A diffuse phase transition study on Ba substituted (Na0.5Bi0.5)TiO3 ferroelectric ceramic

Polycrystalline perovskite lead free material (Na_0.5Bi_0.5)_0.91Ba_0.090TiO₃ was prepared by solid state reaction method. The crystal structure examined by X-ray powder diffraction indicates that the material was single phase with tetragonal structure. Dielectric studies exhibit a diffuse phase transition and characterized by a strong temperature and frequency dispersion of permittivity which relates cation disorder at A-site and exhibits relaxor behaviour. The dielectric relaxation has been modeled using the Vogel-Fulcher relationship, the calculated activation energy found to be E_a = 0.021 eV. Complex impedance analysis indicates the system undergoing a polydispersive non-Debye type relaxation. Also, used to characterize grain and grain-boundary resistivities of Ba substituted (Na_0.5Bi_0.5)TiO₃ ceramic. The phenomenon was also interpreted by accounting for microstructural differences. The corresponding relaxation times were also used to confirm the interpretation of complex impedance spectra. Overlapping of grain boundary and electrode relaxation processes can be separated above about 4000 C. Electrical modulus spectroscopy studies have been performed. The conductivity parameters such as ion-hopping rate (ω_p) and the charge carrier concentration (K¹) have been calculated using Almond and West formalism.     

Dielectric properties of iron doped calcium copper titanate, CaCu2.9Fe0.1Ti4O12

CaCu_2.9Fe_0.1Ti₄O₁₂ (CCFTO) has been prepared by a novel semi-wet route and its dielectric properties have been studied in the temperature range 300-500 K. It is found that dielectric constant (?) decreases drastically in the frequency range 100 Hz to 1 MHz. Complex plane impedance and modulus analysis was done to understand this drastic decrease in ?. Oxidation state of various ions was studied using X-ray photoelectron spectroscopy (XPS). The decrease in the permittivity of CCFTO can be attributed to two factors: the suppression of the Ca/Cu disorder in CCFTO which is observed in CaCu₃Ti₄O₁₂ (CCTO) and the absence of the grain boundary internal barrier layer capacitance mechanism.     

Structure and electrical conduction behavior of LiZnVO4 ceramic prepared by solution-based chemical route

In the present work, an evaluation of the structural and electrical properties of a compound (LiZnVO₄) has been undertaken. This compound was prepared by solution-based chemical route. The electrical properties were measured using a.c. impedance spectroscopy method in the frequency range of 10³-10⁶ Hz at various temperatures from 28 to 300 °C. X-ray diffraction study indicates a rhombohedral unit cell structure with lattice parameters a = 14.1934 Å, b = 14.1934 Å, c = 9.4926 Å, V = 1656.12 (Å)³, α = 90°, β = 90° and γ = 120°. A field emission scanning electron micrograph reveals a polycrystalline texture of the compound with grains of unequal sizes ∼0.2-2.0 μm. The electrical conduction in the material is a thermally activated process due to the bulk effect. Frequency dependence of a.c. conductivity obeys Jonscher's universal law (σ_ac = σ_dc + Aωⁿ).     

Effect of addition of Ba(W0.5Cu0.5)O3 in Pb(Mg1/3Nb2/3)O3-Pb(Zn1/3Nb2/3)O3-Pb(Zr0.52Ti0.48)O3 ceramics on the sintering temperature, electrical properties and phase transition

In this work, we report on the Pb(Mg_1/3Nb_2/3)O₃-Pb(Zn_1/3Nb_2/3)O₃-Pb(Zr_0.52Ti_0.48)O₃ (PMN-PZN-PZT) ceramics with Ba(W_0.5Cu_0.5)O₃ as the sintering aid that was manufactured in order to develop the low-temperature sintering materials for piezoelectric device applications. The phase transition, microstructure, dielectric, piezoelectric properties, and the temperature stability of the ceramics were investigated. The results showed that the addition of Ba(W_0.5Cu_0.5)O₃ significantly improved the sintering temperature of PMN-PZN-PZT ceramics and could lower the sintering temperature from 1005 to 920 °C. Besides, the obtained Ba(W_0.5Cu_0.5)O₃-doped ceramics sintered at 920 °C have optimized electrical properties, which are listed as follows: (K_p = 0.63, Q_m = 1415 and d₃₃ = 351 pC/N), and high depolarization temperature above 320 °C. These results indicated that this material was a promising candidate for high-power multilayer piezoelectric device applications.     

