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By Ragnhild Aune

In fire refining of copper, the affinities of various impurity elements on dissolved oxygen is of great significance. Further, in the design of oxygen probes in liquid copper, the influence of solute interactions on the activity of oxygen need to be considered in order to evaluate the oxygen concentration in molten copper. The present paper presents a series of measurements of the activities of oxygen in liquid Cu-M-o alloys (where M stands for Mn, Zn, As, Se or Te) carned out by the present group employing the solid electrolyte galvanic cell technique. Extreme care was taken to control the oxygen potentials in the inert gas atmosphere, and to keep the oxygen levels very low in the molten metal. The oxygen content was determined by analysis of the samples taken out from the melt. The results obtained showed that Mn has a strong negative influence on the activity coefficient of oxygen in liquid copper. A similar, but less prominent effect was observed in the case of Zn. Arsenic had no influence on the activity of oxygen in Cu (liq.). Se and Te had slight negative effect on oxygen activities in copper at XQ >10-5, while at lower oxygen levels the interaction coefficients were found to be positive. The results obtained were compared with empirical models for the calculation of interaction coefficients available in literature.

Jan 1, 2003

By Ragnhild Aune

In fire refining of copper, the affinities of various impurity elements on dissolved oxygen is of great significance. Further, in the design of oxygen probes in liquid copper, the influence of solute interactions on the activity of oxygen need to be considered in order to evaluate the oxygen concentration in molten copper. The present paper presents a series of measurements of the activities of oxygen in liquid Cu-M-o alloys (where M stands for Mn, Zn, As, Se or Te) carried out by the present group employing the solid electrolyte galvanic cell technique. Extreme care was taken to control the oxygen potentials in the inert gas atmosphere, and to keep the oxygen levels very low in the molten metal. The oxygen content was determined by analysis of the samples taken out from the melt. The results obtained showed that Mn has a strong negative influence on the activity coefficient of oxygen in liquid copper. A similar, but less prominent effect was observed in the case of Zn. Arsenic had no influence on the activity of oxygen in Cu (liq.). Se and Te had slight negative effect on oxygen activities in copper at XO > 10-5, while at lower oxygen levels the interaction coefficients were found to be positive. The results obtained were compared with empirical models for the calculation of interaction coefficients available in literature.

Jan 1, 2003

By Dhanesh Chandra

Long term stability studies were conducted on four variants of LaNi5; 10,000 hydriding/dehydriding cycles were used to evaluate their suitability for a metal hydride cooling system. Thermodynamic and structural studies were conducted to determine changes in these materials during cycling test period. The hydrogen sorption properties of LaNi5.2, and Lao 9Gd0.1Ni5 and LaNi4.75In0.27 were seriously degraded during the tests but the LaNi4.8Sn0.22 hydride was virtually unaffected. Hydride isotherms were measured at the beginning and at intervals through out the test period to observe the nature and extent of damage degradation in the sorption properties. X-ray diffraction studies of the alloys (LaNi5.2, LaO.9Gd0.1Ni5 LaNi4 8Sn0.22) and their respective hydride, before and after test, provided insight with regards to the observed changes in the hydride properties. Electron microscopic studies were also conducted to evaluate the changes in particle sizes.

