Elemental substitution at Tl-site of TlSr2CaCu2O7 superconductor: A review

This review is on the effects of elemental substitutions at the Tl-site of TlSr₂CaCu₂O₇ (Tl-1212) superconductor. The objective of this paper was to determine the elements that enhance or suppress the superconducting transition temperature, T_c of (Tl_1-xM_x)Sr₂CaCu₂O₇ phase. The elements included in this review were M = Pb, Bi, Cr, V, Re, Zr, In, Er, Gd, Na, K, Rb and Se. The relations between transition temperature and the ionic radius, coordination number, valence state and optimization of the hole concentration of the selected elements were studied. The preparation methods, sintering temperature, Tl-1212 phase and structural stability were also discussed. All alkali metals (K, Na and Rb) suppressed the transition temperature of the Tl-1212 phase. The transition temperature generally decreased linearly with ionic radius except for Cr which showed the highest T_c although its ionic radius is smaller.     

The role of amorphous phase content on the electrical properties of atmospheric plasma sprayed (Ba,Sr)TiO3 coatings

(Ba,Sr)TiO₃ coatings deposited on carbon steel substrates were successfully prepared by an atmospheric plasma spray system. Three sets of samples containing different amount of both crystalline and amorphous phases were deposited and consequently studied in order to determine their electrical properties. The results show a clear correlation existing between the amorphous phase content and coating´s electrical properties. The resistivity increases with increase of amorphous phase content. Relative permittivity for low frequencies decreases and become more stable with frequency tuning when amorphous phase content increased. The maximum relative permittivity value is in the range 75–200 for frequency 1 kHz. The loss factor varies between 0.23 and 0.03 for all studied samples. The loss factor is at the lower limit of these values and frequency much less dependent when the coating contains 15 wt% of amorphous phase and more. The band gap of all samples is between 2.75 eV and 2.90 eV. Microstructure and hardness were evaluated in order to determine basic mechanical properties of deposits.     

Processing and enhanced electrical properties of Sr1-x(K0.5Bi0.5)xBi2Nb2O9 lead-free piezoelectric ceramics

Lead-free piezoelectric ceramics, Sr_1−x(K_0.5Bi_0.5)_xBi₂Nb₂O₉ (SKBN-x, x=0, 0.2, 0.5, 1.0), were synthesized by a conventional solid-state reaction. Structural and electrical properties of SKBN-x ceramics were investigated. X-ray diffraction analysis suggested that the substitution led to the formation of a layered perovskite structure. Plate-like morphologies for the grains were clearly observed in all the samples, which are characteristic for layer-structure Aurivillius compounds. The Curie temperature (T_c) is found to shift to higher temperature from 445 °C to 509 °C with increasing (K, Bi) content. Excellent remanent polarization (2P_r∼15 μC/cm²) were obtained for SKBN-0.2 ceramic. High piezoelectric coefficient of d₃₃∼21  pC/N were obtained for the samples at x=0.5. Additionally, thermal annealing studies indicated that the piezoelectric coefficient (d₃₃) of SKBN-0.5 was unchanged even if annealing temperature increased to be 450 °C, demonstrating the ceramics are the promising candidates for high-temperature applications.     

Crystal structure,electrical and magnetic properties of anion-deficient perovskite-like Ba3SmFe2O7.5

Anion-deficient perovskite-like Ba₃SmFe₂O_7.5 was prepared using a glycerol–nitrate synthesis. Using high-temperature X-ray diffraction in situ a crystal structure transition temperature range 800 and 840 °C was established. These results were further confirmed by high-temperature dilatometric analysis. The average thermal expansion coefficient (TEC) of Ba₃SmFe₂O_7.5 is about 12.8 × 10⁻⁶ K⁻¹ between 25 °C and 800 °C. Magnetic experiments proved an excellent phase purity of the oxide and reveal that Fe³⁺ ions stay in high and intermediate spin states in a ratio of 75% and 25% respectively.     

