New dielectric material system of La(Mg1/2Ti1/2)O3–Ca0.6La0.8/3TiO3 for microwave applications

The microstructure and microwave dielectric properties of xLa(Mg_1/2Ti_1/2)O₃–(1 − x)Ca_0.6La_0.8/3TiO₃ ceramics system with ZnO additions (0.5 wt.%) investigated by the conventional solid-state route have been studied. Doping with ZnO (0.5 wt.%) can effectively promote the densification and the dielectric properties of xLa(Mg_1/2Ti_1/2)O₃–(1 − x)Ca_0.6La_0.8/3TiO₃ ceramics. 0.6La(Mg_1/2Ti_1/2)O₃–0.4Ca_0.6La_0.8/3TiO₃ ceramics with 0.5 wt.% ZnO addition possess a dielectric constant (_r) of 43.6, a Q × f value of 48,000 (at 8 GHz) and a temperature coefficient of resonant frequency (τ_f) of −1 ppm/°C sintering at 1475 °C. As the content of La(Mg_1/2Ti_1/2)O₃ increases, the highest Q × f value of 62,900 (GHz) for x = 0.8 is achieved at the sintering temperature 1475 °C. A parallel-coupled line band-pass filter is designed and simulated using the proposed dielectric to study its performance.     

Structure, microstructure and electrical properties of (1 − x − y)Bi0.5Na0.5TiO3–xBi0.5K0.5TiO3–yBi0.5Li0.5TiO3 lead-free piezoelectric ceramics

The ternary system (1 − x − y)Bi_0.5Na_0.5TiO₃–xBi_0.5K_0.5TiO₃–yBi_0.5Li_0.5TiO₃ (abbreviated to BNKLT-x/y) was synthesized by conventional oxide-mixed method. The phase structure, microstructure, and dielectric, ferroelectric and piezoelectric properties of the ceramics were investigated. The X-ray diffraction patterns showed that pure perovskite phase with rhombohedral structure can be obtained in all the ceramics. The grain size varied with x and y. The temperature dependence of dielectric constant and dielectric loss revealed there were two phase transitions which were from ferroelectric (tetragonal) to anti-ferroelectric (rhombohedral) and anti-ferroelectric to paraelectric (cubic). Either increasing x or y content can make T_m (the temperature at which dielectric constant _r reaches the maximum) increase. With the addition of Bi_0.5K_0.5TiO₃, the remanent polarization P_r increased but the coercive field E_c decreased. With the addition of Bi_0.5Li_0.5TiO₃, P_r increased obviously and E_c increased slightly. Due to the stronger ferroelectricity by modifying Bi_0.5K_0.5TiO₃ and Bi_0.5Li_0.5TiO₃, the piezoelectric properties were enhanced at x = 0.22 and y = 0.10, which were as follows: P_r = 31.92 μC/cm², E_c = 32.40 kV/cm, _r = 1118, tan δ = 0.041, d₃₃ = 203 pC/N and K_p = 0.31. The results show that the BNKLT-x/y ceramics are promising candidates for the lead-free materials.     

Low temperature sintering and microwave dielectric properties of (Mg0.7Zn0.3)0.95Co0.05TiO3 ceramics with BaCu(B2O5) additions

The effects of BaCu(B₂O₅) additives on the sintering temperature and microwave dielectric properties of (Mg_0.7Zn_0.3)_0.95Co_0.05TiO₃ ceramics were investigated. The (Mg_0.7Zn_0.3)_0.95Co_0.05TiO₃ ceramics were not able to be sintered below 1000 °C. However, when BaCu(B₂O₅) were added, they were sintered below 1000 °C and had the good microwave dielectric properties. It was suggested that a liquid phase with the composition of BaCu(B₂O₅) was formed during the sintering and assisted the densification of the (Mg_0.7Zn_0.3)_0.95Co_0.05TiO₃ ceramics at low temperature. BaCu(B₂O₅) powders were produced and used to reduce the sintering temperature of the (Mg_0.7Zn_0.3)_0.95Co_0.05TiO₃ ceramics. Good microwave dielectric properties of Q × f = 35,000 GHz, ?_r = 18.5.0 and τ_f = −51 ppm/°C were obtained for the (Mg_0.7Zn_0.3)_0.95Co_0.05TiO₃ ceramics containing 7 wt.% mol% BaCu(B₂O₅) sintered at 950 °C for 4 h.     

