Synthesis and sintering of Mg<Subscript>2</Subscript>Si thermoelectric generator by spark plasma sintering

Raw Mg,Si powder were used to fabricate Mg2Si bulk thermoelectric generator by spark plasma sintering （SPS）.The optimum parameters to synthesize pure Mg2Si powder were found to be 823 K,0 MPa,10 min with excessive content of 10wt% Mg from the stoichiometric Mg2Si.Mg2Si bulk was synthesized and densified simultaneously at low temperature （823 K） and high pressure （higher than 100 MPa） from the raw powder,but Mg,Si could not react completely,and the sample was not very dense with some microcracks on the surface.Then,Mg,Si powder reacted at 823 K,0 MPa,10 min in SPS chamber to form Mg2Si green compact,again sintered by SPS at 1023 K,20 MPa,5 min.The fabricated sample only contained Mg2Si phase with fully relative density.     

Electronic structure and transport coefficients of the thermoelectric materials Bi<Subscript>2</Subscript>Te<Subscript>3</Subscript> from first-principles calculations

The electronic structures of bulk Bi₂Te₃ crystals were investigated by the first-principles calculations. The transport coefficients including Seeback coefficient and power factor were then calculated by the Boltzmann theory, and further evaluated as a function of chemical potential assuming a rigid band picture. The results suggest that p-type doping in the Bi₂Te₃ compound may be more favorable than n-type doping. From this analysis results, doping effects on a material will exhibit high ZT. Furthermore, we can also find the right doping concentration to produce more efficient materials, and present the “advantage filling element map” in detail.     

Preparation and piezoelectric properties of CuO-added (Ag<Subscript>0.75</Subscript>Li<Subscript>0.1</Subscript>Na<Subscript>0.1</Subscript>K<Subscript>0.05</Subscript>)NbO<Subscript>3</Subscript> lead-free ceramics

CuO-doped (Ag_0.75Li_0.1Na_0.1K_0.05)NbO₃ (ALNKN-xCuO, x = 0–2mol%) lead-free piezoelectric ceramics were prepared by the solid-state reaction method in air atmosphere. The effects of CuO addition on the phase structure, microstructure, and piezoelectric properties of the ceramics were investigated. The experimental results show that the ALNKN ceramics without doping CuO possess rhombohedral phase along with K2Nb6O16-type phase and metallic silver phase. For all of the CuO-doped ALNKN ceramics, a pure perovskite structure with the orthorhombic phase was obtained by enclosing the samples in a corundum tube. A homogeneous microstructure with the grain size of about 1 μm was formed for the ceramics with 0.5mol% CuO. The grain size increases with increasing amount of CuO. The temperature dependence of dielectric properties indicates that the ferroelectric phase of the ALNKN-xCuO ceramics becomes less stable with the addition of CuO. The ceramics with x = 1mol% exhibit relatively good electrical properties along with a high Curie temperature. These results will provide a helpful guidance to preparing other AN-based ceramics by solid-state reaction method in air atmosphere.     

Effects of annealing processes on Cu<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Si<Subscript>1-<Emphasis Type="Italic">x</Emphasis></Subscript> thin films

The Cu _x Si_1-x thin films have been grown by pulsed laser deposition (PLD) with in situ annealing on Si (001) and Si (111), respectively. The transformation of phase was detected by X-ray diffraction (XRD). The results showed that the as-deposited films were composed of Cu on both Si (001) and Si (111). The annealed thin films consisted of Cu + η”-Cu₃Si on Si (001) while Cu + η’-Cu₃Si on Si (111), respectively, at annealed temperature (T _a) = 300-600 °C. With the further increasing of T _a, at T _a= 700 °C, there was only one main phase, η”-Cu₃Si on Si (001) while η’-Cu₃Si on Si (111), respectively. The annealed thin films transformed from continuous dense structure to scattered-grain morphology with increasing T _a detected by field emission scanning electron microscope (FESEM). It was also showed that the grain size would enlarge with increasing annealing time (t _a).     

