The influences of firing temperatures and excess PbO on the crystal structure and microstructure of (Pb<Subscript>0.25</Subscript> Sr<Subscript>0.75</Subscript>)TiO<Subscript>3</Subscript> ceramics

Polycrystalline samples of (Pb_0.25Sr_0.75)TiO₃ (PST75) were prepared by the solid-state reaction method. The effects of firing temperatures and excess PbO on PST75 ceramics were investigated. The PST75 was calcined between 600 and 1000 °C for 3 h and the sintering temperature ranged between 1050 and 1250 °C for 2 h. The optimized calcination and sintering conditions were identified as 950 and 1250 °C, respectively. The lattice parameter c increased, while the lattice parameter a decreased with increased firing temperatures. The average particle size and average grain size increased with increased firing temperatures. After the addition of PbO—excess 0, 1, 3, 5, and 10 wt%—in the PST75 samples, the lattice parameter a decreased. The average particle size and the average grain size increased with the increase of PbO. The porous microstructure slightly decreased with an increasing amount of PbO—up to 3 wt%—then slightly increased with the higher excess PbO. The density was improved by adding 3 wt% of excess PbO. A low dielectric loss was observed from the 3 wt% excess PbO sample.     

Optimized sintering properties and temperature stability of MgZrTa<Subscript>2</Subscript>O<Subscript>8</Subscript> ceramics with CuO addition for microwave application

Microwave dielectric ceramics CuO–modified MgZrTa₂O₈ were synthesized by the conventional solid-state reaction method. The effects of CuO additives on the sintering characteristics and microwave dielectric properties have been investigated. With CuO addition, the sintering temperature of MgZrTa₂O₈ ceramics can be effectively lowered from 1475 to 1375 °C without decreasing its dielectric properties obviously and the temperature coefficient of the resonant frequency of MgZrTa₂O₈ ceramics have been optimized to near-zero. The crystalline phase exhibited a wolframite crystal structure and no second phase was detected at low addition levels. The grain growth of CuO–modified MgZrTa₂O₈ ceramics was accelerated due to liquid phase effect. The relative dielectric constants (ε_r) were correlated with apparent density and were not significantly different for all levels of CuO concentration. The quality factors (Q?×??) and temperature coefficient of resonant frequency (τ_?), which were strongly dependent on the CuO concentration, were analyzed by the grain size and the dielectric constant respectively. A best Q?×?? value of 116400 GHz and τ_? value of ?6.19 ppm/℃ were obtained for specimen with 0.05 wt% CuO addition at 1375 °C.     

Effects of LiF addition on the sintering behavior and microwave dielectric properties of Li<Subscript>2</Subscript>Mg<Subscript>3</Subscript>SnO<Subscript>6</Subscript> ceramics

Li₂Mg₃SnO₆ (abbreviation for LMS) ceramics doped with 1–4 wt% lithium fluoride (LiF) were prepared by the conventional solid-state reaction method. The effects of LiF addition on the phase compositions, sintering behaviors and microwave dielectric properties of LMS ceramics were investigated. A small amount of LiF addition could effectively decrease the sintering temperatures due to the liquid phase in the sintering process and induced no apparent degradation of the microwave dielectric properties. The optimized quality factor values for each composition firstly increased and then decreased with the increase of the LiF content. Whereas, the optimized dielectric permittivity increased with increasing of the LiF content. Distinguished microwave dielectric properties with a dielectric constant (ε _r) of 11.13, a quality factor (Q·f) of 104,750 GHz, and a temperature coefficient of resonant frequency (τ _f ) of ?10.83 ppm/°C were obtained for LMS ceramics sintered at 950?°C doped with 3 wt% LiF, which showed that the materials were suitable for the low temperature co-fired ceramics applications (LTCC).     