Jan 1, 1989

By M. J. Soria-Aguilar, F. R. Carrillo-Pedroza, S. Preciado-Nuñez

"Dust originated from the Iron Blast Furnace (BF) and the Basic Oxygen Furnace (BOF) containing alkalis and zinc are not completely recycled because due affects the process efficiency. These types of dust represents an economical lost as a consequence of values contents of iron and carbon. Several processes in aqueous media have been developed to treat the steelmaking dust. This work presents a laboratory study for reduce zinc and alkali containing in BF and BOF dust, using different acid and alkaline solutions and oxidants as ozone. The results obtained show that the elimination of zinc and alkalis can vary from 5 % to 80 % depending on the treatment conditions (the solution, the oxidant and the temperature). The dust obtained from this treatment can to be recycling to the steelmaking processes to recovery iron and carbon values.IntroductionEach one of the steel making industry processes generate several sub-products and residues containing useful units of iron, carbon and other elements that are or could be recycled to the productive process. Some of those sub products are the dust from the gas cleaning system of the blast furnace and the dust from BOF reductive process; such dusts are sent to the sedimentary lagoons. The dust represent a lost of 2 % of the total iron and coal mineral’s content feed to the process.The typical iron, carbon and zinc content of the blast furnace dust is approximately 40, 24 and 0.3 % and the content of the BOF dust are 50, 15 and 0.9 % weight respectively, with physics - chemical characteristics that became them susceptible to be agglomerated and feed to the blast furnace. But the high content of zinc does not allow recycling it into the process. At the blast furnace the presence of zinc propitiate the formation of film in the furnace wall; these elements are vaporized in the low section of the cube of the furnace and they are dragged by the gases to the top and condensed again at the cube. Part of these condensed materials strongly adheres to the furnace cover harming it and reducing the empty space of that section, causing eventually a severe perturbation of the ascendant gas flux [1]."

Jan 1, 2008

By Kenshi Kawabata, Mitsuji Ueda, Junko Umeda, Katsuyoshi Kondoh, Kantarou Kaneko

Solid-state recycling process of in-house scraps of machined magnesium (Mg) alloy wastes has been established to directly produce wrought materials via the repetitively plastic deformation by Roll-compaction (RCP) and the conventional hot extrusion. The coarse chips, wasted in machining AMX602 (Mg-6Al-0.2Mn-2Ca) cast billets used for the gate bar used in Electronic Toll Collection (ETC) of the high-way system, were employed as the input materials in this study. RCP process enabled to serve coarse Mg alloy powder consisting of refined grains and intermetallics with no re-melting. They were easily consolidated by hot extrusion, and their wrought alloys showed both homogeneously refined grains less than 1~2 µm by dynamic recrystallization and randomized texture by repetitive plastic deformation on the input wastes. These materials revealed extremely advanced mechanical properties of high tensile strength of 356MPa and high ductility of 14.8%, compared to the originally virgin materials with 270MPa TS and 5% elongation. When applying the same Mg alloy wastes via RCP process to the mass production in the company, the large-scale extruded materials also indicated the superior tensile properties. It means that this direct solid-state process is held as “Up-grade recycle of metal wastes”.

Jan 1, 2008

By Zongliang Zhang

Electrowinning is a significant step in metal extraction processes. Because the nature of electrowinning is to reduce metal from its oxidized state, substantial energy consumption accompanies it. Electrowinning processes of different metals have much in common—the deposition of the metal on the cathode and the counter-reaction on the anode. An advanced model was developed that can be applied to a variety of metal electrowinning processes. A model for specific metals can be readily obtained by modifying parameters such as potential, kinetics, and side reactions in the model. The model incorporates mass transfer, gas-liquid flow, electrochemistry, and deposition, making it a comprehensive electrowinning model. The model is applied to copper, nickel, and zinc and verified with the experimental results. In addition, the parameter settings and results of different metals were compared, showing that this model has great versatility and accuracy, thereby making it an efficient and effective research tool.

