Dielectric spectroscopy of MgTiO3-based ceramics in the 109–1014Hz region

Magnesium titanate (MgTiO₃) powder was prepared by a chemical route (Pechini method) and different dopants were added to prepare several compositions. These pure and doped compositions were sintered in air and dense ceramics were obtained. The pure MgTiO₃ samples were also subjected to different heat treatments during sintering. Complex permittivity spectra of ceramic samples were determined by various techniques in the 10⁹–10¹⁴ Hz range. These techniques included infrared spectroscopy in transmission and reflectivity modes and microwave dielectric measurements. Extrapolation to microwave frequencies from infrared data, according to the proportionality (v) v, agrees quite well with the microwave data measured at 8 GHz and it is a useful procedure to estimate intrinsic microwave losses. Fast cooling from high temperatures of MgTiO₃ samples increased dielectric loss, probably due to a structural disorder. Dopants have two types of effect depending on whether they form a distinct second phase or a solid solution with MgTiO₃. In this last case intrinsic losses are strongly affected.     

Effects of SrO–B2O3–SiO2 glass additive on the microstructure and dielectric properties of CaCu3Ti4O12

The effect of SrO–B₂O₃–SiO₂ glass additive (SBS) on the microstructure and dielectric properties of CaCu₃Ti₄O₁₂ (CCTO) ceramics was investigated. This SBS–added CCTO ceramics were prepared by the solid state reaction. The undesirable impurity phases Ca₃SiO₅ started appearing in the XRD patterns, suggesting a possible chemical reaction between CaTiO₃ and SiO₂ (the devitrification production of SBS glass). The SBS glass additive promoted the grain growth and densification of CCTO ceramics. Cole–Cole plots of conductance suggested that the resistivity grain boundary decreased with increasing amount of SBS glass (when x = 0–2 wt%), then increased (when x = 2–3 wt%). The addition of SBS glass was desirable to increase the dielectric constants (up to 10⁴) and lowered the dielectric losses of CCTO over the frequency range of 450–40 kHz at the relatively lower sintering temperature for relatively shorter sintering time (1,050 °C, 12 h).     

Preparation and characterization of magnesium/carbonate co-substituted hydroxyapatites

A new synthesis/processing method has been devised to produce magnesium/carbonate co-substituted hydroxyapatite ceramics that do not decompose to tricalcium phosphate (TCP) on sintering. Using this method, a series of magnesium/carbonate co-substituted hydroxyapatite (Mg/CO₃–HA) compositions, containing between 0 and 0.35 wt % Mg and approximately 0.9 wt % CO₃ were prepared. Sintering the Mg/CO₃–HA compositions in a CO₂/H₂O atmosphere yields a single crystalline phase that appears to be identical to stoichiometric HA. In contrast, when the compositions were prepared in the absence of carbonate and were sintered in air, the phase composition was a biphasic mixture of HA and TCP e.g. for 0.25 wt % Mg substitution the phase composition was approximately 60%HA/40% TCP. Clearly, both the synthesis route and the processing (i.e. sintering) route are of importance in the production of a single-phase Mg/CO₃–HA ceramic. Fourier transform infrared (FTIR) spectroscopy has indicated that the Mg/CO₃–HA ceramics still contained carbonate groups after sintering at 1200 °C. Chemical analysis by X-ray fluorescence spectroscopy (XRF) and C–H–N analysis has shown that the cation/anion molar ratio (i.e. [Ca+Mg]/[P+C/2]) of the different compositions were 1.68(±0.01), which is equivalent to the Ca/P molar ratio of stoichiometric HA. Although the magnesium/carbonate co-substitution had a positive effect in preventing phase decomposition during sintering, it appeared to have a negative effect on the densification of the MgCO₃–HA ceramics, compared to stoichiometric HA.     