Structure and dielectric characterization of xNd(Mg1/2Ti1/2)O3-(1 − x)Ca0.6La0.8/3TiO3 in the microwave frequency range

The crystal structures, phase compositions and the microwave dielectric properties of the xLa(Mg_1/2Ti_1/2)O₃-(1 − x)Ca_0.8Sr_0.2TiO₃ composites prepared by the conventional solid state route have been investigated. The formation of solid solution is confirmed by the XRD patterns. Doping with B₂O₃ (0.5 wt.%) can effectively promote the densification and the dielectric properties of xNd(Mg_1/2Ti_1/2)O₃-(1 − x)Ca_0.6La_0.8/3TiO₃ ceramics. It is found that xNd(Mg_1/2Ti_1/2)O₃-(1 − x)Ca_0.6La_0.8/3TiO₃ ceramics can be sintered at 1375 °C, due to the liquid phase effect of B₂O₃ addition observed by Scanning Electronic Microscopy. At 1375 °C, 0.4Nd(Mg_1/2Ti_1/2)O₃-0.6Ca_0.6La_0.8/3TiO₃ ceramics with 1 wt.% B₂O₃ addition possesses a dielectric constant (?_r) of 49, a Q × f value of 13,000 (at 8 GHz) and a temperature coefficients of resonant frequency (τ_f) of 1 ppm/°C. As the content of Nd(Mg_1/2Ti_1/2)O₃ increases, the highest Q × f value of 20,000 GHz for x = 0.9 is achieved at the sintering temperature 1400 °C.     

Phase evolution and microwave dielectric properties of TiO2-modified (Mg0.95Co0.05)2TiO4 ceramics

Phase evolution and microwave dielectric properties of (1 − x)(Mg_0.95Co_0.05)₂TiO₄-xTiO₂ (x = 0-1) ceramics prepared by the conventional mixed oxide route have been investigated. Increasing the TiO₂ content would lead to a main phase transformation from (Mg_0.95Co_0.05)₂TiO₄ to (Mg_0.95Co_0.05)TiO₃, (Mg_0.95Co_0.05)Ti₂O₅ and then TiO₂. Not only did the TiO₂ addition compensate the τ_f, it also lowered the sintering temperature of specimen. A huge drop of Q × f occurs at a 40-60 mol% TiO₂ addition was attributed to the formation of (Mg_0.95Co_0.05)Ti₂O₅ phase. Specimen with x = 0.78 can possess an excellent combination of microwave dielectric properties: ?_r ∼ 24.77, Q × f ∼ 38,500 GHz and τ_f ∼ −1.3 ppm/°C.     

Monoclinic phases and stress-relief conditions in (1 − x)Pb(Mg1/3Nb2/3)TiO3–xPbTiO3 solid solutions

A comparative study on heterophase states in perovskite-type solid solutions of (1 − x)Pb(Mg_1/3Nb_2/3)TiO₃–xPbTiO₃ is carried out for compositions near the morphotropic phase boundary. The conditions for mechanical stress relief at elastic matching of phases are analysed at x = const in a wide temperature range. The heterophase states concerned with the presence of the intermediate monoclinic phase are interpreted using the domain state–interface diagrams calculated for x = 0.28, 0.32 and 0.34. It is shown that optimum volume fraction parameters of the domains in the monoclinic phase of the B type are varied in relatively wide ranges and promote complete stress relief with cubic–monoclinic phase coexistence. Two scenarios of stress relief at x = 0.32 are considered in connection with different heterophase states (either tetragonal–monoclinic of the B type or tetragonal–monoclinic of the C type) in a wide temperature range. Possibilities of elastic matching of two polydomain phases (tetragonal–monoclinic of the B type) with almost equal relative widths of the domains in these phases are shown for x = 0.34. The active role of domains of the monoclinic phases in stress relief and forming the planar unstrained interfaces is discussed.     

