The phase transitions and ferroelectric behavior of dense nanocrystalline BaTiO3 ceramics fabricated by pressure assisted sintering

Dense nanocrystalline BaTiO₃ ceramics with uniform grain sizes of 30 nm was obtained by pressure assisted sintering. The phase transitions were investigated by Raman scattering at temperatures ranging from −190 to 200 °C. With increasing temperature, similar to 3 μm BaTiO₃ normal ceramics, the successive phase transitions from rhombohedral to orthorhombic, orthorhombic to tetragonal, tetragonal to cubic were also observed in 30 nm BaTiO₃ ceramics. Especially, the coexistence of ferroelectric tetragonal and orthorhombic phases was found at room temperature. The ferroelectric behavior was further characterized by P-E hysteresis loop. The experimental results indicate that the critical grain size of the disappearance of ferroelectricity in nanocrystalline BaTiO₃ ceramics fabricated by pressure assisted sintering is below 30 nm.     

Synthesis and physical behaviour of In2S3 films

In₂S₃ layers have been grown by close-spaced evaporation of pre-synthesized In₂S₃ powder from its constituent elements. The layers were deposited on glass substrates at temperatures in the range, 200–350 °C. The effect of substrate temperature on composition, structure, morphology, electrical and optical properties of the as-grown indium sulfide films has been studied. The synthesized powder exhibited cubic structure with a grain size of 63.92 nm and S/In ratio of 1.01. The films grown at 200 °C were amorphous in nature while its crystallinity increased with the increase of substrate temperature to 300 °C. The films exhibited pure tetragonal β-In₂S₃ phase at the substrate temperature of 350 °C. The surface morphological analysis revealed that the films grown at 300 °C had an average roughness of 1.43 nm. These films showed a S/In ratio of 0.98 and a lower electrical resistivity of 1.28 × 10³ Ω cm. The optical band gap was found to be direct and the layers grown at 300 °C showed a higher optical transmittance of 78% and an energy band gap of 2.49 eV.     

Preparation and optical properties of barium titanate thin films

Barium titanate (BTO) films were prepared by sol-gel spin-coating technique. The crystal structure and optical properties of BTO films have been investigated. The results indicate that the BTO films are single perovskite phase having tetragonal symmetry. The band gap of the BTO films increases with the increasing of layer number and decreasing of solution concentration. The transmittance and band gap of the BTO films annealed at 900 °C is more than that of the BTO films annealed at 700 °C when wavelength is 200-1000 nm. When wavelength is 400-1000 nm, the absorption coefficient α obtained by experiment is higher than that obtained by calculation (close to zero).     

The influence of different fabrication processes on characteristics of excess Bi2O3-doped 0.95 (Na0.5Bi0.5)TiO3–0.05 BaTiO3 ceramics

In this study, we will develop the influences of the excess x wt% (x=0, 1, 2, and 3) Bi₂O₃-doped and the different fabricating process on the sintering and dielectric characteristics of 0.95 (Na_0.5Bi_0.5)TiO₃–0.05 BaTiO₃ ferroelectric ceramics with the aid of SEM and X-ray diffraction patterns, and dielectric–temperature curves. The 0.95 (Na_0.5Bi_0.5)TiO₃–0.05 BaTiO₃+x wt% Bi₂O₃ ceramics are fabricated by two different processes. The first process is that (Na_0.5Bi_0.5)TiO₃ composition is calcined at 850 °C and BaTiO₃ composition is calcined at 1100 °C, then the calcined (Na_0.5Bi_0.5)TiO₃ and BaTiO₃ powders are mixed in according to 0.95 (Na_0.5Bi_0.5)TiO₃–0.05 BaTiO₃+x wt% Bi₂O₃ compositions. The second process is that the raw materials are mixed in accordance to the 0.95 (Na_0.5Bi_0.5)TiO₃–0.05 BaTiO₃+x wt% Bi₂O₃ compositions and then calcining at 900 °C. The sintering process is carried out in air for 2 h from 1120 to 1240 °C. After sintering, the effects of process parameters on the dielectric characteristics will be developed by the dielectric–temperature curves. Dielectric–temperature properties are also investigated at the temperatures of 30–350 °C and at the frequencies of 10 kHz–1 MHz.     