Preparation of hydroxyapatite by the hydrolysis of brushite

The conversion of brushite (CaHPO₂ · 2H₂O; DCPD) into hydroxyapatite (HAp) by hydrolysis has been studied by separating the conversion process into two stages, i.e. the structural change of DCPD into HAp (1) and the subsequent compositional increase in Ca/P ratio of the HAp (II). In Reaction I at 40°C, HAp formed most rapidly at around pH 7.5 to 8.0. The complete conversion was observed within 2.5 h at 40°C, 1 h at 60°C and only 5 min at 80°C. The compositions of HAp thus formed were nonstoichiometric and had a Ca/P ratio below 1.60. It was difficult to increase the Ca/P ratio up to the stoichiometric value 1.67, because the adjustment of pH to higher values and/or the addition of Ca²⁺ ions to accelerate the increase in Ca/P ratio, retarded the proceeding of Reaction I. On the other hand, in Reaction II, such pH adjustment and Ca²⁺ addition were remarkably effective in increasing the Ca/P ratio. Consequently, two-stage processing was reasonable and convenient for the preparation of stoichiometric HAp, because it was possible to manage the controlling factors in both Reactions I and II independently. The resulting HAp powders showed a comparatively low crystallinity similar to precipitated HAp and large weight losses (above 6%) on heating, and were composed of dense aggregates of irregular thin microcrystals.     

Microwave sintering improves the mechanical properties of biphasic calcium phosphates from hydroxyapatite microspheres produced from hydrothermal processing

Starting from two microspherical agglomerated HAP powders, porous biphasic HAP/TCP bioceramics were obtained by microwave sintering. During the sintering the HAP powders turned into biphasic mixtures, whereby HAP was the dominant crystalline phase in the case of the sample with the higher Ca/P ratio (HAP1) while α-TCP was the dominant crystalline phase in the sample with lower Ca/P ratio (HAP2). The porous microstructures of the obtained bioceramics were characterized by spherical intra-agglomerate pores and shapeless inter-agglomerate pores. The fracture toughness of the HAP1 and HAP2 samples microwave sintered at 1200 °C for 15 min were 1.25 MPa m^1/2. The phase composition of the obtained bioceramics only had a minor effect on the indentation fracture toughness compared to a unique microstructure consisting of spherical intra-agglomerate pores with strong bonds between the spherical agglomerates. Cold isostatic pressing at 400 MPa before microwave sintering led to an increase in the fracture toughness of the biphasic HAP/TCP bioceramics to 1.35 MPa m^1/2.     

Effects of NaOH concentrations on physical and electrical properties of high calcium fly ash geopolymer paste

The effects of sodium hydroxide (NaOH) concentration on setting time, compressive strength and electrical properties at the frequencies of 100 Hz–10 MHz of high calcium fly ash geopolymer pastes were investigated. Five NaOH concentrations (8, 10, 12, 15 and 18 molar) were studied. The liquid to ash ratio of 0.4, sodium silicate to sodium hydroxide ratio of 0.67 and low temperature curing at 40 °C were selected in making geopolymer pastes. The results showed that NaOH concentration had significant influence on the physical and electrical properties of geopolymer paste. The pastes with high NaOH concentrations showed increased setting time and compressive strength due to a high degree of geopolymerization as a result of the increased leaching of silica and alumina from fly ash. The dielectric constant and conductivity increased with NaOH concentration while tan δ decreased due to an increase in geopolymerization. At the frequency of 10³ Hz, the dielectric constants of all pastes were approximately 10⁴ S/cm and decreased with increased frequency. The relaxation peaks of tan δ reduced with an increase in NaOH concentration and ranged between 2.5 and 4.5. The AC conductivity behavior followed the universal power law and the values were in the range of 3.7 × 10⁻³–1.5 × 10⁻² at 10⁵–10⁶ Hz.     

Dielectric spectroscopy of polypyrrole–γ–Fe2O3 composites

In situ polymerization of pyrrole was carried out in the presence of γ–Fe₂O₃ (FE) to synthesize polypyrrole–γ–Fe₂O₃ composites (PPy/FE) by chemical oxidation method. The PPy/FE composites have been synthesized with various compositions viz., 10, 20, 30, 40 and 50 wt.% of γ–Fe₂O₃ in pyrrole. The AC conductivity was studied in the frequency range 10²–10⁷ Hz. The dielectric behaviour was also investigated in the frequency range 10²–10⁷ Hz. The dimensions of γ–Fe₂O₃ particles in the matrix have a greater influence on the conductivity values and the observed dielectric values.     

