Microwave dielectric properties and co-firing with copper of (Bi1−xCux)(Nb1−xWx)O4 ceramics

Effect of substitution of CuO and WO₃ on the microwave dielectric properties of BiNbO₄ ceramics and the co-firing between ceramics and copper electrode were investigated. The (Bi_1−xCu_x)(Nb_1−xW_x)O₄ (x = 0.005, 0.01, 0.015, 0.02) composition can be densified between 900 and 990 °C. The microwave dielectric constants lie between 36 and 45 and the pores in ceramics were found to be the main influence. The Q values changes between 1400 and 2900 with different x values and sintering temperatures while Q_f values lie between 6000 and 16,000 GHz. The microwave dielectric losses, mainly affected by the grain size, pores, and the secondary phase, are discussed. The (Bi_1−xCu_x)(Nb_1−xW_x)O₄ ceramics and copper electrode was co-fired under N₂ atmosphere at 850 °C and the EDS analysis showed no reaction between the dielectrics and copper electrodes. This result presented the (Bi_1−xCu_x)(Nb_1−xW_x)O₄ dielectric materials to be good candidates for LTCC applications with copper electrode.     

Structure and microwave dielectric properties of Nd(2−x)/3LixTiO3

The structure evolution, and microwave dielectric properties of Nd_(2−x)/3Li_xTiO₃ ceramics (0 ≤ x ≤ 0.5) were investigated in this paper. X-ray diffraction (XRD) and scanning electron microscopy (SEM) results show that samples with x = 0.2–0.4 exhibit single phase. Multi-phases of Nd₂Ti₂O₇, Nd_2/3TiO₃ and Nd₂Ti₄O₁₁ were observed when x = 0 and 0.1. The concentration and ordering degree of A-site decrease with the increase of x value. The dielectric constant increases up to x = 0.2 and then decreases with the further increase of x value. The Qf value decreases with the increase of x value. The temperature coefficient of resonant frequency exhibits negative value and the absolute value decreases greatly with the decrease of x value.     

Microwave dielectric properties of rutile (Zn1/3Nb2/3)0.40(Ti1−xSnx)0.60O2 (0.15 ≤ x ≤ 0.30) ceramics

Microwave dielectric properties of (Zn_1/3Nb_2/3)_0.40(Ti_1−xSn_x)_0.60O₂ ceramics were investigated as a function of SnO₂ content (0.15 ≤ x ≤ 0.30). A single phase with tetragonal rutile structure was obtained through the entire composition. The unit-cell volume of the specimens was increased with SnO₂ content, due to the larger ionic radius of Sn⁴⁺ (0.69 Å) than that of Ti⁴⁺ (0.605 Å) for octahedral site. Dielectric constant (K) of the sintered specimens was affected by the dielectric polarizability. Quality factor (Qf) was dependent on the degree of reduction of Ti⁴⁺ ion. With an increase of SnO₂ content, the temperature coefficient of resonant frequency (TCF) of the specimens decreased due to the decrease of the octahedral distortion of rutile structure.     

Relationships between crystal structure and microwave dielectric properties of (Zn1/3B2/3)xTi1 − xO2 (B = Nb, Ta) ceramics

Dependence of microwave dielectric properties on the crystal structure of (Zn_1/3B_2/3⁵⁺)_xTi_1 − xO₂ (B⁵⁺ = Nb, Ta) ceramics was investigated as a function of Zn_1/3B_2/3⁵⁺O₂ (B⁵⁺ = Nb, Ta) content (0.4 ≤ x ≤ 0.7). Dielectric constant (K) and the temperature coefficient of resonant frequency (TCF) of sintered specimens were strongly dependent on the structural characteristics of oxygen octahedra in rutile structure. Cation rattling and the distortion of oxygen octahedra were dependent on the bond length ratio of apical (d_apical)/equatorial (d_equatorial) of oxygen octahedra. The quality factor (Qf) was dependent on the reduction of Ti ion as well as the microstructure of the sintered specimens.     

