Photocatalytic degradation of organic dyes with H<Subscript>3</Subscript>PW<Subscript>12</Subscript>O<Subscript>40</Subscript>/TiO<Subscript>2</Subscript>–SiO<Subscript>2</Subscript>

H₃PW₁₂O₄₀/TiO₂–SiO₂ was synthesized by impregnation method which significantly improved the catalytic activity under simulated natural light. The properties of the samples were characterized by Fourier transform infrared spectra (FTIR), X-ray powder diffraction pattern (XRD), Scanning electron micrographs (SEM), and Zeta potential. Degradation of methyl violet was used as a probe reaction to explore the influencing factors on the photodegradation reaction. The results show that the optimal conditions are as follows: initial concentration of methyl violet of 10 mg·L^?1, pH of 3.0, catalyst dosage of 2.9 g·L^?1, and light irradiation time of 2.5 h. Under these conditions, the degradation rate of methyl violet is 95.4 %. The reaction on photodegradation for methyl violet can be expressed as the first-order kinetic model, and the possible mechanism for the photocatalysis under simulated natural light is suggested. After used continuously for five times, the catalyst keeps the inherent photocatalytic activity for degradation of dyes. The photodegradation of methyl orange, methyl red, naphthol green B, and methylene blue was also tested, and the degradation rate of dyes can reach 81 %–100 %.     

Synthesis and characterization of Ba<Subscript>0.5</Subscript>Sr<Subscript>0.5</Subscript>Co<Subscript>0.8</Subscript>Fe<Subscript>0.2</Subscript>O<Subscript>3−σ</Subscript>

Perovskite-type Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ (BSCFO) powders were synthesized using two methods, solid-state reaction (SSR) method and citrate-EDTA complexing method (CC-EDTA). Then the powders were pressed to green disks of 19 mm in diameter and sintered at 1140°C for 5 h. The shrinkage rate and relative density of the membranes prepared from the perovskite-type powders were determined and calculated, and the powders and derived membranes were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The results show that the shrinkage rates of the two kinds of disks are nearly the same (about 10%). The disks prepared by the SSR method had a bigger grain size and lower relative density than those prepared by the CC-EDTA method. The conductivity of the membranes prepared by the SSR method was about 38 S/cm, higher than that of the membranes prepared by the CC-EDTA method, which was about 30 S/cm, at the same temperature of 600°C.     

Spark Plasma Sintering of α/β Si<Subscript>3</Subscript>N<Subscript>4</Subscript> Ceramics with MgO-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> and MgO-Y<Subscript>2</Subscript>O<Subscript>3</Subscript> as Sintering Additives

In the present work, the α/β Si₃N₄ ceramics were fabricated by spark plasma sintering (SPS) at 1400-1500 °C for 6 min with 3wt.%MgO + 5wt.%Al₂O₃ and 3wt.%MgO + 5wt.%Y₂O₃ as sintering additives. The results showed that the phase composition, microstructure and mechanical properties of α/β Si₃N₄ ceramics were highly dependent on the type of sintering additive. The incomplete phase transformation from α to β occurred in the presence of an oxynitride (Mg-Al(Y)-Si-O-N) liquid phase. Compared with MgO-Al₂O₃, MgO-Y₂O₃ can significantly improve the β conversion rate of as-sintered α/β Si₃N₄ ceramics. And the as-sintered ceramics using MgO + Al₂O₃ as sintering additives had higher mechanical properties.     

Air Oxidation of a Ni<Subscript>53</Subscript>Nb<Subscript>20</Subscript>Ti<Subscript>10</Subscript>Zr<Subscript>8</Subscript>Co<Subscript>6</Subscript>Cu<Subscript>3</Subscript> Glassy Alloy at 400–550 °C

Air-oxidation behavior of a Ni₅₃Nb₂₀Ti₁₀Zr₈Co₆Cu₃ amorphous ribbon was studied at 400–550 °C. The oxidation kinetics of the amorphous alloy followed a two-stage parabolic rate law with its oxidation rates steadily increasing with temperature. The steady-state oxidation rate constants of the alloy were faster than those of pure Ni. Triplex scales formed on the glassy alloy, containing an outer layer of NiO. The scales formed in the intermediate layer consisted of Nb₂O₅, NiO, and uncorroded α-Ni, while an additional Nb₂Zr₆O₁₇ phase was also detected in the inner layer. The formation of multilayered scales is responsible for the faster oxidation for the Ni6-AR.     