Effect of sintering temperature on the grain growth and electrical properties of barium zirconate titanate ferroelectric ceramics

In the present work, structural, dielectric and ferroelectric properties of barium zirconate titanate ferroelectric ceramics have been investigated. The specimens were synthesized using a solid state reaction technique. The XRD analysis reveals that the synthesized compound was formed with no secondary phases. As the sintering temperature increases from 1,200 to 1,300 °C, the average grain size is observed to increase from ~0.39 to ~6.15 μm. The dielectric measurements as a function of temperature show a decrease in Curie temperature (T_C) on increasing the sintering temperature. The decrease in Curie temperature is attributed to the substitution of Zr⁺⁴ whose ionic radius is larger than Ti⁺⁴. A large increase in the dielectric constant with the increase in grain size is observed. The remanent polarization is also observed to increase with the increase in grain size.     

The effect of sintering temperature on magnetic and dielectric properties of Ho<Subscript>3</Subscript>Fe<Subscript>5</Subscript>O<Subscript>12</Subscript> ceramics

Ho₃Fe₅O₁₂ ceramics were fabricated by the solid-state reaction method. The results revealed an increase of the grain size, dielectric constant, and dielectric loss, while a decrease of the remnant magnetization and coercive field with increasing sintering temperature. A dielectric relaxation behavior was observed, which might be associated with the charge carrier hopping between Fe²⁺ and Fe³⁺. A cole–cole fitting to loss peaks revealed a dependence of the activation energy and the broaden factor on the relative density of the samples. Furthermore, at appropriate frequencies, the 1250 °C-sintered samples showed high dielectric constant, low dispassion, and good temperature stability around room temperature.     

Frequency dependence of dielectric properties of ex situ MgB<Subscript>2</Subscript> bulks

In this study, frequency dependent electrical properties of ex situ polycrystalline MgB₂ sintered at 650–850?°C were investigated. Dielectric permittivity (ε′, ε″), dielectric loss (tan δ), alternating current (AC) conductivity (σ_ac) as a function of frequency (100 Hz–10 MHz) were measured at room temperature. The X-ray diffraction (XRD) and grain morphology were analysed and correlated to the findings in dielectric properties. Due to weakly coupled grains and presence of high fraction of oxides, positive real dielectric permittivity was measured for the ex situ samples as compared with the negative real dielectric permittivity shown by the in situ MgB₂. Nevertheless, the samples sintered at higher temperature showed improved grain connectivity as reflected by the higher AC conductivity and dielectric loss. The semicircle observed in the complex impedance plots together with the combined spectroscopy plots indicates that the electrical behavior of the ex situ samples is mainly due to the bulk and grain boundary responses as opposed to the sole bulk response of the in situ MgB₂. The modelled equivalent circuit also suggests the presence of insulating grain boundary barrier (due to the oxide phases) next to the conducting bulk in the ex situ samples.     

Low temperature sintering and microwave dielectric properties of Li<Subscript>3</Subscript>Mg<Subscript>2</Subscript>NbO<Subscript>6</Subscript> ceramics for LTCC application

The Li₃Mg₂NbO₆ ceramics doped with ZnO-B₂O₃-SiO₂ (ZBS) additives were synthesized via the conventional solid-state reaction process. The influence of ZBS additives on phase composition, sintering behavior, microstructure and microwave dielectric properties of Li₃Mg₂NbO₆ ceramics were investigated in detail. The XRD patterns showed that the sintered specimen presented a single phase and no secondary phase appeared. We found that proper amount of ZBS additives could significantly reduce the sintering temperature from 1250 to 925?°C and promote the densification of Li₃Mg₂NbO₆ ceramics. The ε_r and Q?×?f value were strongly affected by bulk density and grain size, respectively. As ZBS content increased, the τ_f value shifted toward negative direction. In summary, excellent microwave dielectric properties of ε_r?~?14.84, Q?×?f?~?73,987 GHz, τ_f?~??16.05 ppm/°C could be obtained in 0.5 wt.% ZBS modified sample when sintered at 925?°C for 4 h. Furthermore, the material was compatible with Ag electrode, demonstrating that it would be a promising candidate material for LTCC application.     

