Investigation of the specific adsorption of HSO4(SO4) and Cl ions on Co and Fe by radiotracer technique in the course of corrosion of the metals in perchlorate media

The adsorption of sulphate and chloride ions on Co and Fe was studied in 0.5 mol dm⁻³ NaClO₄ supporting electrolyte at various pH values by radiotracer technique in the course of the corrosion (dissolution) of the metals. The effect of the reduction of ClO₄⁻ ions (leading to the formation of Cl⁻ ions) on the radiotracer measurements was investigated. It was found that the adsorption of chloride and sulphate ions occurs in different pH ranges. This phenomenon was explained by the assumption that the adsorption strength of the two species is very different on oxide covered and “pure” metal surfaces.     

Removal of SO4, uranium and other heavy metal ions from simulated solution by sulfate reducing bacteria

In the case of in-situ leaching of uranium, the primitive geochemical environment for groundwater is changed since leachant is injected into the water bearing uranium deposit. This increases the concentration of SO4^2-, uranium and other heavy metal ions and results in the groundwater contamination. The effects of pH values of the simulated solution on the reduction of SO4^2- and the removal of uranium and other heavy metal ions by sulfate reducing bacteria（SRB） were studied. The results show that, when the pH value of the simulated solution is about 8, the reduction rate of SO4^2- by SRB and the removal rate of uranium, Mn^2＋, Zn^2＋, Pb〉 and Fe^2＋ will reach their highest values. A bioremediation technique for remediation of groundwater in in-situ leaching uranium mine can be developed.     

The characterisation of the protective film formed by benzotriazole on the 90/10 copper-nickel alloy surface in H2SO4 media

The nature of the protective film formed by benzotriazole (BTAH) on the surface of the 90/10 CuNi alloy in deaerated 0.5 mol L⁻¹ H₂SO₄ solution containing Fe(III) ions as oxidant was investigated by weight-loss, calorimetric measurements, and by surface-enhanced Raman spectroscopy (SERS). The SERS measurements show that the protective film is composed by the [Cu(I)BTA]_n polymeric complex and that the BTAH molecules are also adsorbed on the electrode surface. A modification of the BET isotherm for adsorption of gases in solids is proposed to describe the experimental results obtained from weight-loss experiments that suggest an adsorption in multilayers. Electrochemical studies of copper and nickel in 0.5 mol L⁻¹ H₂SO₄ in presence and absence of BTAH have also been made as an aid to interpret the results. The calculated adsorption free energy of the cuprous benzotriazolate on the surface of the alloy is in accordance with the value for pure copper.     

Corrosion evaluation and surface characterization of the corrosion product layer formed on Cu-6Sn bronze in aqueous Na2SO4 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 Na₂SO₄ 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 Na₂SO₄ 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.     

Effect of annealing on the morphology evolution and densification of LiMn2O4 film from chitosan-containing solution

Dense LiMn₂O₄ films deposited on a Pt-coated silicon substrate were obtained by annealing the deposited Li–Mn–O-chitosan films under a two-stage heat-treatment procedure. It was demonstrated that the heat-treatment at 300 °C plays an important role in the subsequent densification of LiMn₂O₄ films. This is attributed to the formation and rearrangement of the nano-sized LiMn₂O₄ crystallites. The surface morphology of the calcined Li–Mn–O-chitosan films was highly related to the annealing temperature. Ridge-like bumps formed on the surface of the films after being heated at 200 °C for 1 h. With calcination at 400 °C or higher, the surface morphology turned into a wrinkle-like microstructure. This morphology transformation is ascribed to the flowing characteristics of the Li–Mn–O-chitosan films during heat-treatment and subsequent thermal decomposition of the precursor at higher temperatures. Moreover, the electrochemical tests showed that the 700 °C-annealed LiMn₂O₄ film possesses the highest discharge capacity of 56.3 μA h/(cm² μm) and best capacity retention of 90.7% after 50 charge/discharge cycles of all annealed films.     