By E. A. Chavarriaga, L. J. Jaramillo, O. J. Restrepo

"This paper presents the results of the manufacturing ceramic pigments with spinel structure, using methods of synthesis of low temperature. In this work we obtained spinel structures type by the methods of Self-combustion, Coprecipitation, Microemulsion, Gel citrate and Pechini. These methods become an attractive alternative to traditional method (ceramic method), since we can work at a lower temperature, reducing manufacturing costs, lower fuel consumption, less wear on equipment and other environmental and economic implications. Also it is possible to have control over features such as stoichiometry, morphology of the products, reaction times and structures. The products obtained by these routes will be used in the manufacture of ceramic pigments and characterized using different techniques such as X-ray diffraction (XRD), scanning electron microscopy (SEM) and UV-VIS spectrophotometry.IntroductionSpinels are ternary oxides AB204, where A and B are cations occupying tetrahedral and octahedral positions respectively. These oxides exhibit interesting electrical, magnetic and catalytic properties [1-4], depending on its nature, charging and intrinsic distribution of ions [5].The most widely used method to prepare spinels has been through solid state reaction, which consists of mixed oxides at high temperatures [6, 7]. In the last years, there have been a strong tendency to use chemical routes for the synthesis of crystalline ceramic particles at low temperatures [8,9]. Unconventional methods currently employed for the synthesis of complex oxides are Gel citrate method, Pechini, Spontaneous combustion, Microemulsion and Coprecipitation. Pechini method [10, 11], based on polymeric precursors, does not require high temperatures and allows stoichiometric control for greater reproducibility. This method involves the formation of a polymeric resin between a metal quelate and polyhydroxy acid of alcohol by polyestirification.Coprecipitation is important for many environmental problems related to water resources, including acid mine drainage, migration of radionuclides in waste repositories dirty, transport of contaminant metals in the industry, metal concentrations in aqueous systems and the technology of wastewater treatment. The coprecipitation process can vary in each case; the partition in the solid phase can be carried out by surface adsorption, ion exchange, surface precipitation, occlusion and formation of solid solution. The formation of solid solution is the result of structural incorporation of the marker in structural support sites resulting in a minor component in the solid solution with the host phase that has a very low solubility of pure solid [12]. Synthesis by gel citrate method allows the use of a route to obtain ceramic pigments from a very simple experimental system in which the stoichiometric control, the size and shape of the particles and the purity of the phases obtained can be controlled more accurately [13]."

Jan 1, 2012

By Sanaz Mosadeghsedghi

The feasibility of the application of electrodialysis in separation of light and heavy rare earth elements (REE) in synthetic solutions was investigated. The experiments were carried out using single and binary solutions of a light (cerium) and heavy (ytterbium) REE. The effects of electrical voltage, electrical current, and the addition of complexing agent (EDTA) to increase the separation selectivity were investigated. Separation of Ce and Yb was achieved in binary solutions with and without the addition of EDTA. Higher degrees of separation were seen at higher voltages. Ce–Yb separation was more significant in the presence of EDTA. The separation factor of Ce–Yb and Ce–Yb-EDTA were 1.44 and 2.60, respectively.

By T. A. Venugopalan

The 'Hall-Heroult' Process of reduction of Alumina to Aluminium has remainded basically the same for over 100 years, but the technology has been undergoing drastic changes with respect to selection of materials for Cathode and Anode, and also energy consumption. The latest generation pots have a working life of about 1800-2000 days normally. After the failure of the pots, the Cathode Lining is dug out and disposed of on land. Since the lining contains objectional materials causing pollution, various processes have been tried for re-processing of this waste. However, most of the processes have been unsuccessful from the techno-economic point of view. At Hindalco a new chemical process for converting the fluorine values of the dug out material to Cryolite was developed in 1988 and a" one ton per day Cryolite production plant has been operating since 1989. This process is especially applicable where the integrated Alumina and Smelter Plants exist side by side. The experience in operating this Plant is discussed in detail in the paper.

Jan 1, 1992

By M. A. Barakat

Large amounts of zinc ash and flue dust containing more than 80 % zinc are accumulated during galvanization processes at the surface of molten zinc bath and in the chimney respectively. Pyrometallurgical recovery of zinc from both of the ash and dust samples has been carried out. The ash was sieved with the help of an industrial sieve shaker provided with mesh sieve having a pore size 0.9 mm. The oversize fraction cut (+ 0.9 mm) was melted at 550 °C under ambient conditions. The produced ingot (1) was analyzed whereas the coarse fraction of the produced slag (+ 0.9 mm) was treated as the coarse ash or added to it. The dust was enriched with suitable fluxing salt prior to heat treatment at 600 °C for 1 h. The produced ingot (2) was analyzed whereas the resulting slag was mixed with the fines of the ash and treated by hydrometallurgical processing to prepare valuable salts of zinc. Parameters affecting recovery processes such as time, temperature and flux percentage were studied. Results obtained revealed that the two prepared ingots (1&2) were successfully recovered with recovery efficiency amounts to =85 %. The obtained samples meet the standard specifications with relatively low price. Also in the light of the strict environmental regulations of pollution control, reuse of these wastes materials will help in keeping the environment clean.

