A self-healing protective film prepared on zinc by treatment in a Ce(NO3)3 solution and modification with Ce(NO3)3

A self-healing protective film was prepared on a zinc electrode by treatment in 1 × 10⁻³ M Ce(NO₃)₃ at 30 °C for 30 min to form a thin layer of hydrated Ce₂O₃ and by modification with 114 μg/cm² of Ce(NO₃)₃ · 6H₂O. The film was dried at 30 °C under a dry atmosphere. After the electrode surface was scratched with a knife-edge crosswise and immersed in an aerated 0.5 M NaCl solution at 30 °C for many hours, polarization measurement of the electrode was carried out in the NaCl solution. The protective efficiency of the film was markedly high, 97.7% at the immersion time, t_i=24 h. Neither pit-like anodic dissolution feature nor pit was observed within the scratches at t_i=72 h. X-ray photoelectron spectroscopy and electron-probe microanalysis revealed that Ce³⁺ migrating into the scratches from the film was adsorbed on the hydrated or hydroxylated zinc surface to form a new layer of hydrated Ce₂O₃ within the scratches, resulting in the self-healing activity of the film for preventing zinc corrosion at the scratched surface.     

Improvement in the self-healing ability of a protective film consisting of hydrated cerium(III) oxide and sodium phosphate layers on zinc

A self-healing protective film prepared on a zinc electrode by previous treatment in a Ce(NO₃)₃ solution and coverage with a Na₃PO₄ layer was improved by the addition of Zn(NO₃)₂. The protective and self-healing abilities of the films against corrosion of zinc in an aerated 0.5 M NaCl solution were examined by polarization measurements and observation of pit-like anodic dissolution feature (plf) and pit formation after the electrode was scratched with a knife-edge crosswise and immersed in the solution for many hours. The film prepared on the pretreated electrode coated with 9.98 or 19.9 μg/cm² of Zn(NO₃)₂ · 6H₂O and 55.2 μg/cm² of Na₃PO₄ · 12H₂O was significantly protective and self-healing against zinc corrosion on the scratched electrode. The protective efficiency of the film was more than 96% in the region of the immersion time between 72 and 360 h. No plf was observed at the scratches after immersion for 120 h. Results of Fourier transform infrared reflection and X-ray photoelectron spectroscopies revealed that the film was composed of Na₃PO₄, Zn₃(PO₄)₂ and Ce₂O₃ layers.     

XPS and EPMA studies on self-healing mechanism of a protective film composed of hydrated cerium(III) oxide and sodium phosphate on zinc

A thin, protective film was prepared on a zinc electrode by coverage with a hydrated Ce₂O₃ layer and 0.0552 mg/cm² of a Na₃PO₄·12H₂O deposit layer and by drying the layers at 90 °C for 23 h, as has been reported in the preceding paper. This film was highly self-healing at the scratched electrode in an aerated 0.5 M NaCl solution for many hours. The present investigation deals with elucidation on self-healing mechanism of this film by X-ray photoelectron spectroscopy and electron-probe microanalysis. The scratched surface was covered with deposits of Zn(OH)₂, ZnO and small amount of Zn₃(PO₄)₂. Both cathodic and anodic processes of zinc corrosion were markedly suppressed by coverage of the scratches with the deposits, resulting in the self-healing activity at the scratched electrode in 0.5 M NaCl.     

Analysis of the electrochemical reaction behavior of alloy AZ91 by EIS technique in H3PO4/KOH buffered K2SO4 solutions

The EIS technique was used to analyze the electrochemical reaction behavior of Alloy AZ91 in H₃PO₄/KOH buffered K₂SO₄ solution at pH 7. The corrosion resistance of Alloy AZ91 was directly related with the stability of Al₂O₃ · xH₂O rich part of the composite oxide/hydroxide layer on the alloy surface. The break down of the oxide layer was estimated to occur mainly on the matrix solid solution phase in Alloy AZ91. The mf capacitive loop arose from the relaxation of mass transport in the solid oxide phase in the presence of Al₂O₃ · xH₂O rich part and from Mg⁺ ion concentration within the broken area in the absence of Al₂O₃ · xH₂O rich part in the composite oxide structure on the alloy surface. The lf inductive loop had tendency of disappear when the dissolution rate of the alloy decreased as a result of the formation of the protective oxide layer.     

