Plasma-electrolytic oxidation of titanium in Zr(SO<Subscript>4</Subscript>)<Subscript>2</Subscript>-containing electrolyte

It is shown that anodic oxide coatings with a thickness of several to 300 νm can be obtained on titanium by varying the charge spent on (Q). The prevailing phase in the coatings is ZrO₂ in monoclinic and tetragonal modifications. The content of zirconium in the layers is up to 20 at %. Distributions of titanium, zirconium, and oxygen in the cross sections of the coatings are obtained, and the effect of Q on the formation and elementary and phase compositions of the coatings is studied. Tentative experiments clarifying the effects of bipolar anodic-cathodic polarization and electrolyte aging on the composition of coatings are carried out. The coatings are shown to be stable at temperature variations in the range of 20–700°C and to decrease the contact corrosion current at the (titanium + coating)—St3 steel interface by a digit of 10–15 in 3% NaCl.     

Thermodynamic optimization of the Na<Subscript>2</Subscript>O-B<Subscript>2</Subscript>O<Subscript>3</Subscript> pseudo-binary system

The Na₂O-B₂O₃ system is thermodynamically optimized by means of the CALPHAD method. A two-sublattice ionic solution model, (Na⁺¹)_P(O⁻²,BO₃ ⁻³,B₄O₇ ⁻²,B₃O_4.5)_Q, has been used to describe the liquid phase. All the solid phases were treated as stoichiometric compounds. A set of thermodynamic parameters, which can reproduce most experimental data of both phase diagram and thermodynamic properties, was obtained. Comparisons between the calculated results and experimental data are presented.     

Evaluation of in vitro and in vivo tests for surface-modified titanium by H<Subscript>2</Subscript>SO<Subscript>4</Subscript> and H<Subscript>2</Subscript>O<Subscript>2</Subscript> treatment

Titanium is widely used as an implant material for artificial teeth. Furthermore, various studies have examined surface treatment with respect to the formation of a fine passive film on the surface of commercial titanium and its alloys and to improve the bioactivity with bone. However, there is insufficient data about the biocompatibility of implant materials in the body. The purpose of this study was to examine whether surface modification affects the precipitation of apatite on titanium metal. Specimens were chemically washed for 2 min in a 1∶1∶1.5 (vol.%) mixture of 48 %HF, 60%HNO₃ and distilled water. The specimens were then chemically treated with a solution containing 97%H₂SO₄ and 30%H₂O₂ at the ratio of 1∶1 (vol.%) at 40°C for 1h, and subsequently heat-treated at 400°C for 1h. All the specimens were immersed in HBSS with pH 7.4 at 36.5°C for 15d, and the surface was examined with TF-XRD, SEM, EDX and XPS. In addition, specimens of commercial pure Ti, with and without surface treatment, were implanted in the abdominal connective tissue of mice for 28 d. Conventional aluminum and stainless steel 316L were also implanted for comparison. An amorphous titania gel layer was formed on the titanium surface after the titanium specimen was treated with a solution of H₂SO₄ and H₂O₂. The average roughness was 2.175 μm after chemical surface treatment. The amorphous titania was subsequently transformed into anatase by heat treatment at 400°C for 1h. The average thickness of the fibrous capsule surrounding the specimens implanted in the connective tissue was 47.1μm in the chemically treated Ti, and 52.2, 168.7 and 101.9μm, respectively, in the untreated commercial pure Ti, aluminum and stainless steel 316L.     

Electrochemical Behavior Assessment of Micro- and Nano-Grained Commercial Pure Titanium in H<Subscript>2</Subscript>SO<Subscript>4</Subscript> Solutions

In this study, the electrochemical behavior of commercial pure titanium with both coarse-grained (annealed sample with the average grain size of about 45 µm) and nano-grained microstructure was compared by potentiodynamic polarization, electrochemical impedance spectroscopy (EIS), and Mott-Schottky analysis. Nano-grained Ti, which typically has a grain size of about 90 nm, is successfully made by six-cycle accumulative roll-bonding process at room temperature. Potentiodynamic polarization plots and impedance measurements revealed that as a result of grain refinement, the passive behavior of the nano-grained sample was improved compared to that of annealed pure Ti in H₂SO₄ solutions. Mott-Schottky analysis indicated that the passive films behaved as n-type semiconductors in H₂SO₄ solutions and grain refinement did not change the semiconductor type of passive films. Also, Mott-Schottky analysis showed that the donor densities decreased as the grain size of the samples reduced. Finally, all electrochemical tests showed that the electrochemical behavior of the nano-grained sample was improved compared to that of annealed pure Ti, mainly due to the formation of thicker and less defective oxide film.     