Crystal structure and dielectric properties of La(Mg0.5Ti0.5)O3-Ca0.8Sm0.4/3TiO3 solid solution system at microwave frequencies

The crystal structure and the dielectric properties of (1 − x)La(Mg_0.5Ti_0.5)O₃-xCa_0.8Sm_0.4/3TiO₃ ceramics have been investigated. Ca_0.8Sm_0.4/3TiO₃ was employed as a τ_f compensator and was added to La(Mg_0.5Ti_0.5)O₃ to achieve a temperature-stable material. The formation of (1 − x)La(Mg_0.5Ti_0.5)O₃-xCa_0.8Sm_0.4/3TiO₃ solid solutions were confirmed by the XRD results and the measured lattice parameters for all compositions. The dielectric properties are strongly correlated to the sintering temperature and the compositional ratio of the specimens. Although the ?_r of the specimen could be boosted by increasing the amount of Ca_0.8Sm_0.4/3TiO₃, it would instead render a decrease in the Q × f. The τ_f value is strongly correlated to the compositions and can be controlled by the existing phases. A new microwave dielectric material 0.45La(Mg_0.5Ti_0.5)O₃-0.55Ca_0.8Sm_0.4/3TiO₃, possessing a fine combination of microwave dielectric properties with an ?_r of 47.83, a Q × f of 26,500 GHz (at 6.2 GHz) and a τ_f of −1.7 ppm/°C, is proposed as a very promising candidate material for today's 3G applications.     

Studies on structural and electrical properties of Co1−xNixFe1.9Mn0.1O4 ferrite

Nickel-doped iron-deficient cobalt ferrite with small amount of manganese having the chemical composition Co_1−xNi_xFe_1.9Mn_0.1O₄, with x = 0.2, 0.4, 0.6 and 0.8, were prepared by standard double sintering ceramic method. The spinel phase formation was confirmed by X-ray diffraction (XRD). The DC resistivity measurements with temperature indicate a semiconducting behavior showing a linear decrease with increasing temperature and the doping of Ni enhances the resistivity. Maximum resistivity of the order of 10⁹ Ω cm was found for composition x = 0.8. Room temperature dielectric constant measurements with frequency (100 Hz to 1 MHz), show usual dielectric dispersion. Also, the variation of room temperature AC conductivity as a function of frequency were studied and explained by using Maxwell–Wagner two-layer model. The studies on dielectric constant (′), loss tangent (tan δ) and AC conductivity (σ_AC), at four different frequencies (viz., 1, 10, 100 kHz and 1 MHz), with temperature were made.     

Investigation of the microwave dielectric properties of Ca1−xMgxLa4Ti5O17 ceramics for application in coplanar patch antenna

In this paper, the dielectric properties of Ca_1−xMg_xLa₄Ti₅O₁₇ ceramics at microwave frequency have been studied. The diffraction peaks of Ca_(1−x)Mg_xLa₄Ti₅O₁₇ ceramics nearly unchanged with x increasing from 0 to 0.03. Similar X-ray diffraction peaks of Ca_0.99Mg_0.01La₄Ti₅O₁₇ ceramic were observed at different sintering temperatures. A maximum density of 5.3 g/cm³ can be obtained for Ca_0.99Mg_0.01La₄Ti₅O₁₇ ceramic sintered at 1500 °C for 4 h. A maximum dielectric constant (_r) and quality factor (Q × f) of Ca_0.99Mg_0.01La₄Ti₅O₁₇ ceramic sintered at 1500 °C for 4 h are 56.3 and 12,300 GHz (at 6.4 GHz), respectively. A near-zero temperature coefficient of resonant frequency (τ_f) of −9.6 ppm/°C can be obtained for Ca_0.99Mg_0.01La₄Ti₅O₁₇ ceramic sintered at 1500 °C for 4 h. The measurement results for the aperture-coupled coplanar patch antenna at 2.5 GHz are presented. With this technique, a 3.33% bandwidth (return loss <−10 dB) with a center frequency at approximately 2.5 GHz has been successfully achieved.     