The influence of CO2, AlCl3 · 6H2O, MgCl2 · 6H2O, Na2SO4 and NaCl on the atmospheric corrosion of aluminum

The influence of salt deposits on the atmospheric corrosion of high purity Al (99.999%) was studied in the laboratory. Four chloride and sulfate-containing salts, NaCl, Na₂SO₄, AlCl₃ · 6H₂O and MgCl₂ · 6H₂O were investigated. The samples were exposed to purified humid air with careful control of the relative humidity (95%), temperature (22.0 °C), and air flow. The concentration of CO₂ was 350 ppm or <1 ppm and the exposure time was four weeks. Under the experimental conditions all four salts formed aqueous solutions on the metal surface. Mass gain and metal loss results are reported. The corroded surfaces were studied by ESEM, OM, AES and FEG/SEM equipped with EDX. The corrosion products were analyzed by gravimetry, IC and grazing incidence XRD. In the absence of CO₂, the corrosivity of the chloride salts studied increases in the order MgCl₂ · 6H₂O < AlCl₃ · 6H₂O < NaCl. Sodium chloride is very corrosive in this environment because the sodium ion supports the development of high pH in the cathodic areas, resulting in alkaline dissolution of the alumina passive film and rapid general corrosion. The low corrosivity of MgCl₂ · 6H₂O is explained by the inability of Mg²⁺ to support high pH values in the cathodic areas. In the presence of carbon dioxide, the corrosion induced by the salts studied exhibit similar rates. Carbon dioxide strongly inhibits aluminum corrosion in the presence of AlCl₃ · 6H₂O and especially, NaCl, while it is slightly corrosive in the presence of MgCl₂ · 6H₂O. The corrosion effects of CO₂ are explained in terms of its acidic properties and by the precipitation of carbonates. In the absence of CO₂, Na₂SO₄ is less corrosive than NaCl. This is explained by the lower solubility of aluminum hydroxy sulfates in comparison to the chlorides. The average corrosion rate in the presence of CO₂ is the same for both salts. The main difference is that sulfate is less efficient than chloride in causing pitting of aluminum in neutral or acidic media.     

Self-healing protective films prepared on zinc by treatments with cerium(III) nitrate and sodium phosphate

Chromate-free, self-healing protective films were prepared on a surface of zinc electrode previously treated in a solution of cerium(III) nitrate Ce(NO₃)₃ by coverage of the surface with a layer of sodium phosphate Na₃PO₄. The self-healing ability of the film was examined by polarization measurements of the electrode after scratching the surface with a knife-edge crosswise and immersed in an aerated 0.5 M NaCl solution for many hours and by observation of pit formation at the scratches. A thin film containing 0.0552 mg/cm² of Na₃PO₄·12H₂O prepared on the electrode previously treated in 1×10⁻³ M Ce(NO₃)₃ at 30 °C for 30 min and dried at 90 °C for 23 h was highly self-healing and protective against corrosion of zinc in 0.5 M NaCl at the scratches. No pit was detected at the scratches on the electrode coated with this film after immersion for 72 h.     

An ultrathin polymer coating of carboxylate self-assembled monolayer adsorbed on passivated iron to prevent iron corrosion in 0.1 M Na2SO4

For preparing an ultrathin two-dimensional polymer coating adsorbed on passivated iron, a 16-hydroxyhexadecanoate ion HO(CH₂)₁₅CO₂⁻ self-assembled monolayer (SAM) was modified with 1,2-bis(triethoxysilyl)ethane (C₂H₅O)₃Si(CH₂)₂Si(OC₂H₅)₃ and octadecyltriethoxysilane C₁₈H₃₇Si(OC₂H₅)₃. Protection of passivated iron against passive film breakdown and corrosion of iron was investigated by monitoring of the open-circuit potential and repeated polarization measurements in an aerated 0.1 M Na₂SO₄ solution during immersion for many hours. The time required for passive film breakdown of the polymer-coated electrode was markedly higher in this solution than that of the passivated one, indicating protection of the passive film from breakdown by coverage with the polymer coating. The protective efficiencies of the passive film covered with the coating were extremely high, more than 99.9% in 0.1 M Na₂SO₄ before the passive film was broken down, showing prominent cooperative suppression of iron corrosion in the solution by coverage with the passive film and polymer coating. The polymer-coated surface was characterized by contact angle measurement and electron-probe microanalysis (EPMA). Prevention of passive film breakdown and iron corrosion for the polymer-coated electrode healed in 0.1 M NaNO₃ was also examined in 0.1 M Na₂SO₄.     