A facile route to VN and V2O3 nanocrystals from single precursor NH4VO3

V₂O₃ and VN nanocrystals have been synthesized by the decomposition of the precursor NH₄VO₃ and following nitridation in an autoclave with metallic Na flux at 450–600 °C. X-ray powder diffraction (XRD) recorded the evolution process of the reaction from precursor NH₄VO₃ to hexagonal V₂O₃ and then to NaCl-type VN. In addition, the products were characterized by X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM).     

Electrical characteristics of Li(Ni7/10Fe3/10)VO4 ceramics

The compound [Li(Ni_7/10Fe_3/10)VO₄] was produced by a solution-based chemical route whose electrical properties were investigated using complex impedance spectroscopy technique. X-ray diffraction study reveals an orthorhombic unit cell structure of the compound. Complex electrical impedance analysis exhibits: (i) grain interior, grain boundary and electrode-material interface contributions to electrical response and (ii) the presence of temperature dependent electrical relaxation phenomena in the material. Electrical conductivity study indicates that electrical conduction in the material is a thermally activated process.     

High permittivity and low dielectric loss of the Ca1−xSrxCu3Ti4O12 ceramics

The Ca_1−xSr_xCu₃Ti₄O₁₂ (CSCTO) giant dielectric ceramics were prepared by conventional solid-state method. X-ray diffraction patterns revealed that a small amount of Sr²⁺ (x < 0.2) had no obvious effect on the phase structure of the CSCTO ceramics, while with increasing the Sr²⁺ content, a second phase of SrTiO₃ appeared. Electrical properties of CSCTO ceramics greatly depended on the Sr²⁺ content. The Ca_0.9Sr_0.1Cu₃Ti₄O₁₂ ceramics exhibited a higher permittivity (71,153) and lower dielectric loss (0.022) when measured at 1 kHz at room temperature. The ceramics also performed good temperature stability in the temperature range from −50 °C to 100 °C at 1 kHz. By impedance spectroscopy analysis, all compounds were found to be electrically heterogeneous, showing semiconducting grains and insulating grain boundaries. The grain resistance was 1.28 Ω and the grain boundary resistance was 1.31 × 10⁵ Ω. All the results indicated that the Ca_0.9Sr_0.1Cu₃Ti₄O₁₂ ceramics were very promising materials with higher permittivity for practical applications.     

Synthesis and characterization of proton conducting Sr(Ce1−xZrx)0.95Yb0.05O3−δ by the citrate method

The citrate method was used to synthesize Sr(Ce_1−xZr_x)_0.95Yb_0.05O_3−δ (x = 0.1, 0.2, 0.3, 0.4) and to avoid the drawbacks of the conventional solid state reaction method. The products were characterized by thermal analysis (TG-DTA), X-ray diffraction (XRD), scanning electron microscopy (SEM) and electron probe X-ray microanalyzer (EPMA). The results indicate that the citrate method is an advantageous route in producing Sr(Ce_1−xZr_x)_0.95Yb_0.05O_3−δ materials. Sr(Ce_0.9Zr_0.1)_0.95Yb_0.05O_3−δ powders are composed of nanoscaled crystallites with the average grain size in the range of 60–70 nm. Single phase is confirmed over the whole x range. In addition, chemical stability against CO₂ and electrical conduction behavior of the sintered Sr(Ce_1−xZr_x)_0.95Yb_0.05O_3−δ ceramics were investigated. The chemical stability of the ceramics against CO₂ is certified to increase with the increase in zirconium content. Impedance spectroscopy was used to study the electrical conduction behavior of Sr(Ce_0.9Zr_0.1)_0.95Yb_0.05O_3−δ ceramic.     

