Kinetics of dissolution of synthetic heazlewoodite (Ni3S2) in nitric acid solutions

The dissolution rate of heazlewoodite in nitric acid solution has been determined. The effects of nitric acid concentration, temperature, particle size, stirring intensity and addition of Cu²⁺ ions have been investigated. Solid residues after leaching were examined by SEM, X-ray diffraction and chemical analysis. In the solutions containing less than 2.0 M HNO₃, dissolution was observed to be completely inhibited after 30 min leaching time, and the rate of hydrogen sulphide production was faster than its oxidation to S⁰ and HSO₄^?. In 3 M HNO₃, an abrupt increase in dissolution rate of Ni₃S₂ was found. Two different regions of the dissolution of heazlewoodite were observed below and above 50°C. At temperatures below 50°C, the dissolution rate was very slow, even in 3.0 M HNO₃ solution, and H₂S gas was evolved. Above 50°C, the dissolution rate rapidly increased. Over the temperature interval 60–90°C in 3.0 M HNO₃ dissolution followed a linear rate law, and the activation energy was found to be 42.1 kJ mol^?1. Most of the oxidized sulphide ion was found in the solution as sulphate. The leaching rate was independent of stirring speed. The rate-controlling step of the Ni₃S₂ dissolution is the oxidation of hydrogen sulphide to elemental sulphur or sulphate ions on the Ni₃S₂ surface. Addition of small amounts of Cu²⁺ ions to the nitric acid acted as catalyst for the dissolution of Ni₃S₂. Bubbling air through the leach suspension increased the dissolution rate of Ni₃S₂ in solutions containing less than 2.0 M HNO₃.     

Electrochemical Studies and XPS Analysis of the Surface of Zirconium-702 in Concentrated Nitric Acid With and Without Fluoride Ions

Zirconium exhibited pseudo-passive behavior in fluorinated nitric acid (11.5 M HNO₃ + 0.05 M NaF) as the current density measured from the electrochemical studies was several orders higher than the value in fluoride free nitric acid. Impedance studies on zirconium sample exposed in 11.5 M HNO₃ for 240 h confirmed the formation of the passive film with high polarization resistance value and the calculated thickness of the film based on the capacitance value was about ~4.5 nm. On the other hand, in fluorinated nitric acid, the charge transfer resistance value associated with the zirconium dissolution process was dominant when compared to that of the film formation. Results of X-ray photoelectron spectroscopic investigations upheld the presence of ZrOF₂ and ZrF₄ and indicated that the protective oxide layer growth was restricted by the presence of fluoride ions.     

Metals recovery from spent hydrotreatment catalysts in a fluoride-bearing medium

This work examines the dissolution of spent commercial NiMo/Al₂O₃ and CoMo/Al₂O₃–SiO₂ catalysts in aqueous solutions containing fluoride ions under mild experimental conditions. Solubilization of samples in the presence of fluoride salts alone was insignificant, but solubilization in pure HF was quantitative after 14–16 h. The addition of a strong inorganic acid led to full solubilization after 30 min (NiMo) or 4 h (CoMo) at 50–60 °C and a stirring speed of 400 rpm. This time was reduced by at least 75% when hydrogen peroxide was added. HF was the best source of fluoride ions for dissolving SiO₂ and phosphate-containing species. The recovery of metals from the leach solution could be accomplished very efficiently and with low residue generation.     

Extraction of molybdenum,nickel and aluminium from spent Ni–Mo hydrodesulphurization (HDS) catalyst in oxalic acid solutions

ABSTRACT

Dissolution behaviour of metals in Ni–Mo hydrodesulphurization catalyst waste was investigated in a 1?L jacketed glass reactor. Samples were roasted at 500°C in a tube furnace for the removal of C and S prior to the dissolution experiments. It was determined that roasted samples consisted of mainly 27.692% Al, 20.238% Mo, 5.267% Ni and 4.331% P. Unmilled samples were used for dissolution experiments because dissolution experiments carried out with milled and unmilled samples showed that milling has no significant effect on the dissolution rate. Oxalic acid solutions with 0.25–1 M, reaction temperatures of 25–70°C and solid to liquid ratios of 10–100?g?L^?1 were used as experimental parameters. It was found that the dissolution behaviour of Ni is different from Al, Mo and P. 92% of Mo, 19% of Ni, 28% of Al and 72% of P were dissolved at optimum dissolution conditions.     