Jan 1, 2000

By Maribel L- Saucedo-Muñoz, Toshiyuki Hashida, Victor M. Lopez-Hirata, Shin-Ichi Komazaki

"Small-punch tests were conducted at 4, 77 and 293 K on three types of austenitic stainless steels JNl, JJl and JK2, which were solution treated, water-quenched and then aged at 923, 973, 1023 and 1073 K for 5 h. Small-punch test energy was employed for the evaluation of the aginginduced embrittlement behavior in these materials. Fracture surface of small punch test specimen for the solution treated steels exhibited a ductile fracture, showing the highest SP test energy values. The presence of intergranular brittle fracture was observed in aged specimens. Smallpunch test energy decreased significantly as the aging process progressed. The highest and lowest decrease in small-punch test energy with aging temperature occurred in JNl and JK2 steels, respectively. The decrease in small-punch test energy showed to examine appropriately the aging-induced embrittlement in these materials. The difference in aging-induced embrittlement behavior for these steels was explained based on the volume fraction of intergranular precipitates in aged samples.IntroductionA high level combination of strength and toughness is required for cryogenic structural materials used in the superconducting magnets of fusion nuclear reactor. This requirement is beyond the capability of conventional austenitic stainless steels [1]. The Japan Atomic Energy Research Institute (JAERI) developed new cryogenic JNl, JJl and JK2 austenitic stainless steels. The structure of superconducting magnets is supposed to be constructed by welding thick plates of this kind of steels. Thus, most of the components are exposed to thermal cycles. The slow cooling may cause microstructure changes in both the base material and weld zone. These changes may also decrease the fracture toughness of these materials at cryogenic temperatures. Therefore, it is important to study the effect of thermal aging on fracture toughness behavior for these steels. Konosu et al. [2] carried out a study of the effect of thermal aging on the mechanical properties for JNl steel using tension and fatigue tests. Kwon et al. [3] evaluated the deterioration in fracture toughness at cryogenic temperatures for the isothermally aged JNl steel by means of the Small-Punch (SP) test. No other reports were found about the cryogenic fracture toughness behavior for this kind of steels. To evaluate the cryogenic fracture behavior, the elastic-plastic Jrc value is a good alternative [4,5]; nevertheless, the standard required specimen size makes it difficult to be used for the fracture toughness evaluation in small zones."

Jan 1, 2011

By J. -P. Nepper

It has been possible to largely contain converter aisle emissions of SO2 and fumes in the case of batch-wise operated Peirce Smith converters during normal blowing periods with the help of suitably designed primary hoods. Controlling the escape of off-gas during the periods of turning the converter in or out of the stack has been problematic in the past. Effective automated contro1 systems have been deve1oped for the purpose and successfully applied in smelter operations in Spain, Taiwan and Germany. This has led not only to an effective reduction of emissions in the converter environment but also to an improvement in the converter operation.

Jan 1, 1992

By Yinlun Huang, Cristina Piluso

"Industrial sustainability looks to improve material and energy efficiencies, product quality and variety, and productivity within an industrial zone, thus pursuing the long-term sustainable development of the region. This paper introduces a systems-based modeling methodology, which provides industrial leaders with the ability to evaluate future production options to determine the path with the highest positive impact on both their own sustainability and the sustainability of the overall industrial zone. A comprehensive study on sustainable development of an auto-manufacturing focused industrial zone under uncertainty is illustrated. Introduction Sustainable development refers to a continuous process of improvements that must be followed in order to achieve a state of sustainability. In its most general form, a widely accepted definition of sustainable development was identified in the Brundtland Report as “development that meets the needs of the present without compromising the ability of future generations to meet their own needs” [1]. Sustainability will occur when the material and social conditions can be maintained or improved for human health and the environment over time without exceeding the ecological capabilities that support them [2]. An industrial zone is defined as a geographic area comprised of a network of industrial sectors, each composed of a number of entities. Such a zone is highly integrated and complex, and contains numerous uncertainties due to each industry’s extreme dependencies on its suppliers and customers throughout the product supply chain. In the context of an industrial zone, sustainable development refers to the continuous process of advancements in the zone, and the entities that comprise it, creating more value, wealth, and profits (economically viable dimension), providing environmentally benign products with less raw material consumption and waste generation (environmentally compatible dimension), and collaboration and a direct relationship among all involved in the supply chain, i.e. the corporations, employees, suppliers, investors, communities, customers, etc. (socially responsible dimension). These are the triple bottom lines of industrial sustainability. In order for economic, environmental, and social sustainability improvements to be successfully implemented within an industrial zone, the industrial decision makers must possess system-wide analysis abilities. The analysis of the sustainable development of an industrial zone involves decisions at the local, regional, or national levels, which are complex and involves handling of ill-defined parameters with a high degree of uncertainty due to the imperfect understanding of the underlying issues [3]. This work focuses strictly on the uncertainties in future zone planning and a method and a scenario based approach that can be used to evaluate the sustainable development of an industrial zone among these uncertainties."

