Effects of sintering method and BiFeO3 dopant on the dielectric and ferroelectric properties of BaTiO3–BiYbO3 based solid solution ceramics

(0.95–x) BaTiO₃–0.05 BiYbO₃–x BiFeO₃ (x?=?0, 0.01, 0.02, and 0.04) (abbreviated as (0.95–x) BT–0.05 BY–x BFO) ceramics were fabricated by conventional sintering (CS) and microwave sintering (WS) methods. Effects of sintering method and BFO dopant on the microstructure and electric properties of (0.95–x) BT–0.05 BY–x BFO ceramics were comparatively investigated. X-ray diffraction showed that all CS and WS samples presented a single perovskite phase. It was also found that WS ceramics possessed denser microstructure and finer grains compared to CS samples as indicated by the surface morphology characterization. Dielectric measurements revealed that all samples exhibited the weak relaxation behavior; however, the degree of relaxation behavior of BT–BY based ceramic could be strengthened by addition of BFO and by WS method. Moreover, the temperature and frequency stability could be improved with doped BFO. The density of 0.93BT–0.05BY–0.02BFO ceramic was found to be the largest while that of 0.94BT–0.05BY–0.01BFO ceramic was the smallest, thus, the dielectric constant of 0.93BT–0.05BY–0.02BFO was significantly larger than that of 0.94BT–0.05BY–0.01BFO and 0.94BT–0.05BY–0.04 BFO ceramics. minimum dielectric constant of (0.95–x) BT–0.05 BY–x BFO ceramic was obtained at x?=?0.01. Ferroelectric measurements indicated that all samples showed the slim hysteresis loop. The remnant polarization (P_r) and coercive field (E_C) of (0.95–x) BT–0.05 BY–x BFO ceramics first decreased and then increased with increasing x,the minimum values were obtained at x?=?0.01. Moreover, P_r and E_C of WS ceramics were slightly larger than those of CS ceramics, indicating that higher density and larger grain sizes contributed to enhancing the ferroelectric characteristic. These findings indicate that addition of moderate amount of BFO and use of WS technique can strengthen the degree of relaxation behavior and improve the ferroelectric properties of BT–BY based ceramics.     

Structural,electric and multiferroic properties of Sm-doped BiFeO3 thin films prepared by the sol–gelprocess

Pure polycrystalline Bi_1−xSm_xFeO₃ (BSFO) (x=0–0.12) thin films were successfully prepared on FTO/glass substrates by the sol–gel method. The influence of Sm doping on the structure, dielectric, leakage current, ferroelectric and ferromagnetic properties of the BSFO films was investigated. X-ray diffraction analysis and FE-SEM images both reveal a gradual rhombohedra to pseudo-tetragonal phase transition with the increase of Sm dopant content. On one hand, a proper amount of Sm doping can decrease the leakage current densities of the BSFO thin films. On the other hand, excess Sm substitution for Bi will lead to multiphase coexistence in the film, the lattice inhomogeneity results in more defects in the film, which can increase the leakage current density. The result shows that defects in the complexes lead to electric domain back-switching in the BSFO_x=0.06 thin film, resulting in a decreased dielectric constant, leakage current and remanent polarization. The BSFO_x=0.09 thin film is promising in practical application because of its highest dielectric constant, remanent polarization and remanent magnetization of 203–185, 70 μC/cm² and 1.31 emu/cm³, respectively.     

Influence of O2 pulse on the β-Ga2O3 films deposited by pulsed MOCVD

β-Ga₂O₃ films were deposited on c-plane sapphire substrates by pulsed MOCVD, and the TEGa and O₂ were alternately delivered to the reactor as two pulses. During the growth process, the Ga pulse was kept at 0.1 min, and the O₂ pulse was set at 0.1, 0.2 and 0.3 min, respectively. XRD showed that the β-Ga₂O₃ films still grew preferentially along the (?201) crystal plane family, and no other crystal orientations were observed. The β-Ga₂O₃ films had uniform surface morphology, and grain size increased slightly with the increasing O₂ pulse. XRD rocking curves indicated that the β-Ga₂O₃ film deposited at 0.2 min pulse of O₂ had the best crystalline quality. The PL spectra of all β-Ga₂O₃ films presented the broad UV–visible photoluminescence region from 250 to 800 nm. Three obvious main photoluminescence peaks were observed, corresponding to UV, blue and green emission, respectively. Photodetector was fabricated from the β-Ga₂O₃ film deposited at 0.2 min pulse of O₂, showing stable photoelectric performance, and the photo-dark current ratio was as high as 1.7 × 10⁵ at 15 V.     

