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.     

Chemical and phase composition of nanosize oxide and passive films on Ni-Cr alloys. I. XPS studies of films obtained by alloy oxidation in air

XPS data for thin (less than 100 nm) oxide films obtained by oxidation of Ni-4 Cr and Ni-12.5 Cr alloys at 500°C (0.5 h) are discussed. Thermodynamic analysis of 3 NiO + 2 Cr = Cr₂O₃ + 3 Ni solid-phase reaction is given, in which both the Gibbs energy change in the thermochemical process and the change in the interface energy at the alloy-oxide film boundary are taken into account.     

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.     

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.     

Na<Subscript>2</Subscript>SO<Subscript>4</Subscript>-Deposit-Induced Corrosion of Mo-Containing Alloys

Disk alloys used in advanced gas turbine engines often contain significant amounts of Mo (2 wt% or greater), which is known to cause corrosion under Type I hot corrosion conditions (at temperatures around 900 °C) due to alloy-induced acidic fluxing. The corrosion resistance of several model and commercial Ni-based disk alloys with different amounts of Mo with and without Na₂SO₄ deposit was examined at 700 °C in air and in SO₂-containing atmospheres. When coated with Na₂SO₄ those alloys with 2 wt% or more Mo showed degradation products similar to those observed previously in Mo-containing alloys, which undergo alloy-induced acidic fluxing Type I hot corrosion even though the temperatures used in the present study were in the Type II hot corrosion range. Extensive degradation was observed even after exposure in air. The reason for the observed degradation is the formation of sodium molybdate. Transient molybdenum oxide reacts with the sodium sulfate deposit to form sodium molybdate which is molten at the temperature of study, i.e., 700 °C, and results in a highly acidic melt at the salt alloy interface. This provides a negative solubility gradient for the oxides of the alloying elements, which results in continuous fluxing of otherwise protective oxides.     

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.     

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.     

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 and time dependent passivation of Al 5052 in the presence of H<Subscript>2</Subscript>O<Subscript>2</Subscript>

Corrosion and time–dependent oxide film growth on AA5052 Aluminum alloy in 0.25M Na₂SO₄ solution containing H₂O₂ was studied using electrochemical impedance spectroscopy, potentiodynamic polarization, chronoamperometric and open circuit potential monitoring. It was found that sequential addition of H₂O₂ provokes passivation of AA5052 which ultimately thickens the oxide film and brings slower corrosion rates for AA5052. H2O2 facilitates kinetics of oxide film growth on AA 5052 at 25° and 60 °C which is indicative of formation of a thick barrier film that leads to an increment in the charge transfer resistance. Pitting incubation time increases by introduction of H₂O₂ accompanied by lower pitting and smoother surface morphologies. At short exposure (up to 8 h) to H₂O₂–containing solution, the inductive response at low frequencies predominantly determined the corrosion mechanism of AA5052. On the other hand, at prolonged exposure times (more than 24 h) to 0.25M Na₂SO₄+1vol% H₂O₂ solution, thicker oxide layers resulted in the mixed inductive–Warburg elements in the spectra.     

Chemical observation of anodic TiO<Subscript>2</Subscript> for biomaterial application

Anodic TiO₂ film on Ti a substrate was fabricated at 170 V in sulfuric acid solutions containing phosphoric acid and hydrogen peroxide. The pores in the oxide layer were not uniform in size, shape, or direction of growth, particularly near the interface between the substrate and the oxide layer, compared with those of the surface layer. The formation of an irregular type of pores seemed to be caused by the spark discharge phenomena, which occurred extensively when the anodic voltage was increased. The pore diameter and the cell size increased and the number of cells per unit area decreased over time. From the analysis of chemical states in the XPS spectrum, the incorporated phosphate species were found mostly in the forms of HPO₄, PO₄, and PO₃. In addition, Ti, O, and P were well dispersed in TiO₂ oxide film, as shown in the results of element mapping analyses by an energy dispersive X-ray spectrometer. An SEM observation of osteoblast-likes cells grown on treated TiO₂ oxide film samples for 24h showed clear differences in cell density and spreading pattern. MC3T3 osteoblast-like cells were flat with a polygonal configuration and were attached to the substrate by cellular extensions.     

Influence of processing parameters on the phase composition of ZrN-Si<Subscript>3</Subscript>N<Subscript>4</Subscript> synthesized from zircon

The optimum parameters were determined for synthesizing ZrN-Si₃N₄ composite powder from zircon by carbothermal reduction-nitridation (CTRN) process. The samples were prepared by mixing the carbon black of an average particle size less than 30 μm and the zircon of 40 μm with C/ZrSiO₄ mass ratios of 0.2, 0.3, 0.4, and 0.5. The prepared samples were subjected to the CTRN process at temperatures of 1673, 1723, 1753, and 1773 K for 6, 9, and 12 h. The CTRN process was conducted in an atmosphere-controlled tubular furnace in a nitrogen gas flow of 1.0 L/min. All the products were examined by X-ray powder diffraction to determine the transformation. The results showed that the proper transformation of ZrN-Si₃N₄ occurred at 1773 K for 12 h with a C/ZrSiO₄ mass ratio of 0.4.     