Enhanced magnetic properties of Nd–Fe–B thin films crystallized by heat treatment

Nd₂Fe₁₄B Φ phase crystallites were formed in Nd_16.7Fe_65.5B_17.8 thin films prepared by RF sputtering with subsequent heat treatment. The 2 μm-thick films were deposited onto 0.1 mm Mo sheets at an average substrate temperature (T_s) of 365°C. The enhanced magnetic properties of the magnetically anisotropic thin films were investigated using different heating rates (h_r) of 10°C, 20°C, 50°C and 100°C/min in an annealing experiment. Transformation from the amorphous phase to the crystalline phase is clearly manifested by the formation of fine crystallites embedded as a columnar matrix of Nd₂Fe₁₄B phase. High-resolution scanning electron microscope data of the cross-section of the annealed films show columnar stacking of Nd₂Fe₁₄B crystallites with sizes <500 nm. Transmission electron microscope observations revealed that the microstructure of these films having out-of-plane magnetization consists of uniformly distributed Φ phase with grain size around 400 nm together with small Nd rich particles. This grain size of Φ phase is comparable to the single domain particle diameter of Nd₂Fe₁₄B. Significant change in _iH_c, 4πM_r and 4πM_s with h_r was confirmed. Annealing conditions with a heating rate of 50°C/min to an annealing temperature (T_a) of 650°C for 30 min was consequently found to give optimum properties for the NdFeB thin films. The resulting magnetic properties, considered to be the effect of varying h_r were _iH_c= 1307–1357 kA/m, 4πM_r=0.78–1.06 T and 4πM_s=0.81–1.07 T.     

Trajectory-property relationships in MOD-derived YBCO films

A study of the physical and chemical changes during processing in MOD-derived YBCO films was performed. Fully processed films were 70–85% of theoretical density. The sintering rate increased substantially in the compositional range F/Ba = 1.8–1.5. The activation energy for sintering decreased above a P(H₂O) dependent threshold temperature. XRD indicated this temperature/composition threshold also corresponded to YBCO nucleation, suggesting ex situ YBCO forms in contact with a melt. The ramp rate and P(H₂O) were used to control F/Ba trajectories, which were correlated to performance. The nucleation of YBCO was strongly dependent on processing conditions. Nucleation temperature was varied by at least 60 °C in the study. The optimal YBCO nucleation temperature in the 300–800 nm films was around 725 °C. a-axis grains dominated the microstructures of films where YBCO nucleated at <700 °C. Large second phases, but no a-axis grains, were found when the nucleation temperature was >750 °C.     

Synthesis of nanocrystalline spinel CoFe2O4 via a polymer-pyrolysis route

Nanocrystalline CoFe₂O₄ spinel ferrites were synthesized via the pyrolysis of polyacrylate salt precursors prepared by in situ polymerization of metal salts and acrylic acid. The pyrolytic behaviors of the polymeric precursors were analyzed by use of simultaneous thermogravimetric and differential thermal analysis (TG-DTA). The structural characteristics of the calcined products were obtained by powder X-ray diffraction (XRD), infrared spectroscopy (IR) and transmission electron microscope (TEM). The results revealed that cobalt ferrites had nano-sized morphology and good crystallinity even if calcined at moderate temperature like 500 °C for 3 h. The average size of nanocrystalline cobalt ferrites ranged from 20 to 30 nm with a narrow size distribution, while the particle size increased with the increase of the calcination temperature. Magnetic properties were obtained at room temperature using a vibrating sample magnetometer. The samples exhibited hysteresis loop typical of magnetic behaviors, indicating that the presence of an ordered magnetic structure could exist in the mixed spinel system. The as-calcined cobalt ferrites at 500 °C exhibited the highest magnetization value of 77.4 emu/g at 10 kOe, while the highest remanence and coercivity of 35.6 emu/g and 1445 Oe, respectively, for those calcined at 700 °C were obtained.     