Influences of dopants on microstructure and magnetic properties of (Mg<Subscript>0.476</Subscript>Mn<Subscript>0.448</Subscript>Zn<Subscript>0.007</Subscript>)(Fe<Subscript>1.997</Subscript>Ti<Subscript>0.002</Subscript>)O<Subscript>4</Subscript> ferrites

Influences of addition of CaO, CoO and V2O5 on the microstructure and magnetic properties of (Mg0.476Mn0.448Zn0.007)(Fe1.997Ti0.002)O4 ferrites were investigated. The powders of (Mg0.476Mn0.448Zn0.007) (Fe1.997Ti0.002)O4 composition were prepared by using a conventional ceramic powder processing technique. The experimental results showed that the average grain size of the sintered ferrites codoped with 0.03wt% CaO, 0.04wt% CoO and 0.06wt% V2O5 was about 15 μm; the saturation magnetization of ferrites was 68.78 emu/g. The addition of V2O5 in the ferrites can not only increase value of the saturation magnetization, but also decrease the average grain size of (Mg0.476Mn0.448Zn0.007)(Fe1.997Ti0.002)O4 ferrites. Simultaneous incorporation of CoO, CaO and V2O5 dopants into (Mg0.476Mn0.448Zn0.007)(Fe1.997Ti0.002)O4 ferrites can not only improve the saturation magnetization of the materials, but also inhibit abnormal grain growth.     

Density function theory study of electronic,optical and thermodynamic properties of CaN<Subscript>2</Subscript>, SrN<Subscript>2</Subscript> and BaN<Subscript>2</Subscript>

We put forward a first-principles density-functional theory about the impact of pressure on the structural and elastic properties of bulk CaN₂, SrN₂ and BaN₂. The ground state properties of three alkaline earth diazenides were obtained, and these were in good agreement with previous experimental and theoretical data. By using the quasi-harmonic Debye model, the thermodynamic properties including the debye temperature Θ _D, thermal expansion coefficient α, and grüneisen parameter γ are successfully obtained in the temperature range from 0 to 100 K and pressure range from 0 to 100 GPa, respectively. The optical properties including dielectric function ε(?), absorption coefficient α(?), reflectivity coefficient R(?), and refractive index n(?) are also calculated and analyzed.     

New Mg<Subscript>2</Subscript>Si based alloy for automobile engine cylinder liner

New Mg₂Si based alloy were prepared by mechanical alloying. Sintering temperature was from 825 to 865K, which indicated that few Mg₂Si were produced at lower temperature while MgO were produced at higher temperature. Microstructure image showed that at sintering temperature of 855K, Mg₂Si were mostly synthesized with the reaction of purity magnesia powder and silicon powder. Hardness and wear tests proved that the new synthetic silicon magnesium alloy had higher hardness and good wear resistance. Under the same testing conditions, it is found that the hardness of the new material is 420.50, and pure magnesium is only 41.65.In the same experiments it is also found that under the same pressure, pure magnesium alloys than silicon wearing capacity of pure magnesium is 2 times as high that of Mg₂Si based alloy. It shows that Mg₂Si based alloy is the ideal material for the wear parts of car engine cylinder liner because of its small density, stable dimension, high hardness and wear-resisting.     

Crystallization and luminescence properties of Sm<Superscript>3+</Superscript>-doped SrO-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript> glass-ceramics

The Sm³⁺-doped SrO-Al₂O₃-SiO₂ (SAS) glass-ceramics with excellent luminescence properties were prepared by batch melting and heat treatment. The crystallization behavior and luminescent properties of the glass-ceramics were investigated by DTA, XRD, SEM and luminescence spectroscopy. The results indicate that the crystal phase precipitated in this system is monocelsian (SrAl₂Si₂O₈) and with the increase of nucleation/crystallization temperature, the crystallite increases from 66 % to 79 %. The Sm³⁺-doped SAS glass-ceramics emit green, orange and red lights centered at 565, 605, 650 and 715 nm under the excitation of 475 nm blue light which can be assigned to the ⁴G_5/2→⁶ H _j/2 (j=5, 7, 9, 11) transitions of Sm³⁺, respectively. Besides, by increasing the crystallization temperature or the concentration of Sm³⁺, the emission lights of the samples located at 565, 605 and 650 nm are intensified significantly. The present results demonstrate that the Sm³⁺-doped SAS glass-ceramics are promising luminescence materials for white LED devices by fine controlling and combining of these three green, orange and red lights in appropriate proportion.     