Influence of Li doping on the morphological evolution and optical & electrical properties of SnO2 nanomaterials and SnO2/Li2SnO3 composite nanomaterials

SnO₂ nanomaterials and SnO₂/Li₂SnO₃ composite nanomaterials doped with different Li contents were synthesized via a simple one-step thermal evaporation method. X-ray diffraction patterns showed that with the increase of Li doping, the intensity of Li₂SnO₃ diffraction peaks gradually increased, while that of SnO₂ diffraction peaks gradually decreased. With the increase of Li doping, the width of nanobelts gradually increased, with the morphology changing from banded structure to standard hexagonal sheet structure. The Raman scattering spectra indicated that with the increase of Li doping, the peak of Li₂SnO₃ at 588.8 cm^?1 kept increasing, and the strongest vibration mode A_1g in SnO₂ gradually weakened. X-ray photoelectron spectroscopy revealed that with the increase of Li doping, the surface electrophilic oxygen species in SnO₂/Li₂SnO₃ composite nanomaterials greatly increased. Under the condition of light irradiation with a wavelength of 505 nm, the bright current of the Li-doped SnO₂ samples was higher than the dark current, while that of the SnO₂/Li₂SnO₃ composite nanomaterials was higher than the dark current, which was mainly due to more oxygen vacancies in SnO₂/Li₂SnO₃ composite nanomaterials than electrons excited by light. Consequently, positive photoconductivity gradually weakened, and even the negative photoconductivity emerged.     

Influence of barium borosilicate glass on microstructure and dielectric properties of (Ba,Ca)(Zr,Ti)O3 ceramics

Barium borosilicate (BBS) glass was added as a sintering aid to (Ba_0.7Ca_0.3)TiO₃-Ba(Ti_0.8Zr_0.2)O₃ (BCZT) ceramics at levels from 2 to 15?wt%, yielding enhanced densification. The addition of BBS also induced changes in phase composition, from predominantly tetragonal to orthorhombic at room temperature. It is shown that the changes in phase content are caused by a shift of the orthorhombic to tetragonal phase transformation from below room temperature to ≈50?°C. An additional high temperature transition around 120?°C was also identified. These observations are interpreted in terms of the development of chemical heterogeneity associated with the redistribution of dopant elements (particularly Zr and Ca) through the liquid phase during sintering. The relative permittivity and electric field-induced polarisation values were generally degraded by the presence of the glass phase, but a reduction in ferroelectric hysteresis and improved densification behaviour have potential benefits in dielectric energy storage applications.     

Influence of MeF2 (Me = Mg, Ca, Sr, and Ba) on the electrical properties of glasses in the MeF2-Na2B4O7 system

Glasses in the MeF₂-Na₂B₄O₇ (Me = Mg, Ca, Sr, and Ba) system have been synthesized. It is shown that the glass formation is observed at a MeF₂ content of up to 40 mol %. The influence of the MeF₂ content on the electrical conductivity and the fluorine concentration in the glass bulk is examined. From the analysis of the concentration dependence of the electrical conductivity with due regard for the fluorine content, it is concluded that the glass structure is predominantly built up of the polar groupings Na⁺[BO_4/2]^-, Na⁺[F-BO_3/2], Me _1/2 ²⁺ [BO_4/2]⁻, Me _1/2 ²⁺ [F⁻BO_3/2], [MeF_4/2], and [MeF_6/3] and the BO_3/2 nonpolar structural-chemical units. The electricity transport is governed by the migration of sodium ions formed upon dissociation of the Na+[BO_4/2]^-and Na+[F^-BO_3/2] groupings. An increase in the MeF₂ content leads to a decrease in the total concentration of sodium ions, a decrease in the Na⁺[BO_4/2]^- concentration, and an increase in the Na⁺[F^-BO_3/2] concentration. Upon introduction of MeF₂ up to ∼20 mol %, the fluorine losses during the synthesis are caused by the dehydration of glass melt. An addition of 20–25 mol % MeF₂ brings about the saturation of the glass by the [F^-BO_3/2]-type structural units, so that the fluorine concentration reaches a saturation in the structures of calcium-, strontium-, and barium-containing glasses and increases in magnesium-containing glasses, owing to the formation of the [MgF+_6/3] groupings.     

AC conductivity,electric modulus analysis and electrical conduction mechanism of RbFeP2O7 ceramic compound

In this work, the diphosphate compound, RbFeP₂O₇, was prepared by the conventional solid-state reaction. The X-ray diffraction pattern revealed that the sample presents a single phase, that crystallizes in the monoclinic structure with a P2₁/C space group. Impedance analysis was performed using the equivalent circuit model, and, it indicated the presence of intra- and inter-granular contribution. Furthermore, the electrical conductivity, the dielectric properties and the relaxation behavior of this material were studied in detail using the impedance spectroscopy technique, in a frequency ranging from 200 Hz to 5 MHz at several temperatures. The temperature dependency of frequency exponent 's' shows that the correlated barrier-hopping model (CBH) is the most responsible mechanism for AC conduction in the investigated compound. In terms of CBH model, the values of maximum barrier s height, the hopping distance and the density of localized states are determined and discussed. A correlation between electrical and structural properties was also discussed.     