The effect of thickness and annealing condition on the microstructure and magnetic properties of Fe/Pt multilayer thin films

[Fe(0.5 nm)/Pt(0.5 nm)]₄₀, [Fe(1 nm)/Pt(1.5 nm)]₂₀ and [Fe(3 nm)/Pt(3 nm)]₁₀ multilayer were prepared by DC magnetron sputtering. By conventional furnace annealing (CA) at 270–600 °C for various time, all of the films still remained the disordered structure with the soft magnetic phase. By rapid thermal annealing (RTA) at 500 °C for various time, we obtained the [Fe(1 nm)/Pt(1.5 nm)]₂₀ and [Fe(3 nm)/Pt(3 nm)]₁₀ films with L1₂ ordered FePt₃ phase which was almost ferromagnetic at room temperature. However, the [Fe(0.5 nm)/Pt(0.5 nm)]₄₀ films was still disordered state even under RTA. Compared with CA, RTA exposed an outstanding effect on accelerating the phase transition when the film thickness is over [Fe(0.5 nm)/Pt(0.5 nm)]₄₀.     

Magnetic properties of Sm–Co–B-based nanocomposite magnets

The magnetic properties of nanocomposite melt-spun magnets with composition Sm_16−xCo_68+xB₁₆ (x=0–10, 2 at% interval) and Sm₈Co_92−yB_y (y=10–18, 2 at% interval) have been studied systematically. Several ribbons were fabricated with a wheel speed of 50 m/s, followed by annealing in the temperature range of 700–800°C for 2.5–40 min. XRD results and magnetization versus temperature curves showed that almost all of the samples were composed of the tetragonal Sm₂Co₁₄B and rhombohedral SmCo₁₂B₆ phases which are not magnetically hard at room temperature. However, a relatively high coercivity in the range of 3.5–5.5 kOe has been obtained in these samples. The highest coercivity of 5.5 kOe and a very promising β value of −0.28%/°C were obtained in Sm₈Co₇₄B₁₈ ribbons annealed at 750°C for 5 min. The high coercivities are attributed to the small grain size of the 2 : 14 : 1 phase, in which the large surface areas enhance its effective anisotropy, and make it uniaxial type.     

Preparation and dielectric properties of BaZr0.1Ti0.9O3 ceramics with different grain sizes

BaZr_0.1Ti_0.9O₃ ceramics with grain sizes of 0.75 and 2.60?µm have been prepared via solid-state reaction. Optimum parameters for calcination and sintering have been found in order to obtain pure perovskite phase, high density ceramics and homogeneous microstructures. The dielectric data show a diffuse phase transition with a mixed ferroelectric-relaxor character at a maximum at 87–92°C, with a small thermal hysteresis of 2–3°C. A tendency towards a more diffuse character of the ferro–para phase transition towards the full relaxor behaviour is observed as small in the ceramic grain size. Better dielectric properties in the coarse ceramics with higher permittivity up to 14,000 at the transition temperature by comparison with 5000 for the fine one, are observed as a consequence of higher tetragonal distortion and higher density. The differences in the dielectric spectra found for the two grain sizes were interpreted as a consequence of the higher degree of inhomogeneity in the fine ceramics and to different grain boundary properties induced by the different sintering temperatures.     

Ultrasound induced formation of paraffin emulsion droplets as template for the preparation of porous zirconia

The paraffin particles were prepared by quenching process after sonicating the solution of paraffin and water at 80 °C. The resultant paraffin particles were then used as template for the preparation of macroporous zirconia materials. For this, zirconium normal butoxide (ZNB) modified with triethanolamine (TEA) was first hydrolyzed by water containing the dispersed paraffin particles with the surfactant, Sodium di(2-ethylhexyl) sulfosuccinate. This resulted in the formation of a slurry consisting of hydrolyzed sol and paraffin particles. After centrifugation, a cake packed with hydrated sol and paraffin particles were obtained which was then subjected to heat treatment. The sample obtained after heat treatment contained finely dispersed pores in the size range from 40 nm to 2 μm. Moreover, using the present approach it has also been observed that, change in pore size of zirconia wall is possible with a change in size of the paraffin particles. Thus, the present approach is a novel way of producing porous materials as the particle size of the template could be changed and templates become hard when they were molded as compared to the conventional methods in which there is no change in phase for the templates under 100 °C.     