Effects of electrode on resistance switching properties of ZnMn<Subscript>2</Subscript>O<Subscript>4</Subscript> films deposited by magnetron sputtering

ZnMn₂O₄ films for resistance random access memory (RRAM) were fabricated with different device structures by magnetron sputtering. The effects of electrode on I-V characteristics, resistance switching behavior, endurance and retention characteristics of ZnMn₂O₄ films were investigated. The ZnMn₂O₄ films, using p-Si and Pt as bottom electrode, exhibit bipolar resistive switching (BRS) behavior dominated by the space-charge-limited conduction (SCLC) mechanism in the high resistance state (HRS) and the filament conduction mechanism in the low resistance state (LRS), but the ZnMn₂O₄ films using n-Si as bottom electrodes exhibit both bipolar and unipolar resistive switching behaviors controlled by the Poole-Frenkel (P-F) conduction mechanism in both HRS and LRS. Ag/ZnMn₂O₄/p-Si device possesses the best endurance and retention characteristics, in which the number of stable repetition switching cycle is over 1000 and the retention time is longer than 10⁶ seconds. However, the highest R _HRS/R _LRS ratio of 10⁴ and the lowest V _ON and V _OFF of 3.0 V have been observed in Ag/ZnMn₂O₄/Pt device. Though the Ag/ZnMn₂O₄/n-Si device also possesses the highest R _HRS/R _LRS ratio of 10⁴, but the highest values of V _ON,V _OFF, R _HRS and R _LRS, as well as the poor endurance and retention characteristics.     

Enhanced Ferroelectric Polarization in Laser-ablated Bi<Subscript>4</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> Thin Films by Controlling Preferred Orientation

Polycrystalline Bi₄Ti₃O₁₂ thin films with various fractions of a-axis, c-axis and random orientations have been grown on Pt(111)/Ti/SiO₂/Si substrates by laser-ablation under different kinetic growth conditions. The relationship between the structure and ferroelectric property of the films was investigated, so as to explore the possibility of enhancing ferroelectric polarization by controlling the preferred orientation. The structural characterization indicated that the large growth rate and high oxygen background pressure were both favorable for the growth of non-c-axis oriented grains in the Bi₄Ti₃O₁₂ thin films. The films with high fractions of a-axis and random orientations, i e, f (a-sxis) = 28.3% and f (random) = 69.6%, could be obtained at the deposition temperature of 973 K, oxygen partial pressure of 15 Pa and laser fluence of 4.6 J/cm², respectively. It was also noted that the variation of ferroelectric polarization was in accordance with the evolution non-c-axis orientation. A large value of remanent polarization (2Pr = 35.5 μC/cm²) was obtained for the Bi₄Ti₃O₁₂ thin films with significant non-c-axis orientation, even higher than that of rare-earth-doped Bi₄Ti₃O₁₂ films.     

Effect of magnesium on the C-S-H nanostructure evolution and aluminate phases transition in cement-slag blend

