Effect of excess Pb on microstructures and electrical properties of 0.67Pb(Mg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>)O<Subscript>3</Subscript>–0.33PbTiO<Subscript>3</Subscript> ceramics

0.67Pb(Mg_1/3Nb_2/3)O₃–0.33PbTiO₃ (PMNT) ceramics were fabricated by using their powders synthesized through a sol–gel process. Excess Pb(CH₃COO)₂·3H₂O (0, 2, 5, 10 or 15 mol%) was added to the starting materials to study the effect of excess Pb on the microstructures, ferroelectric and dielectric properties of the PMNT ceramics. All the X-ray diffraction peaks can be indexed using perovskite-type PMNT for the ceramics prepared with excess Pb, while the PMNT ceramics with no excess Pb contain a little pyrochlore phase. The PMNT ceramics prepared with 2 mol% excess Pb are dense and uniform and composed of grains ranging from 3 to 7 μm. They exhibit the largest remnant polarization (P _r = 32.1 μC/cm²) and the highest peak dielectric constant (ε _max = 12,725). When more than 2 mol% excess Pb added, the electrical properties of the PMNT ceramics decreased with increasing excess Pb. Too much excess Pb (over 10 mol%) resulted in abnormal grain growth (>20 μm), large pores and residual PbO in amorphous state in PMNT ceramics, and they impaired the ferroelectric and dielectric properties of PMNT ceramics greatly.     

Structural and electrical properties of Ho<Superscript>3+</Superscript>-modified Pb(Zn<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>)O<Subscript>3</Subscript>–9PbTiO<Subscript>3</Subscript> single crystals

Ho³⁺-modified Pb(Zn_1/3Nb_2/3)O₃–9PbTiO₃ (PZN–9PT) single crystals were grown through a flux method. Phase structure and microstructural morphology of the as-grown single crystals were performed by X-ray diffraction analysis and scanning electron microscopy. The refinement of the lattice parameters were obtained by the Rietveld method. The electrical properties of PZN–9PT single crystals were improved significantly by the modification of Ho³⁺ ions. The rhombohedral–tetragonal phase transition temperature, Curie temperature, coercive field at 15 kV cm^?1, and remnant polarization of Ho³⁺-modified PZN–9PT single crystals were increased by 14, 42 K, 2.4 kV cm^?1, and 7.5 μC cm^?2, respectively (i.e., 375.45, 448.45 K, 5.9 kV cm^?1, and 38.40 μC cm^?2, respectively). Furthermore, Lorentz-type law was used to describe the dielectric relaxor behavior of the as-grown single crystals.     

Microwave dielectric properties of Sr<Subscript>0.7</Subscript>Ce<Subscript>0.2</Subscript>TiO<Subscript>3</Subscript>–Sr(Mg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>)O<Subscript>3</Subscript> ceramics

xSr_0.7Ce_0.2TiO₃–(1???x)Sr(Mg_1/3Nb_2/3)O₃ ceramics, referred to xSCT–(1???x)SMN, were successfully produced by conventional solid-state sintered technology. The compounds, belonging to perovskites with a secondary phase of CeO₂, can be detected even with x down to 0.1 of SCT composition. The overall trend for grain growth illustrates the increase with increasing SCT doping level. The Raman peak at 825 cm^?1 splits into two peaks and causes red shift phenomenon. XPS spectra indicate that Ti and Nb ions exist respectively in tetravalence and pentavalence, and Ce ions exist in trivalence and tetravalence. Dielectrics constant (ε _r ) of SCT–SMN ceramics gradually increases with increasing theoretical dielectric polarizabilities. A wider width of the 825 cm^?1 for FWHM of A_1g mode Raman peaks suggests to a lower Q?×?f value. The increasing tolerance factor in agreement with temperature coefficient of resonant frequency (τ _f ), denotes that the rise of perovskite symmetry. The 0.1SCT–0.9SMN ceramic sintered at 1450?°C for 4 h illustrates excellent microwave dielectric properties with ε _r ?~?35.4, Q?×?f?~?11282 GHz and τ _f ?~?1.7 ppm/°C. Activation energies of 0.1SCT–0.9SMN ceramic at 100, 300 and 500 V, are ~0.436, 0.427 and 0.331 eV, respectively, indicative of a decreased trend with external electric field.     