Effect of substitution of La3+ on structural and electrical properties of Sr(Fe0.5Nb0.5)O3 ceramic

In this work, we have mainly reported the effect of lanthanum substitution on structural, dielectric, impedance and transport properties of strontium iron niobate (i.e., Sr_1-xLa_x(Fe_0.5Nb_0.5)_1-x/4O₃ (x = 0, 0.05, 0.1, 0.15, 0.2)). The materials were synthesized using standard ceramic technology. The preliminary structural analysis was done by using the room temperature X-ray diffraction data. The samples of higher concentrations (x = 0.15 and x = 0.20) show the development of an additional phase (i.e., LaNbO₄ and Sr₃La₄O₉). Studies of frequency and temperature dependence of dielectric parameters exhibit an anomaly and relaxor behavior in the compounds. The electrical impedance and modulus analysis of frequency and temperature-dependent data show the contributions of grains and grain boundaries in the resistive and capacitive properties of the compounds. The study of transport properties of AC conductivity has provided the conduction and relaxation mechanism. The substitution of La³⁺ has significantly changed the dielectric constant, tangent loss, and transport properties of the material.     

Effect of ionic radius on colossal permittivity properties of (A,Ta) co-doped TiO2 (A= alkaline-earth ions) ceramics

(A, B) co-doped TiO₂ ceramics attract great interests due to the excellent dielectric properties. In this work, the (A, Ta) co-doped TiO₂ ceramics were prepared by a solid state reaction process. The effect of the acceptors ionic radius on the structure and properties of TiO₂ ceramics was investigated. According to XRD analysis, the main phase is rutile TiO₂ for all samples. Due to the larger ionic radius, it is hard to replace Ti site in TiO₆ octahedron. As a result, the content of the secondary phase increased with increasing ionic radius. The dielectric properties were significantly enhanced by co-doping of alkaline-earth ions and tantalum ions, and the best dielectric constant obtained at 3% (Sr, Ta) co-doped compositions, where ε’ = 2.1 × 10⁵, tanδ = 0.21. Meanwhile, the XPS analysis suggested that the concentration of the defect dipoles exhibit a maximum in Sr-doped TiO₂ ceramics. The larger ionic radius of the acceptors leads to the more stability of the defect structure. However, for Ba ions, the replacement concentration decreased due to the excessive ionic radius, which in turn reduces the defect concentration. This work is meaningful for the further investigations on TiO₂-based colossal permittivity materials.     

Influence of strontium co-doping on the structural,optical, and electrical properties of erbium-doped ceria electrolyte for intermediate temperature solid oxide fuel cells

This study mainly aimed to elucidate the effects of strontium co-doping on the structural, optical, and electrical properties of erbium-doped ceria (Ce_0.8Er_0.2O_2-δ). Ce_1-x-yEr_xSr_yO_2-δ co-doped electrolytes were synthesized through sol–gel-assisted citric acid–nitrate combustion technique and sintered at 1500?°C for 6?h. X-ray diffraction results confirmed that the sintered electrolytes possessed a cubic fluorite crystal structure. However, a perovskite secondary phase (SrCeO₃) was observed in Ce_0.8Er_0.125Sr_0.075O_2-δ co-doped composition due to the low solubility limit of strontium (~5?mol%) in ceria. UV–Vis spectroscopy showed that the co-doping of strontium from 0?mol% to 7.5?mol% increased the direct band gap from 3.41?eV to 3.43?eV. The relative densities and the grain size were in the range of 96.02–97.68% and 1.5–3.28?µm, respectively, with increasing the strontium content from 0?mol% to 7.5?mol%. Electrochemical impedance spectroscopy showed that the total resistance of Ce_0.8Er_0.2O_2-δ increased as the strontium content increased. Singly doped Ce_0.8Er_0.2O_2-δ electrolyte exhibited the highest ionic conductivity of 18.22 mS/cm at 700?°C and the lowest activation energy of 0.55?eV within 600–800?°C among all other studied electrolytes.     

