Selective Dissolution Of Copper Research Articles

Long-term corrosion of copper alloys in the soil: new aspects of corrosion morphology in archaeological vessels from south-western Iran

A group of copper-based objects excavated at Deh Dumen cemetery, in south-western Iran, was studied and analysed to examine the long-term corrosion morphology and mechanism in the soil burial environment. For this purpose, twenty-two samples from twenty-one copper-based vessels were studied and analysed using X-ray diffraction, scanning electron microscopy—energy dispersive X-ray spectroscopy, micro-Raman spectroscopy and metallography techniques. The results of the analyses showed that the majority of vessels are made of tin bronze, along with two arsenical copper samples. The extent of corrosion observed ranges from very thin corrosion crusts to thick crusts and entirely corroded structures. These three identified corrosion morphologies display a multi-layered corrosion stratigraphy as well as the preserved limit of the original surface. The corrosion crusts include internal tin-rich and external copper-rich layers, and the main corrosion mechanism for the formation of multi-layered corrosion crusts is decuprification or selective dissolution of copper during the long-term burial time in a moderately Cl-contaminated soil. The three identified corrosion morphologies are similar to the previously published morphologies, but some clear deviations are apparent and are discussed here.

Mechanism of incipient annular corrosion of high-tin bronze in simulated soil solution

ABSTRACT The mechanism of Cu–Sn–Pb bronze (18.2 wt-% Sn) in a simulated soil solution was examined using optical microscopy, scanning electron microscopy, scanning Kelvin probe, X-ray photoelectron spectroscopy, X-ray diffraction and electrochemical techniques. The findings demonstrated that the α-phase possessed a more negative corrosion potential, and the central annular position was more active owing to the difference in the solid-solution tin content during casting. Cl− was not directly involved in the production of corrosive products in the early stage of corrosion, but it damaged the copper oxide layer and promoted the loss of copper ions. Subsequently, the tin oxide was gradually produced on the surface, and the selective copper dissolution led to abundant tin compounds on the surface.

In Situ Electrochemical Monitoring of the Crevice Corrosion Process of the 7075-T651 Aluminium Alloy in Acidic NaCl and NaNO3 Solution

The crevice corrosion of the 7075-T651 aluminium alloy was investigated using in situ electrochemical impedance spectroscopy (EIS), potentiodynamic polarization curves (PC), and H+ sensors in acidic NaCl solution with different contents of NaNO3. In the solution without NaNO3, the pH in the crevice increased rapidly and gradually reached a relatively stable status. The corrosion of the aluminium alloy in the crevice was inhibited and crevice corrosion could not be initiated. In the solution with NaNO3, the pH increased rapidly at the initial immersion period and then decreased gradually. The corrosion of the aluminium alloy inside the crevice could be enhanced and the corrosion of the aluminium alloy outside crevice could be inhibited. This triggered crevice corrosion in the solution with NaNO3. The inhibited corrosion outside the crevice can be attributed to the improved passive film of the specimen outside the crevice by nitrate. The accumulated secondary products of ammonia inside the crevice led to selective dissolution of copper, which triggered the nucleation of pitting corrosion and promoted the corrosion of the specimen inside the crevice.

Selective dissolution of copper and iron from molybdenite concentrate using acidic sodium nitrate solution

In this study, the selective dissolution of copper and iron from the molybdenite (MoS2) concentrate consisting of chalcopyrite and pyrite by acidic sodium nitrate leaching has been investigated to improve the quality of molybdenite. The influence of various leaching parameters, namely sodium nitrate (NaNO3) and sulfuric acid (H2SO4) concentration, temperature, contact time, and solid: liquid phase ratio, was examined on the dissolution of copper (Cu) and iron (Fe) from the concentrate. Under the optimized conditions, the extraction of Cu and Fe can achieve 81.4% and 74.1%, respectively, along with a minor amount of molybdenum (Mo) loss in the solution from the concentrate in 240 min leaching. The kinetic study indicated that the impurities removal process was controlled by a mixed mechanism with a corresponding activation energy of 35.77 kJ/mol at the temperature range of 70–97 °C. The XRD and SEM-EDS analysis of the solid residues from the leaching revealed the insolubility of molybdenite in the leaching media. As a result, the molybdenite grade reached 90.73 wt% from an initial value of 81.33 wt%.