Effect of Gd3+ substitution on dielectric properties of nano cobalt ferrite

CoGd_xFe_2 ? xO₄ (x = 0.0, 0.1, 0.3, 0.5) nano magnetic ferrite particles were synthesized by chemical co-precipitation method. The variation of dielectric parameters like dielectric constant, dielectric loss, capacitance and resistance for different Gd³⁺ compositions has been measured at room temperature for frequency dependence in the range of 100 Hz to 10 MHz using impedance analyzer. Results of measurements reveal strong dependence of dielectric parameters on frequency and Gd³⁺ ion content. Dielectric constant, dielectric loss, capacitance and resistance decrease with increasing frequency for all the CoGd_xFe_2 ? xO₄ compositions. Increase in Gd³⁺ ion composition in material, increases the values of dielectric constant, dielectric loss and capacitance while decreases the electrical resistance of nano-particles. A qualitative explanation is given for the composition and frequency dependence of dielectric parameters.     

Kinetics and sintering mechanisms of hydro-thermally obtained hydroxyapatite

In this paper, the kinetics and sintering mechanism of hydro-thermally synthesized hydroxyapatite in the temperature range 900–1100 °C are presented. It was found that at 900 °C, the sintering process is very slow, whereas at 1000, 1050, and 1100 °C is much faster, caused by activated sintering with liquid phase/phase of solution on spots with concentrated material impurity and the formation of reaction/polyeutectic mixtures dominates. The activation energies of sintering were also determined. At all the investigated sintering temperatures, an approximate value of 90 kJ mol⁻¹ was found.     

Influence of Zr doping on the dielectric properties of CaCu<Subscript>3</Subscript>Ti<Subscript>4</Subscript>O<Subscript>12</Subscript> ceramics

Pure and Zr-substituted CaCu₃(Ti_1−x Zr _x )₄O₁₂ (x = 0, 0.01, 0.02, 0.03) ceramics were prepared by the Pechini method. X-ray powder diffraction analysis indicated the formation of single-phase compound, and all the diffraction peaks were completely indexed by the body-centered cubic perovskite-related structure. The effects of Zr⁴⁺ ion substituting partially Ti⁴⁺ ion on the dielectric properties were investigated in frequency range between 100 Hz and 1 GHz. The low frequency (f ≤ 10⁵ Hz) dielectric constant decreases with Zr substitution and the high frequency (f ≥ 10⁷ Hz) dielectric constant is unchanged. Interestingly, a low-frequency relaxation was observed at room temperature through Zr substitution. The observed dielectric properties in Zr-substituted samples were discussed using the internal barrier layer capacitor model. A corresponding equivalent circuit was adopted to explain the dielectric dispersion. The characteristic frequency of low-frequency relaxation rises due to the decrease of the resistivity of grain boundary with Zr substitution, which is likely responsible for the large low-frequency response at room temperature.     

Structural and impedance properties of Ba5DyTi3V7O30

A polycrystalline sample of Ba₅DyTi₃V₇O₃₀ (BDTV) was prepared by a mixed-oxide method at 1,000 °C (sintering temperature). Preliminary X-ray structural analysis confirmed a single-phase formation of the compound. Scanning electron micrograph of the material show uniform distribution of grains of different shape and size on the surface of the sample. Detailed studies of dielectric properties in a wide range of temperature (30–400 °C) and frequencies (10³–10⁶ Hz) exhibit ferroelectric (diffuse) phase transition, which was confirmed by appearance of hysteresis loop at room temperature. Electrical properties (impedance properties) of the material were obtained using a complex impedance technique. The Nyquist plots confirmed the contribution of grain in the material. Studies of electrical conductivity (both dc and ac) over a wide temperature range suggest that the compound exhibits the negative temperature coefficient of resistance behavior. The ac conductivity spectra were found to obey Jonscher’s universal power law.     

Effects of sintering temperature on the microstructure and dielectric properties of titanium dioxide ceramics

Nanostructured (~200 nm grain size) titanium dioxide (TiO₂) ceramics were densified at temperature as low as 800 °C by pressureless sintering in a pure oxygen atmosphere. Phase transition and microstructural development of sintered samples were studied by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Dielectric properties including d.c. conductivity, dielectric constant, loss tangent, and dielectric breakdown strength (BDS) were determined for samples sintered at various temperatures. The influence of sintering temperature on the microstructural development, defect chemistry, and dielectric properties of TiO₂ is discussed. Nanostructured TiO₂ ceramics with high sintering density (>98%) lead to improved dielectric properties; high BDS (~1800 kV/cm), low electrical conductivity (~5 × 10⁻¹⁵ S/cm), high dielectric constant (~130), and low loss tangent (~0.09% at 1 kHz), which is promising for application in high energy density capacitors.     

