Structure and microwave dielectric properties of BaAl2−2xLi2xSi2O8-2x ceramics

BaAl_2-2xLi_2xSi₂O_8-2x (x = 0, 0.005, 0.0075, 0.01, 0.02, 0.03) ceramics were synthesized by solid-state sintering method. Based on density functional theory, the first-principle calculations provided by the Cambridge Sequential Total Energy Package (CASTEP) software were introduced to the BaAl₂Si₂O₈ (BAS) system. In an effort to confirm the site occupied by Li⁺, we discussed the formation energy and final energy of different positions of Li⁺ doped BAS. The result demonstrated that Li⁺ should substitute Al³⁺ to promote the hexacelsian-to-celsian transformation with the aid of generated oxygen vacancies. The sintering behavior, crystal structure, surface appearance, and microwave dielectric properties of samples were investigated. Completely transformed celsian could be obtained when x = 0.005–0.03, which lowered the sintering temperature from 1400 °C (x = 0) to 1300 °C (x = 0.03), as well as strikingly improved the compactness, quality factor (Q × f) value and temperature coefficient of resonant frequency (τ_f) of BAS ceramics. When x = 0.1, unveiling the significant effects of Al-position ion substitution, BaAl_1.98Li_0.02Si₂O_7.98 ceramic sintered at 1350 °C for 5 h exhibited a supreme Q × f value of 48,620 GHz, and the ε_r and τ_f values were 6.99 and -23.29 × 10^?6 °C^?1, respectively.     

Sintering behaviour and microwave dielectric properties of BaAl2−2x(ZnSi)xSi2O8 ceramics

BaAl_2?2x(ZnSi)_xSi₂O₈ (x = 0.2–1.0) ceramics were prepared using the conventional solid-state reaction method. The sintering behaviour, phase composition and microwave dielectric properties of the prepared compositions were then investigated. All compositions showed a single phase except for x = 0.8. By substituting (Zn_0.5Si_0.5)³⁺ for Al³⁺ ions, the optimal sintering temperatures of the compositions decreased from 1475 °C (x = 0) to 1000 °C (x = 0.8), which then slightly increased to 1100 °C (x = 1.0). Moreover, the phase stability of BaAl₂Si₂O₈ was improved. A novel BaZnSi₃O₈ microwave dielectric ceramic was obtained at the sintering temperature of 1100 °C. This ceramic possesses good microwave dielectric properties with ε_r = 6.60, Q × f = 52401 GHz (at 15.4 GHz) and τ_f = ?24.5 ppm/°C.     

Crystal structure and microwave dielectric properties of temperature stable (CoxZn1–x)TiNb2O8 ceramics

(Co_xZn_1–x)TiNb₂O₈ (x = 0.2–0.8) microwave dielectric ceramics were synthesized via the conventional solid-state reaction route, and the correlation of microwave dielectric properties on the crystal structure was discussed. Crystal structures of ceramic samples were systematically investigated by X-ray powder diffraction. Moreover, composition-induced phase transitions were confirmed via the following sequence: for x ≤ 0.2, single-phase orthorhombic ixiolite (ZnTiNb₂O₈) was formed, whereas for 0.3 ≤ x<0.8, ixiolite and rutile coexisted. When x ≥ 0.8, only single-phase rutile was detected. For the (Co_xZn_1–x)TiNb₂O₈ ceramics, the microwave dielectric properties were changed with the crystal structural transitions: the dielectric constant (ε_r) and the temperature coefficient of resonant frequency (τ_f) increased upon increasing the Co²⁺, but the quality factor (Q) decreased. A near-zero τ_f = +1.6 ppm/°C was obtained in the Co_0.38Zn_0.62TiNb₂O₈ ceramics with ε_r = 40.7 and high Q × f = 16 790 GHz. These research outcomes are expected to have great significance for developing microwave dielectric ceramics in practical applications.     

