volumes [1, 2]. Nuclear materials are strictly controlled through the International Atomic Energy Agency. One of the thrust areas supported by the GNEP program is the development of actinide bearing fuels for transmutation in a fast reactor under the U.S. Advanced Fuel Cycle Initiative (AFCI) in order to transmute long-lived transuranic actinide isotopes into shorter-lived fission products [3].MOX fuel has an extensive fast reactor irradiation history and thus is being considered for use as a baseline composition into which minor actinides can be incorporated for use as a transmutation fuel [4]. Irradiation performance data on oxide fuels with high concentrations of minor actinides is limited, which has prompted this study. This paper discusses the characterization results of precursor powders and pellets prepared for the Advanced Test Reactor in Idaho to determine the effects of including minor actinides in the fuel, and addresses two fuel test matrices proposed by Hilton et al. [3]. The pellets will have three compositions: one standard MOX composition, (U0.80Pu0.20)O1.98, and two compositions of MA-MOX with O/M of (U0.75Pu0.20Am0.03Np0.02)O1.98 and (U0.75Pu0.20Am0.03Np0.02)O1.95. The precursor powders, uranium oxide (depleted, DUO2 and highly enriched, HEUO2), neptunium oxide, NpO2, americium oxide, AmO2, and plutonium oxide, PuO2, were characterized using a FEG-SEM for particle morphology, size, and size distribution. The morphology of the actinide powders was studied in the areas of flowability and porosity in order to predict manufacturability. The MOX pellets were characterized using an EPMA in order to determine impurity levels and locations."

Jan 1, 2008

By Bin Xu, Qian Li, Ya-xuan Wang, Yong-bin Yang, Xi Zhang, Tao Jiang

The effects of common associated sulfide minerals including pyrite, arsenopyrite, galena and sphalerite on thiosulfate leaching of gold were studied in this work. Sulfide minerals had significant effects on gold leaching because that the dissolved products of sulfide minerals precipitated on gold surface to form coating layer. The degree of sulfide minerals impact on gold dissolution decreased in the order of pyrite ≈ galena > arsenopyrite > sphalerite, while the degree of effects on thiosulfate consumption decreased in the order of pyrite > arsenopyrite > sphalerite > galena. The additive CMC (Carboxymethyl cellulose) could not only reduce thiosulfate consumption but also increase gold dissolution. The mechanism of this might be that CMC could restrict the decomposition of thiosulfate by cupric ions and the precipitates on gold surface.

Jan 1, 2015

By Keith Rozenburg, Ivar Reimanis, Jesus Chapa

"Experiments in conjunction with finite element analysis (FEA) are used to better predict crack propagation in ductile/brittle graded composites. Cu/W graded composites were fabricated by stacking discrete layers of powders and hot pressing. Crack propagation was studied by loading a notched beam in four point bending and examining the subsequent crack deflection. The notch was placed within a particular composition of material, oriented in a direction perpendicular to the gradient direction. Elastic and plastic mismatch between different constituents in the graded composite induce shifts in the phase angle of loading, thereby causing the crack to deflect. FEA indicates that thermal residual stress has a negligible ""influence on the crack path. The combined FEA and experimental results suggest that elastic mismatch is the single most important material property-related factor in controlling crack deflection.IntroductionMany 'applications would benefit or may even require materials whose performance or functionality must vary spatially. While the concept of functionally graded materials has existed for nearly one hundred years, it is only within the last fifteen years, that research efforts have focused on generic issues in processing, properties and performance of functionally graded materials. This generic research effort has brought together scientists and engineers from traditionally different disciplines to address common issues with graded composites. The current work focuses on issues in structural joining. A wide variety of applications require some type of joining between dissimilar materials. Examples include thermal barrier coatings for turbine engines, wear resistant coatings for tools, ceramic engine parts, and microeiectronic devices, as well as many traditional applications involving metallic welding. The joints may either be discrete, involving a single interface, or they may· be spatially graded in composition. Extensive theoretical and experimental information exists on discrete bimaterial and trimaterial joints, but relatively little exists for graded joints or composites"