The effect of alcohol on the passivation of al alloys in 1 N H<Subscript>2</Subscript>SO<Subscript>4</Subscript> solution

In this study, the influence of different alcohol on the passivation of aluminium alloys have been investigated by using current-potential curves. Experimental results show that the addition of alcohol in H₂SO₄ solution have been changed passivation potential distance of the alloys. Elemental compositions of alloys have also directly affected passivation of alloys. This influence is more effective especially in alloys content higher Si also and less Cu.     

Hot Corrosion Mechanism of Steels Exposed to Heavy Metal Chlorides and Sulphates in SO<Subscript>2</Subscript> Environment

Copper flash smelting produces flue dust containing SO₂-rich exhaust gas, causing corrosion problems in the heat recovery boiler of the gas train. In order to understand the corrosion behaviour of boiler steels, conditions of the boiler were simulated in the laboratory. Corrosion damage occurred as chlorine reacted with steel surfaces forming chlorides which deplete the steels from their alloying metals. At the scale/dust deposit interface, where the highest sulphur partial pressures prevail, a sulphate layer covered the mixed oxide and chloride scale. Molten sulphate deposit reduced the metal loss of AISI 304 steel by preventing chromium chloride diffusion away from the steel surface. The Cr₂O₃ scales were quite stable under molten sulphates. The dust deposit melted partially due to the presence of ZnCl₂ in the deposit which initiated corrosion damage by producing a molten salt layer on the steel surfaces bringing it in contact with aggressive compounds in the copper smelter flue dust.     

Effect of alcohol on the corrosion of al alloys in 1 N H<Subscript>2</Subscript>SO<Subscript>4</Subscript> solution Part I

The aim of this paper is to examine the effects of alcohol (1-buten-3-ol-l, 2-methyl-3-butyn-2-ol, 3-methyl-2-buten-1-ol, 3-methyl-3-buten-1-ol, 3-methyl-1-pentyn-3-ol, 5-hexen-1-ol) on the corrosion of Al alloys. The inhibiting effect of alcohol was investigated by electrochemical current-potential curves, atomic absorption spectrometry (AAS), metal microscopy,SEM and EDS. The results showed that alcohol (1-buten-3-ol, 2-methyl-3-butyn-2-ol, 3-methyl-2-buten-1-ol, 3-methyl-3-buten-1-ol, 3-methyl-1-pentyn-3-ol, 5-hexen-1-ol) had an inhibiting effect on the corrosion of aluminium alloys. Experimental results show that corrosion of alloys in H₂SO₄ solution have been effected by elements in alloys such as Cu, Zn, Mg and adsorption of alcohol on the surface of alloys in H₂SO₄ solution obeys Temkin adsorption isotherm. The use of alcohol in H₂SO₄ solution were shifted corrosion potentials (E_cor) to more negative values and acted as cathodic inhibitors on the aluminum alloys. EDS analysis of alloys displayed different intermetallic compounds on the surface of alloys, which might have changed the activity of alcohols depending on the surface morphology of alloys. This paper has showed that these alcohol inhibited corrosion of aluminium alloys in H₂SO₄ solution. The concentration of 20 mM alcohol was shown that above 90% inhibition was achieved, which is a rather high value.     