The homogeneity range and the microwave dielectric properties of the BaZn2Ti4O11 ceramics

Ceramics with a composition close to BaZn₂Ti₄O₁₁ were synthesized according to various substitutional mechanisms in order to verify an existence of a homogeneity range in the vicinity of this composition. Structural and microstructural investigations showed that the crystal structure of BaZn₂Ti₄O₁₁ was formed in the homogeneity range corresponding to the formula BaZn_2 − xTi₄O_11 − x (0 < x < 0.1). Densely sintered BaZn_2 − xTi₄O_11 − x (0 < x < 0.1) ceramics exhibited a dielectric constant around 30, τ_f = −30 ppm/K and high Q × f values, which increased from 68,000 GHz at x = 0 to 83,000 GHz at x = 0.05. Structurally, the deficiency of Zn in BaZn_2 − xTi₄O_11 − x (0 < x < 0.1) resulted in a slight decrease in the unit-cell volume. The influence of secondary phases in the BaZn₂Ti₄O₁₁-based materials on the microwave dielectric properties was also investigated. A presence of small amounts of ZnO, BaTiO₃, hollandite-type solid solutions (Ba_xZn_xTi_8 − xO₁₆) and BaTi₄O₉ caused a decrease in Q × f values.     

Synthesis and properties of lanthanum hexaaluminate ceramic La1−xCaxAl11−y−zMgyTizO18

The aim of the present work is to obtain ceramic materials with a hexagonal structure and high density, hardness and mechanical strength at lower synthesis temperature. Ceramic samples with nominal composition La_1−xCa_xAl_11−y−zMg_yTi_zO₁₈ (x=0–1; y=0–3; z=0–3,5) are prepared. The samples are sintered at temperature 1500 °C by one-stage and two-stage ceramic technology. By X-ray diffraction and scanning electron microscopy, predominant phase LaAl₁₁O₁₈ and second phases LaAlO₃ and -Al₂O₃ are identified. Ceramic materials are characterized with high physico-mechanical properties and may be find application for production of mill bodies and materials for immobilization of nuclear waste.     

Electrical resistivity and thermopower of (La1−xSrx)MnO3 and (La1−xSrx)CoO3 at elevated temperatures

Electrical resistivity and Seebeck (S) measurements were performed on (La_1−xSr_x)MnO₃ (0.02x0.50) and (La_1−xSr_x)CoO₃ (0x0.15) in air up to 1073 K. (La_1−xSr_x)MnO₃ (x0.35) showed a metal-to-semiconductor transition; the transition temperature almost linearly increased from 250 to 390 K with increasing Sr content. The semiconductor phase above the transition temperature showed negative values of S. (La_1−xSr_x)CoO₃ (0x0.10) showed a semiconductor-to-metal transition at 500 K. Dominant carriers were holes for the samples of x0.02 above room temperature. LaCoO₃ showed large negative values of S below ca. 400 K, indicative of the electron conduction in the semiconductor phase.     

Hydrotreating properties of mixed NbxMo1−xS2 alumina supported catalysts

Niobium-molybdenum disulfide solid solution (Nb_xMo_1−xS₂) has been prepared in a dispersed state on gamma alumina. The existence of this solid solution supported on alumina carrier has been proven with the help of EXAFS technique. The catalytic properties of these materials have been studied in hydrogenation and hydrodesulfurization reactions. Interestingly, as already observed for niobium sulfide, the activity of the Nb_xMo_1−xS₂ solid solution (HDS of DBT, P_tot=33 bar) is not decreased in the presence of H₂S up to p(H₂S)=200 Torr, at least up to x=0.4.     