Tuning of electrical properties of xBi(Zn0.5Ti0.5)O3-(1-x) (Ba0.5Sr0.5)TiO3 ceramics by composition design and bandgap engineering

Herein, the xBi(Zn_0.5Ti_0.5)O₃-(1-x) (Ba_0.5Sr_0.5)TiO₃ (x = 0.05, 0.10, 0.15, 0.20) novel negative temperature coefficient (NTC) ceramic materials were fabricated by solid-state method. X-ray diffraction revealed that xBi(Zn_0·5Ti_0.5)O₃-(1-x) (Ba_0.5Sr_0.5)TiO₃ successfully formed solid solution. The UV–vis diffuse spectra of the samples indicate that the band gap increases with the increasing Bi(Zn_0·5Ti_0.5)O₃ content. The resistance temperature curve showed that with the increase of Bi(Zn_0·5Ti_0.5)O₃ content, the resistivity ρ of the ceramics at 400 °C increased from 5.96 × 10⁶ to 2.67 × 10⁷ Ω cm, as well as an increase in the B_400/800 from 12374.6 to 13469.1 K. The enhanced resistivity is attributed to the increased band gap and reduced carrier pairs caused by the Bi(Zn_0.5Ti_0.5)O₃ modification. The impedance data indicates that the conduction process is activated by thermal. The ceramic samples exhibit the excellent NTC characteristics over a range of 400 °C–1000 °C. Hence, the xBi(Zn_0.5Ti_0.5)O₃-(1-x) (Ba_0.5Sr_0.5)TiO₃ ceramics have the potential to become high temperature NTC ceramics that can operate in a wide temperature range.     

Mono and co-substitution of Sr2+ and Ca2+ on the structural,electrical and optical properties of barium titanate ceramics

In this work, Ba_0.9Sr_0.1TiO₃, Ba_0.7Sr_0.3TiO₃, Ba_0.5Sr_0.5TiO₃, Ba_0.5Ca_0.25Sr_0.25TiO₃ and Ba_0.5Ca_0.5TiO₃ have been synthesized to evaluate the influence of mono and co-substitution of A-site dopants (Sr²⁺ and Ca²⁺) on the structural, electrical and optical properties of BaTiO₃ ceramics. Sr²⁺ added samples showed a tetragonal structure which became slightly distorted with increasing Sr²⁺ concentration and finally achieved a cubic structure for x?=?0.50. Ba_0.5Ca_0.5TiO₃ also retained their tetragonality with limited solubility. Presence of second phase, CaTiO₃ demonstrated the fact of restricted solubility. The concurrent effect of Sr²⁺ and Ca²⁺ didn't alter the tetragonal structure. Sr²⁺ substitution enhanced the apparent density as well as grain size which stimulated the domain wall motion and improved dielectric properties. However, the ferroelectric nature of Ba_1-xSr_xTiO₃ was poor due to the redistribution of point defect at grain boundary. The optical band gap was found to be reduced from 3.48?eV to 3.28?eV with increasing Sr²⁺ content. Co-substitution of cations improved the electrical property significantly. The highest value of dielectric constant was found to be ～547 for Ba_0.5Ca_0.25Sr_0.25TiO₃ ceramics. Both Ba_0.5Ca_0.25Sr_0.25TiO₃ and Ba_0.5Ca_0.5TiO₃ had developed P-E loop having lower coercive field and moderate optical band gap energy. Co-doping with Sr²⁺ and Ca²⁺ was a good approach enhancing materials electrical as well as optical property.     

The electrical properties of (Ba,Ca, Ce,Ti, Zr)O3 thermistor for wide-temperature sensor architecture

A series of new negative temperature coefficient (NTC) thermal materials based on (Ba_0.85Ca_0.15)_1-xCe_x/2(Zr_0.1Ti_0.9)O₃ (0.00 ≤ x ≤ 0.20) ceramics were synthesized by a solid-state method. X-ray diffraction, scanning electron microscope and X-ray photoelectron spectroscopy were used to demonstrate the crystal structure, morphology, and composition of the (Ba_0.85Ca_0.15)_1-xCe_x/2(Zr_0.1Ti_0.9)O₃ ceramics, which were composed of solid solution based on the BaTiO₃ phase. The average grain size of doped ceramic samples experienced the process of first decreasing and then increasing. The doping of Ce has reduced the sintering temperature. The temperature-dependent resistance analysis revealed that with the change of doping amount x, the thermal constant B_300/1200 (1.21 × 10⁴–1.13 × 10⁴ K) and the activation energy E_a300/1200 (0.9777–1.0471eV) was initially increased to maximum values at x = 0.05, followed by the decreasing when x > 0.05. It has been established that the concentration of oxygen vacancies is affected by the transition between Ce⁴⁺ and Ce³⁺ provided by high levels of Ce doping. (Ba_0.85Ca_0.15)_1-xCe_x/2(Zr_0.1Ti_0.9)O₃ ceramics exhibited excellent negative temperature characteristics in the range of 300–1200 °C. Moreover, the temperature resistance linearity was improved after samples were aged. Hence, the (Ba_0.85Ca_0.15)_1-xCe_x/2(Zr_0.1Ti_0.9)O₃ ceramics were regarded as a promising material for high-temperature NTC thermistors in a wide temperature range.     