Jan 1, 2008

By I. Sofia Fernandez del Rio

This paper describes a process for the treatment of the dusts generated during the operation of blast and reverberatory furnaces in the lead smelter, to remove zinc, cadmium, arsenic and halides from the circuit. The process consists of a Pefloles' developed leaching/purification stage and a solvent extraction process developed by Lurgi. The plant capacity is 5,000 tonnes Zn/year. The feed to solvent extraction contains 8 g/1 Zn. Impurities such as copper, iron, arsenic and cadmium are removed by conventional cementation processes. The cadmium product is 99.99 % pure. The solvent extraction process consists of two extraction stages, one washing stage and two stripping stages. D2EHPA is used as the extraction agent and 25% ammonia as the neutralizer. The rich-zinc solution is sent to the electrolytic zinc plant for zinc recovery. The raffinate produced, which is a mixture of ammonium sulfate and chloride, is used for agricultural applications.

Jan 1, 2000

By F. Nava-Alonso, O. Alonso-González, A. Uribe-Salas, R. Pérez-Garibay

"Cyanidation is the most used method to recover gold and silver from their ores. In this process, other metals besides gold and silver may sometimes dissolve and interfere with the efficiency of extraction. Copper is one of those metals, reaching concentrations as high as 1000 mg/L in some cyanidation plants, making difficult the extraction and purification processes, and increasing the operating costs.This preliminary work was intended to study the feasibility of using amines to form a precipitate and to eliminate copper from a synthetic solution containing high copper and cyanide concentrations, as is the case of some cyanidation effluents. The solid formed is removed from the solution using conventional filtration techniques. Seven amines were evaluated at different pH values and amine additions. Up to 90% of copper present may be removed at the natural pH of the effluent (alkaline). The remaining copper would permit to recycle the solution back to the cyanidation process. IntroductionCopper is generally considered the most problematic metal in gold leaching due to the rapid formation of copper cyanide complexes when some readily-soluble minerals are processed (e.g., azurite, malaquite, cuprite, chalcocite and bornite). The copper solubilization as cuprous cyanide complexes leads to a significant economic penalty in terms of excessive cyanide consumption and high cost for cyanide elimination. When activated carbon is used to recover gold and silver, the copper-cyanide complexes decrease the efficiency of the process because of the competition of the cuprocyanides with the aurocyanide for the adsorptive sites on the activated carbon (Rees and Deventer, 1999).Several techniques have been developed to attempt to overcome the problems caused by the copper presence in cyanidation solutions, notably: acidification-volatilization-regeneration (AVR), ion exchange-electrolysis or solvent extraction-electrowinning (Lu et al., 2002). In this work the use of some amines is proposed to remove the copper-cyanide complexes by precipitation of a copper-cyanide-amine solid. The process was evaluated for different amine additions and pH values, using copper-cyanide synthetic solutions of composition similar to that presented by some cyanidation plants with high copper."

Jan 1, 2008

By T. B. Braun

Cathode contamination is the principal factor affecting the quality of electrorefined copper. It is commonly accepted that annealability is unfavorably affected by the following elements, in decreasing order of adverse effect: tellurium, selenium, bismuth, antimony, and arsenic. Silver in cathodes has importance as it represents a nonrecoverable loss of silver to the refinery. Mechanisms for the contamination of cathodes by these elements are examined and the effect of operating variables on contamination, including anode composition, electrolyte composition, electrolyte temperature, addition agent practice, and electrolyte discard rate, are discussed.