Structure and optical properties of sol–gel derived Gd2O3 waveguide films

Pure and rare earth doped gadolinium oxide (Gd₂O₃) waveguide films were prepared by a simple sol–gel process and dip-coating method. Gd₂O₃ was successfully synthesized by hydrolysis of gadolinium acetate. Thermogravimetric analysis (TGA) and differential thermal analysis (DTA) were used to study the thermal chemistry properties of dried gel. Structure of Gd₂O₃ films annealed at different temperature ranging from 400 to 750 °C were investigated by Fourier transform infrared (FT-IR) spectroscopy, X-ray diffraction (XRD) and transmission electron microscopy (TEM). The results show that Gd₂O₃ starts crystallizing at about 400 °C and the crystallite size increases with annealing temperature. Oriented growth of (4 0 0) face of Gd₂O₃ has been observed when the films were deposited on (1 0 0) Si substrate and annealed at 750 °C. The laser beam (λ=632.8 nm) was coupled into the film by a prism coupler and propagation loss of the film measured by scattering-detection method is about 2 dB/cm. Luminescence properties of europium ions doped films were measured and are discussed.     

Densification and conductivity enhancement of Na4Zr2Si3O12-based solid electrolytes using TiO2 as a sintering aid

Densification of Na₄Zr₂Si₃O₁₂ (NZS) solid electrolytes was performed by dispersing TiO₂ (0.8–5.9 wt. %, corresponding to 5–30 mol %) in NZS powders prior to sintering at 1200°C. Increases in pellet density, from ca. 65 to 94% of the theoretical (X-ray density) value, and in electrical conductivity from 10⁻⁷ to 10⁻⁶ S/cm at 50°C were observed for small additions of TiO₂, which acts as a sintering aid. AC impedance spectroscopy reveals that the enhancement is not a bulk effect but instead is associated with a reduction in inter-granular constriction resistances within porous NZS ceramics. The presence of adsorbed water species in NZS powders prepared via a sol-gel route is found to have a dramatic effect on the conductivity enhancement.     

Relationship between electronic and crystal structure in Cu–Ni–Co–Mn–O spinels: Part A: Temperature-induced structural transformation

Local atomic and crystal structures around Cu and Mn atoms in Mn_1.68Cu_0.6Ni_0.48Co_0.24O₄ spinel samples fabricated by metal–organic decomposition synthesis at different annealing temperatures were investigated by X-ray absorption fine structure analysis. There are two distinct copper cations, Cu¹⁺ and Cu²⁺, both of which maintain tetrahedral coordination. The bond-length distances are Cu¹⁺–O = 2.00 Å and Cu²⁺–O = 1.80 Å. The manganese cations are for the most part octahedral. The spinels prepared at low temperature (600 °C) contain smaller (Mn⁴⁺–O = 1.88 Å) undistorted MnO₆ octahedrons corresponding to Mn⁴⁺ valence, whereas the manganese octahedrons in high-temperature materials (800 °C and higher) were larger and had a pronounced tetragonal distortion pertaining to Mn³⁺ oxidation state (Mn³⁺–O = 1.93 Å and 2.11 Å). By rising the fabrication temperatures, relative concentration of the species of Mn⁴⁺ and Mn³⁺ varies as a result of the reaction represented by Cu¹⁺ + Mn⁴⁺  Cu²⁺ + Mn³⁺, implying irreversible temperature-induced structural transformation. Atomic coordinates in the low-temperature phase are similar to those found in the ideal cubic spinel with oxygen parameter u = 0.27, whereas local environments of the Cu and Mn atom correspond to the tetragonal CuMn₂O₄ phase (space group I4₁/amd). Unlike in CuMn₂O₄, orientation of the lattice distortions is random, however, the long-range cubic spinel structure is retained at all time.     