Investigations on Li<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>12</Subscript>/Ti<Subscript>3</Subscript>O<Subscript>5</Subscript> Composite as an Anode Material for Lithium–Ion Batteries

The Ti₃O₅ powder with uniform morphology has been successfully obtained and used to synthesize Li₄Ti₅O₁₂/Ti₃O₅ composite material by ball milling for modifying Li₄Ti₅O₁₂-based, lithium–ion battery anodes. Moreover, according to the relative performance investigations, the synthesized Li₄Ti₅O₁₂/Ti₃O₅ composite shows better electrochemical properties than that of the Li₄Ti₅O₁₂. At a high rate (10 C), the capacity of the Li₄Ti₅O₁₂/Ti₃O₅ composite electrode is 139.8 mAhg^?1, whereas the value of Li₄Ti₅O₁₂ is 121.6 mAhg^?1, showing a capacity enhanced about 14.97%. After 100 cycles at 0.2 C, the discharge capacity of Li₄Ti₅O₁₂/Ti₃O₅ remains at 160 mAhg^?1 with a capacity loss of 2.6%. The results indicate that the Li₄Ti₅O₁₂/Ti₃O₅ composite electrode can be used as anode material with a relatively higher rate capability and excellent cycle performance in lithium–ion batteries.     

Electrochemical and interfacial properties of (PEO)<Subscript>10</Subscript>LiCF<Subscript>3</Subscript>SO<Subscript>3</Subscript>−Al<Subscript>2</Subscript>O<Subscript>3</Subscript> nanocomposite polymer electrolytes using ball milling

Electrochemical and interfacial properties of (PEO)₁₀LiCF₃SO₃−Al₂O₃ composite polymer electrolytes (CPEs) prepared by either ball milling or stirring are reported. Ball milling was introduced into a slurry preparative technique utilizing PEO, lithium salt and Al₂O₃ powder ranging from 5 to 15 wt.%. The ionic conductivity was increased by ball milling over a range of temperatures. In particular, a significant increase at low temperature below the melting point of crystalline PEO was observed. Interfacial stability between lithium electrode and CPE was significantly improved by the addition of alumina as well as by ball milling. The electrochemical stability window produced by (PEO)₁₀LiCF₃SO₃−Al₂O₃ ball milling was higher than that of stirring, which was about 4.4 V. Charge/discharge performance of Li/CPE/S cells with (PEO)₁₀LiCF₃SO₃−Al₂O₃-12 hr ball milling was superior to that of a pristine polymer electrolyte due to the low interface resistance and high ionic conductivity.     

Hydrothermal conversion of Ti-containing minerals in system of Na<Subscript>2</Subscript>O–Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–SiO<Subscript>2</Subscript>–CaO–TiO<Subscript>2</Subscript>–H<Subscript>2</Subscript>O

Titanium has a great effect on the digestion of bauxite in the Bayer process because it reacts readily at high temperatures in alkaline sodium aluminate solution. Under this consideration, the hydrothermal conversion of Ti-containing minerals in the system of Na₂O–Al₂O₃–SiO₂–CaO–TiO₂–H₂O with increased temperatures was studied based on the thermodynamic analysis and systematic experiments. The results show that anatase converts to Al₄Ti₂SiO₁₂ at low temperatures (60–120 °C), which is similar to anatase in crystal structure. As the temperature continues to rise, Al₄Ti₂SiO₁₂ decomposes gradually and converts to Ca₃TiSi₂(Al₂Si_0.5Ti_0.5)O₁₄ at 200 °C. When the temperature reaches 260 °C, CaTiO₃ forms as the most stable titanate species for its hexagonal closest packing with O^2? and Ca²⁺. The findings enhance the understanding of titanate scaling in the Bayer process and clarify the mechanism of how additive lime improves the digestion of diaspore.     

