Iron and chromium doped perovskite (CaMO3 M = Ti,Zr) ceramic pigments,effect of mineralizer

Solid solutions Ca(D_xM_1?x)O₃ (M = Ti, Zr and D = Fe,Cr), have been studied as ceramic pigment in conventional ceramic glazes using 0.5 mol/mol of NH₄Cl as flux agent by solid state reaction and by ammonia coprecipitation route. Ca(Cr_xTi_1?x)O₃ compositions obtained without addition of NH₄Cl as mineralizer, produce pink color in glazes at low x but CaCrO₄ crystallizes when x increases, producing undesired green colors. The crystallization of chromates can be avoided using NH₄Cl as mineralizer, giving a complete solid solution that produce pink color in glazes at low x and dark blue shades at high x. Coprecipitated sample produce blue colors at low x and at low temperature than ceramic sample (1000 °C instead 1200 °C for CE sample). Cr⁴⁺ ion acts as red chromophore, but at higher x values (blue samples) Cr³⁺ ion entrance affects the color. Ca(Fe_xTi_1?x)O₃ system crystallizes perovskite CaTiO₃ and pseudobrookite Fe₂TiO₅ together with rutile as residual crystalline phase, glazed samples change from a yellow to a pink color associated to the increase of pseudobrookite with firing temperature. Ca(Fe_xTi_1?x)O₃ and Ca(Cr_xZr_1?x)O₃ systems crystallize perovskite CaZrO₃ and zirconia (ZrO₂) in both monoclinic and cubic polymorphs, but iron or chromium oxides are not detected in the powders. Coprecipitated sample stabilises cubic form. The solid solution is not reached completely in these samples and is not stable in glazes.     

New pink ceramic pigment based on chromium (IV)-doped lutetium gallium garnet

Lutetium gallium garnet codoped with chromium and calcium (Ca,Cr:LGG) and lutetium gallium garnet with chromium as single dopant (Cr:LGG) have been studied. Samples with Ca_xCr_xLu_3−2xGa₅O₁₂ (x = 0, 0.05, 0.10, 0.15, 0.2, 0.4, 0.6,) and Cr_xLu_3−xGa₅O₁₂ (x = 0.15 and 0.6) compositions were prepared by solid state reaction and the fired samples (1250 °C/6 h) were characterised by XRD, lattice parameters determination, UV–vis–NIR spectroscopy, CIEL*a*b* measurements and SEM/EDX. Moreover, the samples with calcium were tested as ceramic pigments in a conventional glaze matrix. In the Ca,Cr:LGG system solid solutions incorporating both Cr(III) and Cr(IV) ions were obtained. Cr(IV) occupies basically dodecahedral sites substituting for Lu (III) and is the predominant oxidation state up to x = 0.20 composition, giving a pink colouration in the ceramic glaze matrix. In the Cr:LGG system, only Cr(III) enters in solid solution occupying octahedral positions and producing green shades.     

Dielectric properties and related ferroelectric domain configurations in multiferroic BiFeO3–BaTiO3 solid solutions

Dielectric properties and ferroelectric domain configurations of multiferroic xBaTiO₃–(1 ? x)BiFeO₃ (x = 0.10–0.33) solid solutions synthesized by conventional solid-state reaction, were reported. A structural transition from rhombohedral to pseudo-cubic structures appeared around x = 0.33, and the formation of impurity phase of Bi₂Fe₄O₉ was effectively depressed by doping BaTiO₃. Dielectric constants of xBaTiO₃–(1 ? x)BiFeO₃ solid solutions decreased with increasing the frequency, and the degree of decrease was related to the doping content of BaTiO₃. Transmission electron microscopy images revealed that the ferroelectric domain configurations in the multiferroic BiFeO₃–BaTiO₃ solid solutions with rhombohedral symmetry, exhibited a wavy character whereas a predominant intricate domain structure with fluctuating mottled contrast was observed in the multiferroic BiFeO₃–BaTiO₃ solid solution with pseudo-cubic phase structure. The presence of 1/2{1 1 1} superlattice spots in the selected area electron diffraction patterns taken from the multiferroic BiFeO₃–BaTiO₃ solid solutions with rhombohedral symmetry indicated that the ordered regions have a doubled perovskite unit cell.     