Influence of sintering temperature on microstructures and dielectric properties of ZnO-MgO-TiO<Subscript>2</Subscript>-CaO ceramics

Microwave dielectric properties of ZnO–MgO–TiO₂–CaO (ZMTC) ceramics were investigated as a function of sintering temperatures by the conventional solid-state method. Sintering characteristics, microstructures, and microwave dielectric properties of ZMTC ceramics were studied as a function of sintering temperature from 1210 to 1290 °C. The variation trend of ε_r and Q? value was in accordance with variation trend of relative density. With increasing sintering temperature, the density, ε_r and Q? values increased, saturating at 1230 °C with excellent microwave properties of ε_r = 22.5, Q? = 22.1 × 10⁴ GHz, and TCF = 23.1 ppm/°C.     

Magnetic,optical, dielectric,and sintering properties of nano-crystalline BaFe<Subscript>0.5</Subscript>Nb<Subscript>0.5</Subscript>O<Subscript>3</Subscript> synthesized by a polymerization method

A one-pot polymerization method using citric acid and glucose for the synthesis of nano-crystalline BaFe_0.5Nb_0.5O₃ is described. Phase evolution and the development of the crystallite size during decomposition of the (Ba,Fe,Nb)-gel were examined up to 1100 °C. Calcination at 850 °C of the gel leads to a phase-pure nano-crystalline BaFe_0.5Nb_0.5O₃ powder with a crystallite size of 28 nm. The shrinkage of compacted powders starts at 900 °C. Dense ceramic bodies (relative density ≥ 90%) can be obtained either after conventional sintering above 1250 °C for 1 h or after two-step sintering at 1200 °C. Depending on the sintering regime, the ceramics have average grain sizes between 0.3 and 52 µm. The optical band gap of the nano-sized powder is 2.75(4) eV and decreases to 2.59(2) eV after sintering. Magnetic measurements of ceramics reveal a Néel temperature of about 23 K. A weak spontaneous magnetization might be due to the presence of a secondary phase not detectable by XRD. Dielectric measurements show that the permittivity values increase with decreasing frequency and rising temperature. The highest permittivity values of 10.6 × 10⁴ (RT, 1 kHz) were reached after sintering at 1350 °C for 1 h. Tan δ values of all samples show a maximum at 1–2 MHz at RT. The frequency dependence of the impedance can be well described using a single RC-circuit.     

Investigation of density of states and electrical properties of Ba<Subscript>0.5</Subscript>Co<Subscript>0.5</Subscript>Bi<Subscript>2</Subscript>Nb<Subscript>2</Subscript>O<Subscript>9</Subscript> nanoceramics prepared by chemical route

Barium-cobalt-bismuth-niobate, Ba_0.5Co_0.5Bi₂Nb₂O₉ (BCoBN) nanocrystalline ferroelectric ceramic was prepared through chemical route. XRD analysis showed single phase layered perovskite structure of BCoBN when calcined at 650 °C, 2 h. The average crystallite size was found to be 18 nm. The microstructure was studied through scanning electron microscopy. The dielectric and ferroelectric properties were investigated in the temperature range 50–500 °C. The dielectric constant and dielectric loss plot with respect to temperature both indicated strong relaxor behavior. Frequency versus complex impedance plot also supported the relaxor properties of the material. The impedance spectroscopy study showed only grain conductivity. Variation of ac conductivity study exhibited Arrhenius type of electrical conductivity where the hopping frequency shifted towards higher frequency region with increasing temperature. The ac conductivity values were used to evaluate the density of state at the Fermi level. The minimum hopping distance was found to be decreased with increasing temperature.     

Dielectric properties of Na<Subscript>1-<Emphasis Type="Italic">x</Emphasis></Subscript>K<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>NbO<Subscript>3</Subscript> in orthorhombic phase

Pellets of ceramic Na_1−xK_xNbO₃ (x = 0, 0.2 and 0.5), were prepared by conventional solid-state reaction method. Prepared samples were characterized using XRD and SEM. The frequency and temperature variation of dielectric constant, loss tangent and dielectric conductivity of prepared samples were measured in the frequency range from 10 KHz-1 MHz, and in the temperature range from 50–250°C for x = 0.2 and 0.5, and between 50 and 480°C for x = 0 compositions. It was observed that the dielectric constant and loss tangent decrease, and conductivity increases with increasing frequency. Near the transition temperature the material shows anomalous behaviour for the observed properties, and the peaks of dielectric constant and loss tangent were observed shifting towards lower temperature with increasing frequency.     