Bridge polysilsesquioxane xerogels with a bifunctional surface layer of the ≡Si(CH<Subscript>2</Subscript>)<Subscript>3</Subscript>NH<Subscript>2</Subscript>/≡Si(CH<Subscript>2</Subscript>)<Subscript>3</Subscript>SH composition

Xerogels with a bifunctional surface layer of the ≡Si(CH₂)₃NH₂/≡Si(CH₂)₃SH composition are synthesized by hydrolytic co-polycondensation of bis(triethoxy)silane (C₂H₅O)₃Si(CH₂)₂Si(OC₂H₅)₃ and two trifunctional silanes, namely, 3-aminopropyltriethoxysilane and 3-mercaptopropyltrimethoxysilane. Using IR, ¹H MAS NMR, and ¹³C CP/MAS NMR spectroscopic techniques, it is shown that in addition to complexing groups, the surface layer also contains water, silanol groups that are involved in the hydrogen bond formation and also residual ethoxysilyl groups. According to ²⁹SiCP/MAS NMR spectroscopic data, the degree of polycondensation of synthesized xerogels exceeds 80%. It is found that the use of 1,2-bis(triethoxysilyl)ethane as the structuring agent in place of tetraethoxysilane allows one to synthesize bifunctional xerogels with the highly developed biporous structure (S _sp = 607–680 m²/g, V _c = 1.38–1.47 cm³/g, d = 2.9–3.1 and 18.3 nm). Changing the ratio structuring-silane/functionalizing-silane-mixture from 2: 1 to 4: 1 in the reaction system has virtually no effect on the porous structure parameters of final xerogels.     

Performance of Sm<Subscript>0.7</Subscript>Sr<Subscript>0.3</Subscript>CoO<Subscript>3−<Emphasis Type="Italic">δ</Emphasis></Subscript> membrane under CO<Subscript>2</Subscript>-containing atmosphere

The permeability and stability of Sm_0.7Sr_0.3CoO_3?δ (SSCO) regarding the special requirements for carbon capture and storage (CCS) application were investigated. Pure CO₂ was used as the sweep gas at 900 °C, leading to that the oxygen permeation flux decreases by about 34 %. Several cycles of changing the sweep gas between helium and CO₂ indicate the good reversibility of this degradation. Both carbonate formation and adsorption of CO₂ on the membrane surface are responsible for the degradation of the membrane performance. The better CO₂ resistance results from the substitution of Sm for Sr due to the higher acidity of Sm₂O₃ (1.278) than that of SrO (0.978) and a discontinuous layer of carbonate.     

Densification Kinetics of CeO<Subscript>2</Subscript> Reinforced 8 Mol.% Y<Subscript>2</Subscript>O<Subscript>3</Subscript> Stabilized ZrO<Subscript>2</Subscript> Ceramics

The grain growth kinetics of 8YSZ ceramics processed using spark plasma sintering (SPS) has been investigated in the temperature ranging from 1100°C to 1500°C. The activation energy during SPS densification was obtained as 332 kJ/mol with grain boundary diffusion as a dominant mechanism. Further, the effect of CeO₂ on the densification kinetics of 8YSZ ceramic processed via SPS and conventional sintering (CS) has been delineated. The lower grain boundary mobility of CS-processed composites (an order of magnitude lower than SPS) is attributed to the solute drag and lattice distortion mechanism. However, no significant change in the grain boundary mobility was observed with CeO₂ addition (~?14.7–43.9?×?10^?18 m³/N/s for CS and 107.2–116.7?×?10^?18 m³/N/s for SPS) revealing that the defect concentration is nearly constant in 8YSZ. The study highlights the effect of sintering techniques (SPS and CS) and reinforcement (CeO₂) on engineering the desired microstructure of 8YSZ ceramic.     