The microstructural study was conducted on cement and cement-slag pastes immersed in different concentrations of Mg(NO_3)_2 solutions utilizing ~(29)Si, ~(27)Al NMR spectroscopy and XRD techniques. The results show that the hydration of both the cement and cement-slag pastes is delayed when the pastes are cured in Mg(NO_3)_2 solutions as compared to the pastes cured in water. Moreover, Mg~(2+) ions also exhibit an decalcifying and dealuminizing effect on the C-A-S-H in cement and cement-slag pastes, and thereby decrease Ca/Si and Al[4]/Si ratios of the C-A-S-H. The dealuminization of C-A-S-H is mitigated for cement-slag paste as compared to pure cement paste. The depolymerized calcium and aluminum ions from C-A-S-H gel mainly enter the pore solution to maintain the pH value and form Al~[6] in TAH, respectively. On the other hand, Mg~(2+) ions exert an impact on the intra-transition between Al~[6] species, from AFm and hydrogarnet to hydrotalcite-like phase. NO_3~-ions are interstratified in the layered Mg-Al structure and formed nitrated hydrotalcite-like phase(Mg_(1-x)Al_x(OH)_2(NO_3)_x·nH_2O). Results from both ~(27)Al NMR and XRD data show that ettringite seems not to react with Mg~(2+) ions.     

Effect of ECAP on the microstructure and mechanical properties of a high-Mg<Subscript>2</Subscript>Si content Al-Mg-Si alloy

A high-Mg₂Si content Al alloy was extruded by equal channel angular pressing (ECAP) for 8 passes at 250 °C and an ultrafine-grained structure with an average grain size of about 1.5 μm was achieved. The coarse skeleton-shaped Mg₂Si phase presenting in the as-cast alloy are significantly fragmented into fine rod-shaped as well as equiaxed particles mostly less than about 230 nm and become relatively dispersed. The tensile strength 192.8 MPa and the elongation up to 31.3% at ambient temperature are attained in the 8-pass ECAPed alloy versus 163.3 MPa and 9.1% in the as-cast alloy. High-temperature creep test at 250 °C reveals that the ECAPed sample exhibits a high elongation close to 100% at a relatively high creep rate 7.64×10⁻⁵ s⁻¹, compared to the elongation 56% at a low strain rate 1.74×10⁻⁷ s⁻¹ in the as-cast alloy.     

Crystal growth,structure and properties of bismuth triborate BiB<Subscript>3</Subscript>O<Subscript>6</Subscript> crystal

BiB₃O₆ (BIBO) single crystals with size of 46×23×10 mm³ and weight of 26.0 g have been successfully grown by top-seeded method. Problems encountered in the growth process of this crystal have been discussed in detail, and the methods of growing high-quality large crystals have been put forward. The relationship between their structure and properties is studied. The space group of monoclinic BiB₃O₆ is C2 and the cell parameters are a=7.1203(7) Å, b=4.9948(7) Å, c=6.5077(7) Å, β=105.586(8)″, and V=222.93(5) ų. The density of BIBO is 4.8965 g/cm³. The Mohs’s scale of hardness is 5.5–6. There is no cleavage face in the crystal. The transmittance of BIBO is about 80 percent in the range from visible coherent light to near-infrared light. The ultraviolet cutoff wavelength is at 276 nm. BiB₃O₆ is a biaxial crystal and has two sets of axes, and the relative orientation of (X, Y, Z) with regard to (a, b, c) is: X//b, (Y, c)=47.2°, (Z, a)=31.6°, determined by X-ray analysis combined with polarized microscopy. Second-harmonic-generation (SHG) experiments were carried out for the first time. In type I phase-matching (PM) directions (11.1°, 90°) and (168.9°, 90°), SHG conversion efficiencies of two directions for 1.064 μm light are up to 67.7% and 58%, respectively. We have also obtained the third-harmonic-generation (THG) of 1.064 μm. The comparative experiments between BIBO and KTP were carried out on conversion efficiency, transmittance and hardness. All the above results indicate that BiB₃O₆ is a kind of excellent nonlinear optical (NLO) crystal.     