Electrical properties and light up conversion effects in Bi3.79Er0.03Yb0.18Ti3−xWxO12 ferroelectric ceramics

Modified ceramic compositions of Bi_3.79Er_0.03Yb_0.18Ti_3−xW_xO₁₂ with fixed Er and Yb content, and a varying W content (x=0.0, 0.01, 0.03, 0.06 and 0.10) are prepared. The site selectivity of Er³⁺, Yb³⁺, and W⁶⁺ cations is analyzed, and their influence on the electrical and light up conversion properties is studied. Formation of single phase orthorhombic structure is confirmed with enhanced grain growth up to x=0.03, and for (x≥0.04–0.10) the grain growth is inhibited, and the orthorhombic distortion is relaxed. Raman spectroscopy reveals W⁶⁺ cation substitutes preferentially at the B-site replacing Ti⁴⁺ ions in the Bi₄Ti₃O₁₂ lattice structure. Increasing W⁶⁺ donor concentration reduces the conductivity effects by lowering the oxygen vacancies. Reduced dielectric losses (tan δ=0.003) and dispersion with frequency in the range (10⁻²–10 Hz) are observed, and improvements in the remnant polarization (2P_r=28.86 μC/cm²) are seen up to an optimum content of x=0.03. At higher W content (x>0.03), the properties tend to degrade due to structural relaxation and microstructural changes. Up conversion photoluminescence (UC-PL) under 980 nm excitation shows strong emission in the green and red bands due to enhanced crystal field around the Er³⁺ ions for an optimum W content of x=0.06. A weak blue emission band around (~492 nm) is observed by cooperative emission (CE) due to radiative relaxation of an excited Yb–Yb pair from a virtual level. Variation of UC emission intensity with pump-power confirms a two-photon mechanism for the up conversion process.     

The structure and properties of 0.95MgTiO3–0.05CaTiO3 ceramics co-doped with ZnO–ZrO2

The (Mg_0.93Ca_0.05Zn_0.02)(Ti_1?xZr_x)O₃ ceramics were prepared by conventional solid-state route. The dielectric properties and structure of (Mg_0.93Ca_0.05Zn_0.02)(Ti_1?xZr_x)O₃ ceramics were investigated. It has been found that MgTiO₃ and CaTiO₃ are the main phases and a second phase CaZrTi₂O₇ appeared in 95MCT ceramics co-doped with Zn–Zr. With Zn–Zr additive, the sintering temperature of 95MCT ceramics can be reduced to 1300 °C, and adjust the temperature coefficient of dielectric constant. With the increasing of Zr content, dielectric constant ?_r decrease from 22.6 to 19.91 and the temperature coefficient of dielectric constant α_c from 5.93 to 2.52 ppm/°C when x = 0.01, 0.02, 0.03 and 0.04 mol respectively. The 95MCT ceramics with x = 0.02 has a dielectric constant ?_r of 22.02, a dielectric loss of 2.78 × 10^?4 and a temperature coefficient of dielectric constant α_c value of 2.98 ppm/°C.     

Crystal structure,microstructure and electrical properties of (1−x−y)Bi0.5Na0.5TiO3–xBi0.5K0.5TiO3–yBiFeO3 ceramics near MPB prepared via the combustion technique