Effect of excess Pb in PbTiO<Subscript>3</Subscript> precursors on ferroelectric and fatigue property of sol–gel derived PbTiO<Subscript>3</Subscript>/PbZr<Subscript>0.3</Subscript>Ti<Subscript>0.7</Subscript>O<Subscript>3</Subscript>/PbTiO<Subscript>3</Subscript> thin films

A series of Pb_(1+x)TiO₃/PbZr_0.3Ti_0.7O₃/Pb_(1+x)TiO₃ (PTO/PZT/PTO) and PbZr_0.3Ti_0.7O₃ (PZT) thin films were prepared by a sol–gel method. Different excess Pb content (x) (x = 0, 0.05, 0.10, 0.15, 0.20) were added to the PbTiO₃ (PTO) precursors to investigate their effect on ferroelectric and fatigue properties of the PTO/PZT/PTO thin films. X-ray diffraction results show that the crystallization behavior of the PTO/PZT/PTO thin films is greatly affected by the excess Pb content (x) in PTO precursors. Topographic images show that the PTO/PZT/PTO thin films with excess Pb content x = 0.10 appears the densest and the most uniform grain size surface morphology. The ferroelectric and fatigue properties of the films correlate straightforwardly to the crystallization behaviors and excess Pb content (x) in the PTO precursors. The excess Pb content (x) in the PTO layers which acts as a nucleation site or seeding layer for PZT films affects the crystallization of the PTO layer and ultimately affects the perovskite phase formation of the PZT films. With the proper excess Pb content (x = 0.10–0.15) in the PTO precursors, the pure perovskite structure PTO/PZT/PTO thin films, with dense, void-free, and uniform fine grain size are obtained, and a well-saturated hysteresis loop with higher remnant polarization is achieved. Using an appropriate Pb content, the fatigue has been avoided by controlling the inter-diffusion and surface volatilization.     

Electrical properties of B site substituted (K<Subscript>0.48</Subscript>Na<Subscript>0.52</Subscript>)(W<Subscript>2/3</Subscript>Bi<Subscript>1/3</Subscript>)<Subscript>x</Subscript>Nb<Subscript>1−x</Subscript>O<Subscript>3</Subscript> piezoceramics

Lead-free (K_0.48Na_0.52)(W_2/3Bi_1/3)_xNb_1−xO₃ (KNN-WBi) piezoceramics with x ranging from 0.004 to 0.010 were synthesized by conventional ceramic processing. The sintered KNN-WBi ceramics showed perovskite structure without detectable secondary phase containing W and Bi. With increasing x, the orthorhombic-tetragonal phase transition temperature (T _O-T) decreased from 200 to 184 °C whereas, the tetragonal-cubic phase transition temperature (T _C) decreased slightly. With the doping of (W_2/3Bi_1/3), the piezoelectric properties were greatly improved and the piezoelectric constants d ₃₃, k _p, Q _m exhibited maximum values of 136 pC/N, 43.3% and 175, respectively at x = 0.008. The KNN-WBi ceramics also exhibited good ferroelectric properties with remnant polarizations P _r higher than 25 μC/cm² and coercive fields E _c lower than 1,000 V/mm. The results strongly suggest that the B site doping of constructed quinquevalent element is an effective method for the investigation of potassium sodium niobate system.     