Structural and electrochemical characterization of α-MoO3 nanorod-based electrochemical energy storage devices

Orthorhombic molybdenum trioxide (α-MoO₃) nanorods have been synthesized on a large scale by a hydrothermal method for electrochemical energy storage supercapacitor devices. The electrochemical properties of nanorods synthesized at different temperatures were investigated using cyclic voltammetry. The effects of synthesis temperature, scan rate and different scan cycles on the cyclic voltammograms were systematically studied. Nanorods synthesized at 180 °C for 6 h show the best electrochemical properties compared to those synthesized at other temperatures.     

Investigation of the effect of ZrO2 and ZrO2/Al2O3 additions on the hot-pressing and properties of equimolecular mixtures of α- and β-Si3N4

In this work, hot-pressing of equimolecular mixtures of α- and β-Si₃N₄ was performed with addition of different amounts of sintering additives selected in the ZrO₂–Al₂O₃ system. Phase composition and microstructure of the hot-pressed samples was investigated. Densification behavior, mechanical and thermal properties were studied and explained based on the microstructure and phase composition. The optimum mixture from the ZrO₂–Al₂O₃ system for hot-pressing of silicon nitride to give high density materials was determined. Near fully dense silicon nitride materials were obtained only with the additions of zirconia and alumina. The liquid phase formed in the zirconia and alumina mixtures is important for effective hot-pressing. Based on these results, we conclude that pure zirconia is not an effective sintering additive. Selected mechanical and thermal properties of these materials are also presented. Hot-pressed Si₃N₄ ceramics, using mixtures from of ZrO₂/Al₂O₃ as additives, gave fracture toughness, K_IC, in the range of 3.7–6.2 MPa m^1/2 and Vicker hardness values in the range of 6–12 GPa. These properties compare well with currently available high performance silicon nitride ceramics. We also report on interesting thermal expansion behavior of these materials including negative thermal expansion coefficients for a few compositions.     

Influence of the heat treatment on mechanical properties and oxidation resistance of SiC–Si3N4 composites

The basic mechanical properties and oxidation behaviour of liquid-phase-sintered SiC–Si₃N₄ composites were investigated as a function of the heat treatment at oxidising condition at 1350 °C/0–204 h. The results were compared to those obtained for a reference silicon carbide material, prepared by the same fabrication route. The heat treatment at higher temperature had a positive effect on fracture toughness values but no changes of hardness were observed. It was shown that the oxidation resistance increases with increasing temperature of heat treatment from 1650 °C to 1850 °C. Oxidation always followed parabolic rate law indicating diffusion as the rate limiting mechanisms. The addition of silicon nitride content had no significant influence on oxidation resistance of SiC–Si₃N₄ composites.     

Influence of deposition parameters on the dielectric properties of rf magnetron sputtered Ba(ZrxTi1−x)O3 thin films

Ba(Zr_xTi_1−x)O₃ (BZ_xT_1−x in short) thin films have been deposited on Pt/Ti/SiO₂/Si substrates by radio frequency magnetron sputtering and their dielectric properties have been characterized as a function of sputtering parameters. The BZ_xT_1−x thin films are amorphous when sputtered at rf power (R_p)=100 W and substrate temperature (S_T)=300 °C. The crystalline phase of the BZ_xT_1−x thin films appears when the substrate temperature increases from 300 to 400 and 500 °C, respectively, and the films have a high degree of (100) preferred orientation. The dielectric constant decreases with increasing measurement temperature, irrespective of the rf power and Zr content of the BZ_xT_1−x thin films. The BZ_0.3T_0.7 thin films have a low dielectric loss tangent irrespective of the sputtering parameters. The dielectric constant of the BZ_0.3T_0.7 thin film increases with increasing Zr·(Zr+Ti)⁻¹ ratio and deposition temperature but decreases with increasing working pressure. Besides, the dielectric constant suddenly increases from 244.0 to 284.1 when the rf power increases from 100 to 130 W, then it decreases from 284.1 to 270.0 when the rf power increases from 130 to 160 W. The dielectric constant also suddenly increases from 164.1 to 281.5 when the sputtering gas contains O₂ from 0 to 10%, but its variation is insignificant when the sputtering gas contains O₂ from 10 to 20%.     