(1?x?y)Bi_0.5Na_0.5TiO₃–xBi_0.5K_0.5TiO₃–yBiFeO₃ (BNKFT-x/y with 0.12≤x≤0.24, 0≤y≤0.07) lead-free piezoelectric ceramics have been prepared by the combustion technique. The effects of amounts of x and y on structures and electrical properties were examined. Powders and ceramics can be well calcined and sintered at 750 °C for 2 h and 1025–1050 °C, respectively. The results indicated that the crystalline structure and microstructure changed with the increase of x and y concentrations. XRD results of BNKFT-x/0.03 and BNKFT-0.18/y ceramics with 0.12≤x≤0.24 and 0≤y≤0.07 showed the rhombohedral–tetragonal morphotropic phase boundary (MPB). The addition of y caused a promoted grain growth while the addition of x suppressed the grain growth. The highest density (ρ=5.85 g/cm³), superior dielectric properties at T_c (ε_r=7846 and tan δ=0.02), remnant polarization measured at 40 kV/cm (P_r = 20.1 μC/cm²) and piezoelectric coefficient (d₃₃=213 pC/N) were obtained for x=0.18 and y=0.03.     

Nitrate–citrate combustion synthesis of Ce1−xGdxO2−x/2 powder and its characterization

The structure, thermal expansion coefficients, and electric conductivity of Ce_1−xGd_xO_2−x/2 (x = 0–0.6) solid solution, prepared by the gel-combustion method, were investigated. The uniform small particle size of the gel-combustion prepared materials allows sintering into highly dense ceramic pellets at 1300 °C, a significantly lower temperature compared to that of 1600–1650 °C required for ceria solid electrolytes prepared by traditional solid state techniques. XRD showed that single-phase solid solutions formed in all the investigated range. The maximum conductivity, σ_600 °C = 5.26 × 10⁻³ S/cm, was found at x = 0.2. The thermal expansion coefficient, determined from high-temperature X-ray data, was 8.125 × 10⁻⁶ K⁻¹ at x = 0.2.     

Lattice oxygen of La1−xSrxMO3 (M = Mn,Ni) and LaMnO3−αFβ perovskite oxides for the partial oxidation of methane to synthesis gas

The partial oxidation of methane to synthesis gas by using the lattice oxygen of La_1−xSr_xMO₃ (M = Mn, Ni; x = 0–0.4) and LaMnO_3−αF_β (β/(3 − α) = 0.1) perovskite oxides was explored. Approximately 75% CO selectivity at 16% CH₄ conversion with H₂/CO molar ratio of ca. 2.5 can be achieved at 800 °C. The stability of the perovskite structure and the reactivity/selectivity of lattice oxygen are found to be dependent on (i) B-site element, (ii) degree of substitution of La with Sr, and (iii) fluorination of the perovskite oxide.     

Enhanced energy storage properties of BiAlO3 modified Bi0.5Na0.5TiO3–Bi0.5K0.5TiO3 lead-free antiferroelectric ceramics

Lead-free (1−x)(0.75Bi_0.5Na_0.5TiO₃–0.25Bi_0.5K_0.5TiO₃)–xBiAlO₃ (BNT–BKT–100xBA, x=0–0.10) ceramics were prepared by two-step sintering method and their phase structure, micro morphology and electrical properties were systematically investigated. X-ray diffraction analysis indicates a pure perovskite phase for x≤0.06 as well as a structural evolution from a tetragonal toward a pseudocubic phase. Transmission electron microscopy study of the x=0.04 composition reveals the existence of antiferroelectric phase with a⁰a⁰c⁺ oxygen octahedron tilting which is in the form of nano-domains. Polarization-electric field and current-electric field hysteresis loops demonstrate that the increase of BA concentration destroys the ferroelectric order and strengthens antiferroelectric order. A much enhanced energy storage density of 1.15 J/cm³ and efficiency of 73.2% is achieved under 105 kV/cm at x=0.06. In addition, its energy storage property is found to depend weakly on temperature within the measurement range of 25–150 °C.     