Hot Corrosion Behavior of YSZ and CaZrO<Subscript>3</Subscript>/YSZ Composite Thermal Barrier Coatings in Contact with 50V<Subscript>2</Subscript>O<Subscript>5</Subscript> + 50Na<Subscript>2</Subscript>SO<Subscript>4</Subscript> Salts

A novel thermal barrier coating system was formulated to resist hot corrosion environments. In this coating system, 5% CaZrO₃ was added to conventional yttria-stabilized zirconia (YSZ). The above composite coating system was compared with the standard YSZ system in the presence of a mixture of 50% Na₂SO₄ and 50% V₂O₅ at 950 °C. The results demonstrated that the lifetime of the CaZrO₃-added composite system in this highly hostile environment was longer compared with the standard YSZ system. This is due to the fact that the preferential reaction of NaVO₃ shifted from yttria to calcia, forming CaV₂O₄ instead of YVO₄. The preferential reactions are discussed in terms of free energy changes and acid–base theory of molten salts with ceramic oxides. Furthermore, calculations of lattice distortion also proved that the CaZrO₃-added composite system demonstrated less distortion, thus increasing the overall lifetime of the coating system.     

Synthesis of LiFePO<Subscript>4</Subscript> using FeSO<Subscript>4</Subscript>·7H<Subscript>2</Subscript>O byproduct from TiO<Subscript>2</Subscript> production as raw material

As the byproduct of TiO₂ industrial production, impure FeSO₄·7H₂O was used for the synthesis of LiFePO₄. With the purified solution of FeSO₄·7H₂O, FePO₄·xH₂O was prepared by a normal titration method and a controlled crystallization method, respectively. Then LiFePO₄ materials were synthesized by calcining the mixture of FePO₄·xH₂O, Li₂CO₃, and glucose at 700°C for 10 h in flowing Ar. The results indicate that the elimination of FeSO₄·7H₂O impurities reached over 95%, and using FePO₄·xH₂O prepared by the controlled crystallization method, the obtained LiFePO₄ material has fine and sphere-like particles. The material delivers a higher initial discharge specific capacity of 149 mAh·g⁻¹ at a current density of 0.1C rate (1C = 170 mA·g⁻¹); the discharge specific capacity also maintains above 120 mAh·g⁻¹ after 100 cycles even at 2C rate. Thus, the employed processing is promising for easy control, low cost of raw material, and high electrochemical performance of the prepared material.     

Total conductivity,oxygen permeability and stability of perovskite-type oxide BaCo<Subscript>0.7</Subscript>Fe<Subscript>0.2</Subscript>Nb<Subscript>0.1</Subscript>O<Subscript>3−<Emphasis Type="Italic">δ</Emphasis></Subscript>

The total conductivity, oxygen sorption property, oxygen permeability and stability of pure perovskite-type oxide BaC_o0.7Fe_0.2Nb_0.1O_3−δ (BCFNO) in real operating conditions were investigated. Its total conductivity was measured to be 3.6 S·cm⁻¹ at 600°C. Though the total conductivity of the BCFNO membrane is much smaller than that of the Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ (BSCFO) membrane, the oxygen permeability of the BCFNO membrane is similar to that of the BSCFO membrane. SEM observation and EDX analysis of the BCFNO and BSCFO membranes indicated that no segregation of metal ions was found for the used BCFNO membrane while the original perovskite phase of BSCFO decomposed under the experimental condition. The experimental results of oxygen permeability and stability were consistent with the analysis on the oxygen sorption property of perovskites.     