Resistive switching behavior of Ag/Mg<Subscript>0.2</Subscript>Zn<Subscript>0.8</Subscript>O/ZnMn<Subscript>2</Subscript>O<Subscript>4</Subscript>/p<Superscript>+</Superscript>-Si heterostructure devices for nonvolatile memory applications

The Ag/Mg_0.2Zn_0.8O/ZnMn₂O₄/p⁺-Si heterostructure devices were fabricated by sol-gel spin coating technique and the resistive switching behavior, conduction mechanism, endurance characteristic, and retention properties were investigated. A distinct bipolar resistive switching behavior of the devices was observed at room temperature. The resistance ratio R _HRS/R _LRS of high resistance state and low resistance state is as large as four orders of magnitude with a readout voltage of 2.0 V. The dominant conduction mechanism of the device is trap-controlled space charge limited current (SCLC). The devices exhibit good durability under 1×10³ cycles and the degradation is invisible for more than 10⁶ s.     

Catalytic Decomposition of Nitric Oxide by LaCoO<Subscript>3</Subscript> Nano-particles Prepared by Rotary CVD

Catalytic direct decomposition of NO by perovskite-type catalysts has attracted much attention for the various possible components and the unique structure. LaCoO₃ nanoparticles were precipitated on α-Al₂O₃ micro powders by rotary chemical vapor deposition (rotary CVD) and its catalytic performance for the decomposition of NO was investigated. LaCoO₃ nano-particles with 100 nm in average diameter and 1.5% in mass were uniformly dispersed on α-Al₂O₃ powder. The conversion of NO increased with increasing temperature from 400 to 950 °C, and reached 28.7% at 950 °C. The gas velocity of transformed NO on LaCoO₃ nano-particles catalyst per mass unit was 7.7 mL/(g min), showing a good catalytic activity over the calculated results of pure catalysts. After five times of aging performance experiments, the NO conversion kept the same value, showing a good aging performance and thermal stability.     

Progress on RE<Subscript>2</Subscript>O<Subscript>3</Subscript>-Mo/W matrix secondary emitter materials

Two types of secondary emitter materials, the rare earth oxides (RE₂O₃) doped Mo cermet cathodes and the Y₂O₃-W matrix pressed cathode, are introduced in this paper. According to the calculation results, Y₂O₃ exhibits the best secondary emission property among Y₂O₃, La₂O₃, CeO₂ and Lu₂O₃. The rare earth oxides co-doped Mo cathodes in which Y₂O₃ is the main active substance exhibit better secondary emission property than single RE₂O₃ doped Mo cathode. The results obtained by the Monte-Carlo calculation method show that the secondary electron emission property is strongly related to the grain size of the cathode. The decreasing of the grain size reduces the positive charge effect of the rare earth oxide due to the electrons supplement from the metal to the rare earth oxide, whereby the secondary electrons are easier to escape into the vacuum. Y₂O₃ is introduced into Ba-W cathode to fabricate a pressed Y₂O₃-W matrix dispenser cathode. The result indicates that the secondary emission yield of the Ba-W cathode increases from 2.13 to 3.51 by adding Y₂O₃, and the thermionic emission current density (J ₀) could reach 4.18 A/cm² at 1050 °Cb.     

Effect of Constituent Core-sizes on Microstructure and Dielectric Properties of BaTiO<Subscript>3</Subscript>@(0.6Ba-TiO<Subscript>3</Subscript>-0.4BiAlO<Subscript>3</Subscript>) Core-Shell Material

The fundamental characteristics of varied initial core-sizes of BaTiO₃(BT) and its influential role on the morphology and dielectric properties of BaTiO₃@0.6BaTiO₃-0.4BiAlO₃(BT@0.6BT-0.4BA) ceramic samples were studied. Alkoxide sol-precipitation method was adopted as revised chemical route to synthesize the constituent “core” BT powders in a dispersed phase, whereas the distinctive initial nano-sized particles were affected by the pre-calcination temperatures (600-900 °C).The microstructure of the uncoated BT ceramics revealed an exaggerated grain growth with an optimized dielectric constant (ε_max >9 000) whilst the coated ceramics behaved otherwise (grain growth inhibited) when sintered at an elevated temperature. Regardless of the previously studied solubility limit (about 0.1%) of BT-BA samples, BT@0.6BT-0.4BA maintained a maximum dielectric constant (ε_max) ranging from 1 592 to 1 708 and tan δ less than 2% under a unit mole ratio at room temperature. In view of all these analyses, the initial nanometer sizes of the as-prepared BT-core powders combined with the increase effect of cation substitutions of Bi³⁺ and Al³⁺ in the shell content, induced the diffuse transition phase of BT@0.6BT-0.4BA composition.     