Jan 1, 2000

By W. Petruk

A study was performed to determine whether mineral textures affect are breakage during grinding, and to establish a correlation between are breakage and mineral liberation. A base metal are from the Brunswick No. 12 deposit in New Brunswick, Canada was ground for different periods of time in a laboratory ball mill, and both the unbroken are and the ground products were studied by image analysis. Similar size distributions were obtained for material from the 15-minute grind in a laboratory ball mill (K. 0 67 pm), for the grinding circuit discharge from a commercial mill (K. 0 = 59-72 pm), and for pyrite grains in unbroken are (K,. = 74 pm). This similarity indicates that the 1S-minute grind separated weakly adhering pyrite grains along grain boundaries, and represents the limit of easy breakage for the are. At this grind (15 minutes) large discrete are mineral grains and weakly adhering interstitial fillings aIrong pyrite were liberated. On the other hand, the 15-minute grind neither separated rooderately bonded pyrite grains nor released rooderate1y bonded interstitial minerals from pyritei a 45-minute grind (K.. 31 pm) in a laboratory ball mill was required. For Brunswick No. 12 are, a 45-minute grind in a laboratory ball mill (Keo = 31 pm) is equivalent to regrinding in a commercial mill (K ?? Fl:$ 30 pm). Grinding beyond 45 minutes in the laboratory ball mill broke the are by fracturing pyrite across grain boundaries and by Chipping grain edges. Such intense grinding (longer than 45 minutes) did not markedly increase sphalerite liberation. In contrast, the intense grinding increased galena liberation because a significant proportion of the galena occurs as minute inclusions in pyrite. These findings show that ore breakage and coincident liberation depend upon size distributions, intergrowths, and mode of occurrence of the minerals in an ore.

Jan 1, 1988

By Giulio R. Altoé, Sergio N. Monteiro, Ygor M. Moraes, Rômulo L. Loyola, Frederico M. Margem, Gabriel O. Glória

The tensile properties of DGEBA/TETA epoxy matrix composites reinforced with different amounts of PALF fibers were evaluated. Composites reinforced with up to 30% in volume of long, continuous and aligned PALF fibers were tested in an Instron machine at room temperature. The fracture was analyzed by SEM. This one revealed a weak fiber/matrix interface, which could be responsible for the performance of some properties. The results showed significant changes in the mechanical properties with the amount of PALF fibers.

Jan 1, 2015

By A. M. Alfantazi, M. Boissoneault, D. B. Dreisinger, J. Synnott

Acid mist generation is a major concern in zinc, copper and nickel electrowinning industries and there is a strong environmental drive to control its emission into the work environment. Foaming reagents are typically added to the electrolyte to alleviate this problem. In zinc electrowinning, Licorice and Saponin are examples of foaming reagents used for this purpose. In order for the foaming reagent to be effective, its foaming behavior must be determined. In this work, a test procedure was developed to study the foaming characteristics of various surfactants for use as foaming agents to control acid mist in aqueous metal electrowinning. This new test was termed as "mini-flotation test" and it was used to study the foaming behavior of a large number of reagents in an industrial zinc sulfate electrolyte under simulated zinc electrowinning conditions (gas sparging). In addition, the influence of important process parameters such as current density, electrolyte temperature, reagent addition level and sulfuric acid concentration on the foaming characteristics of the electrolyte for each surfactant were investigated. The results of this study have identified the most important factors that influence foam formation, growth and stability. This method could be used as a process control for reagent addition in the cellhouse by generating a calibration curve for the optimum electrolyte conditions.

Jan 1, 1997

By Xiao Songwen

Based on the anion coordination polyhedron growth unit theory, the polymorph transformation mechanism of antimony white (Sb2O3) in hydro-process was investigated. The new findings had been verified in the commercial-scale test and it was shown that adding a small amount of tartrate ions was economical and effective for polymorph transformation of antimony white in hydro-process.