Suspension Plasma Sprayed Sr<Subscript>2</Subscript>Fe<Subscript>1.4</Subscript>Mo<Subscript>0.6</Subscript>O<Subscript>6−<Emphasis Type="Italic">δ</Emphasis></Subscript> Electrodes for Solid Oxide Fuel Cells

In this study, suspension plasma spraying (SPS) was applied to deposit double perovskite Sr₂Fe_1.4Mo_0.6O_6?δ (SFM) which can be used as both cathode and anode for solid oxide fuel cells. The effects of SFM concentration on the electrode phase composition, microstructure, and catalytic performance were investigated. The electrodes showed a dense structure when it was deposited at a concentration of 0.05 mol/L. The cathode performance was limited by the limited three-phase boundaries and poor gas diffusion. At 750 °C, cathode polarization (R _pc) was 0.19 Ω cm². When the SFM concentration increased to 0.075 mol/L, the deposits revealed a porous microstructure with well-bonded fine particles. As a result, the R_pc decreased significantly to 0.078 Ω cm² at 750 °C. However, when the SFM concentration was further increased to 0.1 mol/L, the R _pc increased owing to the limited interface bonding between the non-molten particles. As a result, it was found that the SFM suspension concentration should be optimized to achieve a highly active SFM by SPS process. Moreover, when the optimized deposit was employed as an anode and tested in a hydrogen atmosphere, it showed anode polarization resistance (R_pa) of 1.5 Ω cm² at 750 °C.     

Formation of Al/(Al<Subscript>13</Subscript>Fe<Subscript>4</Subscript> + Al<Subscript>2</Subscript>O<Subscript>3</Subscript>) Nano-composites via Mechanical Alloying and Friction Stir Processing

Combination of mechanical alloying and friction stir processing was used for the fabrication of Al/(Al₁₃Fe₄ + Al₂O₃) nano-composites. Pre-milled hematite + Al powder mixture was introduced into the stir zone generated on 1050 aluminum alloy sheet by friction stir processing. Uniform and active milled powder mixture reacted with plasticized aluminum to produced Al₁₃Fe₄ + Al₂O₃ particles. Al₁₃Fe₄ intermetallic showed elliptical shape with a typical size of ~ 100 nm, while nano-sized Al₂O₃ exhibited irregular floc-shaped particles that formed clusters with the remnant of iron oxide particles in the fine recrystallized aluminum matrix. As the milling time (1-3 h) of the introduced powder mixture increased, the volume fraction of Al₁₃Fe₄ + Al₂O₃ particles increased in the fabricated composite. The hardness and ultimate tensile strength of the fabricated nano-composites varied from 54.5 to 75 HV and 139 to 159 MPa, respectively; these are much higher than those of the friction stir processed base alloy (33 HV and 97 UTS). The highest hardness and strength were achieved for the nano-composite fabricated using the 3-h milled powder mixture; hard nano-sized reaction products and fine recrystallized grains of Al matrix had major and minor roles on enhancing these properties, respectively.     

Structure and magnetic properties of mechanically synthesized (Fe<Subscript>1–<Emphasis Type="Italic">x</Emphasis></Subscript>Ni<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>)<Subscript>75</Subscript>C<Subscript>25</Subscript> nanocomposites

X-ray diffraction, Mössbauer spectroscopy, and magnetic measurements have been used to study the phase formation in (Fe_1–xNi_x) (with х = 0–0.20) nanocomposites upon severe plastic deformation in a planetary ball mill and subsequent annealings. It has been shown that the mechanical synthesis results in the formation of mainly a nickel-alloyed nanocrystalline (Fe, Ni)₃C cementite with a distorted crystal lattice and an amorphous Fe–Ni–C phase. During heating above 300°С, the amorphous phase crystallizes with the formation of cementite, which is characterized by a higher Ni content compared to that in mechanically synthesized cementite. The mechanically synthesized samples exhibit low coercive force (equal to several tens ampere per centimeter). In the course of annealing at temperatures of up to 500–550°С, crystal lattice distortions are removed; this results in reliving the magnetic anisotropy constant and high-coercivity state of cementite. At the same time, Ni-rich cementite areas decompose with the formation of γ-(Fe, Ni, C) phase (austenite); as a result, the average nickel content in the cementite substantially decreases. Annealings at higher temperatures cause the complete decomposition of cementite and lead to an abrupt decrease in the coercive force (Н _с) of samples. Alloying with nickel leads to an increase in the Curie temperature of cementite and a decrease in its specific saturation magnetization, coercive force, and thermal stability.     