Microstructure and electrical properties of Y(NO3)3·6H2O-doped ZnO-Bi2O3-based varistor ceramics

Y(NO₃)₃·6H₂O-doped ZnO-Bi₂O₃-based varistor ceramics were prepared using a solid reaction route. The microstructure, electrical properties, degradation coefficient (D_V), and dielectric characteristics of varistor ceramics were studied in this paper. With increasing amounts of Y(NO₃)₃·6H₂O in the starting composition, Y-containing Bi-rich, Y₂O₃, and Sb₂O₄ phases were formed, and the average grain size decreased. Results also showed that with the addition of 0.16 mol% Y(NO₃)₃·6H₂O, Y(NO₃)₃·6H₂O -doped ZnO-based varistor ceramics exhibit comparatively better comprehensive electrical properties, such as a threshold voltage of 425 V/mm, a nonlinear coefficient of 73.9, a leakage current of 1.78 μA, and a degradation coefficient of 1.7. The dielectric characteristics and lightning surge test also received the same additional content of Y(NO₃)₃·6H₂O. The results confirmed that doping with rare earth nitrates instead of rare earth oxides is very promising route in preparing high-performance ZnO-Bi₂O₃-based varistor ceramics.     

Self-healing mechanism of an organosiloxane polymer film containing sodium silicate and cerium(III) nitrate for corrosion of scratched zinc surface in 0.5 M NaCl

A highly protective and self-healing film of 1,2-bis(triethoxysilyl)ethane (C₂H₅O)₃Si(CH₂)₂Si(OC₂H₅)₃ polymer containing sodium silicate (water glass) Na₂Si₂O₅ and cerium(III) nitrate Ce(NO₃)₃ was prepared on a zinc electrode previously treated in a Ce(NO₃)₃ solution. The film was examined by polarization measurement of the electrode in an aerated 0.5 M NaCl solution after the electrode was scratched and immersed in the solution for 4-72 h. Self-healing mechanism of the film was investigated by X-ray photoelectron spectroscopy and electron-probe microanalysis for the coated electrode surface after scratched and immersed in the NaCl solution. A passive film composed of Zn(OH)₂, ZnSi₂O₅ and Ce³⁺-Si₂O₅²⁻ salt or complex was formed on the scratched surface and preferential deposition of Si₂O₅²⁻ compounds occurred at a defect of the passive film where Cl⁻ accumulated, resulting in suppression of pitting corrosion at the scratch.     

Electrochemical reactivity, surface composition and corrosion mechanisms of the complex metallic alloy Al3Mg2

A corrosion mechanism is proposed for Al₃Mg₂, based on electrochemical tests, XPS, and depth profiling using XPS and ToF-SIMS. After short (∼2 min) solution exposure, the surface consists of a surface film above dealloying. The dealloying is attributed to selective Mg dissolution and the surface rearrangement of Al into islands, although the metallic Al could alternatively be formed by two reduction reactions. The surface film thickness was ∼10 nm. After exposure to ultra-pure water, the composition was AlMg_1.3O_0.2(OH)_5.1 corresponding to Al(OH)₃·1.1 Mg(OH)₂·0.2MgO. After exposure to 0.01 M Na₂SO₄, the composition was AlMg_0.2O_0.4(OH)_2.5 corresponding to Al(OH)₃·0.1Al₂O₃·0.2MgO. Longer exposure produced a thicker surface film, more pronounced metallic Al islands and more MgH₂. Three possibilities are identified for MgH₂ formation. Al(OH)₃ formation is attributed to a precipitation reaction. Bulk nanoporous Al₃Mg₂ formation is predicted to be possible by Mg dealloying of Mg₁₇Al₁₂.     

The ternary system: H2O–Fe(NO3)3–Co(NO3)2 isotherms −15 and −25 °C

The binary system H₂O–Fe(NO₃)₃ has been investigated at temperature ranging between –25 and 47 °C.The solid–liquid equilibria of the ternary system H₂O–Fe(NO₃)₃–Co(NO₃)₂ were studied at −15 and −25 °C by using a synthetic method based on conductivity measurements which allows all the characteristic points of the isotherms to be determined, and the stable solid phases which appear are respectively: ice, Fe(NO₃)₃·9H₂O, Fe(NO₃)₃·6H₂O, Co(NO₃)₂·9H₂O, Co(NO₃)₂·6H₂O and Co(NO₃)₂·3H₂O.     