XPS investigations of electrochemically formed passive layers on Fe/Cr-alloys in 0.5 M H2SO4

Passive layers on Fe20Cr and Fe15Cr were prepared by anodic oxidation in 0.5 M H₂SO₄ and were investigated by X-ray photoelectron spectroscopy. The preparation of the sputter-cleaned samples and their transfer to the ultrahigh vacuum was performed under protection of purified argon without any contact to the laboratory atmosphere. The prepassive layer consists of a homogeneous film with Cr(III)hydroxide and Cr(III)-sulphate with a low content of Fe(II). In the passive potential range a bilayer structure with enrichment of Cr(III)-oxides with an outer hydroxide and an inner oxide part is formed. Iron exists only in a bivalent oxidation state. In the transpassive potential range a pronounced change of the layer composition was observed: The outer part of the transpassive layer is formed predominantly by Fe(III) species whereas the inner part still contains a strong enrichment of Cr₂O₃.     

Influence of MnO2 on the sintering behavior and magnetic properties of NiFe2O4 ferrite ceramics

The samples with small amounts of MnO₂ (0, 0.5, 1.0, 1.5, 2.0, and 2.5 wt%, respectively) were prepared via ball-milling process and two-step sintering process from commercial powders (i.e. Fe₂O₃, NiO and MnO₂). Microstructural features, phase transformation, sintering behavior and magnetic properties of Mn-doped NiFe₂O₄ composite ceramics have been investigated by means of scanning electron microscopy (SEM), differential thermal analyzer, X-ray diffraction (XRD), thermal dilatometer and vibrating sample magnetometer (VSM) respectively. The XRD analysis and the result of differential thermal analysis indicate that the reduction of MnO₂ into Mn₂O₃ and the following reduction of Mn₂O₃ into MnO existed in sintering process. No new phases are detected in the ceramic matrix, the crystalline structure of the ceramic matrix is still NiFe₂O₄ spinel structure. Morphology and the detecting result of thermal dilatometer show that MnO₂ can promote the sintering process, the temperature for 1 wt% MnO₂-doped samples to reach the maximum shrinkage rate is 59 °C lower than that of un-doped samples. For 1 wt% MnO₂-doped samples, the value of the saturation magnetization (M_s) and coercivity (H_c) is 15.673 emu/g and 48.316 Oe respectively.     

Protection of passivated iron from corrosion in 0.1 M KClO4 with and without Cl by coverage with a two-dimensional polymer film of carboxylate ion self-assembled monolayer

A film of two-dimensional polymer was prepared on an iron electrode passivated in a borate buffer solution at pH 8.49, derivatized with 16-hydroxyhexadecanoate ion and then modified with 1,2-bis(triethoxysilyl)ethane (C₂H₅O)₃Si(CH₂)₂Si(OC₂H₅)₃ and octadecyltriethoxysilane C₁₈H₃₇Si(OC₂H₅)₃. The protective ability of the polymer film adsorbed on passivated iron was examined by polarization measurement in oxygenated 0.1 M KClO₄ solutions with and without 1 × 10⁻⁴ and 1 × 10⁻³ M of Cl⁻. The values of the open-circuit potential, E_oc were monitored with the immersion time, t in these solutions. The E_oc value of the passivated electrode in 0.1 M KClO₄ was maintained high, more than −0.2 V/SCE in the initial region of t up to 10 h, indicating the presence of a passive film on the electrode. Thereafter, E_oc decreased to −0.4 V/SCE abruptly, exhibiting breakdown of the passive film. The value of the passivated electrode covered with the polymer film remained almost constant around −0.04 V/SCE during immersion for 45 h. The protective efficiency, P (%) of the polymer film on passivated iron was extremely high, more than 99.9% unless the passive film was broken down, indicating complete protection of iron against corrosion. The times for breakdown on the passivated electrode and polymer-coated one diminished with an increase in the concentration of Cl⁻. The polymer-coated surface was analyzed by electron-probe microanalysis after immersion in 0.1 M KClO₄ for 24 h.     