Influence of initial pH on the microstructure of YBa2Cu3O7−x superconducting thin films derived from DEA-aqueous sol–gel method

A fluorine-free aqueous sol–gel technique was used to fabricate YBCO superconducting thin films. Acetic acid was added in order to modify the complexation process taking place between the metal cations and the organic chelating agents. The electrical resistance and the pH value were used as indicators of the quality of the precursors. When pH=6.5, the precursor solution had the lowest resistance, implying a good ionization of the starting metal elements. By using the optimal precursor, the film was found to have very small sized particles after pyrolysis. Consequently, the annealed YBCO films are characterized by a sharp superconducting transition with a Jc (77 K) of 0.25 MA/cm².     

Effect of plating parameters on the properties of pulse electrodeposited Ni–TiN thin films

The influence of pulse plating parameters on the microstructure, microhardness, and properties of the Ni–TiN thin films was investigated by transmission electron microscopy (TEM), atomic force microscopy (AFM), X–ray diffraction (XRD), scanning electron microscopy (SEM), and corrosion and wear tests. The results indicated the Ni–TiN thin films prepared via electrodeposition at 4 A/dm² current density to show an optimum microhardness and TiN content values of 984.7 HV and 8.69 wt%, respectively. The average grain sizes of Ni and TiN in the films obtained at 200 Hz were 127.8 and 48.5 nm, respectively. Numerous large pores can be noticed in the films prepared at pulse frequencies of 200 Hz and 500 Hz, whereas only a few small pits are visible on the surface of the Ni–TiN thin films deposited at 800 Hz. The films prepared at 20% duty cycle experienced the least weight loss.     

Magnetoelectric properties of 0.5BiFeO3–0.5Pb(Fe0.5Nb0.5)O3 solid solution

Magnetoelectrics are materials that join magnetic and electric orderings in the same phase. They exhibit magnetoelectric coupling which is important from the fundamental and practical point of view. The subject of the paper is a presentation of magnetic, electric and magnetoelectric properties of 0.5BiFeO₃–0.5Pb(Fe_0.5Nb_0.5)O₃ solid solution. The obtained material belongs to oxide perovskite magnetoelectrics of relatively high magnetic and electric ordering temperatures. Both temperatures are considerably above room what suggests potential application possibilities of the material. The magnetic properties were investigated using Mössbauer spectroscopy and magnetization measurements. The solid solution is an antiferromagnet with incomplete compensated magnetic moments. The electrical properties were determined using impedance spectroscopy analysis. There is an observed change of the electrical properties at the magnetic ordering temperature what indicates magnetoelectric coupling in the system. The electrical conductivity mechanism is also proposed. Magnetoelectric voltage coefficient was determined and possible explanation of its changes was proposed.     

High energy density capacitors based on 0.88BaTiO3–0.12Bi(Mg0.5, Ti0.5)O3/PbZrO3 multilayered thin films

Multilayered thin films consisting of both 0.88BaTiO₃–0.12Bi(Mg_0.5,Ti_0.5)O₃ ferroelectric layers and PbZrO₃ antiferroelectric layers were prepared by sol–gel method, exhibiting high dielectric permittivity, large polarization, high recoverable energy storage density and high energy storage efficiency. A maximum polarization of 93 μC/cm², recoverable energy storage density of 24.7 J/cm³ and energy storage efficiency of ~60% have been achieved at an electric field of 1050 kV/cm. Furthermore, the energy storage performance of the multilayered thin films was improved by modified layer-by-layer annealing process, where larger polarization (115 μC/cm²), higher recoverable energy storage density (33 J/cm³) and higher energy storage efficiency (~70%) were obtained.     

Effect of temperature on the growth of α-PbO2 nanostructures

Ordered arrays of α-PbO₂ nanostructures were grown by galvanostatic anodic deposition into the channels of alumina templates. Electrodepositions were performed in an aqueous solution containing lead acetate and sodium acetate at pH 5.4. Bath temperature and electrodeposition time were varied to check their effect on the growth of nanostructures. It has been found that filling of alumina pores is independent of the time and electrodeposition temperature, whilst height and growth kinetics of nanostructures vary with both parameters. Temperature greatly influences morphology: wires grown at room temperature consisted of clusters of particles, leading to poorly compact structures, whilst at 40 °C the formation of compact wires was observed, some of them being partially hollow. Finally, nanowires with a very regular and dense structure were obtained at 60 °C. Also crystalline structure changes with temperature: polycrystalline nanostructures, with a preferential orientation and an average grain size of 21 nm, were obtained at room temperature, whilst at higher temperatures, wires grew almost exclusively along the plane (2 0 0) with an average grain size of approximately 28 nm. Real surface area of nanowires was evaluated from the FEG-SEM images, and it was found two orders of magnitude greater than the geometrical one.     