Jan 1, 2003

By Chen Dong, Yuanling Gao, Jilai Xue, Jun Zhu, Luxing Feng

"Porous Ni-Ti alloy has many applications in a wide range of engineering areas. The porous NiTi alloys were prepared from Ti and Ni powders in sintering process under argon atmosphere. The major chemical compositions of the sintered Ni-Ti body were Ni Ti, Nh Ti4O and Nh Ti, respectively, the internal pore structures were characterized by image analysis technique, which were dependent on various processing parameters such as sintering temperature, amount of poreforming agent, forming pressure, etc. The results show that the porous alloy samples had the characteristics of uniform pore and high open porosity; pore-forming agent and sintering temperature are important factors in porous; pressure affected the sintered products' pore, by affecting the combination of alloy powder with pore-forming agent.IntroductionPorous Ni-Ti alloy materials exhibit not only excellent shape-memory and superelasticity, high yield strength and ductility, good corrosion resistance and biocompatibility, but also have low density, low stiffness, and high energy absorption rate due to their porous structures [1]. In recent years, these porous Ni-Ti alloys have found applications in a wide range of engineering areas, such as bone implants [2-4], impedance-matching connectors [5], energy-absorbing structures [6,7], separators [8] and actuators [9], etc.Pore characteristics can play very important role in determining of the performance of porous NiTi alloys. For example, when the alloys are used to repair or replace hard tissue implant material, the pore shape and size not only determine their mechanical properties, but also have great effect on the fluid transmission of human body. The pore characteristics can also influence the stressstrain behavior of the porous Ni-Ti alloy and, thus, strongly affect their mechanical properties, superelasticity, and fracture mechanisms [10].In this study, the Ni-Ti alloys with high porosity were prepared in a powder sintering process under argon gas. The pore characteristics were investigated using SEM, XRD and image analysis techniques, especially in association with the content of pore-forming agent, sintering temperature and compacting pressure."

Jan 1, 2011

By D. E. Larson

In cooperation with the National Institute of Environmental Health Science and the National Institute for Occupational Safety and Health the U.S. Bureau of Mines conducted grinding research on non-asbestiform tremolite. The goal of this effort was to prepare ground tremolite samples containing a considerable percentage of acicular grains with aspect ratios (approximately = 8um long with widths = 1 um) similar to those of asbestos particles suspected of causing cancer, Optical-and electron-microscopic examinations were used to monitor the size and shape of the grains in the ground products. Although customized milling techniques do have noticeable effects in producing acicular grains, the prismatic nature of fracturing in the non-asbestiform tremolites limited the number of acicular grains that could be purposely produced, and indicates that the likelihood of high concentrations of acicular particles occurring under normal mining and milling conditions is small.

Jan 1, 1991

By Zenjiro Asaki, Teruo Tanabe

"To clarify the formation of light rare earth (R =Ce, Pr, Nd or Sm) -Fe compounds in the reduction-diffusion (RD) process, two kinds of experiments were carried out: (a) RD experiment in which briquettes composed of R oxide powder, Fe (particles or wire) and CaH2 were reacted, and (b) immersion experiment, where an Fe plate was immersed into R-Fe melt having the composition of Fe-side liquidus line in Fe crucible. The compound formation was examined by using XRD, SEM and EPMA. The formation rates of RzFe17 measured by the RD experiment were compared with those obtained by the immersion experiment. The growth rates of compounds obtained in the RD experiment for Pr-Fe and Nd-Fe systems were much lower than those obtained in the immersion experiment. This result was explained by the difference of the reduction rates of R oxides by Ca. The parabolic rate constants for the formation of RzFe17 were separated in two groups of (a) Pr-Fe and Nd-Fe systems and (b) Ce-Fe and Sm-Fe systems. This was discussed in connection with the difference of their crystal structures and the driving force of diffusion. The parabolic rate constants for the formation of compounds in Ce-Fe and Sm-Fe systems decreased in the order of RFez, RFe3 and RzFe17.IntroductionTo understand reaction behaviors in the production of rare earth (R) -iron intermetallic compounds, which have excellent magnetic properties, is very important from engineering point of view. And the reduction-diffusion (RD) process<O has recently attracted attention as one of the promising processes to economically produce R-related materials. A few fundamental studies on the compounds formation in the RD process have previously been reported. Qi, Hino and Yazawa(2) observed the formation of R(Nd, Sm)-Fe and R-Co compounds in the process from various view points. Song and Ogawa(3) measured the growth rates of Nd-Fe and Sm-Fe compounds by using Nd or Sm vapor supplied from Nd-Ca or Sm-Ca melts. The authors have also carried out fundamental studies (4)-(8) to clarify the rate and mechanism in the production of R-Fe intermetallic compounds."