Prevention of passive film breakdown and corrosion of iron in 0.1 M KClO4 with and without Cl by covering with an ultrathin two-dimensional polymer coating and healing treatment in 0.1 M NaNO3

A two-dimensional polymer coating, the self-assembled monolayer of 16-hydroxy hexadecanoate ion HO(CH₂)₁₅ modified with 1,2-bis(triethoxysilyl)ethane (C₂H₅O)₃Si(CH₂)₂Si(OC₂H₅)₃ and octadecyltriethoxysilane C₁₈H₃₇Si(OC₂H₅)₃ was prepared on the passivated iron electrode and further, the passive film was healed by additional treatment in 0.1 M NaNO₃. This electrode was immersed in oxygenated 0.1 M KClO₄ solutions with and without 1 × 10⁻⁴ to 1 × 10⁻² M of Cl⁻. Protection of passive film against breakdown by covering the electrode with the polymer coating was examined by monitoring the open-circuit potential during immersion in the solutions for many hours to determine the time for passive film breakdown, t_bd. Repeated polarization measurements were carried out during immersion in these solutions for obtaining the protective efficiency, P. The t_bd value of the passivated, polymer-coated and healed electrode in 0.1 M KClO₄ solutions with and without Cl⁻ increased with a decrease in the concentration of Cl⁻. No breakdown occurred on the electrode during immersion in 0.1 M KClO₄ solutions with and without 1 × 10⁻⁴ of Cl⁻ for 360 h. The P values were extremely high, more than 99.9% before t_bd, indicating complete protection of iron from corrosion. The effect of healing treatment in 0.1 M NaNO₃ on passive film breakdown was investigated by electron-probe microanalysis.     

A first quantitative XPS study of the surface films formed, by exposure to water, on Mg and on the Mg-Al intermetallics: Al3Mg2 and Mg17Al12

An XPS investigation was carried out of the surface films, formed by exposure to ultrapure water, on mechanically ground Mg and the two Mg-Al intermetallic compounds: Al₃Mg₂ and Mg₁₇Al₁₂. The mechanically ground Mg surface had a film of MgO at the Mg metal surface covered by a Mg(OH)₂ layer, formed by the reaction of the MgO with water vapour in the air. Upon immersion in ultrapure water, this film converted to a duplex film with an inner MgO layer next to the Mg metal and an external porous hydroxide layer. For both intermetallics, the XPS data is consistent with (i) preferential dissolution of Mg and (ii) a 10 nm thick film on the surface after immersion in ultrapure water; the film composition on Al₃Mg₂ was AlMg_1.4O_0.2(OH)_5.4 whilst on Mg₁₇Al₁₂ the composition was AlMg_2.5(OH)₈.     

Photocatalytic effects of TiO2/Fe thin film irradiated with visible light on cellular surface ultrastructure and genomic DNA of bacteria

TiO₂/Fe thin film is thin film modified by metal (Fe) plasma ion implantation. In our previous work, it has been demonstrated to have antimicrobial activity after being irradiated with visible light. However, the mechanism of its antimicrobial activity has not been well known yet. In this study, the effects of TiO₂/Fe thin film irradiated with visible light on the cellular morphology and DNA of the Erwinia carotovora subsp. carotovora ZL1, an important soft rot bacterium of vegetable and ornamental crops were examined. Scanning electron microscopic studies revealed that abnormal ultrastructures were observed on the surface of E. carotovora subsp. carotovora ZL1 cells treated with TiO₂/Fe thin films irradiated with visible light for 60 min. Based on the gel electrophoresis analysis, the genomic DNA of E. carotovora subsp. carotovora ZL1 cells treated with TiO₂/Fe thin films under visible light irradiation was also affected. The results suggest that TiO₂/Fe thin film irradiated with visible light has the potential to disinfect of plant- or public health-concerned pathogens.     

A preliminary study of the redox behavior of tungstate and molybdate ions in Na2SO4 at 1203 K

The redox behavior of W and Mo ions on Pt electrodes in molten Na₂SO₄ at 1203 K has been studied in an O₂-SO₂-SO₃ ambient. W and Mo were added as Na₂MO₄ (M = W, Mo) to the Na₂SO₄ melt. Cyclic voltammograms showed two reduction processes for both species within the Na₂SO₄ stability range. The oxidation sequence for the tungstate ion showed one of the reduction reactions to be irreversible. For molybdate ions there are oxidation reactions corresponding to each of the reduction reactions. The characteristics of the cyclic voltammogram peaks are described.     