Extraction of copper from complex carbonaceous sulfide ore by direct high-pressure leaching

The increase of impurities and complexity of copper ores are among the recent challenges in the mining industry. Complex carbonaceous sulfide ores are extremely difficult to treat due to their mineralogical complexity and impurities of organic carbon and carbonates. This study focuses on the development of a hydrometallurgical process for efficient copper extraction from complex carbonaceous sulfide ore which contains chalcopyrite, carbonates (dolomite and calcite), and carbonaceous gangue minerals. Characterization of the ore sample and leach residues was conducted using XRD and EPMA analysis, while ICP-OES was used for the determination of total dissolved metals in solution. High-pressure leaching of complex carbonaceous sulfide ore in oxygenated sulfuric acid solution was performed and the influence of leaching parameters such as sulfuric acid concentration, temperature, total pressure, and pulp density was studied. The extraction of copper increased with increasing temperature, sulfuric acid concentration, and total pressure. On the other hand, an increase in pulp density resulted in a decline in copper extraction due to an increased slurry viscosity and resistance in the diffusive mass transfer of reactants. Selective dissolution of copper from iron can be achieved by controlling free acidity in the pregnant leach solution (PLS). Under these leaching conditions: 100 g/L, 1 M H2SO4, 160 °C, 1.0 MPa total pressure, the highest copper and iron extractions achieved were 97.55% and 95.37%, respectively. Precipitation of copper from the PLS by NaSH sulfidization was investigated and more than 99.9% of copper was recovered at a Cu: NaSH molar ratio of 1:1.8.

The Influence of Archaeometallurgical Copper Alloy Castings Microstructure towards Corrosion Evolution in Various Corrosive Media

The local patterns at the interfaces of corrosion stratification, developed on two archaeometallurgical bronzes (a Cu-Sn-Pb and a Cu-Zn-Sn-Pb alloy), in the as-cast condition, were assessed by OM and SEM-EDS systematic elemental chemical analyses. Previously, the alloys—whose metallurgical features and electrochemical behaviour were already well studied—have been subjected to laboratory corrosion experiments. The corrosion procedures involved electrochemical anodic polarization experiments in various chloride media: 0.1 mol/L NaCl, 0.6 mol/L NaCl and two other synthetic chloride-containing solutions, representing electrolytes present in marine urban atmosphere and in the soil of coastal sites. The characterization of the Cu-Sn-Pb alloy electrochemical patinas after anodic sweep (OCP+ 0.6 V) revealed that the metal in all electrolytes undergoes extensive chloride attack and selective dissolution of copper which initiates from the dendritic areas acting as anodic sites. The most abundant corrosion products identified by FTIR in all electrochemical patinas were Cu2(OH)3Cl), Cu2(OH)2CO3 and amorphous Cu and Sn oxides. The characterization of the Cu-Sn-Pb alloy electrochemical patina after slow anodic sweep (OCP+ 1.5 V) in 0.1 mol/L NaCl reveals selective oxidation of dendrites and higher decuprification rate in these areas. Corrosion products of Sn-rich interdendritic areas are dominated by oxygen species (oxides, hydroxides, hydroxyoxides) and Cu-rich dendrites by chlorides. In the case of Cu-Zn-Sn-Pb, Zn in dendritic areas is preferentially attacked. The alloy undergoes simultaneous dezincification and decuprification, with the former progressing faster, especially in dendritic areas. The two processes at the alloy/patina interface leave behind a metal surface where α-dendrites are enriched in Sn compared to the alloy matrix. The results of this study highlight the dynamic profile of corrosion layer build-up in bronze and brass. Moreover, the perception of the dealloying mechanisms progression on casting features, at mid-term corrosion stages, is extended.