Phase composition,crystal structure and microwave dielectric properties of Mg2−xCuxSiO4 ceramics

In this work, the Mg_2-xCu_xSiO₄(x = 0–0.40) microwave dielectric ceramics were prepared using solid-state reaction method. Compared with the Mg₂SiO₄ sample, the Cu-substituted Mg samples could be sintered at a lower temperature. The Mg_2?xCu_xSiO₄ ceramics exhibit the composite phases of Mg₂SiO₄ and a small quantity of MgSiO₃. The Cu²⁺ ion presented a solid solution with the Mg₂SiO₄ phase and preferentially occupy Mg(1) site. The distortion of MgO₆ octahedron was modified by Cu²⁺ ions, resulting in a positive change in the temperature coefficient of resonance frequency (τ_f) values. Excellent microwave dielectric properties of ε_r = 6.35, high Qf of ～ 188,500 GHz and near zero τ_f = ?2.0 ppm/°C were achieved at x = 0.08 under sintering at 1250 °C for 4 h. Thus, the fabricated ceramics were considered as possible candidates for millimeter-wave device applications.     

Effect of Ga3+ substitution on the microwave dielectric properties of 0.67CaTiO3–0.33LaAlO3 ceramics

0.67CaTiO₃–0.33La(Al_1−xGa_x)O₃ (0≤x≤0.4) (CTLAG) ceramics with pure perovskite structure were prepared by a conventional two-step solid-state reaction process. The effect of Ga³⁺ substitution for Al³⁺ on the microwave dielectric properties of the ceramics was subsequently investigated. As Ga content increased, the ionic polarizability increased and led to an increase of the dielectric constant (ε_r). Meanwhile, both the tolerance factor (t) of CTLAG ceramics and A-site bond valence were considered to have effect on the temperature coefficient of the resonant frequency (τ_f) with the increase of Ga content. Results also showed that the quality factor (Q×f ) varied with increasing Ga³⁺ content because of not only intrinsic factor but also extrinsic factors such as the bimodal grain size distribution, the variation of relative density, and the packing fraction. Excellent microwave dielectric properties with ε_r≈45.81, Q×f≈34,152 GHz, and τ_f≈3.09 ppm/°C were achieved for 0.67CaTiO₃–0.33La(Al_0.9Ga_0.1)O₃ ceramics sintered at 1420 °C for 4 h.     

Synthesis,characterization, and microwave dielectric properties of ZnTiTa2O8 ceramics with ixiolite structure obtained through the aqueous sol–gel process

Nano-sized ZnTiTa₂O₈ powders with ixiolite structure, with particle sizes ranging from 10 nm to 30 nm, were synthesized by thermal decomposition at 950 °C. The precursors were obtained by aqueous sol–gel and the compacted and sintered ceramics with nearly full density were obtained through subsequent heat treatment. The microstructure and electrical performance were characterized by field emission scanning electron microscopy, x-ray diffraction, and microwave dielectric measurements. All the samples prepared in the range 950–1150 °C exhibit single ixiolite phase and relative density between ~87% and ~94%. The variation of permittivity and Q·ƒ value agreed with that of the relative density. Pure ZnTiTa₂O₈ ceramic sintered at 1050 °C for 4 h exhibited good microwave dielectric properties with a permittivity of 35.7, Q·ƒ value of 57,550 GHz, and the temperature coefficient of resonant frequency of about −24.7 ppm/°C. The relatively low sintering temperature and excellent dielectric properties in the microwave range would make these ceramics promising for applications in electronics.     

Structure and microwave dielectric properties of Ba1−xSrxMg2V2O8 ceramics

The Ba_1−xSr_xMg₂V₂O₈ (0≤x≤0.4) microwave dielectric ceramics were fabricated by a standard solid-state reaction method. The formation of a continuous solid solution within the whole composition range was identified. The ceramic samples could be well densified in the temperature range of 885–975 °C in air for 4 h. The permittivity ε_r was found to increase with increasing ionic polarizabilities. The Q×f values were believed to be closely related with packing fraction and grain refinement. The Sr²⁺ substitution contributed to a monotonous increase of the A-site bond valence, such that the τ_f value experienced a considerable variation from negative to positive values. The optimum microwave dielectric properties of an ε_r of 13.3, a high Qxf of 86,640 GHz (9.6 Hz) and a near-zero τ_f of −6 ppm/°C could be yielded in the x=0.15 sample when sintered at 915 °C for 4 h.     