Spectrophotometric study of the anodic corrosion of Ti/RuO2 electrode in acid sulfate solution

Electrochemical properties of RuO₂-based electrode, particularly the oxygen evolution and anodic dissolution of RuO₂ have been investigated in 0.5 mol dm⁻³ H₂SO₄ solution by means of polarization measurements and product analysis. It has been demonstrated that it is possible to determine very low concentration of dissolved ruthenium species (8 × 10⁻¹⁰ mol dm⁻³ Ru) by a sensitive spectrophotometric method based on the ruthenium-catalyzed ceric-arsenite reaction.Finally, the probable mechanism of anodic dissolution of RuO₂-based electrode, has been proposed.     

Environmental factors affecting the corrosion behavior of reinforcing steel II. Role of some anions in the initiation and inhibition of pitting corrosion of steel in Ca(OH)2 solutions

Potential-time curves are constructed for the steel electrode in naturally aerated Ca(OH)₂ solutions simulating the corrosion behavior in concrete. Cl⁻ and SO₄²⁻ ions cause the destruction of passivity and initiation of pitting corrosion. The rate of oxide film growth by Ca(OH)₂ and oxide film destruction by Cl⁻ and SO₄²⁻ ions follows a direct logarithmic law as evident from the linear relationships between the open-circuit potential and the logarithm of immersion time. Chromate, phosphate, nitrite, tungstate and molybdate ions inhibit the pitting corrosion of steel. The rate of oxide film healing and thickening increases with their concentrations. In presence of constant inhibitor concentration, the efficiency of pitting inhibition increases in the order: (weak) CrO₄²⁻ < HPO₄²⁻ < NO₂⁻ < WO₄²⁻ < MoO₄²⁻ (strong).     

Kinetic study on the surface treatment of a Zr0.9Ti0.7Ni1.1Co0.1Mn0.6V0.2 electrode with a boiling alkaline solution

The effect of surface treatment of Zr_0.9Ti_0.1Ni_1.1Co_0.1Mn_0.6V_0.2 alloy electrodes with a boiling 6 M KOH solution for different periods of time was discussed quantitatively by comparison of exchange current density measured by micropolarization method and charge-transfer resistance measured by ac impedance method. The initial activation, exchange current density and charge transfer resistance were greatly improved by increasing alkali treatment time. In particular, the alkali treatment for 2 h showed sufficient electrocatalytic activity and activation effect. The alkali treatment was effective for the progress of the pulverization as well as the removal of the surface Zr-oxide layer. Additionally, the increase in the Ni component on the alloy surface as a result of the alkali treatment was responsible for the above improvement.     

Analysis of diamond-like carbon and Ti/MoS2 coatings on Ti–6Al–4V substrates for applicability to turbine engine applications

Ti–6Al–4V substrates have been coated by diamond-like carbon (DLC) films, with no surface pretreatment, and have been coated by Ti/MoS₂ films, with a simple surface pre-cleaning. The DLC films were deposited by planar coil r.f. inductively-coupled plasma-enhanced chemical vapor deposition (r.f. ICPECVD); the Ti/MoS₂ films were deposited by magnetron sputtering. Both the DLC and Ti/MoS₂ films were characterized by pull tests, hardness tests, scanning electron microscopy (SEM), and wear tests (pin-on-disk and block-on-ring) to compare their adhesion, hardness, surface topology, and wear properties to plasma-sprayed Cu–Ni–In coating currently used for turbine engine applications. The DLC films were easily characterized by their optical properties because they were highly transparent. We used variable-angle spectroscopic ellipsometry (VASE) to characterize thickness and to unequivocally extract real and complex index of refraction, providing a rapid assessment of film quality. Thicker coatings yielded the largest hardness values. The DLC coatings did not require abrasive pretreatment or the formation of bond-layers to ensure good adhesion to the substrate. Simple surface pre-cleaning was also adequate to form well-adhered Ti/MoS₂ on Ti–6Al–4V. The results show that the DLC and Ti/MoS₂ coatings are both much better fretting- and wear-resistant coatings than plasma-sprayed Cu–Ni–In. Both show excellent adhesion to the substrates, less surface roughness, harder surfaces, and more wear resistance than the Cu–Ni–In films.     