Relationship between structure and properties in high-temperature Bi(Al0.5Fe0.5)O3-PbTiO3 piezoelectric ceramics

Ceramic samples of xBi(Al_0.5Fe_0.5)O₃-(1 − x)PbTiO₃ (BAF-PT, x = 0.05-0.5) solid solutions were fabricated using the conventional solid state reaction method. X-ray diffraction analysis revealed that all compositions can form single perovskite phase with tetragonal symmetry. The relationship between the tetragonal lattice parameters, tetragonality c/a, cell volume, and ferro-piezoelectric characterization as a function of x was systematically investigated. The BAF modification can effectively improve the poling condition at a proper BAF content. A combination of piezoelectric constant of d₃₃ (50-60 pC/N), electromechanical planar coupling coefficients of k_p (20.3-22.5%), and high Curie temperature T_c (>478 °C) suggested that BAF-PT could be a good candidate for high-temperature piezoelectric applications.     

Simple hydrothermal synthesis and sintering of Na0.5Bi0.5TiO3 nanowires

Single-crystalline Na_0.5Bi_0.5TiO₃ (NBT) nanowires, with diameters of 100 nm and lengths of about 4 μm, were synthesized by using a simple hydrothermal method. Phase composition, morphology and microstructure of the as-prepared powders were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscope (TEM). The effects of reaction temperature and reaction time on precipitation of the NBT nanowires were investigated. It was found that reaction time significantly influenced the growth behavior of the powders in the hydrothermal system. Based on the experimental results, the one-dimensional (1D) growth mechanism of the NBT was governed by a dissolution-recrystallization mechanism. NBT ceramics derived from the nanowires showed typical characteristics of relaxor ferroelectrics, with diffuseness exponent γ of as high as 1.73.     

Phase constituents and microstructure of laser cladding Al2O3/Ti3Al reinforced ceramic layer on titanium alloy

Laser cladding of the Fe₃Al + TiB₂/Al₂O₃ pre-placed alloy powder on Ti-6Al-4V alloy can form the Ti₃Al/Fe₃Al + TiB₂/Al₂O₃ ceramic layer, which can greatly increase wear resistance of titanium alloy. In this study, the Ti₃Al/Fe₃Al + TiB₂/Al₂O₃ ceramic layer has been researched by means of electron probe, X-ray diffraction, scanning electron microscope and micro-analyzer. In cladding process, Al₂O₃ can react with TiB₂ leading to formation of amount of Ti₃Al and B. This principle can be used to improve the Fe₃Al + TiB₂ laser cladded coating, it was found that with addition of Al₂O₃, the microstructure performance and micro-hardness of the coating was obviously improved due to the action of the Al-Ti-B system and hard phases.     

Synthesis and functional properties of the Ni1−xMnxFe2O4 ferrites

Nanocrystalline Ni_1−xMn_xFe₂O₄ (x = 0; 0.17; 0.34; 0.5) ferrite powders were successfully synthesized using the sol-gel combustion method, by using nitrates as cations source and citric acid (C₆H₈O₇) as combustion/chelating agent. The reaction advancement was observed by means of IR absorption spectroscopy, by monitoring two characteristic bands for the spinel compounds at about 600 cm⁻¹ and 400 cm⁻¹, respectively. The as-synthesized powders were characterized by IR spectroscopy, X-ray diffraction (XRD) and scanning electronic microscopy (SEM). The magnetic study shows that the saturation magnetization decreases with increasing the Mn addition, as result of the particle size reduction. The dielectric properties were measured as a function of frequency in the range of 10 Hz to 1 MHz. The real part of permittivity has values of ∼88 at 1 kHz and ∼7 at 1 Hz for x = 0. An increasing dielectric permittivity with increasing the amount of Mn is observed. For all the investigated compositions, both the real and imaginary parts of permittivity decrease with frequency.     

Origin of giant dielectric constant in Ba[(Fe1−xCox)1/2Nb1/2]O3

The X-ray diffraction Rietveld refinement of Ba[(Fe_1−xCo_x)_1/2Nb_1/2]O₃ with 0 ≤ X ≤ 1 shows cubic structure formation with space group P_m3_m. No distinct tilting of oxygen octahedron is observed. The dielectric measurement of such a cubic system exhibited giant values (?′ > 10⁴) in the temperature range of 298-483 K and frequency range of 10²-10⁵ Hz. An analysis of the permittivity, electric modulus, and electrical conductivity properties in these systems confirmed the presence of oxygen vacancies induced dipolar relaxation. Our investigations show that the observed extremely high dielectric constant values are predominantly the result of oxygen vacancies induced dipoles produced at the grain boundaries. Additional significant intrinsic contributions to the permittivity comes from the directly doped electrons at the unit cell, as indicated by the enhancement in the observed values of the permittivity on replacement of Fe³⁺ (3d⁵) by Co³⁺ (3d⁶). The contributions of the doped free charges and the oxygen vacancy induced dipoles are separated using the Jump Relaxation Model.     

