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.     

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.     

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.     

Effect of Pb substitution on the microstructure and ferroelectric properties of Ba<Subscript>0.7</Subscript>Sr<Subscript>0.3</Subscript>TiO<Subscript>3</Subscript> ceramic

Ferroelectric Ba0.7Sr0.3TiO3（BST） and partially Pb^2＋ substituted for Ba^2＋ ceramics （Ba0.7-xPbx）Sr0.3TiO3 （x=0.1-0.4, BPST） were prepared by using conventional solid-reaction method. XRD analysis shows that the samples microstructure changes from cubic phase to tetragonal one with the Pb^2＋ content increasing. ESEM analysis shows that the Pb^2＋ substituted samples have a denser and more uniform surface morphology than that of pure BST. Measured electrical properties suggest that the Pb^2＋ substitution for Ba^2＋ in the BST system enhances the ferroelectric performance obviously when x=0.2. In addition, the substitution increases the samples Curie temperature （To） r （Ba0.5Pb0.2）Sr0.3TiO3 ceramic has good ferroelectric properties measured at a maximal electric field of 30 kV/cm under the condition of room temperature. The corresponding saturated polarization （Ps）, remnant polarization （Pr） and coercive field （Ec） is respectively 15.687 μC/cm^2, 8.100 μ C/cm^2 and 6.611 kV/cm. The measured Tc of （Ba0.5Pb0.2）Sr0.3TiO3 is 117 ℃.     

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).     

Dielectric properties of Bi<Subscript>4</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> ceramics by impedance spectroscopic method

Various lead-free ceramics have been investigated in search for new high-temperature dielectrics. In particular, Bi₄Ti₃O₁₂ is a type of ferroelectric ceramics, which is supposed to replace leadcontaining ceramics for its outstanding dielectric properties in the near future. Ferroelectric ceramics of Bi₄Ti₃O₁₂ made by conventional mixed oxide route have been studied by impedance spectroscopy in a wide range of temperature. X-ray diffraction patterns show that Bi₄Ti₃O₁₂ ceramics are a single-phase of ferroelectric Bi-layered perovskite structure whether it is calcined at 800 °C or after sintering production. This study focused on the effect of the grain size on the electric properties of BIT ceramics. The BIT ceramics with different grain sizes were prepared at different sintering temperatures. Grain becomes coarser with the sintering temperature increasing by 50 °C, relative permittivity and dielectric loss also change a lot. When sintered at 1 100 °C, r values peak can reach 205.40 at a frequency of 100 kHz, the minimum dielectric losses of four different frequencies make no difference, all close to 0.027. The values of E _a range from 0.52 to 0.68 eV. The dielectric properties of the sample sintered at 1 100 °C are relatively better than those of the other samples by analyzing the relationship of the grain, the internal stresses, the homogeneity and the dielectric properties. SEM can better explain the results of the dielectric spectrum at different sintering temperatures. The results show that Bi₄Ti₃O₁₂ ceramics are a kind of dielectrics. Thus, Bi₄Ti₃O₁₂ can be used in high-temperature capacitors and microwave ceramics.     

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.     

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.     

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.     

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.     

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.     

Effects of H<Subscript>2</Subscript>/CO/CH<Subscript>4</Subscript> syngas composition variation on the NO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> and CO emission characteristics in a partially-premixed gas turbine combustor

This paper reports the effects of variations in the fuel composition of H₂/CO/CH₄ syngas on the characteristics of NO _x and CO emissions in a partially-premixed gas turbine combustor. Combustion tests were conducted on a full range of fuel compositions by varying each component gas from 0% to 100% at heat inputs of 40 and 50 kW_th. Flame temperature, combustor liner temperature, ignition delay time, and flame structure were investigated computationally and experimentally to judge whether they are significant indicators of NO _x and CO formation. The characteristics of and reasons for NO _x and CO emissions were investigated by analyzing the emission mechanisms and relationships among fuel property, equivalence ratio, flame temperature, liner temperature, flame shape. The flame structures were investigated using the following flame visualization methods: (1) time-averaged OH* chemiluminescence and its Abel-deconvolution; (2) direct photography; and (3) instantaneous OH-PLIF. The flame structures were greatly changed by the fuel composition and heat input, and they were subjected to key affecting parameters of the temperatures of the flames and the liners. NO _x and CO emissions also largely varied according to fuel composition and heat input, showing neither linearly nor exponentially clear proportional trends toward the syngas compositions because of the singular conditions. For example, only the 100% CO flame at low load emitted lots of CO, whereas complete combustion was observed in other cases. However, the qualitative observations showed that the root causes of NO _x emission behaviors were flame temperature and flame structure, which were directly related to the residence time in the flame. Various sets of practical test results were obtained, and these results could contribute to the optimal selection of the fuel-feeding condition when fuel is changed from natural gas to syngas in order to minimize NO _x and CO emissions with stable combustion.     

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 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.     

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.     

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.     

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.     

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.     

Low temperature synthesis of amorphous La<Subscript>0.7</Subscript>Zn<Subscript>0.3</Subscript>MnO<Subscript>3</Subscript> films grown on p<Superscript>+</Superscript>-Si substrates and its resistive switching properties

Amorphous La_0.7Zn_0.3MnO₃ (LZMO) films were deposited on p⁺-Si substrates by sol-gel method at low temperature of 450 °C. The Ag/LZMO/p⁺-Si device exhibits invertible bipolar resistive switching and the R _HRS/R _LRS was about 10⁴-10⁶ at room temperature which can be kept over 10³ switching cycles. Better endurance characteristics were observed in the Ag/LZMO/p⁺-Si device, the V _Set and the V _Reset almost remained after 10³ endurance switching cycles. According to electrical analyses, the conductor mechanism was in low resistor state (LRS) governed by the filament conductor and in the high state (HRS) dominated by the traps-controlled space-charge-limited current (SCLC) conductor.