Acid dissolution of willemite (Zn,Mn)2 SiO4) and hemimorphite (Zn4Si2O7(OH)2 H2O)

The influence of temperature, pH, acid type, and surface area on the kinetics of the acid dissolution of natural and synthetic willemites and natural hemimorphites has been investigated. Specific rate constants, based upon areas determined by krypton adsorption measurements, were estimated from the experimental data obtained. For both willemite and hemimorphite, the rates of dissolution in different acids are shown to be related to the relative strengths of zinc-acid anion complexes. The reactivity of willemite toward acids increases with increasing replacement of zinc by manganese. Mixed chemical/diffusion control is responsible for the observed rates of willemite dissolution under the conditions studied (HNO₃, HCl, HClO₄, H₃PO₄, H₂SO₄, pH 0.31 to 3.00,T 21 to 94 °C). Estimates of the relative contributions of chemical and diffusional resistances to the overall rate have been made for the dissolution of manganese-free willemite in sulfuric acid solutions. The experimentally measured rates have been demonstrated to be in reasonable agreement with predicted overall dissolution rates. Proposals are made regarding the nature of the diffusion and chemical steps involved in the dissolution process. Hemimorphite was found to be considerably more reactive than willemite and its dissolution is primarily diffusion controlled under the conditions studied (T 20 to 76 °C, pH 2 to 3.5). Formerly a Postgraduate Research Student, Department of Metallurgy and Materials Science, Royal School of Mines, Imperial College, London     

Problems in the separation of radium from uranium ore tailings

The radium content of a representative sandstone type of uranium ore was found to be distributed uniformly according to particle size before leaching, but in sulfuric acid-leached tailings was found predominantly in the ?325 mesh fraction. The radium leaching characteristics from both ore and sulfate-leached tailings were investigated. Several 1 M salt solutions showed poor to moderate RaSO₄ dissolution from “slimes solids” tailings, while 3 M HNO₃ or HCl solutions dissolved approximately 95% of the radium content of either ore or tailings. Tests are reported in which ?325 mesh sand particles were coated with alkaline-earth sulfates by a special technique to simulate slime solids tailings. The dissolution of RaSO₄ from these coated sands was decreased by the presence of BaSO₄, but increased by the presence of CaSO₄. The interrelationships in the dissolution of mixtures of CaSO₄, SrSO₄, BaSO₄, and RASO₄ are shown, and a generalized equation for the estimation of the dissolution of a minor component is presented.     

Differences in oxides on large-and small-grained 304 stainless steel

The oxides formed on large-grained (∼40 °m) and small-grained (∼4 μm) 304 stainless steel oxidized in air at 800 °C have been examined and compared by Auger electron spectroscopy to learn more about the role of grain boundaries in the oxidation of the materials. For vacuum preannealed specimens, relatively thick iron oxides formed over the grains and thin, chromium-rich oxides formed over grain boudaries of large-grained material. The oxide formed over the entire surface of the small-grained material was a thin chromium-rich layer similar to that formed over grain boundaries of the large-grained samples. The oxidation of both small- and large-grained samples was consistent with selective formation of Cr₂O₃ at grain boundaries followed by a lateral diffusion of Cr and spreading of Cr₂O₃. A protective Cr₂O₃ layer formed readily on small-grained material but not on large-grained material. In contrast to the differences in oxide morphology for small- and large-grained preannealed specimens, oxide morphologies were similar for small- and large-grained material when the outer surface layer was removed by polishing after annealing and before oxidation tests. Surface differences, not adequately defined by Auger and SEM studies, caused marked changes in oxide morphologies for large-grained material. The difference in oxidation behavior before and after polishing was attributed to enhanced oxidation at grain boundaries during the vacuum preannealing treatment and to differences in defect concentrations in the surface region.     

The effect of the elemental sulfur reaction product on the leaching of galena in ferric chloride media

The dissolution of galena in 0.3 M FeCl₃-0.3 M HC1 solutions containing 0 to 6 M LiCl was studied at 80 °C, and parabolic kinetics were observed at all LiCl concentrations. The leaching rate increases gradually with increasing LiCl concentrations to ≈4 M LiCl; the presence of >4 M LiCl results in a rapid increase in the leaching rate. The solubility of PbCl₂ in 0.3 M FeCl₃-0.3 M HC1 solutions containing 0 to 6.5 M LiCl was measured over the temperature range of 50 °C to 90 °C. The solubility increases systematically with increasing temperature and LiCl concentration. The parabolic kinetics, coupled with the correlation between the leaching rate and the solubility of PbCl₂, suggest that the dissolution of galena is controlled by the outward diffusion of the PbCl₂ reaction product through the constantly thickening layer of elemental sulfur formed during leaching. This conclusion is also supported by various morphological studies which consistently indicated a thin layer of PbCl₂ between the corroding galena and the porous elemental sulfur reaction product.     