Aging and thermal stability of [001]<Subscript>c</Subscript>- and [111]<Subscript>c</Subscript>-poled 0.63Pb(Mg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>)O<Subscript>3</Subscript>–0.37PbTiO<Subscript>3</Subscript> single crystals

The aging characteristics and thermal stability of [001]_c- and [111]_c-poled tetragonal 0.63Pb(Mg_1/3Nb_2/3)O₃–0.37PbTiO₃ single crystals have been studied. For [001]_c-poled crystal, the d₃₃, \(\varepsilon _{{33}}^{T}\), k_t, and k₃₃ increase slightly during the aging process due to the gradual depolarization of the single-domain state. On the contrary, the electromechanical properties of [111]_c-poled crystal decrease quickly with the aging time due to the growth and combination of micro-domains. The temperature-dependent electromechanical properties indicate that the [111]_c-poled multi-domain crystal is more stable than [001]_c-poled single-domain crystal. In addition, the second poling can effectively enhance the piezoelectric constant d₃₃ of the [111]_c-oriented multi-domain crystals from 1032 pC/N after the first poling to 1247 pC/N.     

Structural and electrical properties of Bi<Subscript>1/2</Subscript>Na<Subscript>1/2</Subscript>TiO<Subscript>3</Subscript>–BaTiO<Subscript>3</Subscript>–Sr<Subscript>3</Subscript>CuNb<Subscript>2</Subscript>O<Subscript>9</Subscript> lead-free piezoelectric ceramics

The structure, microstructure, field-induced strain, ferroelectric, piezoelectric and dielectric properties of (1 ? x) (Bi_0.5Na_0.5)_0.935Ba_0.065TiO₃–xSr₃CuNb₂O₉ (BNT-BT6.5–xSCN, with x = 0, 0.003, 0.006, 0.009) ceramics were investigated. X-ray diffraction patterns show that all samples are pure perovskite structure and Sr₃CuNb₂O₉ (SCN) effectively diffused into the 0.935Bi_0.5Na_0.5TiO₃–0.065BaTiO₃ (BNT–BT6.5) solid solution which also reflected in the Raman spectra and the energy disperse spectroscopy (EDS) analysis. With the increases of SCN content, the coercive field (E _c  = 18.41 kV/cm) decreases greatly, whereas the remnant polarization (P _r  = 29.11 μC/cm²) increases a little at x = 0.003 which is showed in the polarization hysteresis (P–E) loops, the result indicate that the ferroelectric order would be disrupted. Around critical composition (x = 0.003) at a driving field of 60 kV/cm, a large unipolar strain of 0.29 % with a normalized strain (d ₃₃ ^*  = 483 pm/V) is obtained at room temperature. The results indicate that BNT-BT6.5-xSCN ceramics with excellent properties are promising to replace lead-based piezoelectric ceramics and can be used in practical applications.     

Kinetics of Thermal Transformation of Mg<Subscript>3</Subscript>(PO<Subscript>4</Subscript>)<Subscript>2</Subscript> · 8H<Subscript>2</Subscript>O to Mg<Subscript>3</Subscript>(PO<Subscript>4</Subscript>)<Subscript>2</Subscript>

The kinetics of thermal dehydration of Mg₃(PO₄)₂ · 8H₂O was investigated using thermogravimetry at four different heating rates. The activation energies of the dehydration step of Mg₃(PO₄)₂ · 8H₂O were calculated through the isoconversional Ozawa and Kissinger-Akahira-Sunose (KAS) methods and iterative methods, which were found to be consistent and indicate a single mechanism. The possible conversion function of the dehydration reaction for Mg₃(PO₄)₂ · 8H₂O has been estimated through the Coats and Redfern integral equation, and a better kinetic model such as random nucleation of the “Avrami–Erofeev equation (A _3/2 model)” was found. The thermodynamic functions (ΔH*, ΔG*, and ΔS*) of the dehydration reaction are calculated by the activated complex theory and indicate that it is a non-spontaneous process when the introduction of heat is not connected.     

Optical and photoelectric properties of α-Dy<Subscript>2</Subscript>S<Subscript>3</Subscript> and α-Dy<Subscript>2</Subscript>S<Subscript>3</Subscript>〈Pb〉 films

A process is described for the growth of thin crystalline α-Dy₂S₃ films by thermal evaporation from separate dysprosium and sulfur sources. The films were doped with Pb, and their reflection and transmission spectra were measured at room temperature and photon energies in the range (0.3−5.2) × 10⁻¹⁹ J. The α-Dy₂S₃ films were shown to have an exponential absorption edge. The photoconductivity of the doped films was measured at photon energies in the range (0.3−5.2) × 10⁻¹⁹ J and temperatures from 115 to 400 K.     