Jan 1, 1976

By Helvio P. G. Santafé Jr., Ruben J. S. Rodriguez, Sergio N. Monteiro, Teresa E. Castillo

"The coir fiber extracted from the husk of the coconut fruits are worldwide available in tropical regions as a low cost lignocellulosic by-product for many applications including composite filler in automobile parts. Possible uses above room temperature require information on the thermal behavior of these coir fiber composites. Therefore, the objective of this work was to perform thermogravimetric, TGA and DTG, analysis on polyester matrix composites incorporated with different volume fractions of coir fiber. In general, it was found that thermal degradation associated with weight loss occurred in three stages. Changes were also observed in the DTG peaks that could be attributed to the coir fiber participation through the decomposition of its lignocellulosic structure.IntroductionThe development of new materials has always been motivated by the need of improved properties. This was the case of modem composites with combination of properties that surpass those of conventional monolithic metallic alloys, ceramic or polymers, from which composites are made. A typical example is the synthetic fiber reinforced composite with specific strength i. e, ultimate stress divided by density, higher than any other monolithic material. Today, however, our global society is concerned with serious environmental problems and thus demanding that new materials be developed with distinct characteristics. They are known as environmentally correct and are expected to be sustainable, which corresponds to the condition of being biodegradable, renewable, recyclable and neutral with respect to C02 emission, considered the main responsible for global warning [1]. Synthetic fiber composites cannot meet these requirements. Consequently, new composite reinforced with cellulose-based natural fiber are being developed [2-8] and are already replacing the synthetic ones in several engineering fields including the automobile industry [9-11]. These composites have additional advantages owing to the lignocellulosic fiber benefits of being diversified, abundant, less expensive, lighter and of societal interest [8]. In some cases even technical advantages such as non-abrasive effect to processing equipments and more flexibility exist in comparison to synthetic fibers."

Jan 1, 2011

By Fatma Arslan

Alada (Kayseri-Turkey) lead-zinc sulfide-oxide ores contain 10.17% Pb, 10.98 %Zn, 164 g/t Cd and 57 g/t Ag. During the laboratory scale flotation tests of these ores, it was found that almost all zinc was remained in the tailings that contain 12.31% Zn, 1.35%Pb, 198.3 g/t Cd, and 22.3%Fe. Three different methods were studied such as basic (NaOH) leaching, roasting+acidic (H2SO4) leaching and direct acidic (H2SO4) leaching for recovering metals that these tailings contain. In the direct acidic leaching, which gave the best results, dissolution efficiencies of 91.5% zinc, 78.2% cadmium, and 14.3% iron were reached at the optimum leaching conditions while Pb remained in the leach residues and the acid consumption was 422.3 kg/ton of tailings.

Jan 1, 2006

By M. Cross, K. Pericleous, A. Mouchmov

"Copper - nickel - sulphide alloys are typically cooled and solidified in 4, 8 and 16 tonne ingots. These ingots exhibit a variation of grain size distribution and macro segregation of the prime alloy components throughout. The former is assumed to be primarily due to the dominant relation between grain growth rate and the cooling profile, whilst the latter is heavily influenced by buoyancy driven residual convection. The objective of this research program is to examine the extent to which it is possible to develop a 'broad brush' computational model of this ingot cooling process, that can predict some 'integral' measure of the grain size (e.g. average diameter) and the macro-segregation as a function of operating conditions.A computational modeling software framework, PHYSICA+ is used to simulate the complex process of ingot casting, which involves coupling between different physical phenomena. The entire model involves:(i) a 'broad brush' grain growth model that could be used in the prediction of micro/macro-structure of alloy ingot cooling processes,(ii) a heat transfer and solidification model which takes into account a second phase transformation of P NhS2 to heazlewoodite, and (iii) NS fluid flow simulation which provides a good basis for further micro/macro segregation modeling.At this stage some results of the 3D convection driven thermal cooling and solidification profiles will be shown, together with the 'integral' model for the grain size prediction."

Jan 1, 2001

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.