Corrosion behaviour of low-Cr high-Al stainless steels in 65% boiling HNO3

The corrosion resistance of low-Cr high-Al steels has been tested in 65% boiling HNO₃ solution. Comparison of this resistance and that of stainless steels 304, 430 and 410 under the same conditions reveals that Al has a beneficial effect on the corrosion resistance of Fe-Cr-Ni steels. The reduction of about 7% Cr can be compensated by about 5% Al provided that Ni is maintained at about 15–18%.     

Effect of nitrogen content on the environmentally-assisted cracking susceptibility of duplex stainless steels

The effect of nitrogen content on the stress corrosion cracking (SCC) behavior of 22 pct Cr duplex stainless steel (DSS) in chloride solutions was investigated in this study. Slow strain rate testing (SSRT) was employed to evaluate the SCC susceptibility. The experimental results showed that the tensile strength and ductility of 22 pct Cr DSS increased with increasing amount of nitrogen (in the range of 0.103 to 0.195 wt pct). Slow strain rate testing results indicated that 22 pct Cr DSSs were resistant to SCC in 3.5 wt pct NaCl solution at 80 °C. However, environmentally assisted cracking occurred in 40 wt pct CaCl₂ solution at 100 °C and in boiling 45 wt pct MgCl₂ solution at 155 °C, respectively. The effects of environment and nitrogen content in DSS on the cracking susceptibility are discussed in this article. Selective dissolution of ferrite phase was found to participate in the SCC process for tests in CaCl₂ solution. At temperatures above 80 °C, dynamic strain aging was found to occur in various environments at a strain beyond plastic deformation.     

Effect of Microstructure of 304L SS and Thermal Aging of 304L SS Weld on the Corrosion Behavior in Simulated High Level Waste

The effect of oxidizing ions present in simulated high level liquid waste (HLW) on the corrosion behaviour of solution annealed, sensitized 304L SS and 304L SS weld was investigated by potentiodynamic anodic polarization technique. Potentiodynamic anodic polarization studies showed a higher passivation current density and increased corrosion potential (E_corr) in simulated HLW when compared to 3 M HNO₃ in all the specimen mentioned above. In addition, the effect of microstructure of thermally aged 304L SS weld on the corrosion behavior was investigated in simulated HLW medium. Thermal ageing of 304L SS weld was carried out at 1023 K/100 h. Optical microscopy confirmed step microstructure for solution annealed and ditch microstructure for the sensitized specimens. The weld region was found to possess delta-ferrite distributed in austenite matrix. Thermal ageing resulted in fragmentation/dissolution of delta-ferrite and transformation of delta-ferrite to carbides and sigma phases. The thermally aged 304L SS weld specimen showed only a marginal decrease in corrosion resistance in simulated HLW when compared to the 304L SS weld.     

Hot corrosion of Fe-Cr-Ni-AI-Si alloys in molten carbonate

The change in weight of five newly developed steel alloys containing Fe, 10–11.3 % Cr, 15–18.27 % Ni, 4.98–5.76 % Mn, 4.18–5.52 % Al and 0.36–1.5 % Si together with Inconel 690 and stainless steel 304 has been investigated in Na₂CO₃ + K₂CO₃ eutectic mixture at 800°C under atmospheric pressure and under isothermal and cyclic conditions. The scales formed were examined with optical and scanning electron microscopy and were analysed by energy dispersive X-ray diffraction techniques. It has been shown that the corrosion resistance of the alloys is far better than that of stainless steel 304, but slightly less than that of Inconel 690. The relatively high contents of Si and Al gave alloy 5 its highest corrosion resistance. About 0.2 % N were found to refine the grains without the danger of depleting the grain boundaries from Al and Cr. The results have been explained in the light of the alkaline conditions prevailing in the carbonate melt.     