De-Alloyed PtCu/C Catalysts of Oxygen Electroreduction

Platinum-containing bimetallic nanoparticles manifest high functional characteristics as electrocatalysts. To use PtCu/C catalysts in low-temperature fuel cells, it is necessary to minimize selective copper dissolution, as copper cations can pollute the polymer membrane and decrease its proton conductivity. The work determines the composition, measures the electrochemically active surface area, and studies the electrochemical behavior of PtCu/C catalysts containing nanoparticles with a “core–shell” structure in the initial state (as-prepared) and after pretreatment in solutions of different acids. The comparative determination of catalyst activity in an electrochemical cell and their testing in a membrane-electrode assembly of fuel cells showed that pretreated PtCu/C materials with a much better stability as compared to Pt/C were also noninferior to the latter as regards their activity in the oxygen electroreduction reaction.

Synthesis of PtCu/С Electrocatalysts with Different Structures and Study of Their Functional Characteristics

PtCu/C electrocatalysts with similar compositions but different distributions of components in bimetallic nanoparticles were obtained by simultaneous and sequential reduction of copper(II) and platinum( IV) in a carbon suspension. The catalyst obtained by multistage synthesis while sequentially increasing the Pt(IV) concentration in the precursor solution added at each stage showed the highest stability and activity in oxygen electroreduction in acidic media. This catalyst was least liable to selective dissolution of copper during its operation. The influence of the architecture of bimetallic PtCu nanoparticles on the electrochemical behavior of the catalysts is due to the peculiarities of the structure rearrangement of nanoparticles during the enrichment of the protective surface layer with platinum.

Evaluation of the protectiveness of an organosilane coating on patinated Cu-Si-Mn bronze for contemporary art

A 3-mercapto-propyl-trimethoxysilane coating (PropS-SH) applied on Cu-Si-Mn bronze, patinated by “liver of sulphur”, was investigated as a non-toxic alternative to Incralac®, usually applied on outdoor artistic bronzes. Electrochemical testing was performed in synthetic acid rain. Exposure to temperature/UV cycles and accelerated corrosion test simulating unsheltered exposure to rainwater was also carried out. The exposed samples were characterised by FEG-SEM coupled with EDS on FIB cross-sections and XPS on free surfaces. The black patina without protective coating was scarcely protective against bronze corrosion and easily transformed into cuprous oxide. PropS-SH coating fully preserved the black patina microstructure and phase constituents (cuprous oxide and cuprous sulphide). The PropS-SH coating also resulted more protective than Incralac® when aged under run-off conditions. Selective dissolution of copper from the silicon bronze alloy was observed on both uncoated and Incralac®-coated bronze, leading to the formation of an internal Si-rich corrosion layer.

Effect of the Composition and Structure of Pt(Cu)/C Electrocatalysts on Their Stability under Different Stress Test Conditions

Stability is one of the most important characteristics of electrocatalysts used in low-temperature fuel cells with a proton exchange membrane. The corrosion-morphological stability of supported electrocatalysts containing platinum and platinum-copper nanoparticles with ~20 wt % Pt was evaluated under the conditions of voltammetry stress testing corresponding to different degradation mechanisms. The effect of the difference in the architecture of Pt–Cu nanoparticles on the stability of catalysts and changes in their composition as a result of stress tests were studied. At close values of the electrochemically active surface area (ECAS), the carbon-supported bimetallic catalysts demonstrated significantly higher stability compared to the commercial Pt/C catalysts. The Pt(Cu)/C catalyst obtained by sequential deposition of copper and platinum showed the highest resistance to the degradation and selective dissolution of copper during the testing.

Multianalytical study of corrosion layers in some archaeological copper alloy artefacts

Corrosion layers in some copper and bronze archaeological objects from Haft Tappeh archaeological site, southwest Iran, were studied. For this purpose, optical microscopy, scanning electron microscopy with energy dispersive X-ray microanalysis, micro-Raman spectroscopy and X-ray diffraction methods were applied to observe corrosion stratigraphy and their characteristics as well as identification of chemical composition and phase determination of different corrosion layers. Based on optical and electron microscopy, three different corrosion strata were identified in cross section of different metallic objects including various red, green, white-grey powdery and dark internal compact layers. Scanning electron microscopy with energy dispersive X-ray microanalysis on different corrosion layers revealed that Cu, Sn and Cl are the main elements in the chemical composition of different layers. Tin-rich phases were detected in white-grey and dark layers that may be formed because of the internal oxidation of tin as well as the decuprification (selective dissolution of copper) phenomena occurring during long-term burial period in the soil. Also, the XRD and micro-Raman spectroscopy results proved that the main corrosion products are nantokite (CuCl), copper trihydroxychlorides and copper oxides. The combination of these analytical methods allows us to explore the surface and internal corrosion layers of the archaeological copper and bronze samples, and major interest is on studying their chemistry, microstructural properties and corrosion stratigraphy. Copyright © 2015 John Wiley & Sons, Ltd.