Effect of refractory nitride nanoadditives on the properties of (Bi,Pb)<Subscript>2</Subscript>Sr<Subscript>2</Subscript>Ca<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>10+δ</Subscript>

We have investigated the interaction between (Bi,Pb)₂Sr₂Ca₂Cu₃O_10+δ (Bi-2223) and small additions (0.05–0.3 wt %) of nitride powders (TaN, AlN, HfN, NbN, Si₃N₄, TiN, and ZrN) with a particle size from 0.02 to above 0.5 μm and the effect of these nitrides on the microstructure, phase composition, distribution, and morphology of the resulting second-phase inclusions. The concentration and particle size of the nitrides and sintering conditions are shown to influence the superconducting transition temperature T _c, critical current density j _c, irreversible remanent magnetization, bulk density, and mechanical properties of the Bi-2223/nitride composites.     

Phase formation and microstructure of Nd<Superscript>+3</Superscript> doped Pb(Mg<Subscript>1/3</Subscript>Nb<Subscript>2/3</Subscript>)O<Subscript>3</Subscript> prepared by sol–gel method

The aim of this study was to investigate the effects of the rare earth element neodymium on the phase formation and microstructural development of relaxor ferroelectric lead magnesium niobate, Pb(Mg_1/3Nb_2/3)O₃ (PMN) system. Perovskite phase PMN powders were prepared using the sol–gel method and the effect of neodymium doping was investigated at different doping levels ranging from 0.1 mol% to 30 mol%. The precursors employed in the sol–gel process were lead (II) acetate, magnesium ethoxide, and niobium (V) ethoxide. All the experiments were performed at room temperature while the calcination temperatures ranged between 800 °C and 1,100 °C. Results showed that it was possible to obtain the pure perovskite phase at 950 °C using the sol–gel method. Nd⁺³ addition influenced the phase formation and microstructure of the multicomponent system. Pyrochlore was detected along with the perovskite phase above 10 mol% Nd. Results also demonstrated that grain size of the synthesized powders depended on the Nd⁺³ concentration.     

A physicochemical study of the Sb<Subscript>2</Subscript>Se<Subscript>3</Subscript>–Nd<Subscript>2</Subscript>Se<Subscript>3</Subscript> system

We have studied phase relations in the Sb₂Se₃–Nd₂Se₃ system and mapped out its T–x phase diagram using differential thermal analysis, X-ray diffraction, microstructural analysis, microhardness tests, and density measurements. The system contains one compound, with the composition NdSbSe₃, which melts incongruently at 865 K and crystallizes in orthorhombic symmetry with the following lattice parameters: а = 12.77(1) Å, b = 14.08(1) Å, and c = 5.82(5) Å (Z = 8, ρ_meas = 6.20 g/cm³, ρ_x = 6.38 g/cm³). At room temperature, the Nd₂Se₃ solubility in Sb₂Se₃ is 5 mol % and the Sb₂Se₃ solubility in Nd₂Se₃ is 2.5 mol %. The Sb₂Se₃–Nd₂Se₃ system has a eutectic located at 15 mol % Nd₂Se₃, with a melting point at 755 K. The electrical conductivity and thermoelectric power of the (Sb₂Se₃)_1–x (Nd₂Se₃) _x solid solutions have been measured as functions of temperature.     