Microwave dielectric properties of the (BaxSr1−x)TiO3 thin films on alumina substrate

Barium strontium titanate, (Ba_xSr_1?x)TiO₃ (BST) thin films have been prepared on alumina substrate by sol–gel technique. The X-ray patterns analysis indicated that the thin films are perovskite and polycrystalline structure. The interdigital electrode with 140 nm thickness Au/Ti was fabricated on the film with the finger length of 80 μm, width of 10 μm and gaps of 5 μm. The temperature dependence of dielectric constant of the BST thin films in the range from ?50 °C to 50 °C was measured at 1 MHz. The dielectric properties of the BST thin films were measured by HP 8510C vector network analyzer from 50 MHz to 20 GHz.     

Effect of the Nb2O5 content on electrical properties of lead-free BaTiO3–Bi0.5Na0.5TiO3 ceramics

(1−x)BaTiO₃–xBi_0.5Na_0.5TiO₃ (BT–BNT) ceramics were prepared by the solid-state reaction method. With an increase of BNT content, both the Curie temperature and the room temperature resistivity increased. At 1 mol% BNT addition, the sample was not semiconducting, due to Bi₂O₃ volatilization resulting from the decomposition of pre-calcined BNT during sintering. Appropriate extra Nb₂O₅ doping in the raw materials could offset Bi₂O₃ volatilization and neutralize the redundant acceptor Na⁺ ions. When the extra Nb₂O₅ content was 0.6 mg, the sample room-temperature resistivity was 6.3×10³ Ω cm, with the Curie point about 135 °C and a high PTC effect of ∼3 orders of magnitude.     

Effect of sintering temperature on the microstructure and mechanical properties of ZrO2-3 mol%Y2O3 sol–gel films

The microstructural evolution and mechanical properties of ZrO₂-3 mol%Y₂O₃ films were investigated as a function of the sintering temperature in the range from 100 °C to 1500 °C, using a battery of characterization techniques including X-ray diffraction (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM) and nanoindentation. It was found that the crystallization occurs at temperatures close to 300 °C. A gradual increase in the grain and crystallite sizes is observed as the sintering temperature increases up to 1000 °C, and above this sintering temperature the tendency changes abruptly with a rapid increase in these values. Although Young's modulus of the coatings did not change with sintering temperature, a slight decrease was observed in the hardness values above 1000 °C which is attributed to microstructure coarsening. Finally, a slight degradation of the films occurs above 1300 °C, which is due to the occurrence of a process of grain spheroidization.     

Stabilization of α-BiFeO3 structure by Sr2+ and its effect on multiferroic properties

We report a study on the effect of the substitution of Bi³⁺ by Sr²⁺ on the stabilization of R3c structure of Bi_1?xSr_xFeO₃ (0 ≤ x ≤ 0.3, Δx = 0.05), and its effect in the magnetic and dielectric behavior. Stoichiometric mixtures of Bi₂O₃, Fe₂O₃ and SrO were mixed and milled for 5?h using a ball to powder weight ratio of 10:1 by high-energy ball milling. The obtained powder were pressed at 900?MPa to obtain cylindrical pellets and sintered at 800?°C for 2?h. X-ray diffraction and Rietveld refinement were used to evaluate the effect of Sr²⁺ on the crystal structure. In addition, vibrating sample magnetometry (VSM) and dielectric tests were used for describing the multiferroic behavior. The results show that Sr-doped BiFeO₃ particles present rhombohedral structure (R3c) characteristic of α-BiFeO₃ when the doping is below 0.10?mol of Sr. Additionally, a gradual decrease in the amount of secondary phases with the increase of the amount of strontium is observed. For doping concentration higher than 0.15?mol of Sr, a phase transition to an orthorhombic symmetry (β-BiFeO₃, Pbnm) is detected. Besides, changes in relative intensities of reflection peaks planes (110) and (104) are associated with the phase transformations and with the magnetic and dielectric behavior. The α-BiFeO₃ phase show antiferromagnetic behavior and high values of dielectric permittivity, whereas the β-BiFeO₃ phase show a ferromagnetic behavior and low dielectric permittivity.     