Defect versus nanocrystal luminescence emitted from room temperature and hot-implanted SiO2 layers

Silicon nanocrystals have been synthesized in SiO₂ matrix using Si ion implantation. Si ions were implanted into 300-nm-thick SiO₂ films grown on crystalline Si at energies of 30–55 keV, and with doses of 5×10¹⁵, 3×10¹⁶, and 1×10¹⁷ cm⁻². Implanted samples were subsequently annealed in an N₂ ambient at 500–1100°C during various periods. Photoluminescence spectra for the sample implanted with 1×10¹⁷ cm⁻² at 55 keV show that red luminescence (750 nm) related to Si-nanocrystals clearly increases with annealing temperature and time in intensity, and that weak orange luminescence (600 nm) is observed after annealing at low temperatures of 500°C and 800°C. The luminescence around 600 nm becomes very intense when a thin SiO₂ sample is implanted at a substrate temperature of 400°C with an energy of 30 keV and a low dose of 5×10¹⁵ cm⁻². It vanishes after annealing at 800°C for 30 min. We conclude that this luminescence observed around 600 nm is caused by some radiative defects formed in Si-implanted SiO₂.     

Magnetic properties in BaFe12O19 nanoparticles prepared under a magnetic field

It was observed that the nanocrystallites of BaFe₁₂O₁₉ formed at 140°C under a 0.25 T magnetic field exhibited a higher saturation magnetization (6.1 emu/g at room temperature) than that of the sample (1.1 emu/g) obtained under zero magnetic field. Both of the two approaches yielded plain-like particles with an average particle size of 12 nm. However, the Curie temperature (T_c), a direct measuring of the strength of superexchange interaction of Fe³⁺–O²⁻–Fe³⁺, increased from 410°C for the nanoparticles prepared without an external field applied to 452°C for the particles formed under a 0.25 T magnetic field, which indicates that external magnetic fields can improve the occupancy of magnetic ions and then increase the superexchange interaction. This was confirmed by electron paramagnetic resonance and Mössbauer spectrum analysis. The results present in this paper suggest that in addition to oxygen defects, surface non-magnetic layer and a fraction of finer particles in the superparamagnetic range, cation vacancies should be responsible for the decreasing of saturation magnetization in magnetic nanoparticles.     

Phase evolution during the melting and recrystallization of ceramic core in the (Bi,Pb)-2223 tape

The phase evolution during melting and recrystallization of (Bi,Pb)₂Sr₂Ca₂Cu₃O₁₀ ((Bi,Pb)-2223) core in a Ag-sheathed monofilamentary tape has been investigated. The tape was fabricated by PIT process with powders containing nearly pure (Bi,Pb)-2223 phase. Short samples were melted at 805 °C, 808 °C, 812 °C, 816 °C, 831 °C, slowly cooled at 1.5 °C/h under flowing 1.6% O₂ balanced with argon and quenched in air at room temperature. X-ray diffraction (XRD) and scanning electron microscopy coupled with energy dispersive spectroscopy (SEM/EDS) were applied for the phase identification. The results show that (Bi,Pb)-2223 core is partially melted into a liquid and alkaline earth cuprates (AECs), mainly 2:1-AEC, at 805 °C, 808 °C, 812 °C, and well reforms directly from the melt during the slow cooling. More (Bi,Pb)-2223 phase is decomposed at temperatures higher than 816 °C, but cannot recrystallize, indicating that a partial melting at some temperatures around a given temperature range is essential to (Bi,Pb)-2223 phase reformation. The melt composition moves from that between “2223” and “2212” stoichiometries towards 2212-like stoichiometry with increasing temperature. This seems to lead to the conclusion that (Bi,Pb)-2223 phase decomposes incongruently into a 2212-like liquid and (Ca,Sr)-cuprates. 2:1-AEC plays the most important role in (Bi,Pb)-2223 melt-recrystallization process. Our results also reveal that plate-like shape (Bi,Pb)-2223 grains can be obtained via melting and recrystallization if the optimum processing conditions are used.     