Acid-acid function of Eichhornia crassipes roots as inhibitor for mild steel in 0.5 M H<Subscript>2</Subscript>SO<Subscript>4</Subscript> solution

The inhibitory potential of an acid extract of Eichhornia crassipes constituents on corrosion of mild steel in 0.5 M H₂SO₄ solution was the basis of this study. Acid extract of the root was employed to create the same type of environment for acidic cleaning and pickling. The roots of Eichhornia crassipes (water hyacinth) were sun-dried and pulverized into powdered form. Acid extraction was carried out by weighing 10 g of the pulverized roots into a beaker containing 1000 mL of 0.5 M H₂SO₄, placed in water bath at 90°C for 6 h and filtered the second day. The mild steel with a known weight was immersed inside the respective concentration of the blank and inhibitors (2–10% vol/vol) solutions at room temperature, after which it was retrieved and weighed at 1-day interval progressively for 12 days. A collection of compositional data was from AAS, FTIR. Polarization resistant, current density (I _corr), and corrosion potentials (E _corr) obtained from Methro Ohms Potentiostat. Phytochemical screening of the corrosion product was carried out using Spectrophotometer. Polarization calculation shows that the root acid extracts on mild steel have corrosion resistance potentials even after preserving it for 60 days.     

The corrosion inhibition of Ti-alloy (VT-9) in mixture of H<Subscript>2</Subscript>SO<Subscript>4</Subscript>-NaF by organic compounds

This investigation deals with corrosion behavior of high strength titanium alloy in concentrated sulphuric acid solution containing different concentrations (500, 1000, 1500 ppm) of fluoride ion (F⁻) using various organic compounds (MPA, L-OH, NFP) as inhibitor, potentiodynamically. The open circuit potential values noted before and after each experiment, varied appreciably. These values were negative before polarization but after completion of the experiment turned positive and remained stable over long period of time. It is observed that cathodic current density values increase with increasing cathodic potential (more negative) and fluoride ion. The values of cathodic Tafel slopes derived from the curves (∼110 − 140 mV/dec I) indicate hydrogen evolution reaction (h.e.r). The corrosion potential (E _corr) varied slightly with addition of inhibitors. The corrosion current densities (I _corr) increased with increasing fluoride ion concentration, but these values decreased appreciably when inhibitor (MPA) was used. SEM micrograph reveals reduction of pits in the presence of inhibitor (MPA). So this concludes that organic compound was used in this case acts as a good inhibitor. The article is published in the original.     

Experimental evaluation of quinolinium and isoquinolinium derivatives as corrosion inhibitors of mild steel in 0.5 M H<Subscript>2</Subscript>SO<Subscript>4</Subscript> solution

The 1-methylquinolinium iodide (I) Qui⁺, I^– and 2-methylisoquinolinium iodide isoQui⁺, I^– were investigated as a corrosion inhibitors for mild steel in sulfuric acid using electrochemical impedance spectroscopy and potentiodynamic polarization techniques. The results indicated that the corrosion inhibition efficiency and extent of surface coverage were increased with increase in inhibitors concentrations. Polarization curves revealed that both inhibitors acted as a mixed-type inhibitor. The thermodynamic parameters were evaluated for corrosion inhibition process. The adsorption of both inhibitors on mild steel surface obeyed Langmuir adsorption isotherm.     

Investigation of Corrosion Protection Performance of Multiphase PEO (Mg<Subscript>2</Subscript>SiO<Subscript>4</Subscript>, MgO,MgAl<Subscript>2</Subscript>O<Subscript>4</Subscript>) Coatings on Mg Alloy Formed in Aluminate-Silicate- based Mixture Electrolyte

Plasma electrolytic oxidation (PEO) coatings in the aluminate-silicate-based mixture electrolyte solution with different duty cycles were successfully applied on Mg alloy. The corrosion behavior of the samples was evaluated by water contact angle test, potentiodynamic polarization, electrochemical impedance spectroscopy (EIS) and immersion tests. Hydrophobic PEO coating could be obtained by adjusting the duty cycle of the applied electric signal. This coating considerably diminished the Mg dissolution and could enhance the impedance values of Mg alloy in 3.5 wt % NaCl solution. However, the surface of other PEO coated samples showed more hydrophilic properties compared to that of the uncoated sample. Dense structure of the modified PEO multiphase (including Mg₂SiO₄, MgO and MgAl₂O₄ phases) coating and also its appropriate thickness provided an effective barrier to remarkably delay corrosive solution penetration into the PEO coating. This phenomenon led to major decrease in anodic current density of alloy in chloride solution.     