An investigation into the leaching behaviour of copper oxide minerals in aqueous alkaline glycine solutions

Copper oxide minerals are normally extracted by acidic leaching followed by copper recovery with solvent extraction and electrowinning. However, copper oxide deposits often containing large amounts of acid consumable gangue leads to a very high acid consumption. In addition, if the oxide deposit also contains precious metals and iron bearing minerals, significant (lime) neutralisation costs are incurred to establish the conditions for subsequent cyanidation, with concomitant production of gypsum, potential formation of silver-locking jarosites and potential gel formation when acids interact with layer silicate minerals. In this study, an alternative aqueous alkaline glycine system has been employed to evaluate the batch leaching behaviour of copper oxide mineral specimens of the minerals azurite, chrysocolla, cuprite and malachite. The effects of glycine concentration and pH were investigated at ambient temperature and atmospheric pressure. Glycine concentration and pH both had a major effect on the copper extraction. Complete extraction of copper from azurite was achieved in <6h when glycine to copper ratio was 8:1. However, further investigation established the optimum leaching conditions as being pH11 and glycine to copper ratio of 4:1. Under such conditions 95.0%, 91.0%, 83. 8% and 17.4% of copper was extracted after 24h from the azurite, malachite, cuprite, and chrysocolla mineral specimens respectively. While the dissolution rates of the copper oxide minerals are markedly slower than acid leaching, the selective dissolution of copper over acid-consuming gangue minerals shows much potential. It was shown through UV–Vis spectroscopy that dissolved copper is in the cupric state and forms a neutral copper-glycinate complex under alkaline conditions. The study has shown that copper extraction from malachite, azurite and cuprite in aqueous alkaline glycine solutions is fast, whereas Cu extraction from chrysocolla was found to be poor and slow.

Evaluation of the performances of a biological treatment on tin-enriched bronze.

Recently, research gives emphasis to eco-friendly and sustainable approaches for the preservation of cultural heritage that could offer advantages in terms of compatibility, durability and safety. Hence, a biological treatment, based on a specific fungal strain of Beauveria bassiana, is exploited for the stabilization of soluble and/or active bronze corrosion products, converting them into copper oxalates. The chemical stability of the latter represents a real improvement for the long-term preservation of bronze, especially in case of exposure to acid rain. However, the corrosion behaviour of bronze differs from that of pure copper due to the presence of additional alloying elements. In natural environments, the selective dissolution of copper leads to a relative tin-enrichment within the corrosion layers, mostly in unsheltered areas exposed to rainwater runoff. To understand the influence of tin-enrichment on the formation of oxalates, pure tin and artificially tin-enriched bronze coupons were treated with this novel biological system and, in the case of bronze coupons, exposed to accelerated ageing. Tin enrichment and accelerated ageing were performed through runoff tests. Before and after treatment and ageing, the sample surface was characterized through Fourier transform infrared (FTIR) and Raman spectroscopies, scanning electron microscopy coupled to energy dispersive spectroscopy (SEM-EDS). Metals released in the ageing solutions were analysed through atomic absorption spectrometry (AAS). The analytical results allowed to better understand the response of unsheltered areas from outdoor bronze monuments to the biological treatment proposed.

Planar Arrays of Nanoporous Gold Nanowires: When Electrochemical Dealloying Meets Nanopatterning.