SmAlO<Subscript>3</Subscript> + Ba(Zn<Subscript>1/2</Subscript>Nb<Subscript>2/3</Subscript>)O<Subscript>3</Subscript>: microwave ceramic composite

The 0.1SmAlO₃ + 0.9Ba(Zn_1/2Nb_2/3)O₃ composite is prepared through the solid state ceramic route. The structure of the materials is studied using X-Ray diffraction analysis. The microstructure is studied using scanning electron microscopy and the elemental composition by energy dispersive spectrometry. The dielectric properties in the radio and microwave frequencies are measured. The photoluminescence property of the sample is also analyzed. The material has dielectric constant (ε _r ) = 37, temperature coefficient of resonant frequency (τ _f ) = +25 ppm/°C and high quality factor. The measured values of ε _r and τ _f are compared with the corresponding theoretical values. The composite is useful in the field of optoelectronics and microwave communication.     

Spectroscopic characterisation of local structure in Y<Subscript>2</Subscript>O<Subscript>3</Subscript>–B<Subscript>2</Subscript>O<Subscript>3</Subscript>–Bi<Subscript>2</Subscript>O<Subscript>3</Subscript> glasses doped with gadolinium

Gadolinium doped bismuth borate glasses containing up to 30 mol% Y₂O₃ were prepared by fast melt quenching method. The effect of yttrium on the local order in 3B₂O₃ · Bi₂O₃ and B₂O₃ · Bi₂O₃ glass matrices, particularly on the bismuth sites, was investigated by infrared (IR) spectroscopy and electron paramagnetic resonance (EPR) of Gd³⁺ ions. The IR results show that the local structure is more ordered in the glass system with higher bismuth content and the progressive addition of yttrium increases the local disorder in both bismuth–borate glass matrices. The EPR results indicate that Gd³⁺ ions occupy both bismuth and yttrium sites and reflect the same structural disorder like that suggested by IR results.     

Effect of sintering temperatures on properties of BaO–B<Subscript>2</Subscript>O<Subscript>3</Subscript>–SiO<Subscript>2</Subscript>–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> glass/silica composites for CBGA package

BaO–B₂O₃–SiO₂–Al₂O₃ (BBSA) glass/silica composites synthesized by solid-state reaction method were developed for CBGA packages, and the effects of sintering temperature (900–950 °C) on the phase transformation, microstructure, thermal, mechanical and electrical properties were investigated. XRD results show that the major phases quartz and cristobalite, and the minor phase BaSi₂O₅ are detected in BBSA composites. Furthermore, it was found that the quartz phase transforms to cristobalite phase at 930–940 °C. The formation of cristobalite phase with higher coefficient of thermal expansion (CTE) led to the increase of CTE value of BBSA composites. However, excessive cristobalite phase content would degrade the mechanical properties and the linearity of thermal expansion of the ceramics. BBSA composites sintered at 920 °C exhibited excellent properties: low dielectric constant and loss (ε_r = 6.2, tanδ = 10^?4 at 1 MHz), high bending strength (179 MPa), high CTE (12.19 ppm/°C) as well as superior linearity of the thermal expansion.     

Influence of Bi substitution on microwave dielectric properties of BaO–La<Subscript>2</Subscript>O<Subscript>3</Subscript>–Sm<Subscript>2</Subscript>O<Subscript>3</Subscript>–TiO<Subscript>2</Subscript> ceramics

The influences of Bi substitution on microwave dielectric properties of Ba₄(La_0.5Sm_0.5)_9.33Ti₁₈O₅₄ solid solutions were investigated. Dielectric ceramics with general formula Ba₄(La_(0.5−z)Sm_0.5Bi _z )_9.33Ti₁₈O₅₄, z = 0.0–0.2 were prepared by conventional solid state route. The structural analysis of all the samples was carried out by X-ray diffraction and scanning electron microscopy. The dielectric properties were investigated as a function of Bi contents using open-ended coaxial probe method in the frequency range 0.3–3.0 GHz at room temperature. Dielectric constant varies from 83 to 88 and loss tangent from 2.1 × 10⁻³ to 5.5 × 10⁻³ at 3 GHz with temperature coefficient of resonant frequency changing from 106.7 to −8.4 ppm/oC as Bi contents increases from z = 0.00–0.20. It has been found that dielectric constant and temperature coefficient of resonant frequency improve whereas loss tangent is adversely affected with increase in Bi substitution.     