Evolution of structure and electrical properties with lanthanum content in [(Bi1/2Na1/2)0.95Ba0.05]1−xLaxTiO3 ceramics

Lead-free perovskite [(Bi_1/2Na_1/2)_0.95Ba_0.05]_1−xLa_xTiO₃ (x = 0.00–0.10) ceramics were fabricated via the solid state reaction method and their crystal structures and electrical properties were systematically studied. Transmission electron microscopy examination reveals a transition from a rhombohedral R3c phase with micron-sized complex domains to a mixture of rhombohedral R3c and tetragonal P4bm phases with nanodomains as La content was increased. X-ray diffraction analysis on bulk samples, however, indicates a pseudocubic structure in La-doped compositions. Electrical poling seems to transform the pseudocubic structure to a rhombohedral phase in compositions with 0.00 < x < 0.03. With La addition, the depolarization temperature (T_d) is observed to decrease and the dielectric constant (ɛ_r) within 100–350 °C becomes more temperature independent, promising for applications in high-temperature capacitors. Electric field-induced polarizations and strains display complex changes with respect to La concentration, with the highest strain of 0.35% achieved in the composition x = 0.04 under 70 kV/cm at room temperature. The piezoelectric coefficient d₃₃ initially increases with La content, reaching a maximum value of 151 pC/N in the composition x = 0.02, and then diminishes.     

Environmental-friendly yellow pigment based on Tb and M (M = Ca or Ba) co-doped Y2O3

A yellow inorganic ceramic pigment with general formula Y_1.86?xM_xTb_0.14O_3?x/2 (M = Ca and/or Zn) with x = 0.06, 0.32 and 0.64 were synthesized by a modified Pechini method. XRD, SEM and HRTEM/EDX analysis showed the formation of solid solution at 1300 °C when x = 0.06 and 0.32. The best b* yellow coordinates were obtained for Ca and Zn co-doped Y_1.86Tb_0.14O₃ samples. The intensity of the yellow colour in the samples is related to the presence of Tb⁴⁺ ions. Samples with higher concentration of Tb⁴⁺ ions lead to a better yellow colour. The chemical stability of these pigments was determinate in an industrial glaze. The glazing tests indicated that the powder samples with x = 0.06 and 0.32 fired at 1300 °C were stable in the glaze. These results make it a potential candidate for environmental friendly yellow ceramic pigment to be used in applications such as pigment for glazes or inkjet printers.     

Spark plasma sintering of MgAl2O4–YCr0.5Mn0.5O3 composite NTC ceramics

New high temperature negative temperature coefficient (NTC) thermistor ceramics based on a xMgAl₂O₄–(1 − x)YCr_0.5Mn_0.5O₃ (x = 0.1, 0.4, 0.6) composite system have been successfully fabricated through spark plasma sintering (SPS) with a low sintering temperature and a short sintering period. The X-ray diffraction analysis indicates that the SPS-sintered composite ceramics consist of a cubic spinel MgAl₂O₄ phase and an orthorhombic perovskite YCr_0.5Mn_0.5O₃ phase isomorphic to YCrO₃. The SPS-sintered composite ceramics have high relative density ranging from 94.1 to 97.4% of the theoretical density. X-ray photoelectron spectroscopy analysis corroborates the presence of Cr³⁺, Cr⁴⁺, Mn³⁺, and Mn⁴⁺ ions on lattice sites, which may result in the hopping conduction. The obtained ρ₂₅, B_25–150, and B_700–1000 of the SPS-sintered composite NTC thermistors are in the range of 1.53 × 10⁶–9.92 × 10⁹ Ω cm, 3380–5172 K, and 7239–9543 K, respectively. These values can be tuned by adjusting the MgAl₂O₄ concentration.     