Mechanism of Dissolution Behavior of the Secondary Alumina

The study on dissolution of alumina in aluminum electrolyte has never been suspended. The raw materials used in aluminum smelter are made up of primary alumina and secondary alumina. The latter is the by-product of a dry scrubbing system. The differences in dissolution behavior of these two kinds of alumina are studied in this article. A see-through cell was used for observing the dissolution behavior of alumina. It was found that the dissolution rate of the secondary alumina was significantly faster than that of the primary alumina. The effect of possible impurities in the secondary alumina on the dissolution behavior, including carbon dust, hydrogen fluoride (HF), and other fluorides (Na₅Al₃F₁₄, Na₃AlF₆, AlF₃), was investigated. The carbon dust played an important role in improving the dissolution behavior. However, fluorides and chemisorbed HF have little effect on the dissolution behavior of the secondary alumina.     

A kinetic model for the hydrochloric acid leaching of kaolinite clay in the presence of fluoride ions

The dissolution of kaolinite clay in hydrochloric acid solutions has been carried out in the presence of fluoride ions. Leaching in the presence of fluoride ions activates the clay for leaching, making higher extractions possible at lower roasting and leaching temperatures. The activation energy for the leaching of clay calcined at 540°C is decreased from 71 kJ/mol to 23 kJ/mol in the presence of fluoride ions. Dissolution in the presence of fluoride appears to fit a second-order reaction mechanism.     

Leaching behavior of ilmenite with sulfuric acid

A study of the rate of dissolution of ilmenite in sulfuric acid solutions has been carried out. The effects of temperature, particle size, stirring speed, and concentration of sulfuric acid on the rate of dissolution of ilmenite has been investigated. Temperature range studied in this investigation was 88° to 115°C, and the Arrhenius activation energy was found to be 64.4 kJ (15.4 kcal) per mole. The rate of dissolution increased with concentration of sulfuric acid up to about 14 M sulfuric acid and decreased beyond this concentration. The maximum recovery at 14 M H₂SO₄ can be explained partially by the fact that H⁺ ion concentration peaks at about this concentration. Furthermore, reaction products, TiOSO₄ and FeSO₄, cover the surface of ilmenite when high concentrations of sulfuric acid are used, while these products are dissolved in water and removed from the surface when diluted sulfuric acid is involved. Based on the results obtained in this study, it can be concluded that the overall leaching of ilmenite with sulfuric acid at 88° to 115°C is described best by surface chemical reaction limiting with an order of 0.55 with respect to sulfuric acid concentration.     

Microstructural aspects of the dissolution and melting of Al2Cu phase in Al-Si alloys during solution heat treatment

The dissolution and melting of Al₂Cu phase in solution heat-treated samples of unmodified Al-Si 319.2 alloy solidified at ≈10 °C were studied using optical microscopy, image analysis, electron probe microanalysis (EPMA), and differential scanning calorimetry (DSC). The solution heat treat-ment was carried out in the temperature range 480 °C to 545 °C for solution times of up to 24 hours. Of the two forms of Al₂Cu found to exist,i.e., blocky and eutectic-like, the latter type is more pronounced in the unmodified alloy (at ≈10 °C) and was observed either as separate eutectic pockets or precipitated on preexisting Si particles, β-iron phase needles, or the blocky Al₂Cu phase. Dissolution of the (Al + Al₂Cu) eutectic takes place at temperatures close to 480 °C through frag-mentation of the phase and its dissolution into the surrounding Al matrix. The dissolution is seen to accelerate with increasing solution temperature (505 °C to 515 °C). The ultimate tensile strength (UTS) and fracture elongation (EL) show a linear increase when plotted against the amount of dissolved copper in the matrix, whereas the yield strength (YS) is not affected by the dissolution of the Al₂Cu phase. Melting of the copper phase is observed at 540 °C solution temperature; the molten copper-phase particles transform to a shiny, structureless phase upon quenching. Coarsening of the copper eutectic can occur prior to melting and give rise to massive eutectic regions of (Al + Al₂Cu). Unlike the eutectic, fragments of the blocky Al₂Cu phase are still observed in the matrix, even after 24 hours at 540 °C.     