Effect of ceramic bonding phases on the thermo-mechanical properties of Al2O3–C refractories

Ceramic bonding phases of non-oxide whiskers can enhance the hot strength and the thermal shock resistance of Al₂O₃–C refractories. In this paper, the effect of different metals on the microstructure and thermo-mechanical properties of Al₂O₃–C refractories has been investigated. Thermodynamic calculation of Al–Si–O–C–N systems shows that Al₄C₃, AlN, SiC and β-Sialon are stable at elevated temperature. AlN with the shape of short column can be generated in Al₂O₃–C refractories with metallic Al, which leads to high hot modulus of rupture (HMOR) and poor resistance to thermal shock. SiC whiskers formed in Al₂O₃–C refractories with metallic Si give rise to low HMOR and good resistance to thermal shock. When metallic Si and Al are added together in the refractories, β-Sialon (z=2) with plane structure can be generated under the action of catalyst (nano-sized Ni). The existence of the catalyst promotes the diffusion of Al and O in Si₃N₄ crystals and contributes to the generation of plane-shaped β-Sialon. The corresponding HMOR and residual cold modulus of rupture respectively increase to about 20 MPa and 10.3 MPa. The plane-shaped β-Sialon can significantly enhance both hot strength and thermal shock resistance of Al₂O₃–C refractories.     

The influence of SrSO4 on the tribological properties of NiCr–Al2O3 cermet at elevated temperatures

The tribological properties of NiCr–40 wt%Al₂O₃ (NC40A) cermet-based self-lubricating composites containing 10 wt%–30 wt% SrSO₄ against alumina ball were investigated at elevated temperatures. The results indicated that the friction coefficients and wear rates were significantly reduced by adding different amounts of SrSO₄ above 200 °C. NC40A–10SrSO₄ composite exhibited satisfactory tribological properties above 200 °C due to the formation of synergistic lubricating films SrAl₄O₇ and NiCr₂O₄ on the contact surface, while low friction coefficient and wear rate of NC40A–30SrSO₄ composite at 400 °C were attributed to the synergistic lubricating effect of Sr₄Al₂O₇, SrAl₂O₄ and NiCr₂O₄.     

Effect of the B2O3 addition on the sintering behavior and microwave dielectric properties of Ba3(VO4)2–Zn1.87SiO3.87 composite ceramics

The effect of the B₂O₃ addition on the low-temperature sintering, microstructure and microwave dielectric properties of the Ba₃(VO₄)₂–Zn_1.87SiO_3.87 composite ceramics was investigated. The results indicate that the addition of B₂O₃ can effectively promote the densification and further improve the microwave dielectric properties of the composite. The low-temperature sintering mechanism was ascribed to the formation of the liquid phase owing to the reaction between the additive B₂O₃ and the residual SiO₂ in the composite. B₂O₃–SiO₂ liquid phases can not only lower the sintering temperature, but also speed up the grain growth of the composite ceramics. The rapid grain growth occurs as the B₂O₃ content is more than 6 wt%. The 3 wt% B₂O₃ doped 0.5Ba₃(VO₄)₂–0.5Zn_1.87SiO_3.87 ceramics can be well sintered at 925 °C and exhibit excellent microwave dielectric properties of Q×f∼40,800 GHz, ε_r∼10 and τ_f∼0.5 ppm/°C.     

Photocatalytic activity of thin TiO2 films deposited using sol–gel and plasma enhanced chemical vapor deposition methods

Thin titanium dioxide films, deposited using RF PECVD and sol–gel techniques, were studied comparatively with respect to their bactericidal as well as self-cleaning properties. The effect of the deposition process on film morphology, chemical and crystalline structure, bactericidal activity and hydrophilic properties was investigated using scanning electron microscopy (SEM), atomic force microscopy (AFM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), surface profilometry, optical microscopy and contact angle measurements. It was found that the bactericidal activity of amorphous TiO₂ films, produced using the RF PECVD method, as either comparable to or better than those of crystalline (anatase) films deposited by means of the sol–gel technique. One reason for such advantageous behavior of plasma deposited materials is thought to be their substantially higher surface roughness, as revealed by AFM measurements. The hydrophilic effect, induced with UV irradiation, was strongest in the case of sol–gel films, but the RF PECVD synthesized coatings were found to be only slightly less hydrophilic. The conclusion follows that both sol–gel and RF PECVD techniques are equally capable of producing titanium dioxide films of high photocatalytic quality.