AFeO3 (A=La, Nd, Sm) and LaFe1−xMgxO3 perovskites as methane combustion and CO oxidation catalysts: structural, redox and catalytic properties

Catalytic methane combustion and CO oxidation were investigated over AFeO₃ (A=La, Nd, Sm) and LaFe_1−xMg_xO₃ (x=0.1, 0.2, 0.3, 0.4, 0.5) perovskites prepared by citrate method and calcined at 1073 K. The catalysts were characterized by X-ray diffraction (XRD). Redox properties and the content of Fe⁴⁺ were derived from temperature programmed reduction (TPR). Specific surface areas (SA) of perovskites were in 2.3–9.7 m² g⁻¹ range. XRD analysis showed that LaFeO₃, NdFeO₃, SmFeO₃ and LaFe_1−xMg_xO₃ (x·0.3) are single phase perovskite-type oxides. Traces of La₂O₃, in addition to the perovskite phase, were detected in the LaFe_1−xMg_xO₃ catalysts with x=0.4 and 0.5. TPR gave evidence of the presence in AFeO₃ of a very small fraction of Fe⁴⁺ which reduces to Fe³⁺. The fraction of Fe⁴⁺ in the LaFe_1−xMg_xO₃ samples increased with increasing magnesium content up to x=0.2, then it remained nearly constant. Catalytic activity tests showed that all samples gave methane and CO complete conversion with 100% selectivity to CO₂ below 973 and 773 K, respectively. For the AFeO₃ materials the order of activity towards methane combustion is La>Nd>Sm, whereas the activity, per unit SA, of the LaFe_1−xMg_xO₃ catalysts decreases with the amount of Mg at least for the catalysts showing a single perovskite phase (x=0.3). Concerning the CO oxidation, the order of activity for the AFeO₃ materials is Nd>La>Sm, while the activity (per unit SA) of the LaFe_1−xMg_xO₃ catalysts decreases at high magnesium content.     

Synthesis, characterisation and properties of (Ba1 − xSrx) (Nd1/2Nb1/2) O3 ceramics for application as dielectric resonators in microwave circuits

The (Ba_{1 − x}Sr_x) (Nd_1/2Nb_1/2) O₃ ceramics have been prepared by the conventional ceramic route for different values of x. Addition of a small amount of CeO₂ (1 wt%) as a sintering aid increased the density of the samples. The structure and microstructure of the sintered samples are studied by X-ray diffraction and SEM methods. The dielectric properties of the samples are measured in the microwave frequency region as a function of composition. The dielectric constant decreases as x increases. The coefficient of thermal variation of resonant frequency decreases as the Sr content increases and goes to the negative side. The dielectric properties of (Ba_{1 − x}Sr_x) (Nd_1/2Nb_1/2) O₃ are in the range suitable for application as dielectric resonators in microwave circuits.     

Preparation, microstructure and microwave dielectric properties of ZrxTi1−xO4 (x=0.40–0.60) ceramics

Zr_xTi_1−xO₄ (x=0.40–0.60) ceramics sintered without additives were prepared from powders made by the coprecipitation of metal salts from aqueous solutions in order to investigate the existence range of a homogeneous phase and the relationships between composition, microstructure and the dielectric properties. XRD, TEM, SEM, EDS, and the dielectric measurements were used to characterize the products. A homogeneous solid solution was obtained. Its crystal structure was isomorphous with ZrTiO₄. The variation of the lattice parameters with TiO₂ content was discussed. The optimum sintering temperature of samples was dependent of composition. TiO₂ suppressed the densification and acted as a grain growth enhancer during the sintering process. With the increase in TiO₂ content the relative densities of the sintered bodies decrease, while the grain sizes increase. The dielectric properties at microwave frequency (1.8 GHz) in this system, especially Q value, were poor, due to low densification, impurities and lattice defects. The dielectric constant _r and Q value exhibited a significant dependence on the relative density and composition. Both _r and Q increased with the increase in relative density, but they were primarily influenced by the composition and the effect of the relative density could be ignored when the relative density was greater than 90% theoretical. _r increased slightly with increasing TiO₂ content, while Q value decreased.     