Microwave sintering of calcium phosphate ceramics

Microwave sintering of hydroxyapatite (HAP) and tri-calcium phosphate (TCP) ceramics were studied using a commercial 2.45 GHz, 3 KW fully automated microwave system. Four different powder compositions, apart from pure HAP and TCP, were prepared with small amount of different oxide additives e.g., magnesium oxide, zinc oxide and titanium oxide. All samples were densified at 1250 °C for 30 min. Sintered samples had high density and homogeneous microstructure for all compositions. Phase analysis using XRD showed no major variations from starting materials. Presence of additives increased compressive strength between 100 and 200%. Fractured surfaces showed clear signs of intergranular fracture in undoped HAP and TCP while in doped samples, fracture modes were either transgranular or mixed mode. In comparison to conventional sintering, microwave sintering of calcium phosphate ceramics was found to be economically exciting due to substantial reduction in processing time and energy expenditure due to volumetric heating of samples.     

Nonlinear electrical characteristics and dielectric properties of (Ca, Ta)-doped TiO2 ceramics

TiO₂ ceramics doped with 1.0 mol% Ca and different concentrations of Ta were obtained by sintering processing at 1450°C. The microstructures, nonlinear electrical behavior and dielectric properties of the ceramics were investigated. The samples have nonlinear coefficients of = 2.0–5.0 and ultrahigh relative dielectric constants which is up to 10⁵. Especially, the effects of Ta dopant on the nonlinear electrical characteristics and dielectric properties of the (Ca, Ta)-doped TiO₂ ceramics were studied in detail. When the concentration of Ta is 2.0 mol%, the sample exhibits the highest nonlinear coefficient and a comparatively lower dielectric constant. By analogy to a grain-boundary atomic defect model, the effects of Ta and the nonlinear electrical behavior of the TiO₂ system were explained.     

Fibrous growth of tricalcium phosphate ceramics

Structural transformation and sintering processes of tricalcium phosphate (TCP) ceramics prepared from defective hydroxyapatite (Ca9HPO4(PO4)5OH) were studied by X-ray diffraction (XRD) and atomic force microscopy (AFM). Starting powders with Ca/P ratio 1.5 were obtained by adding 0.5 l of 0.3 M H3PO4 solution to an equal volume of 0.45 M Ca(OH)2. In the prepared ceramics, the onset temperature for transformation of defective hydroxyapatite into TCP (witlokite) agrees with the onset temperature for sintering (800 °C). Sintering occurs through the formation of a fibrous structure, which resembles biological hard tissue. In the 1000–1200°C range, these fibres coalesce into grains of up to 0.6 m in size with a fibrous-laminar morphology. At the end of this sintering stage witlokite transforms into TCP. At about 1450°C, partial decomposition of TCP into Ca2P2O7+Ca4P2O9 is observed. AFM observations suggest that Ca2P2O7 is segregated in the liquid state and increases the velocity of grain growth (up to 12 m).     

Influence of calcination,sintering and composition upon microwave properties of the Ba6−xSm8+2x/3Ti18O54-type oxide

Dielectric ceramic compositions for microwave applications belonging to the (BaO) (Sm₂O₃) (TiO₂) ternary phase diagram were studied. Calcination, sintering, microwave properties and influence of secondary phases were investigated. By varying composition and/or sintering process, a high dielectric constant with low dielectric losses and modulable negative or positive temperature coefficient of the resonant frequency can be reach.     

Enhanced thermal conductivity and dielectric properties of Al/β-SiCw/PVDF composites

Polymeric composites with high thermal conductivity, high dielectric permittivity but low dissipation factor have wide important applications in electronic and electrical industry. In this study, three phases composites consisting of poly(vinylidene fluoride) (PVDF), Al nanoparticles and β-silicon carbide whiskers (β-SiC_w) were prepared. The thermal conductivity, morphological and dielectric properties of the composites were investigated. The results indicate that the addition of 12 vol% β-SiC_w not only improves the thermal conductivity of Al/PVDF from 1.57 to 2.1 W/m K, but also remarkably increases the dielectric constant from 46 to 330 at 100 Hz, whereas the dielectric loss of the composites still remain at relatively low levels similar to that of Al/PVDF at a wider frequency range from 10⁻¹ Hz to 10⁷ Hz. With further increasing the β-SiC_w loading to 20 vol%, the thermal conductivity and dielectric constant of the composites continue to increase, whereas both the dielectric loss and conductivity also rise rapidly.     