Kinetics of forward extraction of Ti（IV） from H_2SO_4 medium by P_（507） in kerosene using the single drop technique

The kinetics of forward extraction of Ti(IV) from H2SO4 medium by P507 in kerosene has been investigated using the single drop technique.In the low concentration region of Ti(IV),the rate of forward extraction at 298 K can be represented by F(kmol·m-2·s-1)=10-5.07 [TiO 2 + ][H+]-1 [NaHA 2 ](o)·Analysis of the rate expression reveals that the rate determining step is(TiO)(i)2+ +(HA 2)(i)-[TiO(HA2)](i)+.The values of Ea,H±,S±,and G±298 are calculated to be 22 kJ·mol-1,25 kJ·mol-1,-218 J·mol-1·K-1,and 25 kJ·mol-1,respectively.The experimental negative S± values indicate that the reaction step occurs via SN2 mechanism.     

Residual protective effect of <Emphasis Type=Italic>o</Emphasis>-oxyazomethine derivatives against iron corrosion in 1 M H<Subscript>2</Subscript>SO<Subscript>4</Subscript> solution

The residual protective effect of n-component mixtures of o-oxyazomethine derivatives at the corrosion of iron in 1 M H₂SO₄ decreases with time and an increase in temperature of the environment and increases with an increase in the polarity of substituent groups in the molecules and the inhibitor concentration in the solution. These regularities are interpreted based on the principle of the linear free-energy relation.     

Corrosion Behavior and Microhardness of Ni-P-SiO<Subscript>2</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Nano-composite Coatings on Magnesium Alloy

In the present work, nano-composites of Ni-P-SiO₂-Al₂O₃ were coated on AZ91HP magnesium alloy. The surface morphology of the nano-composite coating was studied by field emission scanning electron microscopy (FESEM). The amount of SiO₂ in the coating was determined by energy-dispersive analysis of x-ray (EDX), and the crystalline structure of the coating was examined by x-ray diffractometer (XRD). All the experiments concerning the corrosion behavior of the coating carried out in 3.5 wt.% NaCl solution and evaluated by electrochemical impedance spectroscopy (EIS) and polarization technique. The results showed that an incorporation of SiO₂ and Al₂O₃ in Ni-P coating at the SiO₂ concentration of 10 g/Land 14 g/LAl₂O₃ led to the lowest corrosion rate (i _corr = 1.3 µA/cm²), the most positive E _corr and maximum microhardness (496 VH). Furthermore, Ni-P-SiO₂-Al₂O₃ nano-composite coating possesses less porosity than that in Ni-P coating, resulting in improving corrosion resistance.     

Hydrogen generation from the H<Subscript>2</Subscript>O/H<Subscript>2</Subscript>O<Subscript>2</Subscript> /MnMoO<Subscript>4</Subscript> system

Hydrogen gas as a clean energy resource was found to be largely bubbled from the H₂O/H₂O₂/MnMoO₄ system. The MnMoO₄ powder was synthesized by a sol-gel method and was characterized with x-ray diffraction, transmission electron microscopy, and x-ray photoelectron spectrometry. The efficiency of the hydrogen generation increases with increasing H₂O₂ proportion, amount of MnMoO₄ powder, and intensity of light resource. A mechanism is suggested for hydrogen generation from the H₂O/H₂O₂/MnMoO₄ system.     

Anisotropy of optical transmission and photoluminescence in ZnIn<Subscript>2</Subscript>S<Subscript>4</Subscript> and ZnIn<Subscript>2</Subscript>S<Subscript>4</Subscript>: Cu single crystals

Significant anisotropy of the optical transmission associated with the exponential increasing of the absorption coefficient and the anisotropy of the photoluminescence were found in ZnIn₂S₄ and ZnIn₂S₄:Cu single crystals. It was shown that the peculiarities of the investigated photoluminescence spectra are associated with optical transitions involving donor and acceptor levels. The possibility was found to control the spectra’s shape and intensity using doping and variation of the technological parameters to allow preparing ZnIn₂S₄ single crystals with alternation of three and one packet polytypes.     

