Composition dependence of phase structure and electrical properties of (1−y)Bi1−xNdxFeO3−yBiScO3 ceramics

In this work, we have studied a new lead-free ceramic of(1-y)Bi_(1-x)Nd_xFeO_(3-y)BiScO_3(0.05≤x≤0.15 and 0.05≤y≤0.15) prepared by a conventional solid-state method, and the influences of Nd and Sc content on their phase structure and electrical properties were investigated in detail. The ceramics with 0.05≤x≤0.10 and 0.05≤y≤0.15 belong to an R3 c phase, and the rhombohedral-like and orthorhombic multiphase coexistence is established in the composition range of 0.125≤x≤0.15 and y=0. The electrical properties of the ceramics can be enhanced by modifying x and y values. The highest piezoelectric coefficient(d33~51 p C/N) is obtained in the ceramics with x=0.075 and y=0.125, which is superior to that of a pure BiFeO_3 ceramic. In addition, a lowest dielectric loss(tan δ~0.095%, f=100 k Hz) is shown in the ceramics with x=0.15 and y=0 due to the involvement of low defect concentrations, and the improved thermal stability of piezoelectricity at 20–600oC is possessed in the ceramics. We believe that the ceramics can play a meaningful role in the high-temperature lead-free piezoelectric applications.     

Effects of Excess Barium on the Structure and Electrical Properties of (Ba,Ca)TiO<Subscript>3</Subscript> Piezoelectric Ceramics with High Mechanical Quality Factors

Manganese-doped Ba_0.925Ca_0.075TiO₃ lead-free piezoelectric ceramics (abbreviated as BCT) with high mechanical quality factor were synthesized by conventional solid-state reaction method. The effects of excess Ba on the crystal structure, microstructure, and electrical properties of the ceramics were systematically investigated. X-ray diffraction and Raman spectra revealed that Ca²⁺ ions were pushed from Ba sites to Ti sites of BCT when 1.5 mol% extra Ba²⁺ ions were added after sintering. The grain size of the ceramics was decreased by adding extra Ba²⁺ ions. The mechanical quality factor and resistivity of the ceramics decreased dramatically when the excess Ba was more than 1.5 mol%. High piezoelectric coefficients ( d₃₃ = 150–190 pC/N ) and high mechanical quality factors ( Q_m = 1 000–1 200 ) were obtained in the ceramics when the excess of Ba was between 0.5 mol% and 1 mol%. These results indicated that the properties of BCT ceramics could be tailored by adjusting the content of Ba.     

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.     

Improved Breakdown Strength in (Ba<Subscript>0.6</Subscript>Sr<Subscript>0.4</Subscript>)<Subscript>0.85</Subscript>Bi<Subscript>0.1</Subscript>TiO<Subscript>3</Subscript> Ceramics with Addition of CaZrO<Subscript>3</Subscript> for Energy Storage Application

(Ba_0.6Sr_0.4)_0.85Bi_0.1TiO₃ ceramics doped with x wt%CaZrO₃ (x= 0-10) were synthesized by solid-state reaction method. The effects of CaZrO₃ amount on the dielectric properties and structure of (Ba_0.6Sr_0.4)_0.85Bi_0.1TiO₃ ceramics were investigated. X-ray diffraction results indicated a pure cubic perovskite structure for all samples and that the lattice parameter increased till x=5 and then slightly decreased. A homogenous microstructure was observed with the addition of CaZrO₃. Dielectric measurements revealed a relaxor-like characteristic for all samples and that the diffusivity γ reached the maximum value of 1.78 at x=5. With the addition of CaZrO₃, the dielectric constant dependence on electric field was weakened, insulation resistivity enhanced and dielectric breakdown strength improved obviously and reached 19.9 kV/mm at x=7.5. In virtue of low dielectric loss (tan δ<0.001 5), moderate dielectric constant (ε_r >1 500) and high breakdown strength (E_b >17.5 kV/mm), the CaZrO₃ doped (Ba_0.6Sr_0.4)_0.85Bi_0.1TiO₃ ceramic is a potential candidate material for high power electric applications.     