Ternary dissolution kinetics in the Fe-Ni-P system

The dissolution of (FeNi)₃P in the ternary Fe-Ni-P system has been studied by optical and electron microprobe techniques. Precipitates of (FeNi)₃P, initially in equilibrium with their ternary matrix (a at 750°C, y at 875°C), were examined after being partially dissolved by heating at 975°C. In addition, diffusion couples with starting compositions similar to the equilibrated ternary alloys were examined after also being heat treated at 975°C. Phosphide, (FeNi)₃P, dissolution in the α or γ phase is diffusion controlled at 975°C. The ternary dissolution paths observed in each of the diffusion couples are unique and the same as those observed in the comparable alloys. The dissolution rate of (FeNi)₃P is controlled by the diffusion rate of P in the α or y phases. The Ni interface compositions in (FeNi)₃P and α or γ and the dissolution path through the ternary are determined by the rate of dissolution and the major Ni ternary diffusion coefficients. It is possible to calculate both the dissolution path and rate for (FeNi)₃P by using the binary dissolution equations in combination with the Fe-Ni-P diagram and the major (ternary) diffusion coefficients. In addition, numerical solutions can be correctly calculated for diffusion controlled dissolution where impingement of overlapping gradients occurs.     

Method for measuring transformation energy and quantitative characterization of transformation-induced plasticity

A method for measuring transformation energy (E _pt) of strain-induced martensite (SIM) and quantitative characterization of transformation-induced plasticity is developed using characteristics of the tensile curve of three metastable austenitic stainless steels, 10Cr18.5Ni8.5Mnl.9Si0.9, 19Cr17.5Ni7.4Mn2.3Si1.0, and 10Cr16.2Ni11.8Mn1.2Si0.7. The results show that the E _pt of tested materials at −196 °C is 11.3, 14.7, and 20.1×10⁶ J/m³, respectively; E _pt remains constant in the stages of elasto-plastic instability and stress plateau of tensile curves. As the E _pt, which mainly depends on chemical composition of materials, increases, M _s decreases, but the minimum strainproducing M transformation, e _ph, increases. The average plasticity increment (D) induced by M transformation is 0.17 to 0.20 for the metastable austenitic stainless steels, and it decreases with increasing carbon content of steels. The decrease of stacking fault energy (SFE) is beneficial to the D value.     

Corrosion and Passive Film Formation Studies on Modified 9Cr–1Mo Steel in Different Sodium Hydroxide Concentrations at Room Temperature and in Boiling Condition

Studies were carried out on modified 9Cr–1Mo steel to understand its corrosion as well as passive film characteristics in caustic environment. Potentiodynamic anodic polarization studies were carried out in 1–8 M sodium hydroxide solutions at room temperature (RT) and in boiling conditions. The specimens were passivated at 0.0 V(SCE) for 1 h in 3 and 8 M sodium hydroxide solutions at RT as well as in boiling condition. Laser Raman spectroscopic (LRS) analysis was carried out to examine the nature of oxides/hydroxides formed on the surface of the specimens. Corrosion rates increased by one order of magnitude whereas passive current density increased by almost two orders of magnitude in boiling solution compared to the RT values. Appearance of only maghemite (γ-Fe₂O₃) peaks in passivated steel in 3 M sodium hydroxide solution at RT compared to that in the 8 M sodium hydroxide solution, which showed Fe(OH)₂, maghemite, magnetite, goethite (α-FeOOH) and CrO(OH), Cr₂O₃ peaks, indicated corrosion attack on the outer layer of the passive film. The passivated steel specimens in 3 and 8 M boiling solutions showed maghemite, magnetite, goethite, hematite (α-Fe₂O₃) (only in 8 M) and extremely weak peaks of Cr(OH)₃ and Cr₂O₅. These observations indicated dissolution of the outermost part of the passive film with superficial attack on the inner part of the passive film exposing Cr oxide/hydroxides in boiling 3 M solution. However, passivated steel in 8 M solution showed molybdenum oxides, apart from the other iron and chromium oxides/oxyhydroxides. The scanning electron microscopic (SEM) studies on the morphology of the corrosion products along with LRS analysis/characterization confirmed these observations. These results showed increased corrosion attack during passivation with increase in concentration of alkali and temperature.     

Low-cycle fatigue and cyclic stress-strain behavior of incoloy 800

Strain-controlled low-cycle fatigue tests of solution-annealed Incoloy 800 were performed at temperatures of 538°, 649°, 704°, and 760°C using axial strain rates of 4 × 10^-3 and 4 × 10^-4 sec^-1. A few hold-time tests were also performed to indicate a noticeable reduction in fatigue life at hold times of 10 and 60 min. A comparison of these fatigue data with similar results for AISI 304 stainless steel indicates essentially identical behavior. An extensive study is made of the cyclic stress-strain behavior of Incoloy 800 and the relationship between the cyclic strain-hardening exponent and fatigue behavior is confirmed. Exponents onN _f in the elastic and plastic strain range terms of the total strain range equation are identified and compared with those used in the Universal Slopes equation.