Preparation and characterization of selenite substituted hydroxyapatite

Selenite-substituted hydroxyapatite (Se-HA) with different Se/P ratios was synthesized by a co-precipitation method, using sodium selenite (Na₂SeO₃) as a Se source. Selenium has been incorporated into the hydroxyapatite lattice by partially replacing phosphate (PO₄^3 ?) groups with selenite (SeO₃^2 ?) groups. X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), and transmission electron microscopy (TEM) techniques reveal that substitutions of phosphate groups by selenite groups cause lower carbonate groups occupying at phosphate sites and change the lattice parameters of hydroxyapatite. The powders obtained are nano-crystalline hydroxyapatite when the Se/P ratios are not more than 0.1. The particle shape of Se-HA has not been altered compared with selenite-free hydroxyapatite but Se-incorporation reduces the crystallite size. The crystallinity was reduced as the Se/P ratios increased until amorphous phase (Se/P = 0.3) appeared in the Se-HA powder obtained, and then another crystal phase presented as calcium selenite hydrate (Se/P = 10). In addition, the sintering tests show that the Se-HA powders with the Se/P ratio of 0.1 have thermal stability at 900 °C for 2 h; hence they have great potential in the fabrication of bone repair scaffolds.     

Structural and dielectric properties of parylene-VT4 thin films

58% semi-crystalline thin parylene-VT4 (–H₂C–C₆F₄–CH₂−)_n films, have been investigated by dielectric spectroscopy for temperature and frequency ranges of [−120 to 380 °C] and [0.1–10⁵ Hz] respectively. The study comprises a detailed investigation of the dielectric constant, dielectric loss and AC conductivity of this fluoropolymer. Dielectric behavior of parylene-VT4 is represented by a low dielectric constant with values in the range of 2.05–2.35 while the dielectric losses indicate the presence of two relaxation processes. Maxwell−Wagner−Sillars (MWS) polarization at the amorphous/crystalline interfaces with activation energy of 1.6 eV is due to the oligomer orientation. Electrical conductivity obeys to the well-known Jonscher law. The plateau in the low frequency part of this conductivity is temperature-dependent and follows an Arrhenius behavior with activation energy of 1.17 eV (deep traps) due to the fluorine diffusion. Due to its thermal stability with a high decomposition temperature (around 400 °C under air and 510 °C under nitrogen) and due to its good resistivity at low frequency (10¹⁵–10¹⁷ Ω m⁻¹), parylene-VT4 constitutes a very attractive polymer for microelectronic applications as low k dielectric. Moreover, when parylene-VT4 is subjected to an annealing, the dielectric properties can be still more improved.     

Transitions of barium strontium titanate ferroelectric ceramics for different strontium content

Ceramic based barium strontium titanate (BST) solid solutions with the formula Ba_1 − xSr_xTiO₃ are very important candidates for a wide range of device applications. Several doped (Mn and Mg) and undoped samples were prepared by standard solid-state reaction. Special emphasis was put on compositions with x = 0.35 and 0.60, with high potential for applications. The samples were sintered at temperatures in the 1200 ÷ 1260 °C range. Structural X-ray diffraction analysis preformed confirms the perovskite structure. The dielectric parameters were investigated in a wide temperature range between − 150 and 150 °C. The temperature was cyclically changed in both directions, up and down, at a rate of less than 2 °C/min. Both permittivity and dielectric loss were measured at low frequencies, 1 kHz. The peak values of the permittivity are increasing from 2000 to 4000 with the sintering temperature increase. Moreover the dielectric parameters were measured at room temperature in microwave domain (1 ÷ 2 GHz). The Curie temperature of BST samples with x = 0.35 and x = 0.6 is in agreement with the Curie point dependence on Sr content, as we have previously reported.