Spontaneous Magnetic Transitions and Corresponding Magnetoelastic Properties of Intermetallic Compounds <Emphasis Type="Italic">R</Emphasis>Mn<Subscript>2</Subscript>Ge<Subscript>2</Subscript> (<Emphasis Type="Italic">R</Emphasis>=Gd,Tb and Dy)

The spontaneous magnetic transitions and corresponding magnetoelastic properties of intermetallic compounds RMn₂Ge₂ (R=Gd, Tb and Dy) were investigated by using the X-ray diffraction method and magnetic measurement. The results showed that the compounds experience two magnetic transitions, namely the second-order paramagnetic to antiferromagnetic transition at temperature T_N (T_N=368, 423 and 443 K for GdMn₂Ge₂, TbMn₂Ge₂ and DyMn₂Ge₂, respectively) and the first-order antiferromagnetic - ferrimagnetic transition at temperature T_t (T_t=96, 80 and 40 K for GdMn₂Ge₂, TbMn₂Ge₂ and DyMn₂Ge₂, respectively) as the temperature decreases. The temperature dependence of the lattice constant a(T) displays a negative magnetoelastic anomaly at the second-order transition point T_N and, at the first-order transition T_t, a increases abruptly for GdMn₂Ge₂ and TbMn₂Ge₂, Δa/a about 10^-3. Nevertheless, the lattice constant c almost does not change at these transition points indicating that such magnetoelastic anomalies are mainly contributed by the Mn-sublattice. The transitions of the magnetoelastic properties are also evidenced on the temperature dependence of magnetic susceptibility χ. The first-order transition behavior at T_t is explained by the Kittel mode of exchange inversion.     

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).     

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.     

Remarkable improvement of ferroelectric properties and leakage current in BiFeO<Subscript>3</Subscript> thin films by nd modification

Ferroelectric and leakage properties are important for ferroelectric applications. Pure and Nd-doped (x=0.05-0.20) BiFeO3 thin films were fabricated by sol-gel method on FTO substrates. The phase structure, surface morphology, leakage current, ferroelectric properties, and optical properties of BiFeO₃^- based thin films were investigated. The substitution of Nd³⁺ ions for the Bi3+ site converts the structure from rhombohedral to coexisting tetragonal and orthorhombic. Nd doping improves the crystallinity of BiFeO₃ thin films. The leakage current of Nd-doped BiFeO₃ decreases by two to three orders of magnitude compared with that of pure BiFeO₃. Among the samples, 15% Nd-doped BiFeO₃ exhibits the strongest ferroelectric polarization of 17.96 μC/cm². Furthermore, the absorption edges of Bi_1-xNd _x FeO₃ thin films show a slight red-shift after Nd doping.     

Morphology study of oriented SmBCO film deposited by MOCVD

c-axis-oriented SmBa_2Cu_3O_7(SmBCO) films have been deposited on(100)- LaA1O_3(LAO)substrate by metal organic chemical vapor deposition(MOCVD) technique.The effects of deposition temperature(T_(dep)) and total pressure(P_(tot)) on the orientation and microstructure of SmBCO films were investigated.The orientation of SmBCO films transformed from α-axis to c-axis with increasing of T_(dep) from 900 to 1 100℃.At T_(dep)=1 050℃,SmBCO films had c-axis orientation and tetragon surface.At P_(tot)~(dep)=400-800 Pa and T_(dep)=1 050 ℃,totally c-axis-oriented SmBCO films were obtained.The R_(dep) of SmBCO films increased firstly and then decreased with increasing P_(tot).The surface of SmBCO films exhibited tetragon morphology at 1 050 ℃ and400 Pa.Maximum thickness of SmBCO film deposited was 1.2μm at P_(tot)= 600 Pa,and the corresponding R_(dep)was 7.2 μm·h~(-1).     

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.     