Leakage currents in Ti−O/Ta<Subscript>2</Subscript>O<Subscript>5</Subscript> thin film deposited on Ta/Ti/Al<Subscript>2</Subscript>O<Subscript>3</Subscript>

The electrical characteristics of Ta/Ta₂O₅ films and Ta/Ti−O/Ta₂O₅ films deposited by RF reactive sputtering on Ta/Ti/Al₂O₃ substrates were investigated. Ta was used for the bottom and upper electrodes in order to simplify the fabrication process. Dielectric materials were annealed at 700°C for 60 sec under vacuum. XRD analysis showed that Ta was crystalline and Ta₂O₅ was amorphous in an as-deposited state, but amorphous Ta₂O₅ was transformed to a crystalline state by rapid thermal heat treatment. We compared lnJ-E², C−V, and C−F of both as-deposited and annealed dielectric thin films deposited on the Ta bottom electrode. From these results, we concluded that introducing a Ti−O buffer layer could reduce the leakage current. The conduction mechanisms of Ti−O/Ta₂O₅ could be interpreted appropriately by hopping conduction and space-charge-limited current.     

Ferromagnetic manganites La<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Ca<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>MnO<Subscript>3</Subscript>

A brief review of properties of the ferromagnetic manganites La_{1 − x} Ca _x MnO₃ is given. Lattice properties, magnetic properties, transport phenomena, magnetic resonance, and the results of neutron diffraction and optical studies are considered. Special attention is paid to effects observed near the Curie temperature.     

Embrittlement and conditions of the optimization of magnetic properties in the amorphous alloy Co<Subscript>69</Subscript>Fe<Subscript>3.7</Subscript>Cr<Subscript>3.8</Subscript>Si<Subscript>12.5</Subscript>B<Subscript>11</Subscript> in the absence of a viscous–brittle transition

The influence of the holding time upon annealing on the temperature of the viscous–brittle transition (temperature of embrittlement) T_f in a cobalt-based amorphous alloy of the composition Co₆₉Fe_3.7Cr_3.8Si_12.5B₁₁ with a very low saturation magnetostriction λ_s (<10^–7) has been studied. It has been established that the dependence of the embrittlement temperature T_f on the of time of holding t_a can be described by an Arrhenius equation and that the embrittlement at the annealing temperatures above and below 300°C is described by different kinetic parameters. In the alloy under study, irrespective of the holding time, embrittlement occurs in a very narrow range of annealing temperatures, which does not exceed 5 K. Based on the experimental data on the evolution of the hysteresis magnetic properties upon the isochronous annealings and upon the isothermal holding, the regime of heat treatment that ensures a very high (about 50000) magnitude of the permeability µ₅ (H = 5 mOe, f = 1 kHz) without the transition of the alloy into a brittle state has been determined.     

Tribological Behavior of Plasma-Sprayed Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-20 wt.%TiO<Subscript>2</Subscript> Coating

Al₂O₃-20 wt.% TiO₂ ceramic coatings were deposited on the surface of Grade D steel by plasma spraying of commercially available powders. The phases and the microstructures of the coatings were investigated by x-ray diffraction and scanning electron microscopy, respectively. The Al₂O₃-20 wt.% TiO₂ composite coating exhibited a typical inter-lamellar structure consisting of the γ-Al₂O₃ and the Al₂TiO₅ phases. The dry sliding wear behavior of the coating was examined at 20 °C using a ball-on-disk wear tester. The plasma-sprayed coating showed a low wear rate (~4.5 × 10^?6 mm³ N^?1 m^?1), which was <2% of that of the matrix (~283.3 × 10^?6 mm³ N^?1 m^?1), under a load of 15 N. In addition, the tribological behavior of the plasma-sprayed coating was analyzed by examining the microstructure after the wear tests. It was found that delamination of the Al₂TiO₅ phase was the main cause of the wear during the sliding wear tests. A suitable model was used to simulate the wear mechanism of the coating.