Synthesis and characterization of Li<Subscript>1.3</Subscript>Al<Subscript>0.3</Subscript>Ti<Subscript>1.7</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>-coated LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript> by wet chemical route

Li_1.3Al_0.3Ti_1.7(PO₄)₃-coated LiMn₂O₄ was prepared by wet chemical route. The phase, surface morphology, and electrochemical properties of the prepared powders were characterized by X-ray diffraction, scanning electron micrograph, and galvanostatic charge-discharge experiments. Li_1.3Al_0.3Ti_1.7(PO₄)₃-coated LiMn₂O₄ has similar X-ray diffraction patterns as LiMn₂O₄. The corner and border of Li_1.3Al_0.3Ti_1.7(PO₄)₃-coated LiMn₂O₄ particles are not as clear as the uncoated one. The two powders show similar values of lithium-ion diffusion coefficient. When cycled at room temperature and 55°C for 40 times at the charge-discharge rate of 0.2C, Li_1.3Al_0.3Ti_1.7(PO₄)₃-coated LiMn₂O₄ shows the capacity retentions of 98.2% and 93.9%, respectively, which are considerably higher than the values of 85.4% and 79.1% for the uncoated one. Both the capacity retention differences between Li_1.3Al_0.3Ti_1.7(PO₄)₃-coated LiMn₂O₄ and LiMn₂O₄ cycling at room temperature and 55°C become larger with the increase of charge-discharge rate. When the charge-discharge rate reaches 2C, the capacity retention of LATP-coated LiMn₂O₄ becomes 8.4% higher than the uncoated LiMn₂O₄ for room temperature cycling, and it becomes 11.1% higher than the latter when cycled at 55°C.     

Effects of caustic sodium concentration and molecular ratio of Na<Subscript>2</Subscript>O to Al<Subscript>2</Subscript>O<Subscript>3</Subscript> on agglomeration in the precipitation process

The supersaturation of sodium aluminate solution (liquor) is a prerequisite for agglomeration and the key factors that determine supersaturation of liquor are caustic sodium concentration (N_k) and molecular ratio of Na₂O to Al₂O₃ (α_k). In this paper, the effects of N_k and α_k on the agglomeration process of seeded precipitation were studied. The results show that the N_k plays an important role in the agglomeration process. The supersaturation of liquor decreases with the increasing of N_k and so not only does the precipitation ratio of liquor decrease but also the particle size of agglomerate decreases. The supersaturation of liquor decreases with the increasing of α_k and so the precipitation rate and depth of liquor decrease and thus the agglomeration of fine particles is weakened.     

Synthetically Controlled,Carbon-Coated Co<Subscript>2</Subscript>SnO<Subscript>4</Subscript>/SnO<Subscript>2</Subscript> Composite Anode for Lithium-ion Batteries

The inherent drawbacks of Co₂SnO₄ in demonstrating the closer-to-theoretical capacity value behavior and the inadmissible volume-expansion-related capacity fade behavior have been surpassed by choosing a tailor-made material composition of Co₂SnO₄/SnO₂, prepared at two different temperatures such as 400°C and 600°C to obtain residual carbon-containing and carbon-free compositions, respectively. Among the products, carbon-coated Co₂SnO₄/SnO₂ composite exhibits better electrochemical performance compared with that of the carbon-free product mainly because of the beneficial effect of carbon in accommodating the volume-expansion-related issues arising from the alloying/de-alloying mechanism. A combination of conversion reaction and alloying/de-alloying mechanism is found to play a vital role in exhibiting closer-to-theoretical capacity values. In other words, an appreciable specific capacity value of 834 mAh g^?1 has been exhibited by Co₂SnO₄/SnO₂ anode containing carbon coating, thus, demonstrating the possibility to improve the electrochemical performance of the title anode through carbon coating, which is realized as a result of the addition of carefully manipulated synthesis conditions.