Microwave synthesis and sintering characteristics of CaCu<Subscript>3</Subscript>Ti<Subscript>4</Subscript>O<Subscript>12</Subscript>

CaCu₃Ti₄O₁₂ (CCTO) was synthesized and sintered by microwave processing at 2·45 GHz, 1·1 kW. The optimum calcination temperature using microwave heating was determined to be 950°C for 20 min to obtain cubic CCTO powders. The microwave processed powders were sintered to 94% density at 1000°C/60 min. The microstructural studies carried out on these ceramics revealed the grain size to be in the range 1–7 μm. The dielectric constants for the microwave sintered (1000°C/60 min) ceramics were found to vary from 11000–7700 in the 100 Hz–00 kHz frequency range. Interestingly the dielectric loss had lower values than those sintered by conventional sintering routes and decreases with increase in frequency.     

Enhanced thermal stability in K<Subscript>2</Subscript>O-metakaolin-based geopolymer concretes by Al<Subscript>2</Subscript>O<Subscript>3</Subscript> and SiO<Subscript>2</Subscript> fillers addition

Based on the principle of stability of geopolymer gel as refractory binder, a geopolymeric paste in the K₂O–Al₂O₃–SiO₂ system was developed and used to produce refractory concretes by adding various amount of α-quartz sand (grain size in the range 0.1 μm to 1 mm) and fine powder alumina (grain size in the range 0.1–100 μm). The consolidated samples were characterized before and after sintering using optical dilatometer, DSC, XRD and SEM. The total shrinkage in the range of 25–900 °C was less than 3%, reduced with respect to the most diffused potassium or sodium based geopolymer systems, which generally records a >5% shrinkage. The maximum shrinkage of the basic geopolymer composition was recorded at 1000 °C with a 17% shrinkage which is reduced to 12% by alumina addition. The temperature of maximum densification was shifted from 1000 °C to 1150 or 1200 °C by adding 75 wt% α-quartz sand or fine powder alumina respectively. The sequences of sintering of geopolymer concretes could be resumed as dehydration, dehydroxylation, densification and finally plastic deformation due to the importance of liquid phase. The geopolymer formulations developed in this study appeared as promising candidates for high-temperature applications: refractory, fire resistant or insulating materials.     

Effect of Bi and Li co-substituted SrTiO<Subscript>3</Subscript> ceramics on structural and dielectric properties

Polycrystalline Sr_(1–x)(Bi, Li)_xTiO₃ ceramics (x = 0 and 0.02) are prepared by a microwave processing method. The effect of co-substitution on structural, dielectric properties and ac-conductivity were investigated. The XRD of ceramics shows single phase with cubic structure. The lattice parameter of the compounds is estimated from the XRD patterns which confirm the incorporation of Bi and Li in SrTiO₃ ceramics. Studies revealed that the dielectric constant and dielectric loss increased with an increase of temperature and decreased with an increase in frequency. The maximum dielectric constant obtained at room temperature is around 570 and increased to around 10⁴ at 600 °C measured at 1 kHz frequency whereas the maximum dielectric loss measured was 0.048 at 600 °C and the loss measured at room temperature is 0.02. The activation energy of the samples were investigated using Arrhenius plots.     

Effects of sintering temperature on the properties of Mn/Y codoped Ba<Subscript>0.67</Subscript>Sr<Subscript>0.33</Subscript>TiO<Subscript>3</Subscript> ceramics for tunable application

(Ba_0.67Sr_0.33)_1?3x/2Y _x Ti_1?y/2Mn _y O₃ [BST(Mn + Y), x = 0.006, y = 0.005] ceramics were fabricated by using citrate–nitrate combustion derived powder. Microstructure and dielectric properties of the BST(Mn + Y) ceramic samples were investigated within the sintering temperature ranged from 1220 to 1300 °C. Sintering temperature has a great influence on the microstructure and electrical properties of the ceramic samples. The dielectric properties, ferroelectric properties, and tunability are enhanced by optimizing sintering temperature. The relatively high tunability of 40 % (1.5 kV/mm DC field, 10 kHz) was obtained, and relatively low dielectric loss, <0.0052 (at 10 kHz, 20 °C) was acquired for BST(Mn + Y) samples sintered at 1275 °C for 3 h. Both the low dielectric loss and enhanced tunable properties of BST(Mn + Y) are useful for tunable devices application.     