Crystal structure and microwave dielectric properties of Zn0.9Ti0.8−xSnxNb2.2O8 ceramics

The crystal structure and microwave dielectric properties of Zn_0.9Ti_0.8?xSn_xNb_2.2O₈ (x = 0.00, 0.05, 0.10, 0.15) ceramics sintered at temperatures ranging from 1100 °C to 1140 °C for 6 h were investigated. A single phase with ixiolite structure was obtained. With the increase of Sn content, the dielectric constant decreased attributed to the decrease of dielectric polarizability. The Qf value decreased with the decrease of packing fraction and grain size. The temperature coefficient of resonant frequency (τ_f) increased due to the increase of the bond valence of Zn_0.9Ti_0.8?xSn_xNb_2.2O₈ ceramics. The excellent microwave dielectric properties of ? = 35.05, Qf = 49,100 GHz, τ_f = ?27.6 × 10^?6/°C were obtained for Zn_0.9Ti_0.8?xSn_xNb_2.2O₈ (x = 0.05) specimens sintered at 1120 °C for 6 h.     

Effects of ionic polarizability and crystal structure on microwave dielectric properties of RE2O3 (RE = La,Eu) ceramics with opposite τf and high Q

Hexagonal La₂O₃ and monoclinic Eu₂O₃ ceramics were prepared, and their microwave dielectric properties were investigated. La₂O₃ sintered at 1400 °C exhibited promising microwave dielectric properties of ε_r = 18.6, Q×f = 71,400 GHz, and a negative τ_f of − 35.1 ppm/°C, while Eu₂O₃ sintered at 1500 °C possessed relative lower ε_r and Q×f values of 17.9 and 35,000 GHz, respectively, with an abnormally positive τ_f of + 19.6 ppm/°C. The difference in their microwave dielectric properties is mainly due to lattice-induced strain, which can be characterized by bond valence. To investigate the degradation of RE₂O₃ (RE = La, Eu) ceramics in air, a series of La_2−xEu_xO₃ (x = 0.5, 1, and 1.5) ceramics were prepared. The results of the present study suggest that the introduction of Eu³⁺ effectively prevents the decomposition of La₂O₃.     

Effects of TiO2 additive on ultra-low-loss MgO–LiF microwave dielectric ceramics

MgO ceramics have good microwave dielectric properties, but the high sintering temperatures limit its application. The effects of TiO₂ additive on the phase composition and microwave dielectric properties of MgO ceramics with 4mol%LiF were investigated by solid state reaction method. TiO₂ and MgO form Mg₂TiO₄ in a magnesium-rich environment with 4mol%LiF at about 900 °C, which as a solid solution or second phase had a huge impact on MgO ceramic with 4mol % LiF. When the content of TiO₂ less than 2mol %, Mg₂TiO₄ as a solid solution in MgO ceramics, which made the grain of MgO larger. When the content of TiO₂ more than 2mol %, Mg₂TiO₄ as a second phase in MgO ceramics, which made the microwave dielectric properties of MgO ceramics bad. Typically, the MgO-4mol%LiF-0.5mol%TiO₂ ceramic sintered at 1075 °C for 6 h acquired the best dielectric properties: ε_r = 9.7, Qf = 617,000 GHz and τ_f = −59.49 ppm/°C.     

Effects of Magnesium–Tungsten co-substitution on crystal structure and microwave dielectric properties of CaTi1-x(Mg1/2W1/2)xO3 ceramics

CaTi_1-x (Mg_1/2W_1/2)_xO₃ (x = 0, 0.02, 0.04, 0.06, 0.08) dielectric ceramics were synthesized via the traditional solid-state reaction method. Crystal structure and microwave dielectric properties of CaTi_1-x (Mg_1/2W_1/2)_xO₃ system were systematically investigated based on chemistry bond theory (P–V-L theory) for the first time. The pure perovskite phase was obtained for all doped samples, as confirmed through the XRD and Rietveld refinement results. The lattice characteristics were closely related to the microwave dielectric properties. The bond ionicity, lattice energy, and bond energy affected the dielectric constant, quality factor, and temperature stability of the ceramic material. Through the use of (Mg_1/2W_1/2)⁴⁺ doped on B-site, the CaTi_1-x (Mg_1/2W_1/2)_xO₃ system can maintain a high dielectric constant (ε_r > 100) while effectively reducing the τ_f value from 800 ppm/^°C to less than 300 ppm/^°C and improving the Q × f value to 9650 GHz (at 3.76 GHz).     