Nanoporous materials are of great interest for various technological applications including sensors based on surface-enhanced Raman scattering, catalysis, and biotechnology. Currently, tremendous efforts are dedicated to the development of porous one-dimensional materials to improve the properties of such class of materials. The main drawback of the synthesis approaches reported so far includes (i) the short length of the porous nanowires, which cannot reach the macroscopic scale, and (ii) the poor organization of the nanostructures obtained by the end of the synthesis process. In this work, we report for the first time on a two-step approach allowing creating highly ordered porous gold nanowire arrays with a length up to a few centimeters. This two-step approach consists of the growth of gold/copper alloy nanowires by magnetron cosputtering on a nanograted silicon substrate, serving as a physical template, followed by a selective dissolution of copper by an electrochemical anodic process in diluted sulfuric acid. We demonstrate that the pore size of the nanowires can be tailored between 6 and 21 nm by tuning the dealloying voltage between 0.2 and 0.4 V and the dealloying time within the range of 150-600 s. We further show that the initial gold content (11 to 26 atom %) and the diameter of the gold/copper alloy nanowires (135 to 250 nm) are two important parameters that must carefully be selected to precisely control the porosity of the material.

Multianalytical study of corrosion layers in some archaeological copper alloy artefacts

Corrosion layers in some copper and bronze archaeological objects from Haft Tappeh archaeological site, southwest Iran, were studied. For this purpose, optical microscopy, scanning electron microscopy with energy dispersive X‐ray microanalysis, micro‐Raman spectroscopy and X‐ray diffraction methods were applied to observe corrosion stratigraphy and their characteristics as well as identification of chemical composition and phase determination of different corrosion layers. Based on optical and electron microscopy, three different corrosion strata were identified in cross section of different metallic objects including various red, green, white‐grey powdery and dark internal compact layers. Scanning electron microscopy with energy dispersive X‐ray microanalysis on different corrosion layers revealed that Cu, Sn and Cl are the main elements in the chemical composition of different layers. Tin‐rich phases were detected in white‐grey and dark layers that may be formed because of the internal oxidation of tin as well as the decuprification (selective dissolution of copper) phenomena occurring during long‐term burial period in the soil. Also, the XRD and micro‐Raman spectroscopy results proved that the main corrosion products are nantokite (CuCl), copper trihydroxychlorides and copper oxides. The combination of these analytical methods allows us to explore the surface and internal corrosion layers of the archaeological copper and bronze samples, and major interest is on studying their chemistry, microstructural properties and corrosion stratigraphy. Copyright © 2015 John Wiley &amp; Sons, Ltd.

The effect of flotation and parameters for bioleaching of printed circuit boards

Waste electrical and electronic equipment (WEEE) is currently one of the fastest growing waste streams in the world. Typical for WEEE is the high content of valuable and precious metals, as well as harmful contaminants like halogens, flame retardant chemicals and plastics. Currently, WEEE treatment and metal recovery methods are imperfect, polluting and energy intensive. In this paper, novel treatment possibilities are outlined for printed circuit boards (PCB) utilizing both the flotation separation technique and acid bioleaching. Flotation, conducted after crushing and sieving of PCB, produced two fractions: metal-rich concentrate, which is more suitable for pyrometallurgical treatment than untreated PCB, and metal-poor froth suitable for acid bioleaching. It was seen that especially low pH (1.6), high initial Fe2+ concentration (7.8g/l) and low PCB froth concentration in the bioleaching solution (50g/l) were beneficial for the rapid and selective dissolution of copper. With these parameters, 99% of copper was solubilized from PCB froth in bioreactor treatment, with Cu (6.8g/l) and Fe (7.0g/l) being the only major metallic elements in bioleaching solution.

Selective dissolution of copper from copper-chromium spent catalyst by baking–leaching process