Synthesis of MnxZn（1-x）Fe2O4 Nanopartieles by Ball-milling Hydrothermal Method

SMnxZn1-xFe2O4 （x=1,0.9,0.8,0.7,0.6,0.5,0.25,0） nanoparticles were prepared by ball-milling hydrothermal and investigated by X-ray diffraction, DTG and TEM. Nanocrystallite grain size was determined by X-ray linewidth to be from 63 A to 274 A. The thermal properties indicate absorbed water still remain at low temperature, crystalline wate will be decomposed from 230 ℃ to 260 ℃, partial Mn^2＋ will be oxidized near 730 ℃. TEM shows the ferrite particles pocess a spherical morphology and uniform nanosize.     

Entransy dissipation minimization for generalized heat exchange processes

This paper investigates the MED(Minimum Entransy Dissipation) optimization of heat transfer processes with the generalized heat transfer law q ∝(△(T~n))~m T. For the fixed amount of heat transfer, the optimal temperature paths for the MED are obtained. The results show that the strategy of the MED with generalized convective law q ∝(△T)~m T is that the temperature difference keeps constant, which is in accordance with the famous temperature-difference-field uniformity principle, while the strategy of the MED with linear phenomenological law q ∝△(T~(-1)) is that the temperature ratio keeps constant. For special cases with Dulong-Petit law q ∝(△T)~(1.25) and an imaginary complex law q ∝(△(T~4))~(1.25), numerical examples are provided and further compared with the strategies of the MEG(Minimum Entropy Generation), CHF(Constant Heat Flux) and CRT(Constant Reservoir Temperature) operations. Besides, influences of the change of the heat transfer amount on the optimization results with various heat resistance models are discussed in detail.     

Effect of Cu-Ti-C reaction composition on reinforcing particles size of TiC<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>/Cu composites

TiC _x /Cu composites were fabricated by combustion synthesis and hot press technology. Using XRD, SEM, EDS, FESEM analysis methods, the effects of various carbon sources and different Cu contents on the microstructures of TiC _x /Cu composites and the size of TiC _x particles were investigated. Results showed that TiC _x reinforcing particles size increases with decreasing Cu content in Cu-Ti-C reaction system. With carbon nanotubes (carbon black) serving as carbon source, the generated TiC _x particles size transits from nanometer to submicron when Cu content corresponding to the reaction system is reduced to 60 vol% (70 vol%); while graphite serves as carbon source, there is no clear limiting concentration. C particles with smaller size, larger specific surface area and better distribution result in finer TiC _x particles, which is more beneficial to generating nano-sized TiC _x /Cu composites.     

Elimination of Voids at Interface of <Emphasis Type="Italic">β</Emphasis>-SiC Films and Si Substrate by Laser CVD

Void-free β-SiC films were deposited on Si(001) substrates by laser chemical vapor deposition using hexamethyldisilane (HMDS) as the precursor. The effect of the time of introducing HMDS, i e, the substrate temperature when HMDS introduced (T_in), on the preferred orientation, surface microstructure and void was investigated. The orientation of the deposited SiC films changed from <001> to random to <111> with increasing T_in. The surface showed a layer-by-layer microstructure with voids above T_in ? 773 K, and then transformed into mosaic structure without voids at T_in= 298 K. The mechanism of the elimination of voids was discussed. At T_in =298 K, Si surface can be covered by an ultrathin SiC film, which inhibits the out-diffusion of Si atoms from substrate and prohibites the formation of the voids.     

Electronic Structure and Optical Properties of LiBiO<Subscript>3</Subscript> Doped with V,Nb, and Ta

The crystal structure, band structure, density of states, Mulliken charge, bond population and optical properties for LiBi_1-xM_xO₃ (M=V, Nb, and Ta) were investigated using hybrid density functional theory. It was found that LiBiO₃ doped with V, Nb, and Ta presented distinctly stronger covalent interactions in M-O (M=V, Nb, and Ta) than Bi-O, thus resulting in mild distortion of the structure and facilitating the separation of photogenerated carriers. Furthermore, the hybridizations of Bi-6s, M-d (M=V, Nb, and Ta) and O-2p widened the valence and conduction bands, which promoted transmission of photogenerated carriers in the band edge and thus caused better photocatalytic performance.     