Influence of sintering aids and excess Lithium on the conductivity of perovskite-type Li3/8Sr7/16Zr1/4Nb3/4O3 solid electrolyte

Perovskite-structured Li_3/8Sr_7/16Zr_1/4Nb_3/4O₃ solid-state Lithium-conductors were prepared by conventional solid-state reaction method. Influence of sintering aids (Al₂O₃, B₂O₃) and excess Lithium on structure and electrical properties of Li_3/8Sr_7/16Zr_1/4Nb_3/4O₃ (LSNZ) has been investigated. Their crystal structure and microstructure were characterized by X-ray diffraction analysis and scanning electron microscope, respectively. The conductivity and electronic conductivity were evaluated by AC-impedance spectra and potentiostatic polarization experiment. All sintered compounds are cubic perovskite structure. Optimal amount of excess Li₂CO₃ was chosen as 20 wt% because of the total conductivity of LSNZ-20% was as high as 1.6×10⁻⁵ S cm⁻¹ at 30 °C and 1.1×10⁻⁴ S cm⁻¹ at 100 °C, respectively. Electronic conductivity of LSNZ-20% is 2.93×10⁻⁸ S cm⁻¹, nearly 3 orders of magnitude lower than ionic conductivity. The density of solid electrolytes appears to be increased by the addition of sintering aids. The addition of B₂O₃ leads to a considerable increase of the total conductivity and the enhancement of conductivity is attributed to the decrease of grain-boundary resistance. Among these compounds, LSNZ-1 wt%B₂O₃ has lower activation energy of 0.34 eV and the highest conductivity of 1.98×10⁻⁵ S cm⁻¹ at 30 °C.     

Dielectric properties of rare earth doped (Sr,Ba)Nb2O6 Ceramics

The influence of rare earth addition on the microstructure and phase transition of Sr_0·61Ba_0·39Nb₂O₆ ceramics was investigated. Sr_0·61Ba_0·39Nb₂O₆ undoped and doped with 0·3 and 1·0 wt% La₂O₃ and 0·3 wt% Nd₂O₃ were prepared by the conventional ceramic method. Dielectric measurements were performed in order to characterize the phase transition in these ceramics. The addition of RE elements decreased the maximum dielectric constant (ε_MAX) and its correspondent temperature (T_MAX) and increased the dielectric losses in all studied samples. A peak broadening and an increasingly Curie–Weiss behavior was verified for a La, while an inverse dependence occurred for Nd doping.     

Structural and electrical properties of lead free ceramic: Ba(La1/2Nb1/2)O3

Abstract

Abstract

Lead free perovskite Ba(La_1/2Nb_1/2)O₃ was prepared by conventional ceramic fabrication technique at 1375°C for 7?h in air atmosphere. The crystal symmetry, space group and unit cell dimensions were estimated using Rietveld analysis. X-ray diffraction analysis indicated the formation of a single phase monoclinic structure with space group P2/m. Energy dispersive X-ray analysis and scanning electron microscopy studies were carried to study the quality and purity of the compound. Permittivity data showed low temperature coefficient of capacitance (T _CC = 11%) up to 100°C. The circuit model fittings were carried out using the impedance data to find the correlation between the response of real system and idealised model electrical circuit. Complex impedance analyses suggested the dielectric relaxation to be of non-Debye type. The correlated barrier hopping model was employed to successfully explain the mechanism of charge transport in Ba(La_1/2Nb_1/2)O₃. The AC conductivity data were used to evaluate the density of states at Fermi level, minimum hopping length and apparent activation energy.     

Influence of Ca substitution on microstructure and electrical properties of Ba(Zr,Ti)O3 ceramics

In the present work, lead-free (Ba_1?xCa_x)(Zr_0.04Ti_0.96)O₃ (x=0.00–0.09) ceramics were fabricated via a solid-state reaction method. The microstructure and electrical properties of the ceramics were investigated. The microstructure of the BCZT ceramics showed a core shell structure at compositions of x=0.03 and 0.06. The substitution of small amount of Ba²⁺ by Ca²⁺ resulted in an improvement of the piezoelectric, dielectric and ferroelectric properties of the ceramics. The orthorhombic–tetragonal phase transition was found in the composition of x≤0.03. Piezoelectric coefficient of d₃₃～392 pC/N and lowest E_c～3.3 kV/cm with highest P_r～14.1 μC/cm² were obtained for the composition of x=0.03 while its Curie temperature (T_C) was as high as 125 °C. However, the ferroelectric to paraelectric transition temperature had slightly shifted towards room temperature with increasing Ca²⁺ concentration.