The selective leaching of copper from the spent Cu-Cr catalyst was carried out with H2SO4. The effect of different parameters such as acid concentration, pulp density, temperature and particle size on leaching was investigated. The maximum extraction of copper and chromium was 67.25 and 2.3%, respectively at particle size 45–53μm, pulp density 2.5%, temperature 90°C, time 180min. Therefore, baking followed by leaching approach was adopted for dissolution of spent copper-chromium catalyst using H2SO4 to enhance the metal leaching efficiency. At the optimum baking–leaching condition i.e. baking time 2h, baking temperature 300°C, baking acid concentration 0.5M, leaching temperature 35°C, time 60min, [H2SO4] 4%, P.D. 2.5%, the extraction of copper and chromium was 99.9% and 1.2%, respectively, ensuring the selective dissolution of copper. The XRD and Fe-SEM-Edax characterization analysis of typical samples (original, baked mass and typical residue) were compared and reported. The XRD and Fe-SEM-Edax analysis of the baked mass indicated the complete sulfation of copper and chromium by H2SO4 yielding CuSO4 (H2O) and (Cr)2(SO4)3, respectively in solid phase. The absence of XRD peaks corresponding to CuSO4·H2O in the final typical leach residue (obtained at optimum baking–leaching condition) confirmed the complete dissolution of copper from Cu-Cr catalyst.

Pulse-reverse electrodeposition for mesoporous metal films: combination of hydrogen evolution assisted deposition and electrochemical dealloying

Hydrogen evolution assisted electrodeposition is a new bottom-up technique allowing the fast and simple synthesis of nanometals. Electrochemical dealloying is a top-down approach with the same purpose. In this work, we show that a combination of these two methods in sequence by pulse-reverse electrodeposition can be used to prepare high-surface-area nanostructured metals. Highly porous adherent platinum is obtained by the deposition of CuPt alloy during the cathodic cycles and the selective dissolution of copper during the anodic cycles. The convection created by the movement of the hydrogen bubbles increases the deposition rate and removes the dissolved copper ions from the diffusion layer, which ensures the deposition of a film with the same stoichiometry throughout the whole process. Due to the relatively high ratio of copper atoms on the surface in the as-deposited layer, it is proposed that the dealloying kinetics is significantly higher than that usually observed during the dealloying process in a model system. The proposed approach has several advantages over other methods, such as a very high growth rate and needlessness of any post-treatment processes. A detailed analysis of the effect of pulse-reverse waveform parameters on the properties of the films is presented. Mesoporous platinum with pores and ligaments having characteristic sizes of less than 10 nm, an equivalent surface area of up to ca. 220 m(2) cm(-3), and a roughness factor of more than 1000 is fabricated.

Fabrication and electrochemical property of hierarchically porous Au-Cu films

The paper presented an alloying/dealloying process for the fabrication of hierarchically porous alloy films (HPAFs). The fabrication process involved electrodeposition of copper on the substrate, annealing to produce new alloy phases, and selective dissolution of copper from the surface. Scanning electron microscopy (SEM) images suggested that the HPAFs were composed of large-sized ligament-channels structures (several micrometers) coupled with small-sized ligament-pores (tens nanometers) interpenetrating the big architectures. Energy dispersive X-ray analysis spectra (EDS) revealed the nonuniform distribution in chemical composition of the large-sized ligament-channel structures. Moreover, we demonstrated that the resulting materials showed catalytic activity for methanol electro-oxidation in alkali solution. We believe that the resulting HPAFs electrode is prospective in the fields of catalysis, sensors, and so on.

Corrosion evaluation and surface characterization of the corrosion product layer formed on Cu–6Sn bronze in aqueous Na 2SO 4 solution

The binary bronze alloy Cu–6Sn corrosion, and formation and properties of corrosion product layer (patinas) during 12 days of exposure to 15 mM Na 2SO 4 aqueous solution were investigated by a range of diverse experimental techniques. For the reasons of comparison, some techniques were applied, in parallel, to copper. Gravimetric measurements revealed lower corrosion rates of bronze than those of copper, probably caused by the presence of tin compounds in the corrosion product layer. Cyclic voltammetry results showed that the oxidation processes on bronze are affected by the formation of tin oxide species. Electrochemical impedance spectroscopy showed that, as opposed to copper which produced only two time constants, bronze corrosion resistance was dominated by the additional high-frequency time constant representing redox processes occurring at the corrosion product surface. SEM, ATR FTIR and PIXE results suggest that Cu–6Sn bronze corrosion in 15 mM Na 2SO 4 solution was impeded by the formation of two-layered structure of corrosion products that formed due to selective dissolution of copper at the layer/solution interface, leaving the outer layer enriched in highly corrosion resistant Sn oxi/hydrohide species.