Synthesis and conductivity of GdPO4 nanorods: Impacts of particle size and Ca doping

A series of Gd_1−xCa_xPO₄·nH₂O nanorods were prepared using a simple hydrothermal reaction which was optimized by tuning the pH values of the precursor. The resulted nanorods were characterized by X-ray diffraction, transmission electron microscopy, Fourier transformation infrared spectroscopy, and alternative current impedance technique. It is demonstrated that all Gd_1−xCa_xPO₄·nH₂O nanorods crystallized in a pure hexagonal structure. For x = 0, the particle dimension decreased with increasing the pH value. For x > 0, the solid solution limit of Ca²⁺ in GdPO₄·nH₂O nanorods was about 3 mol%, below which the lattice volume increased with increasing the doping level of Ca²⁺. The conductivities of nanorods were highly dependent on both the particle size and Ca²⁺ concentration, as indicated by the increased conductivity as particle size reduces or Ca²⁺ doping level increases. These observations were understood in terms of the dehydration and the introduction of HPO₄²⁻ defects by Ca²⁺ doping.     

Ba4In2−x(CO3)1+xO6−2.5x and Ba4In0.8Cu1.6(CO3)0.6O6.2—new indium oxycarbonates closely related to n=3 Ruddlesden–Popper phases

Investigations of phase relations in the Ba-rich part of the In₂O₃–BaO(CO₂)–CuO pseudo-ternary system at 900 °C have revealed the existence of new indium–copper oxycarbonate – Ba₄In_0.8Cu_1.6(CO₃)_0.6O_6.2. Rietveld refinement of the X-ray powder diffraction data combined with infrared studies gives evidence that this phase is a oxycarbonate crystallising in the tetragonal structure (space group I4/mmm) with unit cell parameters: a=4.0349(1) Å and c=29.8408(15) Å. In the binary part of the In₂O₃–BaO(CO₂) system we have identified the occurrence of Ba₄In_2−x(CO₃)_1+xO_6−2.5x oxycarbonate solid solution showing a crystal structure also described by I4/mmm space group, but with the unit cell parameters: a=4.1669(1) Å and c=29.3841(11) Å for x=1. The existence range of this phase, −0.153<x<0.4, includes chemical compositions of earlier found phases: Ba₅In_2+xO_8+0.5x with 0≤x≤0.45 (known as the -solid solution), as well as the binary Ba₄In₂O₇ phase. The crystal structures of both new oxycarbonates are isomorphic and related to n=3 member of the Ruddlesden–Popper family.     

Structural, morphological and electrical properties of spray deposited CdIn2Se4 thin films

Semiconducting n-CdIn₂Se₄ thin films have been deposited on to the amorphous and fluorine doped tin oxide (FTO) coated glass substrates using spray pyrolysis technique. The influence of solution concentration on to the photoelectrochemical, structural, morphological, compositional, thermal and electrical properties has been investigated. The PEC characterization shows that the short circuit current (I_sc) and open circuit voltage (V_oc) are at their optimum values (I_sc = 1.04 mA and V_oc = 409 mV) at the optimized precursor concentration (12.5 mM). The structural analysis shows the films are polycrystalline in nature having cubic crystal structure. The average crystallite size determined was in the range of 50-66 nm. Surface morphology and film composition have been analyzed using scanning electron microscopy and energy dispersive analysis by X-rays, respectively. The addition of solution concentration induces a decrease in the electrical resistivity of CdIn₂Se₄ films up to 12.5 mM solution concentration. The type of semiconductor was examined from thermoelectric power measurement.     