AMnO3 (A=La, Nd, Sm) and Sm1−xSrxMnO3 perovskites as combustion catalysts: structural, redox and catalytic properties

Catalytic combustion of methane has been investigated over AMnO₃ (A = La, Nd, Sm) and Sm_1−xSr_xMnO₃ (x = 0.1, 0.3, 0.5) perovskites prepared by citrate method. The catalysts were characterized by chemical analysis, XRD and TPR techniques. Catalytic activity measurements were carried out with a fixed bed reactor at T = 623–1023 K, space velocity = 40 000 N cm³ g⁻¹ h⁻¹, CH₄ concentration = 0.4% v/v, O₂ concentration = 10% v/v.

Specific surface areas of perovskites were in the range 13–20 m² g⁻¹. XRD analysis showed that LaMnO₃, NdMnO₃, SmMnO₃ and Sm_1−xSr_xMnO₃ (x = 0.1) are single phase perovskite type oxides. Traces of Sm₂O₃ besides the perovskite phase were detected in the Sm_1−xSr_xMnO₃ catalysts for x = 0.3, 0.5. Chemical analysis gave evidence of the presence of a significant fraction of Mn(IV) in AMnO₃. The fraction of Mn(IV) in the Sm_1−xSr_xMnO₃ samples increased with x. TPR measurements on AMnO₃ showed that the perovskites were reduced in two steps at low and high temperature, related to Mn(IV) → Mn(III) and Mn(III) → Mn(II) reductions, respectively. The onset temperatures were in the order LaMnO₃ > NdMnO₃ > SmMnO₃. In Sm_1−xSr_xMnO₃ the Sr substitution for Sm caused the formation of Mn(IV) easily reducible to Mn(II) even at low temperature. Catalytic activity tests showed that all samples gave methane complete conversion with 100% selectivity to CO₂ below 1023 K. The activation energies of the AMnO₃ perovskites varied in the same order as the onset temperatures in TPR experiments suggesting that the catalytic activity is affected by the reducibility of manganese. Sr substitution for Sm in SmMnO₃ perovskites resulted in a reduction of activity with respect to the unsubstituted perovskite. This behaviour was related to the reduction of Mn(IV) to Mn(II), occurring under reaction conditions, hindering the redox mechanism.     

Methane combustion and CO oxidation on LaAl1−xMnxO3 perovskite-type oxide solid solutions

Structural, redox and catalytic deep oxidation properties of LaAl_1−xMn_xO₃ (x=0.0, 0.05, 0.1, 0.2, 0.4, 0.6, 0.8, 1.0) solid solutions prepared by the citrate method and calcined at 1073 K were investigated. XRD analysis showed that all the LaAl_1−xMn_xO₃ samples are single phase perovskite-type solid solutions. Particle sizes and surface areas (SA) are in the 280–1180 Å and 4–33 m² g⁻¹ ranges, respectively. Redox properties and the content of Mn⁴⁺ were derived from temperature programmed reduction (TPR) with H₂. Two reduction steps are observed by TPR for pure LaMnO₃, the first attributed to the reduction of Mn⁴⁺ to Mn³⁺ and the second due to complete reduction of Mn³⁺ to Mn²⁺. The presence of Al in the LaAl_1−xMn_xO₃ solid solutions produces a strong promoting effect on the Mn⁴⁺→Mn³⁺ reducibility and inhibits the further reduction to Mn²⁺. Both for methane combustion and CO oxidation all Mn-containing perovskites are much more active than LaAlO₃, so pointing to the essential role of the transition metal ion in developing highly active catalysts. Partial dilution with Al appears to enhance the specific activity of Mn sites for methane combustion.     