Blue-violet ceramic pigments based on Co and Mg Co2−xMgxP2O7 diphosphates

Solid solutions of Co and Mg diphosphates with compositions Co_2?xMg_xP₂O₇ (x = 0, 0.1, 0.2, 0.3, 0.5, 0.7, 1.0, 1.5 and 1.8) have been prepared and characterized for the first time as alternative low-toxicity blue ceramic pigments. The compositions were prepared through the conventional coprecipitation route and calcined up to 1000 °C/2 h. Samples were characterized by thermal analysis, XRD, SEM/EDX, UV–vis-NIR spectroscopy and colour measurements (CIE-L^*a^*b^*). Isostructural Co_2?xMg_xP₂O₇ diphosphate solid solutions (monoclinic system and P21/c spatial group) formed successfully within the studied range of compositions, accompanied only by a minor quantity of residual Co or Mg orthophosphates (M₃(PO₄)₂). Interestingly, the obtained solid solutions developed nice blue-violet colourations even with high Mg doping after enamelling within double-firing (x = 1.5–1.8) and single-firing (x = 1.0–1.5) ceramic glasses. These optimal compositions containing a minimized Co amount (measured values around 7–16 wt%) could be therefore less toxic alternatives to the conventional Co₃(PO₄)₂ blue ceramic pigment.     

Dielectric and piezoelectric properties of low temperature synthesized iso-valent modified BT ceramics

Ba_(1?x)Y_xTiO₃ (where Y = Ca, Mg and Sr, x = 0.02, 0.04, 0.06 and 0.08) ferroelectric ceramic samples were synthesized in single perovskite phase by modified solid state reaction (MSSR) route. For single perovskite phase formation and dense grain morphology, 900 °C and 1300 °C were optimized as calcination and sintering temperatures. With the increase of substitutions% of Ca in BCT ceramic samples, the position of T_c increases slightly, whereas with the increase of Mg and Sr substitution% in BMT and BST systems, the position of T_c decreased but remains above RT. Decreased processing temperature with low temperature coefficient of capacitance made BCT ceramic samples useful for dielectric applications. Symmetric nature of the S–E loops indicated the increase of piezoelectric nature with the increase of Ca substitution% in BCT system.     

Phase-microstructure evolution and microwave dielectric characteristic of (1−x)(Sr0.5Ce0.5)TiO3+δ−xNdAlO3 solid solution

A perovskite solid solution (1−x)(Sr_0.5Ce_0.5)TiO_3+δ−xNdAlO₃, x = 0.1 to 0.4 was prepared by conventional solid state method. X-ray diffraction spectra revealed a single phase with tetragonal structure, indicating that doping of NdAlO₃ significantly stabilized the perovskite-like structure. The addition of NdAlO₃ facilitated the formation of large plate-like grains with porous microstructure. The dielectric constant (ε_r) decreased with increasing x because of the small ionic polarizability of NdAlO₃. The Q × f value was strongly dependent on the microstructure of these ceramics. The temperature coefficient of resonant frequency (τ_f) gradually shifted to near zero with a rise of x, which resulted from the decrease in tolerance factor (t). The solid solution with x = 0.4 sintered at 1550 °C for 4 h showed a good combination of dielectric properties: ε_r = 72, Q × f = 12052 GHz and τ_f = +5 pmm/°C.     

Synthesis,structure and oxygen thermally programmed desorption spectra of La1−xCaxAlyFe1−yO3−δ perovskites

Perovskites La_1−xCa_xAl_yFe_1−yO_3−δ (x, y = 0 to 1) were prepared by high-temperature solid-state synthesis based on mixtures of oxides produced by colloidal milling. The XRD analysis showed that perovskites La_0.5Ca_0.5Al_yFe_1−yO_3−δ with a high Fe content (1 − y = 0.8–1.0) were of orthorhombic structure, perovskites with a medium Fe content (1 − y = 0.8–0.5) were of rhombohedral structure, and perovskite with the lowest Fe content (1 − y = 0.2) were of cubic structure. Thermally programmed desorption (TPD) of oxygen revealed that chemical desorption of oxygen in the temperature range from 200 to 1000 °C had proceeded in the two desorption peaks. The low-temperature α-peak (in the 200–550 °C temperature range) was brought about by oxygen liberated from oxygen vacancies; the high-temperature β-peak (in the 550–1000 °C temperature range) corresponded to the reduction of Fe⁴⁺ to Fe³⁺. The chemidesorption oxygen capacity increased with increasing Ca content and decreased with increasing Al content in the perovskites. The Al³⁺ ions restricted, probably for kinetic reasons, the reduction of Fe⁴⁺ and the high-temperature oxygen desorption associated with it.     