Catalytic combustion of methane over Pt and PdO-supported CeO<Subscript>2</Subscript>–ZrO<Subscript>2</Subscript>–Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>/γ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> catalysts

Catalytic combustion of methane was investigated on Pt and PdO-supported CeO₂–ZrO₂–Bi₂O₃/γ-Al₂O₃ catalysts prepared by a wet impregnation method in the presence of polyvinylpyrrolidone. The catalysts were characterized by X-ray fluorescence analysis, X-ray powder diffraction, X-ray photoelectron spectra, transmission electron microscopy, and BET specific surface area measurements. The Pt/CeO₂–ZrO₂–Bi₂O₃/γ-Al₂O₃ and PdO/CeO₂–ZrO₂–Bi₂O₃/γ-Al₂O₃ catalysts were selective for the total oxidation of methane into carbon dioxide and steam, and no by-products such as HCHO, CO, and H₂ were obtained. The catalytic activities of the PdO/CeO₂–ZrO₂–Bi₂O₃/γ-Al₂O₃ catalysts were relatively higher than those of the Pt-supported catalysts, due to the facile re-oxidation of metallic Pd into PdO based on lattice oxygen supplied from the CeO₂–ZrO₂–Bi₂O₃ bulk. A decrease in the calcination temperature during the preparation process was found to be effective in enhancing the specific surface area of the catalysts, whereby particle agglomeration was inhibited. Optimization of the PdO amount and calcination temperature enabled complete oxidation of methane at temperatures as low as 320 °C on the 11.6 wt% PdO/CeO₂–ZrO₂–Bi₂O₃/γ-Al₂O₃ catalyst prepared at 400 °C.     

Temporal Stability of Magnetization of ε-In<Subscript>0.24</Subscript>Fe<Subscript>1.76</Subscript>O<Subscript>3</Subscript> Nanoparticles

The kinetics of spontaneous demagnetization in nanoparticles of the exotic epsilon-phase of indium-doped iron(III) oxide (ε-In_0.24Fe_1.76O₃) has been studied using the method of accelerated testing of magnets for temporal stability in a magnetization-reversal field. Time dependences of the magnetization of nanoparticles measured in a wide range of magnetic fields exhibited rectification in semilogarithmic coordinates. The dependence of the magnetic viscosity on the magnetic field has been measured and used for determining the fluctuation field and activation volume. A relationship between the magnetic viscosity and magnetic noise caused by random thermoinduced magnetization reversal in separate nanoparticles is established.     

Ferroelectric and piezoelectric properties of new NaNbO<Subscript>3</Subscript>–Bi<Subscript>0.5</Subscript>K<Subscript>0.5</Subscript>TiO<Subscript>3</Subscript> lead-free ceramics

New lead-free ceramics (1–x)NaNbO₃–xBi_0.5K_0.5TiO₃ have been fabricated by the conventional ceramic sintering technique, and their ferroelectric and piezoelectric properties have been studied. The results of X-ray diffraction reveal that Bi_0.5K_0.5TiO₃ diffuses into the NaNbO₃ lattices to form a new perovskite-type solid solution with orthorhombic symmetry. The addition of a small amount of Bi_0.5K_0.5TiO₃ (x ≥ 0.025) transforms the ceramics from antiferroelectric to ferroelectric. The ceramic with x = 0.10 possesses the largest remanent polarization P _r and thus exhibits the optimum piezoelectric properties, giving d ₃₃ = 71 pC/N, k _p = 16.6% and k _t = 39.7%. The ceramics with low doping level of Bi_0.5K_0.5TiO₃ are normal ferroelectrics and the ferroelectric-paraelectric phase transition becomes diffusive gradually with the doping level x of Bi_0.5K_0.5TiO₃ increasing. Our results show the (1–x)NaNbO₃–xBi_0.5K_0.5TiO₃ ceramics is one of the good candidates for lead-free piezoelectric and ferroelectric materials.