Jan 1, 1998

By Steven R. Pittman, Colin McCullough, Peter Galuska

"Traditionally Continuous Fiber Aluminum Matrix Composites have been fabricated using high strength fibers and high strength matrices, often commercial alloys, with the goal of producing high strength composites. However the specific role of the choice of matrix alloy on composite properties has not been well established. One way to control composite tensile strength is to use coatings to introduce a low strength interface between fiber and matrix which tends to reduce the importance of the matrix selection, but unfortunately renders the transverse strength unacceptably low. Thus using a system with strong bonding between fiber and matrix is desirable, such as an alumina fiber / aluminum alloy matrix system. In this case the transverse strength is a strong function of the matrix strength. However the longitudinal strength then depends largely on the characteristics of the matrix. The important role of the matrix is discussed using examples of alumina fibers in various aluminum alloy matrices. The key attributes are matrix constituent phases, alloy chemistry, alloy reactivity with the fiber, and matrix strength. From the understanding developed in these systems a set of design rules may be established for selecting an optimum matrix. IntroductionAluminum matrix composites (AMC's) reinforced with continuous fibers offer very attractive property gains over AI alloys, such as strength, stiffness, and fatigue resistance. These gains are magnified when specific mechanical properties are compared which make them attractive candidates for replacing steel, nickel, titanium and aluminum alloy parts in weight critical applications (1). Many systems have been tried in the past; B/AI, C/AI, SiC/AI, Si-Ti-C-O/AI and AI203/AI. Technically B/AI was a very good system but was expensive in regard to both fiber cost and fabrication and SiC/AI and C/AI systems are still plagued with reactivity problems. The Si-Ti-C-O/AI appears to be a good strength system but with lower stiffness. Until recently, the AI203/AI was a low strength system, in part due to a lack of a high strength fiber. Recently 3M introduced a high strength AI203 fiber - Nextel™ 610, which leads to high strength composites (1,2) and may also be both low cost and also compatible with less expensive casting approaches for fabrication."

Jan 1, 1996

By Kang Wan, Lei Tang, Jianchao Li, Jieyu Zhang, Minqi Sheng, Jifang Xu

"The viscous flow phenomenon in slag close to the liquidus temperature was considered. A simple approach that liquidus temperatures of melt could be derived from viscosity data was employed. The potential of this method for estimating the liquidus temperatures of pure water and binary alloy was demonstrated. The liquidus temperatures of the CaO-Alz03 based slags obtained from the second derivative method depends upon the number of viscosity values available at different temperature intervals. The results indicated that plots start deviating from the straight-line behavior at temperature as expect, and the second derivatives show the break points at a certain temperature, which is the liquidus temperature. Comparisons among the present observations as well as the characteristic temperature of the selected slags, which measured by the hemisphere method and DSC, indicated that it is possible to get a reasonable idea of estimate the liquidus temperatures from activation energies for viscous flow.IntroductionThe liquidus temperature of slag, which has a significant effect on the kinetics of chemical reactions and the slag-metal separation, is extremely important for metallurgical operations. Experimental measurements of the liquidus temperatures of slags are difficult, since slags invariable supercool. In addition, behavior of a single constituent in a multi-component slag is different in different circumstances due to its interaction with other constituents. Hence, it is essential to study the liquidus temperature of each particular slag resulting from a special process. Usually, the compositions of the slags aimed to the single liquid region of the phase diagram. However, the phase diagram of many slag systems, which back often to the 1950's, involves considerable uncertainties. Many liquidus temperatures are given as dotted lines in Slag Atlas [1]. Disagreements between the phase diagram and the reality have been found [2]."