Electronic and structural properties of SnxTi1−xO2 solid solutions: a periodic DFT study

The structural and electronic properties of selected compositions of Sn_xTi_1−xO₂ solid solutions (x=0, 1/24, 1/16, 1/12, 1/8, 1/6, 1/4, 1/2, 3/4, 5/6, 7/8, 11/12, 15/16, 23/24 and 1) were investigated by means of periodic density functional theory (DFT) calculations at B3LYP level. The calculations show that the corresponding lattice parameters vary non-linearly with composition, supporting positive deviations from Vegard’s law in the Sn_xTi_1−xO₂ system. Our results also account for the fact that chemical decomposition in Sn_xTi_1−xO₂ system is dominated by composition fluctuations along [0 0 1] direction. A nearly continuous evolution of the direct band gap and the Fermi level with the growing value of x is predicted. Ti 3d states dominate the lower portion of the conduction band of Sn_xTi_1−xO₂ solid solutions. Sn substitution for Ti in TiO₂ increases the oxidation–reduction potential of the oxide as well as it renders the lowest energy transition to be indirect. These two effects can be the key factors controlling the rate for the photogenerated electron–hole recombination. These theoretical results are capable to explain the enhancement of photoactivity in Sn_xTi_1−xO₂ solid solutions.     

Formation of LiNixCo1−xO2 by decarbonization of organic gel precursors through treatment with nitric acid and hydrogen peroxide

We have used a complex sol–gel process to synthesize a family of compounds LiNi_xCo_1−xO₂ (x = 0, 0.25, 0.5, 0.75, 1). These compounds are candidates for electrode materials in high-energy-density batteries. Starting sols were prepared from xNi²⁺ + (1 − x) Co²⁺ acetates/ascorbic acid aqueous solutions by alkalizing with LiOH and NH₃. With thermal treatment in air, nickel carbonates formed in quantities roughly proportional to Ni concentration. The carbonate impurities could not be fully removed by heating in air to high temperatures. Because formation of pure layered oxides was inhibited by the presence of the carbonates, we developed a new way to remove them from just-formed precursors by treating the intermediate phases (those formed after calcination at 750 °C) with concentrated HNO₃ and H₂O₂. All resulting powders were phase pure by X-ray diffraction and were easily friable. Various electrochemical properties of compacts prepared from these powders were measured.     

Microwave absorption materials — IV Preparation of the mixed layer structure phases, RexTa1−xS2 and OsxTa1−xS2, and some electrical and magnetic properties

The binary systems ReS₂–TaS₂ and OsS₂-TaS₂ are studied. Mixed layer structure (MLS) phases are found in Re_xTa_1−xS₂ with a composition range of 0.25x0.5, as well as in the Os_xTa_1−xS₂ with a composition range of 0.26x0.33. The MLSs of both phases are constructed by a random and mixed stacking of the 2Hb-layers and 3R-layers. The magnetic susceptibilities of samples from both phases show a weak Pauli-paramagnetism. The paramagnetic moment and the electrical conductivity of both phases decrease as the composition x increases. The behaviour of the paramagnetic moment and the electrical conductivity of those phases offer us a good example of the number of conduction electrons and their effect.     

Effect of glass additions on the sintering and microwave properties of composite dielectric ceramics based on BaO–Ln2O3–TiO2 (Ln = Nd, La)

Ten weight percent BBZS (Bi₂O₃, B₂O₃, ZnO and SiO₂) glass was added to x(Ba₄Nd_9.333Ti₁₈O₅₄) − (1 − x)(BaLa₄Ti₄O₁₅) (BNLT, 0 ≤ x ≤ 1) composite dielectric ceramics to lower their sintering temperature whilst retaining microwave properties useful for low temperature co-fired ceramic and antenna core technology. With the addition of 10 wt% BBZS glass, dense BNLT composite ceramics were produced at temperatures between 950 and 1140 °C, depending on composition (x), an average reduction of sintering temperature by 350 °C. X-ray diffraction, scanning and transmission electron microscopy and Raman spectroscopy studies revealed that there was limited inter-reaction between BLT/BNT and the BBZS glass. Microwave property measurement showed that the addition of BBZS glass to BNLT ceramics had a negligible effect on _r and τ_f, although deterioration in the measured quality factor (Qf) was observed. The optimised composition (xBNT − (1 − x)BLT)/0.1BBZS (x = 0.75) had _r  61, τ_f  38 ppm/°C and Qf  2305 GHz.     