Preparation and luminescence characterization of new carbonate (Y2(CO3)3·nH2O:Eu) phosphors via the hydrothermal route

A new Eu³⁺-activated Y₂(CO₃)₃·nH₂O phosphor was successfully prepared via the hydrothermal process using urea as a reaction agent. Y₂(CO₃)₃·nH₂O:Eu³⁺ phosphors displayed an intense red emission at 615 nm due to the ⁵D₀ → ⁷F₂ transition of Eu³⁺ ions under 254 nm excitation. The intensity of this emission was significantly increased with a rise in the hydrothermal temperatures. The study of photoluminescence properties demonstrated that Y³⁺ ions were replaced by Eu³⁺ ions in the host lattice at the 9-coordination sites. With an increase in heating temperatures, the morphology of Y₂(CO₃)₃·nH₂O:Eu³⁺ powders changed from a spherical to a rod-like shape. Calcination at elevated temperatures resulted in thermal decomposition of Y₂(CO₃)₃·nH₂O:Eu³⁺ to form Y₂O₃:Eu³⁺. The formed Y₂O₃:Eu³⁺ powder exhibited a rod-like morphology with an intense red emission.     

Corrosion prevention of passivated iron in 0.1 M NaCl by coverage with an ultrathin polymer coating and healing treatment in 0.1 M NaNO3

An ultrathin, ordered and two-dimensional polymer coating was prepared on a passivated iron electrode by modification of 16-hydroxyhexadecanoate ion HO(CH₂)₁₅CO₂⁻ self-assembled monolayer with 1,2-bis(triethoxysilyl)ethane (C₂H₅O)₃Si(CH₂)₂Si(OC₂H₅)₃ and octadecyltriethoxysilane C₁₈H₃₇Si(OC₂H₅)₃. Subsequently, the electrode was healed in 0.1 M NaNO₃. Protection of passivated iron against passive film breakdown and corrosion of iron was examined by monitoring of the open-circuit potential and repeated polarization measurements of the polymer-coated and healed electrode in an aerated 0.1 M NaCl solution during immersion for many hours. Localized corrosion was markedly prevented by coverage with the polymer coating and the healing treatment in 0.1 M NaNO₃. Prominent protection of iron from corrosion in 0.1 M NaCl was observed before the breakdown occurred. The electrode surface covered with the healed passive film and polymer coating was analyzed by contact angle measurement, X-ray photoelectron spectroscopy and electron-probe microanalysis.     

Hydrothermal synthesis of Cu3(OH)2V2O7·nH2O nanoparticles and its application in lithium ion battery

Well crystallized copper vanadium oxide hydroxide hydrate (Cu₃(OH)₂V₂O₇·nH₂O) nanoparticles have been successfully synthesized by a simple hydrothermal method. The morphology and structure of the as-synthesized products were characterized by field emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and Raman spectroscopy. The composition of Cu₃(OH)₂V₂O₇·nH₂O was studied by thermal analysis (TG, DTA), which indicates that there are two molecules of water in a Cu₃(OH)₂V₂O₇·nH₂O molecular formula. Electrochemical properties of Cu₃(OH)₂V₂O₇·2H₂O nanoparticles as positive electrode of lithium ion battery were studied by conventional charge/discharge tests at different current density, showing steady initial discharge platforms near 1.7 V. The first discharge capacity of Cu₃(OH)₂V₂O₇·2H₂O electrode arrives at 868 and 845 mAh g⁻¹ at current density of 0.01 and 0.02 mA cm⁻², respectively.     

Preparation of chromate-free, self-healing polymer films containing sodium silicate on zinc pretreated in a cerium(III) nitrate solution for preventing zinc corrosion at scratches in 0.5 M NaCl

Self-healing protective films of 1,2-bis(triethoxysilyl)ethane (C₂H₅O)₃Si(CH₂)₂Si(OC₂H₅)₃ (abbreviated to BTESE) polymer containing sodium silicate Na₂Si₂O₅ (water glass) and cerium(III) nitrate Ce(NO₃)₃ were prepared on a zinc electrode previously treated in a 1×10⁻³ M Ce(NO₃)₃ solution at 30 °C for 30 min. After the surface of coated electrode was crosswise scratched with a knife edge, the electrode was immersed in an aerated 0.5 M NaCl solution at 30 °C for many hours and polarization measurements of the scratched electrode were carried out for estimating the self-healing effects of the films on zinc corrosion at the scratches. The optimal quantities of Na₂Si₂O₅, Ce(NO₃)₃ and BTESE in the films were determined by polarization measurements and observation of pit formation at the scratches. No pitting corrosion occurred at the scratches on the zinc electrode covered with a film composed of their optimal quantities after immersion in the solution for 72 h.     