Synergism between red tetrazolium and uracil on the corrosion of cold rolled steel in H2SO4 solution

The synergism between red tetrazolium (RT) and uracil (Ur) on the corrosion of cold rolled steel (CRS) in H₂SO₄ solution is first investigated by weight loss, potentiodynamic polarization, and atomic force microscope (AFM). Effects of inhibitor concentration (25-500 mg l⁻¹), temperature (20-50 °C), and acid concentration (1.0-5.0 M) on synergism are discussed systematically. The results reveal that RT has a moderate inhibitive effect, and its adsorption obeys the Freundlich adsorption isotherm. For Ur, it has a poor effect. However, incorporation of RT with Ur significantly improves the inhibition performance, and produces synergistic inhibition effect.     

Inhibition effect of 6-benzylaminopurine on the corrosion of cold rolled steel in H2SO4 solution

The inhibition effect of 6-benzylaminopurine (BAP) on the corrosion of cold rolled steel (CRS) in 1.0-7.0 M H₂SO₄ at 25-50 °C was studied by weight loss and potentiodynamic polarization methods. Fourier transform infrared spectroscopy (FTIR) and atomic force microscope (AFM) were used to characterize the CRS surface. The results showed that BAP was a good inhibitor in 1.0 M H₂SO₄, and the adsorption of BAP obeyed the Temkin adsorption isotherm. Polarization curves showed that BAP acted as a mixed-type inhibitor in sulfuric acid. Depending on the results, the inhibitive mechanism was proposed.     

Effect of Mo and Mn additions on the corrosion behaviour of AISI 304 and 316 stainless steels in H2SO4

The work addresses the influence of Mn and Mo additions on corrosion resistance of AISI 304 and 316 stainless steels in 30 wt.% H₂SO₄ at 25 and 50 °C. Corrosion mechanism was determined by gravimetric tests, DC polarization measurements and electrochemical impedance spectroscopy (EIS). The morphology and nature of the reaction products formed on the material surface were analysed by scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDX) and X-ray photoelectron spectroscopy (XPS). Reduction of temperature from 50 to 25 °C drastically decreased the corrosion rate of AISI 304 and 316 stainless steels in sulphuric acid solution. Mn additions did not affect significantly the general corrosion resistance due to its low ability to form insoluble compounds in acid medium. Meanwhile, the formation of molybdenum insoluble oxides enhanced the corrosion performance.     

Role of Cr ions on the microstructure development, and magnetic phase evolution of Ni0.7Zn0.3Fe2O4 ferrite nanoparticles

A series of ferrite samples with the chemical formula Ni_0.7Zn_0.3Cr_xFe_2−xO₄ (x = 0.0-0.5) were prepared by a sol-gel auto-combustion method and annealed at 600 °C for 4 h. The resultant powders were investigated by various techniques, including X-ray diffractometry (XRD), vibrating sample magnetometry (VSM), and permeability studies. The prepared samples have a cubic spinel structure with no impurity phase. As the Cr³⁺ content x increases, bulk density and crystallite size decrease, whereas porosity increases. The saturation magnetization decreases linearly from 58.31 to 42.90 emu/g with increasing Cr³⁺ content. However, coercivity increases with increasing Cr³⁺ substitution. The magnetic moments calculated from Neel's molecular-field model are in agreement in the experiment results. The initial permeability (μ_i) decreases with increasing Cr³⁺ substitution. The decrease in initial permeability (μ_i) is attributed to decrease in magnetization on addition of Cr³⁺. The real part of the permeability decreases gradually with increasing frequency in accordance with Snoek's law. The Curie temperature decreases linearly with increasing Cr³⁺ content.