Structural investigation of the alluaudite-like mixed-valence iron phosphate: Na1.25Mg1.10Fe1.90(PO4)3

A new mixed-valence iron phosphate Na_1.25Mg_1.10Fe_1.90(PO₄)₃ has been synthesized as single crystals by a flux technique and its structure has been refined from X-ray data to a residual R₁ = 0.032. The compound crystallizes in the monoclinic space group C2/c with the parameters: a = 11.7831(3) Å, b = 12.4740(3) Å, c = 6.3761(2) Å, β = 113.643(2)° and Z = 4. The structure belongs to the alluaudite structural type, and thus it obeys to the X(2)X(1)M(1)M(2)₂(PO₄)₃ general formula. The X(2) and X(1) sites are occupied by sodium while the M(1) and M(2) sites feature a statistical distribution of iron and magnesium.

Additional information about the cation distribution has been extracted from a Mössbauer spectroscopy study which confirmed the mixed valency of the compound. A magnetic susceptibility study has also been undertaken and has shown the compound to be antiferromagnetic with a Neel temperature of about 35 K.     

High temperature transformations of the Au7Cu5Al4 shape-memory alloy

The β-phase of Au₇Cu₅Al₄ undergoes a reversible shape-memory phase transformation, however there has been some uncertainty regarding the crystal structure or structures of the parent phase. Here we show that, under equilibrium conditions, the parent phase possesses the L2₁ structure between its A_p (about 79 °C) and ∼630 °C, and the B2 primitive cubic structure between ∼630 °C and its melting point. It melts directly from B2 into the liquid state and hence never achieves the random bcc A2 structure that has been previously mooted. Splat-cast samples of the alloy are martensitic, proving that development of equilibrium order and defect concentration are not pre-requisites for the A → M transformation to occur.     

Structural and piezoelectric properties of LiNbO3-modified BiScO3–PbTiO3 ceramics

Piezoelectric perovskite materials based on the solid solution (1 − x)BiScO₃–xPbTiO₃ (BSPT) have been attracting attention for their high Curie temperature (T_c = 450 °C) and excellent piezoelectric properties. The LiNbO₃ (LN), which has a T_c as high as 1150 °C, has been recently reported forming a phase pure perovskite solid solution with some perovskite structure compounds. In the current work, the effects of LN substitution on the structural and electrical properties of BSPT ceramics were investigated in the 0.36BiScO₃–0.64{(1 − x)PbTiO₃–xLiNbO₃} (BSPTLNx) system. The results of LN addition in the BSPT ceramics show significant enhancement of the piezoelectric properties. The piezoelectric constant d₃₃, planar electromechanical coupling coefficient and remnant polarization P_r values reached 465 pC/N, 0.57 and 48 μC/cm², respectively, for x = 0.04. The T_c gradually decreases with increasing LN content in the BSPTLNx system, due to the structure transform from the tetragonal to the rhombohedral. A typical relaxor behavior is also produced with the LN substitution in the BSPTLNx system.     

Effects of Al and Al4C3 contents on combustion synthesis of Cr2AlC from Cr2O3-Al-Al4C3 powder compacts

Preparation of the ternary carbide Cr₂AlC was conducted by combustion synthesis in the mode of self-propagating high-temperature synthesis (SHS) from the Cr₂O₃-Al-Al₄C₃ powder compact. Effects of the contents of Al and Al₄C₃ on the product composition and combustion behavior were studied by formulating the reactant mixture with a stoichiometric proportion of Cr₂O₃:Al:Al₄C₃ = 3:5x:y, where x and y varied from 1.0 to 1.5. When compared to those of the powder compact with Cr₂O₃:Al:Al₄C₃ = 3:5:1 (i.e., x = y = 1.0), the combustion temperature and reaction front velocity increased with content of Al, but decreased with that of Al₄C₃. Besides Cr₂AlC and Al₂O₃, the final products always contained a secondary phase Cr₇C₃ that was substantially reduced by adopting additional Al and Al₄C₃ in the reactant compacts. For the sample with Cr₂O₃:Al:Al₄C₃ = 3:7.5:1 (x = 1.5), solid state combustion reached a peak temperature of 1245 °C and yielded Cr₂AlC with a trivial amount of Cr₇C₃. Although Cr₇C₃ was lessened by introducing extra Al₄C₃, the increase of Al₄C₃ from y = 1.1 to 1.5 produced almost no further reduction of Cr₇C₃ in the final product. This is partly attributed to the low combustion temperature in the range of 1065-1095 °C for the samples with additional Al₄C₃, and in part, due to the role of Al₄C₃ which might react with Cr to form Cr₇C₃, Cr₂Al, and Cr₂AlC.