X-ray diffraction study of Ba0.985Na0.015Ti0.985Nb0.015O3, Ba0.6Na0.4Ti0.6Nb0.4O3 and Ba0.3Na0.7Ti0.3Nb0.7O3 compositions

The Ba_0.985Na_0.015Ti_0.985Nb_0.015O₃, Ba_0.6Na_0.4Ti_0.6Nb_0.4O₃ and Ba_0.3Na_0.7Ti_0.3Nb_0.7O₃ compositions of the (1 − x) BaTiO₃–xNaNbO₃ (BTNNx) system have been studied by X-ray diffraction and by measurements of dielectric properties. The specimens with composition BTNN (x = 0.015, 0.40 and 0.70) have been refined by the JANA program from X-ray powder diffraction data. Ceramic samples with composition (1 − x) BaTiO₃ + xNaNbO₃ (where x = 0.015, 0.40 and 0.70) were prepared by calcinations from appropriate mixture of BaCO₃, TiO₂, Na₂CO₃ and Nb₂O₅. The calcined powder was sintered at temperature range 1200–1400 °C. As the composition x increased from 0.015 (and 0.70), the ferroelectric ceramics (x = 0.015, FE) with tetragonal phase changed to the ferroelectric relaxors (RFE, x = 0.40). RFE ceramics showed a peculiar diffuse phase transition and dielectric relaxation at the low temperature (down to 180 K) due to a frustration between RFE and FE state. These ceramics present the classical ferroelectric character when 0 ≤ x < 0.075 and 0.55 < x ≤ 1 and relaxor character when 0.075 ≤ x ≤ 0.55.     

Sinterability and dielectric properties of Ba0.55Sr0.4Ca0.05TiO3-CaTiSiO5-Mg2TiO4 composite ceramics

The composite ceramics of Ba_0.55Sr_0.4Ca_0.05TiO₃-CaTiSiO₅-Mg₂TiO₄ (BSCT-CTS-MT) were prepared by the conventional solid-state route. The sintering performance, phase structures, morphologies, and dielectric properties of the composite ceramics were investigated. The BSCT-CTS-MT ceramics were sintered at 1100 °C and possessed dense microstructure. The dielectric constant was tailored from 1196 to 141 as the amount of Mg₂TiO₄ increased from 0 to 50 wt%. The dielectric constant and dielectric loss of 40 wt% Ba_0.55Sr_0.4Ca_0.05TiO₃-10 wt% CaTiSiO₅-50 wt% Mg₂TiO₄ was 141 and 0.0020, respectively, and the tunability was 8.64% under a DC electric field of 8.0 kV/cm. The Curie peaks were broadened and depressed after the addition of CaTiSiO₅. The optimistic dielectric properties made it a promising candidate for the application of tunable capacitors and phase shifters.     

Structural, magnetic and electrical properties of (La0.70−xNdx)Sr0.30Mn0.70Cr0.30O3 with 0 ≤ x ≤ 0.30

The structural, magnetic and electrical properties of (La_0.70−xNd_x)Sr_0.30Mn_0.70Cr_0.30O₃ perovskites (0 ≤ x ≤ 0.30) prepared by the usual ceramic procedure were investigated. Structural Rietveld refinement revealed that these compounds crystallize in a rhombohedral perovskite structure when x = 0, 0.10 and 0.20, while for x = 0.30 the structure becomes orthorhombic (Pbnm). It was found that the substitution of La by Nd reduces the Curie temperature (T_C). The FC, ZFC, M(H) and AC susceptibility measurements show typical canted-antiferromagnetism for the Nd-doped samples, in which a ferromagnetic component coexists with predominant antiferromagnetic interactions. The values of the magnetization (M(H)) decrease very slightly when increasing the Nd content, compared to the undoped sample (M_S values at 5 T and 2 K are, respectively, 47.9, 47.3 and 47.5 emu/g for x = 0.10, 0.20 and 0.30, compared to 48.2 emu/g for x = 0), indicating that the Nd³⁺ contribution is negligible compared to the total moment of the ferromagnetic (Mn/Cr) network. The resistivity increases by several orders of magnitude with Nd-doping and the semi-conducting behaviour persists in the whole temperature range. The interaction between Mn⁴⁺–O–Cr³⁺and Cr³⁺–O–Cr³⁺ is responsible for the semi-conducting state.     