Enhanced dielectric and electrical properties in CaZrO3-doped X8R BaTiO3-based ceramics sintered at medium temperature

Lead-free X8R BaTiO₃-based ceramics were prepared by conventional solid-state method. The influence of the composition and procedures on the microstructures, lattice parameters and dielectric properties of ceramics materials were systemically studied. XRD results indicate that no secondary phase is formed in the CaZrO₃-doped samples after sintering. The content of Ca²⁺ ions and Zr⁴⁺ ions decrease from grain boundaries to grain interiors referring to EDS results, which indicate that the ions mainly locate in the grain boundaries. The Curie temperatures of all CaZrO₃ doped samples increase due to the increasing tetragonality caused by the addition of CaZrO₃. SEM micrographs reveal that the grain size of CaZrO₃-doped BaTiO₃-based samples are not uniform, ranging from 0.2 to 0.8 µm. Furthermore, samples doped with 1.0 wt % CaZrO₃ exhibit optimal dielectric properties with high temperature stability of capacitance, due to the fine-grain microstructures. Moreover, we obtained a lead-free high performance X8R dielectric ceramic composition sintered at medium temperature (1,135 °C).     

Very high thermal stability with excellent dielectric,and non-ohmics properties of Mg-doped CaCu<Subscript>3</Subscript>Ti<Subscript>4.2</Subscript>O<Subscript>12</Subscript> ceramics

In this work, the nominal CaCu_3?xMg_xTi_4.2O₁₂ (0.00, 0.05 and 0.10) ceramics were prepared by sintering pellets of their precursor powders obtained by a polymer pyrolysis solution method at 1100 °C for different sintering time of 8 and 12 h. Very low loss tangent (tanδ)?<?0.009–0.014 and giant dielectric constant (ε′) ～?1.1?×?10⁴–1.8?×?10⁴ with excellent temperature coefficient (Δε′) less than ±?15% in a temperature range of ??60 to 210 °C were achieved. These excellent performances suggested a potent application of the ceramics for high temperature X8R and X9R capacitors. It was found that tanδ values decreased with increasing Mg²⁺ dopants due to the increase of grain boundary resistance (R_gb) caused by the very high density of grain, resulting from the substitution of small ionic radius Mg²⁺ dopants in the structure. In addition, CaCu_3?xMg_xTi_4.2O₁₂ ceramics displayed non-linear characteristics with the significant enhancements of a non-linear coefficient (α) and a breakdown field (E_b) due to Mg²⁺doping. The high values of ε′ (14012), α (13.64) and E_b (5977.02 V/cm) with very low tanδ value (0.009) were obtained in a CaCu_2.90Mg_0.10Ti_4.2O₁₂ ceramic sintered at 1100 °C for 8 h.     

Effect of Sintering Temperature on the Microstructure,Electrical, and Magnetic Properties of Bi 0 . 8 5 Eu 0 . 1 5 FeO 3 Ceramics

Polycrystalline Bi _0.85Eu _0.15FeO ₃ ceramics were synthesized by solid-state reaction method with rapid liquid phase sintering process at various sintering temperatures. The dependence of structural, microstructural, electrical, and magnetic properties on sintering temperature was systematically investigated. X-ray diffraction measurements reveal that single perovskite phase is developed in Bi _0.85Eu _0.15FeO ₃ ceramics sintered at 850 and 870^° C, while secondary phases can be detected in the samples sintered at 890^° C due to the volatilization of Bi ³⁺ ions, and the crystallinity increases with increasing sintering temperature from 850 to 890 °C. The scanning electron microscopy investigation has suggested that the grain size increases with increasing sintering temperature from 855 t o 890^° C; while the pore size decreases with increasing sintering temperature from 850 to 870^° C and then increases with a further increase of sintering temperature. The electrical and magnetic measurements show that the leakage current, dielectric constant, dielectric loss, and magnetic properties are strongly dependent on the sintering temperature. The Bi _0.85Eu _0.15FeO ₃ ceramics sintered at 870^° C have the lower leakage current, higher dielectric constant, and lower dielectric loss. The room temperature magnetization increases with increasing sintering temperature from 850 to 890 °C. The possible reason for all the above observations was discussed.     