Preparation and Properties of Sapphire by Edge-defined Film-fed Growth (EFG) Method with Different Growth Directions

Sapphire, belonging to hexagonal crystal system, is typically anisotropic which makes it direction-sensitive. To research the effects of growth directions on properties of sapphire, c-[0001] seed(c-sapphire) and a-[11-20] seed(a-sapphire) were used to prepare sapphire by edge-defined film-fed growth(EFG) method. The samples were analyzed through lattice integrity, dislocation and corrosion performance by double-crystal XRD, OM, AFM, SEM and EDX. It was shown that the lattice integrities of two growth-direction crystals were both well due to the small FWHM values. While the average densities of dislocation in c-sapphire and a-sapphire were 9.2×103 and 3.9×103 cm-2 respectively, the energy of dislocation in c-sapphire was lower than that in a-sapphire. During Strong Phosphoric Acid(SPA) etching, the surface of c-sapphire basically kept smooth but in a-sapphire there were many point-like corrosion pits where aluminum and oxygen atoms lost by 2:1. Our work means that it will be promising for growing c-[0001] seed sapphire by EFG if aided by parameter optimization.     

Thermodynamic assessment of solar-aided carbon dioxide conversion into fuels via Tin oxides

The conversion of CO_2 to liquid hydrocarbon fuels using solar energy is gaining attraction as a means to deal with climate change and energy depletion,and assessment for related thermochemical cycles has attracted great interests in recent years.Here,we perform the thermodynamical analysis on solar-aided CO_2 conversion reactions based on Tin oxides.The equilibrium compositions,production purity and CO_2 conversion are obtained.Also,the variations of conversion efficiency with respect to temperature,normal beam solar insolation,mean flux concentration ratio,initial CO_2 to SnO ratio and heat recuperation percentage are revealed.Our results indicate the initial CO_2 to SnO ratio,χ_(ini),has an evident impact on conversion efficiency andχ_(ini)=0.5,T=700 K andχ_(ini)=1,T=950 K,are favourable for solid C and gaseous CO production,respectively.The calculated maximum cycle efficiency with direct work production is 0.340 at T=950 K andχ_(ini)=1,demonstrating the high conversion efficiency of the proposed system.     

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.     

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.     

Vacuum degree effects on betavoltaics irradiated by <Superscript>63</Superscript>Ni with differently apparent activity densities

For many current betavoltaics, beta sources and PN junction energy conversion units are separated. The air gap between the two parts could stop part of decay beta particles, which results in inefficient performance of the betavoltaic. By employing ⁶³Ni with an apparent emission activity density of 7.26×10⁷ and 1.81×10⁸ Bq cm^?2, betavoltaic performance levels were calculated at a vacuum degree range of 1×10⁵ to 1×10^?1 Pa and measured at 1.0×10⁵ and 1.0×10⁴ Pa, respectively. Results show that betavoltaic performance levels improve significantly as the vacuum degree increases. The maximum output power (P _max) exhibits the largest change, followed by short-circuit current (I _sc), open-circuit voltage (V _oc), and fill factor. The vacuum degree effects on I _sc, V _oc, and P _max of the betavoltaic with low apparent activity density ⁶³Ni are more significant than those of the betavoltaic with high apparent activity density ⁶³Ni. Moreover, the improved efficiencies of the measured performances are larger than the calculated efficiencies because of the low ratio of I _sc and reverse saturation current (I ₀). The values of I ₀, ideality factor, and shunt resistance were estimated to modify the equivalent circuit model. The calculation results based on this model are closer to the measurement results. The results of this research can provide a theoretical foundation and experimental reference for the study of vacuum degree effects on betavoltaics of the same kind.