Jan 1, 2013

By Yoshihiko Maeda

It is said that the 21 st century will be an era of the remedy of the global environment. In order to reserve natural resources for the future and to avoid the dispersion of heavy metals after usage and to avoid pollution problems, it is extremely important to recycle heavy metals as much as possible by reasonable recovery procedures. The nonferrous metal industry is expected to play a important role in the recycling of heavy metals that are originally their products. From the depressed metal price experienced in Japan in 1980th due to the sudden change in current exchange rate between US dollar and Japanese yen, one of major nonferrous metal company, Dowa Mining, has diversified its business area not only to the so-called down stream, but also to the environmental business including metal recycling, industrial waste treatment and soil remediation by utilizing technologies and facilities once used or still used for mining and smelting of copper, zinc, lead and precious metals. In this paper some of these applications will be presented.

Jan 1, 2003

By Kenneth S. Coley, Michael Pomeroy, Elaine Chen

Recent work on modeling of BOF steelmaking is reviewed, highlighting the critical aspects of each approach. It is concluded that the most successful models should be based on a deep understanding of the mechanisms and kinetics of the critical reactions. The importance of the decarburization mechanism is discussed with particular reference to its role in droplet swelling or bloating which has a profound influence on the droplet residence time in the slag. Conditions which cause bloating are discussed and the rate determining step is proposed to be primarily nucleation of CO bubbles inside the metal droplet with some influence from growth by reaction at the bubble/metal interface. The discrepancy in the super-saturation ratio required for classical nucleation is discussed and an approach using a surface tension modifying parameter is illustrated. Finally, the role of CO nucleation in controlling the driving force for dephosphorization is discussed.

Jan 1, 2014

By John J. Dunkley

Recent years have seen the increased use of hydrometallurgy in the smelting and refining of metals. However this is often used as a final refining step, following an initial pyrometallurgical smelting process. Huge amounts of material are produced as melts which have to be cast, comminuted, and taken up into solution or leached. A common method is to granulate the melt and then grind it. In the case of metallic melts this can be difficult or unfeasible due to the ductility of the granulated particles. Water atomisation is capable of replacing the granulation and grinding stages with a single process step that can process in excess of 30t/hour of melt into particles as fine as 50 microns. Applications in operation in Co, Cu, Ni, Ag, Au, Pt and Rh refining are discussed together with potential applications in copper smelting.

Jan 1, 2003

By M. C. Furerstenau

Adsorption behavior of various surfactants on sulfide minerals is very much affected by the nature of the surface of the mineral. Since sulfides are naturally meta-stable, oxidation occurs when they are exposed to air, especially in aqueous environments. As a result. oxygen assumes a major role in sulfide flotation. Mechanisms of adsorption of various thiol collectors on sulfide minerals have been reviewed. The electrochemical behavior of various sulfide minerals has also been reviewed. Flotation behavior of galena, chalcocite, sphalerite, pyrite, chalcopyrite and pentlandite has been presented together with the. flotation of copper sulfide- nickel sulfide ore.

Jan 1, 1993

By Takafumi Kondo, Satoshi Yamashita, Noboru Masuko

"Aqueous oxidation of phosphite ions to phosphate ions with dissolved oxygen was examined at 80° C and pH 4.5 mainly from the stichiometric point of view. Dissolved oxygen alone can not oxidize sodilim phosphite in aqueous solution, but when sulfur dioxide is coexistent, cooperative oxidation for both sulfite and phosphite can occur in aqueous solution. Sulfur dioxide itself is well known as a reducing agent, but it also reacts as an oxidation-promoting agent for other species under a certain condition. So sulfur dioxide is· a promising cheap reagent for waste phosphite processing.IntroductionIn a liquid-phase oxidation reaction using the dissolved oxygen gas, the eoexistence of a copper salt is required generally. Recently, it was reported that the oxidation reaction progressed by using mixed gas of sulfur dioxide and oxygen without the copper catalysis, and the attention has been collected1·3). The present authors also noticed the phenomenon since the early time and have been studying on the reaction mechanism of sulfur dioxide in liquid phase oxidation 4l. It was found that; by using the SO2-O2 mixed gas, the oxidation of phosphite ions to phosphate ions proceeded efficiently in sulfuric acid solutions. In the present report, the applicability of SO2-O2 mixed gas as a cheap oxidizing agent to the industrial processing of the waste solution of electroless nickel· plating is investigated. It is well known that the sulfur oxide dissolved in aqueous solution is oxidized ·by the oxygen in the air to sulfuric acid according to the following equation"