Catalytic activity of nanometer La1−xSrxCoO3 (x = 0, 0.2) perovskites towards VOCs combustion

Combustive oxidation of volatile organic compounds (VOCs), such as propyl alcohol, toluene and cyclohexane, were studied. The combustion was catalyzed by nanoparticles of La_1−xSr_xCoO₃ (x = 0, 0.2) perovskites prepared by a co-precipitation method. The results showed high activities of the perovskite catalysts. Compared to LaCoO₃, in particular, La_0.8Sr_0.2CoO₃ was much higher in catalytic ability. The total oxidation of VOCs followed the increasing order: cyclohexane < toluene < propyl alcohol. The T_99% of cyclohexane was 40 °C lower than that of toluene, which appeared to be determined by the bond strengths of the weakest C–H and C–C bonds. The 100-h stability experiments showed that La_1−xSr_xCoO₃ (x = 0, 0.2) perovskite was highly stable.     

Structure and properties analysis for low-loss (Mg1−xCox)TiO3 microwave dielectric materials prepared by reaction-sintering method

(Mg_1?xCo_x)TiO₃ (x = 0.00–0.09) ceramics were prepared by reaction sintering method. The correlations of crystal structure and the properties were analyzed on the basis of Rietveld refinement for specimens with different x. For x ≤ 0.5, solid solution phases with the ilmenite structure were obtained, which can be confirmed by the X-ray diffraction patterns and the lattice parameters measured. Whereas for x > 0.05, secondary phase was detected besides the main phase. Dielectric properties were closely related with theoretical dielectric polarizabilities, packing fraction and average octahedral distortion. By increasing x from 0.00 to 0.09, the Q × f value of the specimen decreased from a maximum of 289,400 GHz to 228,100 GHz. A fine combination of microwave dielectric properties (?_r ～ 16.1, Q × f ～ 289,400 GHz, τ_f  ～ ?54.4 × 10^?6/°C) was achieved for MgTiO₃ ceramics sintered at 1350 °C for 4 h.     

Phase formation and transitions in the lead nickel niobate–lead zirconate titanate system

Despite the many previous studies of the synthesis and characterization of several perovskite ferroelectric materials which have potential applications in electronic and medical diagnostic devices, the synthesis and phase formation of the whole series in the solid solution of (1 ? x)Pb(Ni_1/3Nb_2/3)O₃–xPb(Zr_1/2Ti_1/2)O₃ (PNN–PZT) system has rarely been studied. In this work, the phase formation, morphology, particle size and chemical composition of perovskite powders in the (1 ? x)PNN–xPZT system were investigated. Powders were prepared by a modified mixed-oxide synthesis route for various chemical compositions under different calcination temperatures. It is found that the perovskite phase undergoes a pseudo-cubic to tetragonal transition as composition changes. The degree of spherical shape and agglomeration were observed to increase with increasing PZT content.     

Influence of addition of copper cadmium ferrite on the dielectric and electrical behavior of BaSrTiO3 ceramics

Polycrystalline composites of (1 ? x) (Ba_0.7Sr_0.3TiO₃)–x(Cu_0.5Cd_0.5Fe₂O₄) (x = 0.15, 0.30, 0.45) were prepared by a modified wet chemical method. X-ray diffraction studies at room temperature confirmed the formation of polycrystalline composite with perovskite–spinel structure. Scanning electron micrographs also suggest polycrystalline microstructure with the grains of unequal size distributed throughout the pellet samples. Dielectric studies of the composites reveal that the effect of ferrite in the composites is to shift the ferroelectric–non-ferroelectric phase transition to higher temperature side. Complex impedance spectroscopy analysis indicated negative temperature coefficient of resistance behavior identical to semiconductors. The activation energy calculated from the temperature dependence of conductivity pattern shows that the conduction process can occur due to the hopping of electrons between Fe³⁺ and Fe²⁺, leading to the contribution of both single and doubly-ionized oxygen vacancies.