Remanence of the interparticle interactions and its influence on the microwave absorption in Co-ferrite

Cobalt ferrite nanoparticles were obtained by the sol–gel method at several annealing temperatures: 400, 450, 500, 550 and 600 °C. X-ray diffraction (XRD) and transmission electron microscopy (TEM) showed the formation of the spinel phase with a nanoparticle size in the 17–26 nm range as function of the annealing temperature. The Mössbauer spectra at room temperature showed the presence of a partial inverse spinel structure. Saturation magnetization and the coercive field are strongly dependent on the annealing temperature and they can be associated with variations of the nanoparticles size. Microwave power absorption (MPA) (dP/dH) measurements were carried out as a function of DC field (H_DC) in asymmetric sweeps in the 0 kOeH_DC9 kOe range, at X-band (9.4 GHz), for all annealing temperatures. The large hysteresis in the MPA is due to interparticle interaction associated with its demagnetizing-like nature.     

Temperature‐dependent Raman spectroscopy of BaTiO3 nanorods synthesized by using a template‐assisted sol–gel procedure

In the present work, multiphase polycrystalline BTO nanorods were synthesized using template‐assisted sol–gel deposition and their structural evolution was studied using thermo Raman spectroscopy, X‐ray diffractometry and high‐resolution transmission electron microscopy (HRTEM). In the BTO nanorods, the tetragonal phase was the dominant one, while both Raman and HRTEM indicated a coexistence with the high‐temperature hexagonal polymorph. This phase was stable across the whole of the investigated temperature range (from −95 °C to 200 °C). The investigated nanorods underwent a diffuse phase transition from tetragonal to cubic with respect to the temperature, whereas the final phase‐transition temperature was shifted to higher values compared to that expected for BTO. The low‐temperature orthorhombic‐to‐rhombohedral phase transition was also shifted to higher temperatures. These differences could be explained by the strain induced by the presence of hexagonal nanolamellas intergrown within the tetragonal nanocrystals. This result indicates that the temperature of the ferroelectric phase transition in polycrystalline BTO nanorods can be manipulated by introducing a stable hexagonal phase. Copyright © 2012 John Wiley & Sons, Ltd.     

Improved microstructure, dielectric and ferroelectric properties of microwave-sintered Sr0.5Ba0.5Nb2O6

Ferroelectric strontium barium niobate (SBN) powder was synthesized by solid-state route. The green compacts were sintered in the temperature range 1250–1350 °C in a microwave furnace. The microstructural study, using SEM, revealed the grain size in the range 2–20 μm without microcracks, depending on the sintering temperature. This is in contrast to that obtained conventionally for sintered SBN powder synthesized by solid-state route, which resulted in duplex microstructure with microcracks [N.S. VanDamme, A.E. Sutherland, L. Jones, K. Bridger, S.R. Winzer, J. Am. Ceram. Soc. 74 (1991) 1785; P.K. Patro, A.R. Kulkarni, C.S. Harendranath, Ceram. Int. 30 (2004) 1405; P.K. Patro, Trans. Ind. Inst. Metals 59 (2006) 229]. Impedance analyzer and ferroelectric hysteresis loop tracer were used for the dielectric, ferroelectric, I–V and electric fatigue measurements. Microwave sintering also resulted in a dielectric maxima ε_max 2590 at 1 kHz (compared to 1103 for conventional sintering [P.K. Patro, A.R. Kulkarni, C.S. Harendranath, Ceram. Int. 30 (2004) 1405]) for the sintering temperature of 1350 °C. Similar improvement in microwave-sintered SBN was observed depending on their sintering condition. The origin of this difference is attributed to microstructural differences arising from difference in heating method. In this paper the observed dielectric and ferroelectric behavior have been correlated with different sintering conditions and consequent microstructure due to microwave sintering.