Jan 1, 2000

By William Petruk

Many gold operations lose gold during processing because some ore characteristics which affect recoveries have not been determined, and consequently the plant could not be designed to account for them. The ore characteristics can be determined with mineralogical techniques by analyzing the plant feed, final tailings and mill products. The plant feed and/or final tailings are commonly analyzed first as a separate project. Mill products are analyzed only if the process employs a minerals separation circuit to produce a concentrate (e.g. secondary flotation circuit to concentrate gold-bearing arsenopyrite), and if assays and materials balances indicate a recovery problem in the minerals separation circuit. Many ores have been evaluated at CANMET on a confidential cost-recovery basis by custom-designing a work plan which was dependent upon the problem and on the characteristics of the ore. The reasons for gold losses have been identified in most cases, and suggestions for modifying flowsheets have been proposed. The methods used in performing the analyses are described in this paper, and non-confidential results from in-house projects are provided as examples of the benefits of such analyses. The analytical methodology involves a combination of the following procedures: -producing heavy mineral concentrates and identifying the gold minerals in the concentrates; -determining quantities of invisible gold in gold-bearing sulphides, sulpharsenides, etc. by SIMS; -determining quantities and liberation characteristics of all gold minerals and gold-bearing minerals in the sample; -finding and identifying gold minerals in silicates; -extensive grinding and cyanidation to determine the ultimate amount of cyanidable gold; -determining impact of clay minerals and graphite; -performing a mineral balance for the gold in each sample; -performing a materials balance to determine the distribution of the gold minerals, gold-bearing minerals, and other minerals throughout the flowsheet, and; -interpreting the results.

Jan 1, 1995

By Batric Pesic

The interactions of mineral-pyrite with T. ferrooxidans were studied by using a cyclic voltametry technique. The interactions with bacteria were examined during the entire growth stage of bacteria (fermentation), The pyrite ?surface invariably drastically changed &apos; its. properties at the second day of fermentation. Beyond two .. days of fermentation, the cyclic voltamograms were insensitive to convective diffusion produced by stirring. The product layer was examined by SEM,. X-ray diffraction and chemical analysis. The SEM study revealed that bacteria populated the pyrite surface at an extremely high density levels. The high density of bacteria, and the solid reaction products formed on the pyrite surface created conditions for pore diffusion which explained why the CVs became .insensitive to convective diffusion in solution (stirring). The x-r:ay diffraction study confirmed jarosite as a product layer. A mechanism of T. ferrooxidans cells serving as nucleation sites for jiarosite formation is proposed.

Jan 1, 1991

By Xiaoming Huaa

The effect of the anodic polarization on the composition and morphology of the surface layer formed on chalcopyrite during ammonia–ammonium chloride leaching was investigated. The anodic polarization on the chalcopyrite electrode was used for oxidation and dissolution of chalcopyrite, and the resulting oxidized layers were characterized by XPS, SEM and optical microscopy. The results show that oxide layers exist on the chalcopyrite surface with or without any anodic polarization in the leaching solution at ambient atmosphere. However, the composition and morphology of the layers are strongly depended on the extent of polarization. The distribution of FeOOH and Fe2O3 within the oxidized layer was inhomogeneous for the sample at the open circuit potential (OCP). The composition and morphology of the oxidized layers which were formed at anodic potentials lower than 0.3 V versus SCE were similar to those of the chalcopyrite at the OCP. At anodic potentials above 0.4 V, the oxidized layers contained many cracks, and they were fragile and exfoliated. Furthermore, the sulfide had been oxidized to sulfur species with higher oxidation states. The oxidation of the chalcopyrite seemed to undergo a cyclically oxidative process that suggested growth and spallation of oxidation layers on chalcopyrite in a layer-by-layer sequence.