An Investigation on Hydrogen Storage Kinetics of the Nanocrystalline and Amorphous LaMg<Subscript>12</Subscript>-type Alloys Synthesized by Mechanical Milling

Nanocrystalline and amorphous LaMg₁₂-type LaMg₁₁Ni + x wt% Ni (x = 100, 200) alloys were synthesized by mechanical milling. Effects of Ni content and milling time on the gaseous and electrochemical hydrogen storage kinetics of as-milled alloys were investigated systematically. The electrochemical hydrogen storage properties of the as-milled alloys were tested by an automatic galvanostatic system. And the gaseous hydrogen storage properties were investigated by Sievert apparatus and a differential scanning calorimeter (DSC) connected with a H₂ detector. Hydrogen desorption activation energy of alloy hydrides was estimated by using Arrhenius and Kissinger methods. It is found that the increase of Ni content significantly improves the gaseous and electrochemical hydrogen storage kinetic performances of as-milled alloys. Furthermore, as ball milling time changes, the maximum of both high rate discharge ability (HRD) and the gaseous hydriding rate of as-milled alloys can be obtained. But the hydrogen desorption kinetics of alloys always increases with the extending of milling time. Moreover, the improved gaseous hydrogen storage kinetics of alloys are ascribed to a decrease in the hydrogen desorption activation energy caused by increasing Ni content and milling time.     

Structural characteristics and photocatalytic activity of ambient pressure dried SiO<Subscript>2</Subscript>/TiO<Subscript>2</Subscript> aerogel composites by one-step solvent exchange/surface modification

An ambient pressure synthesis of SiO₂/TiO₂ binary aerogel was prepared through the low-cost precursors of titanium tetrachloride (TiCl₄) and sodium silicate (Na₂O·nSiO₂). After gelation, solvent exchange and surface modification were performed simultaneously and the modified gel was finally dried under ambient pressure. Microstructural analyses by transmission electron microscope (TEM) indicate that fabricated SiO₂/TiO₂ aerogel composite shows similar sponge-like nanostructure as silica aerogel, and the Brunauer–Emmett–Teller (BET) analysis shows that the specific surface area of the composite reaches 605 m²/g, and the average pore size is 9.7 nm. Such binary aerogel exhibits significant photocatalytic performance in this paper for treating model pollutant of methyl orange (MO), and the decolorizing efficiency of MO is detected as 84.9% after 210 mins exposure to UV light irradiation. Degraded gel suspends in the water so as to separate from solution for reuse, and after 4 times recycling, 70% degradation efficiency can be easily reached when composite catalyzed system is exposed for 210 mins under UV irradiation.     

Effect of Ga<Subscript>2</Subscript>O<Subscript>3</Subscript> on structure and properties of calcium aluminate glasses

The effect of Ga₂O₃ on the structure and properties of calcium aluminate glasses fabricated by vacuum melting process was investigated by Raman spectrum, differential scanning calorimeter (DSC), and infrared spectrum methods. The results show that calcium aluminate glass network only consists of [AlO₄] tetrahedral units. With the gradual addition of Ga₂O₃, the quantity of [GaO₄] tetrahedral units increases. Substitution of Ga₂O₃ for Al₂O₃ results in a decrease in T _g T _x, and T _p, and an increase in the thermal stable index ΔT. Similarly, the absorption band around 3.0 μm obviously reduces and the transparency in 4.0-6.0 μm rapidly increases with increasing Ga₂O₃ content. However, the chemical stability of calcium aluminate glasses decreases if Ga₂O₃ is introduced due to the increasing of [GaO₄] units in the glass network.