Electrical conductivity of composite DLC-C<Subscript>2</Subscript>N films

Electrical conductivity of films of CN _x vacuum condensates which are considered as composites consisting of domains of diamond-like carbon and C₂N has been studied. It is supposed that the conductivity of such a medium is determined exclusively by interphase boundaries which separate unlike domains from one another. The dependence of the electrical resistivity on the average content of nitrogen in the films in terms of such a model satisfactorily agrees with literature experimental results.     

Experimental determination of NH<Subscript>4</Subscript>NO<Subscript>3</Subscript>-KNO<Subscript>3</Subscript> binary phase diagram

The solid-state phase transitions in ammonium nitrate (AN)-potassium nitrate (KN) system, and the equilibrium AN-KN phase diagram have been determined by using differential scanning calorimetry and high-temperature in situ x-ray diffractometry. Sample preparation was performed in a special “dry room” with very low humidity. A single phase region (AN III) with no phase transitions to 373 K was observed in the composition range 5 to 20% KN; this is critical for use in air bag gas generators. The high-temperature KN phase (KN I) has a wide range of stability from 20 to 100 wt.% KN. There are one eutectic, two eutectoid, three peritectoid, and one congruent transformations in this phase diagram. Two new nonstoichiometric phases were found at lower temperatures in the mid-composition range between the AN and KN terminal solid solutions. Details of the phase equilibria are presented.     

Solid reaction mechanism of CaHPO4·2H2O ＋ CaCO3 with and without yttria

The effect of yttria on the solid reaction mechanism of a CaHPO₄·2H₂O + CaCO₃ system at different temperatures was experimentally studied. The samples with and without yttria were subjected to thermogravimetric/differential scanning calorimetry measurement. The samples were heat treated at the temperatures corresponding to the peaks on the DSC spectra, and the resulted phase compositions were identified by X-ray diffraction. The transformation mechanism was deduced by comparing the phases obtained at different temperatures. The results show that the transformations at below 1073 K are not affected by yttria, but all those at above 1073 K are completely altered. The formation temperature of hydroxyapatite decreases by 134 K, and the decomposition temperature increases by 38 K. The polymorphous transformation of Ca₃(PO₄)₂ from β phase to α phase increases by 47 K. The thermodynamic properties of the transformations at above 1073 K are also modified by the addition of yttria; that is, the endothermal peaks are substituted by exothermal peaks.     

Microstructure and growth morphology of Frank-Kasper phase in rapidly solidified Mg<Subscript>32</Subscript>Al<Subscript>17</Subscript>Zn<Subscript>32</Subscript> ternary alloys

In the present investigation, the microstructures and growth morphology of Mg₃₂(Al,Zn)₄₉ Frank-Kasper phase in rapidly solidified Mg₃₂Al₁₇Zn₃₂ ternary alloys were studied in detail. The samples were characterised by X-ray diffraction analysis (XRD), scanning electron microscopy (SEM), field-emission scanning electron microscopy (FE-SEM) and energy dispersive spectrum (EDS). The results show that the microstructures mainly consist of Mg₃₂(Al,Zn)₄₉ Frank-Kasper phase and interdendritic Mg-rich Φ-phase. Under rapid solidification condition, Mg₃₂(Al,Zn)₄₉ Frank-Kasper phase reveals a perfect faceted dendritic characteristic in the shape of a three-fold symmetric microstructure with doublet tips in the axes direction. Observations for fracture surfaces show that the growth morphology of Mg₃₂(Al,Zn)₄₉ grains was truncated cubic, and its growth mechanism was also discussed.     

Nanostructure and energy properties of the stainless steel <Emphasis Type="Italic">X18N10T</Emphasis> surface studied by scanning tunneling microscopy and scanning tunneling spectroscopy. 2. Measurements at different potentials in HCl and H<Subscript>2</Subscript>SO<Subscript>4</Subscript> solutions

Stainless steel Kh18N10T is studied by electrochemical scanning tunneling microscopy (ESTM) and electrochemical scanning tunneling spectroscopy (ESTS) at the interface with solutions of 0.01 N HCl and 0.1 N H₂SO₄ at the controlled sample and tip potentials. The sample potential varied from ?0.46 to +1.14 V in 0.01 N HCl and from ?0.06 to +0.74 V (NHE) in 0.1 N H₂SO₄. It is shown that although in the studied acid solutions at the controlled potential the surface is smother than in air, this does not allow one to determine the extremal values of parameters α, β, and γ corresponding to individual properties of Fe, Cr, and Ni or their oxides. It is shown that compared to the steel nanorelief, the sample potential has a stronger effect on the electrophysical properties that determine the tunneling transfer of electrons.