Characterization and dielectric behavior of V2O5-doped 0.9Mg0.95Co0.05TiO3–0.1Ca0.6La0.8/3TiO3 ceramic system at microwave frequency

The microwave dielectric properties and the microstructures of Mg_0.95Co_0.05TiO₃–Ca_0.6La_0.8/3TiO₃ ceramics, prepared by a mixed oxide route, have been investigated. With small amount of V₂O₅ additions, the sintering temperatures of 0.9Mg_0.95Co_0.05TiO₃–0.1Ca_0.6La_0.8/3TiO₃ ceramics can be lowered to 1250 °C. The microwave dielectric properties are found strongly correlated with the sintering temperature as well as the amount of V₂O₅ additions. The Q × f value of 0.9Mg_0.95Co_0.05TiO₃–0.1Ca_0.6La_0.8/3TiO₃ increased with increasing temperature to 1250 °C and decreased thereafter. The decrease in Q × f value was coincident with the abnormal grain growth. A maximum Q × f value of 58,000 (GHz) associated with a dielectric constant (?_r) of 21.7 and a temperature coefficient (τ_f) of ?10 ppm/°C, was achieved for 0.25 wt.% V₂O₅-doped samples at 1250 °C. Moreover, a cross-coupled compact hairpin filter with designed center frequency of 2.0 GHz is designed and fabricated using the proposed dielectric ceramic to study its performance. It also showed a substantial reduction in both insertion loss and size in comparison with other dielectrics FR4 and alumina.     

Low-firable high-K dielectric in the Zrx(Zn1/3Nb2/3)1−xTiO4 ceramic system

Composite ceramics in the solid solution of Zr_x(Zn_1/3Nb_2/3)_1−xTiO₄ (x = 0.1-0.4) have been prepared by the mixed oxide route. Formation of solid solution was confirmed by the X-ray diffraction patterns. The microwave dielectric properties, such as dielectric constant (?_r), Q × f value and temperature coefficient of resonant frequency (τ_f) have been investigated as a function of composition and sintering temperature. With x increasing from 0.1 to 0.4, the dielectric constant decreases from 70.9 to 43.2, and the τ_f decreases from 105 to 55 ppm/°C. The Q × f value, however, increases with increasing x value to a maximum 26,600 GHz (at 6 GHz) at x = 0.3, and then decreases thereafter. For low-loss microwave applications, a new microwave dielectric material Zr_0.3(Zn_1/3Nb_2/3)_0.7TiO₄, possessing a fine combination of microwave dielectric properties with a high ?_r of 51, a high Q × f of 26,600 GHz (at 6 GHz) and a τ_f of 70 ppm/°C, is suggested.     

Reaction-sintering method for ultra-low loss (Mg0.95Co0.05)TiO3 ceramics

Microwave dielectric properties and microstructures of (Mg_0.95Co_0.05)TiO₃ ceramics prepared by a new sintering method (reaction-sintering method) were investigated. A pure phase of (Mg_0.95Co_0.05)TiO₃ was obtained by the new method and excellent dielectric properties were observed due to uniformities of the microstructure and the phase. In contrast, the secondary phase (Mg_0.95Co_0.05)Ti₂O₅ was observed in samples prepared by conventional sintering method. In order to study the influence of secondary phase on the microwave dielectric properties quantitatively, the weight fraction of (Mg_0.95Co_0.05)Ti₂O₅ was calculated on the basis of Rietveld refinement. The pore-free?_r values of specimens prepared by two different methods indicated that porosity plays an important role in the ?_r values of (Mg_0.95Co_0.05)TiO₃ ceramics. Specimens sintered by reaction-sintering method at 1350 °C for 4 h possess excellent dielectric properties with an ?_r of 16.3, a Q × f value of 244,500 GHz, and a τ_f value of −53.5 ppm/°C.     