Enhanced dielectric tunability properties of Ba(ZrxTi1−x)O3 thin films using seed layers on Pt/Ti/SiO2/Si substrates

The compositionally graded and homogeneous Ba(Zr_xTi_1−x)O₃ (BZT) thin films were fabricated on LaNiO₃ (LNO) buffered Pt/Ti/SiO₂/Si and Pt/Ti/SiO₂/Si substrates by a sol–gel deposition method, respectively. These films crystallized into a single perovskite phase. The BZT thin films deposited on LaNiO₃/Pt/Ti/SiO₂/Si substrates had a highly (1 0 0) preferred orientation and exhibited a preferred (1 1 0) orientation when the thin films were deposited on Pt/Ti/SiO₂/Si substrates. The LNO and Ba(Zr_0.30Ti_0.70) served as seed layer on Pt/Ti/SiO₂/Si substrates and analyze the relationship of seed layer, microstructure and dielectric behavior of the thin films. The compositionally graded thin films from BaTiO₃ to BaZr_0.35Ti_0.65O₃ were fabricated on LNO/Pt/Ti/SiO₂/Si substrates. The tunability behavior of compositionally graded films was analyzed in order to produce optimum effective dielectric properties. The dielectric constant of BaZr_xTi_1−xO₃ compositionally graded thin films showed weak temperature dependence. This kind of thin films has a potential in a fabrication of a temperature stable tunable device.     

Fabrication and thermoelectric properties of heavily rare-earth metal-doped SrO(SrTiO3)n (n = 1, 2) ceramics

To clarify the effect of substitutional electron doping on the thermoelectric figure of merit (ZT = S²σTκ⁻¹) of Ruddlesden–Popper phase SrO(SrTiO₃)_n (or Sr_n+1Ti_nO_3n+1), measurements were conducted for several thermoelectric parameters, e.g. electrical conductivity (σ), Seebeck coefficient (S) and thermal conductivity (κ), of (Sr_1−xRE_x)_n+1Ti_nO_3n+1 (n = 1 or 2, RE (rare earth): La or Nd, x = 0.05 and 0.1) dense ceramics prepared by a conventional solid-state reaction and hot-pressing technique. Crystal structures of the resultant ceramics were represented as (Sr_1−xRE_x)_n+1 Ti_nO_3n+1 evaluated by powder X-ray diffraction followed by the Rietveld analysis. All the ceramics exhibited electrical conductivity and the σ values simply depended on the dopant concentration, indicating that both La³⁺ and Nd³⁺ ions act as electron donors. The |S| values increased with temperature due to decrease in the chemical potential. Significant reduction of the κ values was observed as compared to cubic-perovskite SrTiO₃. The ZT value increased with temperature and reached 0.15 at 1000 K for (Sr_0.95La_0.05)₃Ti₂O₇.     

Ce1−xCuxO2−x/Al2O3/FeCrAl catalysts for catalytic combustion of methane

A series of the Ce_1−xCu_xO_2−x/Al₂O₃/FeCrAl catalysts (x = 0–1) were prepared. The structure of the catalysts was characterized using XRD, SEM and H₂-TPR. The catalytic activity of the catalysts for the combustion of methane was evaluated. The results indicated that in the Ce_1−xCu_xO_2−x/Al₂O₃/FeCrAl catalysts the surface phase structure were the Ce_1−xCu_xO_2−x solid solution, -Al₂O₃ and γ-Al₂O₃. The surface particle shape and size were different with the variety of the molar ratio of Ce to Cu in the Ce_1−xCu_xO_2−x solid solution. The Cu component of the Ce_1−xCu_xO_2−x/Al₂O₃/FeCrAl catalysts played an important role to the catalytic activity for the methane combustion. There were the stronger interaction among the Ce_1−xCu_xO_2−x solid solution and the Al₂O₃ washcoats and the FeCrAl support.