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.     

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.     

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.     

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.     

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.     

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.     

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.     

Accelerated Hot Corrosion Studies of D-Gun-Sprayed Cr<Subscript>2</Subscript>O<Subscript>3</Subscript>–50% Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Coating on Boiler Steel and Fe-Based Superalloy

In the current investigation, Cr₂O₃–50% Al₂O₃ coating was deposited on ASTM-SA213-T-22 boiler steel and Fe-based superalloy Superfer 800H by D-gun spray process. The high-temperature corrosion performance of the coated as well as bare alloys was evaluated in Na₂SO₄–60%V₂O₅ molten salt, an aggressive environment at 900 °C under cyclic conditions. The kinetics of the corrosion were analyzed by the change in weight measurements which were taken after each cycle (i.e., 1-h heating in a tube furnace followed by 20-min cooling in ambient air) for a total period of 50 cycles. The X-ray diffraction and scanning electron microscopy/energy-dispersive X-ray analysis techniques were used for the analysis of corrosion products. During investigations, it was found that both the selected bare alloys have suffered intensive spallation in the form of removal of their oxide scales, which may be attributed to the formation of non-protective Fe₂O₃-dominated oxide scales, whereas the coated alloys have shown lesser weight gains along with better adhesiveness of the oxide scales with the substrate till the end of the experiment. The oxides of chromium and aluminum were the main phases revealed in the oxide scales of the coated specimens, which are reported to be protective against the hot corrosion.     

Phase and Microstructure Evolution and Toughening Mechanism of a Hierarchical Architectured Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–Y<Subscript>2</Subscript>O<Subscript>3</Subscript> Coating under High Temperature

In recent years, numerous techniques have been developed to mimic nacre-like hierarchical architectures in order to improve the damage tolerance of materials. We present herein a simple strategy to fabricate such a hierarchical architectured Al₂O₃–Y₂O₃ composite coating via atmospheric plasma spraying. The evolution of the phase and microstructure of the Al₂O₃–Y₂O₃ composite coating were characterized under conditions of high-temperature exposure in air at 800-1350 °C. The hardness and porosity of several typical coatings were determined. In situ formation of dense hierarchical architectured Al₂O₃–YAG composite coating with improved hardness was achieved after heat treatment at 1350 °C. Compared with Al₂O₃ coating, elevated toughness was found for the hierarchical architectured Al₂O₃–YAG composite coating, which can be ascribed to the distribution of YAG phase that contributed to crack termination and deflection, and microbridging. After thermal aging treatment at 1350 °C, the hierarchical architectured Al₂O₃–YAG composite coating was quite stable after 100 h of thermal exposure. Furthermore, the Al₂O₃–Y₂O₃ composite coating exhibited superior sintering resistance compared with the Al₂O₃ coating.     

The effect of Al<Subscript>2</Subscript>O<Subscript>3</Subscript> nanoparticles on tribological and corrosion behavior of electroless Ni–B–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> composite coating

In this study, the Ni–B–Al₂O₃ composite was successfully coated on the surface of Ck45 steel by elecroless method. X-Ray diffraction analysis (XRD) and scanning electron microscopy (SEM) were utilized in order to investigate and identify the coating properties. Wear behavior of the coating was studied by the pinon- disk test. Corrosion behavior of the Ni–B and Ni–B–Al₂O₃ coatings was investigated by using Tafel polarization diagrams in the 3.5% NaCl solution at room temperature. The obtained data demonstrate that the addition of Al₂O₃ nanoparticles to the coating has resulted in improving the tribological behavior of the coating due to the presence of the composite nanoparticles. Also, the results of electrochemical testing show that corrosion resistance of the electroless Ni–B coating with Al₂O₃ nanoparticles has dramatically increased.     

In situ Formed α-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Nanocrystals Repaired the Preexisting Microcracks in Plasma-Sprayed Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Coating via Stress-Induced Phase Transformation

In the present study, the phase composition and generation mechanism of the nanocrystals located in the microcracks of plasma-sprayed Al₂O₃ coating were reevaluated. The Al₂O₃ coatings were investigated using transmission electron microscopy and x-ray diffraction. We supply the detailed explanations to support the new viewpoint that in situ formation of α-Al₂O₃ nanocrystals in the preexisting microcracks of the as-sprayed Al₂O₃ coating may be due to the stress-induced phase transformation. Owing to the partially coherent relationship, the phase interfaces between the α-Al₂O₃ nanocrystals with the preferred orientation and the γ-Al₂O₃ matrix may possess better bonding strength. The α-Al₂O₃ nanocrystals could repair the microcracks in the coating, which further strengthens grain boundaries. Grain boundary strengthening is beneficial to the coating fracture toughness enhancement.     

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.     

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.     

Phase Equilibria in the Sb<Subscript>2</Subscript>Te<Subscript>3</Subscript>–InSb System

The phase diagram of the (Sb₂Te₃)_100?x –InSb _x system was determined based on x-ray diffraction (XRD) analysis, differential thermal analysis (DTA), and microhardness and density measurements. An intermediate compound with composition Sb₂Te₃·2InSb was formed as a result of syntectic reaction, melting incongruently at 553 °C. This compound has tetragonal lattice with unit cell parameters of a = 4.3937 Å, b = 4.2035 Å, c = 3.5433 Å, α = 93.354°, and β = γ = 90°. Sb₂Te₃·(2 + δ)InSb (?1 ≤ δ ≤ +1) and (Sb₂Te₃)_100?x (InSb) _x (90 ≤ x ≤ 100) solid solutions exist in the investigated system, based on the intermediate compound Sb₂Te₃·2InSb and on InSb, respectively. Also, two invariant equilibria exist in the system, with eutectic point coordinates at compositions of x = 60 and x ≈ 85 mol% InSb and eutectic temperatures of T _E = 541 and T _E ≈ 501 °C, respectively.     

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.     

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.     

<Superscript>57</Superscript>Fe Mössbauer spectroscopy of synthesized ɛ-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> nanoparticles

Magnetic nanoparticles have promising applications in many areas, for example optics, electronics, biology, medicine, etc. The primary goal of this study was to synthesize nanoparticles of magnetic ?-Fe₂O₃ embedded in amorphous SiO₂. The structure and properties of the final product have been found to depend strongly on the initial conditions of preparation. The Mössbauer spectroscopy analysis of the samples was complemented by the study of X-ray powder diffraction, magnetic measurements, and high-resolution transmission electron microscopy.