Dielectric and magnetic properties of 0.7Bi(Fe1−xCrx)O3–0.1BaTiO3–0.2PbTiO3 solid solutions

0.7Bi(Fe_1−xCr_x)O₃–0.1BaTiO₃–0.2PbTiO₃ (x = 0, 0.1, 0.2, 0.3) solid solutions were prepared by the traditional ceramic process. X-ray diffraction results revealed that the samples with x = 0–0.3 showed pure perovskite structure. Frequency and temperature dependences of dielectric constants and dielectric loss of the samples were investigated. Both dielectric constant and the loss tangent increased at given frequencies (100 Hz–1 MHz), while the Curie temperature of the solid solutions decreased with increasing Cr content. Room temperature magnetic hysteresis loops indicated that an appropriate amount of Cr could improve magnetization of the solid solutions.     

x(Mg0.7Zn0.3)0.95Co0.05TiO3-(1−x)(La0.5Na0.5)TiO3 ceramic at microwave frequency with a near zero temperature coefficient of resonant frequency

Dielectric properties of x(Mg_0.7Zn_0.3)_0.95Co_0.05TiO₃-(1?x)(La_0.5Na_0.5)TiO₃ ceramic were investigated at microwave frequencies. A nearly 0 ppm/°C temperature coefficient of resonant frequency was realized at x = 0.9. A two-phase system was confirmed by XRD analysis. A dielectric material applicable to microwave devices with a Q × f of 20,000–87,000 GHz and a dielectric constant of 21.27–26.2 was obtained at 1100 °C after 4 h of sintering. The microwave dielectric material 0.9(Mg_0.7Zn_0.3)_0.95Co_0.05TiO₃-0.1(La_0.5Na_0.5)TiO₃ sintered at 1150 °C for 4 h has a dielectric constant of 24.56, a Q × f of 68,000 GHz, and a τ_f value of 0 ppm/°C. It is proposed as a candidate dielectric for GPS patch antennas.     

Thermoelectric properties of hot-pressed Zn4Sb3−xTex

A series of samples have been fabricated through vacuum melting method followed by hot-pressing for Zn₄Sb_3−xTe_x (x = 0.02–0.08), XRD patterns indicated that all the samples were single-phased β-Zn₄Sb₃. Electrical conductivity and Seebeck coefficient were evaluated in the temperature range of 300–700 K, showing p-type conduction. The thermoelectric figure of merit (ZT) was increased with the increase of Te content. ZT values of 0.8 and 1.0 were obtained at 673 K for Zn_4.08Sb₃ and Zn₄Sb_2.92Te_0.08, respectively.     

Hydrogenation of CaLi2−xMgx (0 ≤ x ≤ 2) with C14 Laves phase structure

CaLi_2−xMg_x (0 ≤ x ≤ 2) which has the C14-type Laves phase structure has been successfully synthesized and hydrogenated. The C14-type Laves phase structure was kept after hydrogenation of CaLi_2−xMg_x (x = 0.2, 0.5, 1). After hydrogenation of CaLi₂ and CaMg₂, the Laves phase disappeared. The CaH₂ and LiH phases were formed from CaLi₂ and the CaH₂ and Mg phases from CaMg₂, respectively. CaLi_2−xMg_x (0 < x < 2) ternary alloys formed stable hydride phases with the C14-type Laves phase structure in contrast to CaLi₂ and CaMg₂ binary alloys.     

A novel proton conducting Ba0.95K0.05Ce0.6Zr0.2Gd0.16Zn0.04O3−δ for SOFC

A new proton conducting Ba_0.95K_0.05Ce_0.6Zr_0.2Gd_0.16Zn_0.04O_3−δ electrolyte membrane was prepared on NiO-based anode support by suspension spray followed by a co-sintering at 1400 °C for 4 h. Chemical stability test shows that this new proton conductor displays adequate chemical stability against CO₂ at intermediate temperatures. The conductivity of Ba_0.95K_0.05Ce_0.6Zr_0.2Gd_0.16Zn_0.04O_3−δ in humidified H₂ is about 50% higher than that of BaCe_0.6Zr_0.2Gd_0.16Zn_0.04O_3−δ from 500 to 800 °C. With La_0.8Sr_0.2MnO_3−δ cathode, fuel cell with Ba_0.95K_0.05Ce_0.6Zr_0.2Gd_0.16Zn_0.04O_3−δ electrolyte shows 1.02 V of OCV and 354 mW/cm² of maximum power density at 700 °C, respectively. And the cell performance did not degrade after running at least for 10 h.