Al2O3-ZrO2 mixed oxide composite incorporated aluminium rich zinc coatings for high wear resistance

Corrosion resistance and wear resistance are the two important parameters for high performance of zinc galvanic coating. In the present work, the improvement of these two characteristics was achieved by the incorporation of Al₂O₃-ZrO₂ mixed oxide composite in the coating. Al₂O₃-ZrO₂ mixed oxide composite was synthesized from ZrOCl₂·8H₂O. Aluminium rich zinc coatings with high sliding wear resistance was developed from a galvanic bath containing the mixed oxide. Based on the performance of the coating during physicochemical and electrochemical characterization, the concentration of mixed oxide composite in the bath was optimized as 0.50 wt% Al₂O₃-0.50 wt% ZrO₂. While rich in Al-metal content in the coating caused high corrosion resistance, the incorporation of the mixed oxide improved structural characteristics of the coating resulting in high wear resistance also. The coating was nonporous in nature and even the interior layers had high stability. The coatings have potential scope for high industrial utility.     

Synthesis of CeO2/TiO2 nanoparticles by laser ablation of Ti target in cerium (III) nitrate hexahydrate (Ce(NO3)3·6H2O) aqueous solution

A new synthesis process, laser ablation in an aqueous solution of target material, was applied to synthesize nanostructured CeO₂/TiO₂ catalyst particles. Reactivity within the laser plume (plasma) can be used to synthesize CeO₂ from an aqueous solution, 2 M cerium (III) nitrate hexahydrate (Ce(NO₃)₃·6H₂O) aqueous solution, and to fabricate TiO₂ from Ti target. CeO₂/TiO₂ nanoparticles were successfully synthesized by the laser ablation of Ti target in 2 M cerium (III) nitrate hexahydrate (Ce(NO₃)₃·6H₂O) aqueous solution. Laser ablation of Ti in a liquid environment and chemical reactions of the solution within a plasma plume are discussed.     

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.     

H2S and O2 influence on the corrosion of carbon steel immersed in a solution containing 3 M diethanolamine

Aqueous solutions with 3 mol L⁻¹ (M) diethanolamine (DEA) concentration are extensively used in the gas processing industry to remove acid gases. However, the degradation of the DEA and the formation of heat-stable salts (HSS) lead to severe corrosion problems. Even worse, equipment corrosion can be magnified by the unavoidable presence of sulphide acid and dissolved oxygen as a result of hydrocarbon (natural gases and crude oil) processing. The aim of this work is to study the combined corrosion effects of DEA, sulphide acid and oxygen on carbon steel. Electrochemical methods revealed that in the 3 M DEA medium without oxygen, corrosion processes are modulated by adsorbed DEA film formation. Furthermore, it was shown that the addition of oxygen and 15 × 10⁻³ mol L⁻¹ (15 mM) H₂S produced the formation of an adherent film on the carbon steel surface. Chemical analyses by EDAX revealed a homogeneous film of corrosion products composed of iron oxide and sulphide formed in DEA solution containing O₂ and H₂S, respectively. Equivalent circuits were used to estimate the parameters associated with ion diffusion through the formed corrosion films. The results showed that the presence of H₂S induced the formation of thin iron sulphide films that provide protective properties to the metal. It is concluded that the presence of oxygen in a sweetening plant should be avoided as DEA degradation can be produced with the subsequent decrease in chelating process efficiency and the increase in corrosion problems.     

Luminescent properties of UV excitable blue emitting phosphors MSr4(BO3)3:Ce (M = Li and Na)

A series of Ce³⁺ doped novel borate phosphors MSr₄(BO₃)₃ (M = Li or Na) were successfully synthesized by traditional solid-state reaction. The crystal structures and the phase purities of samples were characterized by powder X-ray diffraction. The optimal concentrations of dopant Ce³⁺ ions in compound MSr₄(BO₃)₃ (M = Li or Na) were determined through the measurements of photoluminescence spectra of phosphors. Ce³⁺ doped phosphors MSr₄(BO₃)₃ (M = Li or Na) show strong broad band absorption in UV spectral region and bright blue emission under the excitation of 345 nm light. In addition, the temperature dependences of emission spectra of M_1+xSr_4−2xCe_x(BO₃)₃ (M = Li or Na) phosphors with optimal composition x = 0.05 for Li and x = 0.09 for Na excited under 355 nm pulse laser were also investigated. The experimental results indicate that the M_1+xSr_4−2xCe_x(BO₃)₃ (M = Li or Na) phosphors are promising blue emitting phosphors pumped by UV light.