Effect of replacement of MgO by CaO on sintering,crystallization and properties of MgO–Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–SiO<Subscript>2</Subscript> system glass-ceramics

The effects of replacement of MgO by CaO on the sintering and crystallization behavior of MgO–Al₂O₃–SiO₂ system glass-ceramics were investigated. The results show that with increasing CaO content, the glass transition temperature firstly increased and then decreased, the melting temperature was lowered and the crystallization temperature of the glass-ceramics shifted clearly towards higher temperatures. With the replacement of MgO by less than 3 wt.% CaO, the predominant crystalline phase in the glass-ceramics fired at 900 °C was found to be α-cordierite and the secondary crystalline phase to be μ-cordierite. When the replacement was increased to 10 wt.%, the predominant crystalline phase was found to be anorthite and the secondary phase to be α-cordierite. Both thermal expansion coefficient (TCE) and dielectric constant of samples increases with the replacement of MgO by CaO. The dielectric loss of sample with 5 wt.% CaO fired at 900 °C has the lowest value of 0.08%. Only the sample containing 5 wt.% and10 wt.% CaO (abbreviated as sample C5 and C10) can be fully sintered before 900 °C. Therefore, a dense and low dielectric loss glass-ceramic with predominant crystal phase of α-cordierite and some amount of anorthite was achieved by using fine glass powders (D₅₀ = 3 μm) fired at 875–900 °C. The as-sintered density approaches 98% theoretical density. The flexural strength of sample C5 firstly increases and then decreases with sintering temperature, which closely corresponds to its relative density. The TCE of sample C5 increases with increasing temperature. The dielectric property of sample C5 sintered at different temperatures depends on not only its relative density but also its crystalline phases. The dense and crystallized glass-ceramic C5 exhibits a low sintering temperature (≤900 °C), a fairly low dielectric constant (5.2–5.3), a low dielectric loss (≤10⁻³) at 1 MHz, a low TCE (4.0–4.25 × 10⁻⁶ K⁻¹), very close to that of Si (∼3.5 × 10⁻⁶ K⁻¹), and a higher flexural strength (≥134 MPa), suggesting that it would be a promising material in the electronic packaging field.     

Structural,electrical and magneto-electric characteristics of complex multiferroic perovskite Bi<Subscript>0.5</Subscript>Pb<Subscript>0.5</Subscript>Fe<Subscript>0.5</Subscript>Ce<Subscript>0.5</Subscript>O<Subscript>3</Subscript>

The polycrystalline sample of bismuth based-complex multiferroic of a composition Bi_0.5Pb_0.5Fe_0.5Ce_0.5O₃ was prepared by a high-temperature solid-state reaction technique (calcinations temperature = 900 °C, sintering temperature = 960 °C, time = 4 h). Preliminary structural analysis using XRD data exhibits the formation of a single-phase compound. Studies of surface morphology of the ceramic sample of the compound, recorded at room temperature using a scanning electron microscope, show uniform distribution of grains of different size with few voids. Detailed studies of dielectric properties (ε_r, tan δ) supported the existence of multiferroic properties in the above complex system. The analysis of impedance parameters, recorded in a wide frequency (1 kHz–1 MHz) and temperature (room temperature to 450 °C) range of the material provide better understanding of (a) role of grains and grain boundaries in resistive and capacitative characteristics, (c) structure-properties relationship and (b) type of relaxation process occurred in the material. Study of temperature dependence of dc conductivity of the compound shows the existence of negative temperature coefficient of resistance in it. The nature of variation of ac conductivity with temperature of the material follows the Josher’s universal power law. Study of magneto-electric characteristics of the sample at room temperature has provided many useful and new data on magneto-electric coupling coefficient of different orders.