Influence of Li2O–B2O3–SiO2 glass on the sintering behavior and microwave dielectric properties of BaO–0.15ZnO–4TiO2 ceramics

This paper reports the investigation of the performance of Li₂O–B₂O₃–SiO₂ (LBS) glass as a sintering aid to lower the sintering temperature of BaO–0.15ZnO–4TiO₂ (BZT) ceramics, as well as the detailed study on the sintering behavior, phase evolution, microstructure and microwave dielectric properties of the resulting BZT ceramics. The addition of LBS glass significantly lowers the sintering temperature of the BZT ceramics from 1150 °C to 875–925 °C. Small amount of LBS glass promotes the densification of BZT ceramic and improves the dielectric properties. However, excessive LBS addition leads to the precipitation of glass phase and growth of abnormal grain, deteriorating the dielectric properties of the BZT ceramic. The BZT ceramic with 5 wt% LBS addition sintered at 900 °C shows excellent microwave dielectric properties: ε_r=27.88, Q×f=14,795 GHz.     

Effect of yttria substitution on structure,optical and mechanical properties of (Gd,Y)2O3–MgO nanocomposite ceramics

A citrate-nitrate combustion method was applied to synthesize fine composite Gd_2-xY_xO₃-MgO (x = 0, 0.02, 0.2, 0.3, 0.4, 0.6) nanopowders. Y₂O₃ substitution inhibited Gd₂O₃ phase transition from cubic structure to monoclinic structure during sintering, thereby stabilizing its cubic structure to room temperature. This approach led to nanocomposite ceramics with a grain size of about 190 nm and increased the transmittance to 85% over the 3–5 μm wavelength range when x = 0.3. However, the addition of Y₂O₃ weakened the mechanic properties of the nanocomposite ceramics.     

Effects of La2O3–B2O3 on the flexural strength and microwave dielectric properties of low temperature co-fired CaO–B2O3–SiO2 glass–ceramic

The La₂O₃–B₂O₃ (LB) addition, synthesized using the traditional solid-state reaction process, was chosen as a novel sintering aid of the low temperature co-fired CaO–B₂O₃–SiO₂ (CBS) glass–ceramic. The effects of LB on the flexural strength and microwave dielectric properties have been investigated. The LB addition promotes the crystallization of the CaSiO₃ but high amount of the LB addition leads to the formation of more pores. The CBS sample with 4 wt% LB addition sintered at 850 °C for 15 min shows good properties: flexural strength = 193 MPa, ?_r = 6.26 and loss = 9.96 × 10^?4 (10 GHz).     

Effects of BaO–SiO2 glass particle size on the microstructures and dielectric properties of Mn-doped Ba(Ti,Zr)O3 ceramics

The sintering behavior, microstructures and dielectric properties of Mn-doped Ba(Ti, Zr)O₃ (BTZ) ceramics with different particle sizes of BaO–SiO₂ glass (D50 ranging between 185 and 1200 nm) were investigated. From the metallographic observation, adding finer glass frit revealed more homogeneous compositional distribution. It was found that better spreading of the glass phase could be achieved by adding finer glass particles that could penetrate the BTZ ceramic interface more easily, thus enhancing the grain growth. The extent of the incorporation between glass and ceramic increased with smaller glass particles, and the Curie temperature was altered accordingly. Microstructural evaluation conducted by using X-ray diffraction (XRD) and transmission electron microscopy (TEM) with an energy-dispersive X-ray spectrometer (EDS) indicated the glass particle size has a dramatic influence on the sintering behavior and microstructure of Mn-doped BTZ ceramics. The relationship between microstructures and dielectric properties was also discussed in this study.     

Effect of Li2CO3–Bi2O3 doping on the low-temperature sintering,structure, and dielectric and mechanical properties of MgO–TiO2(w) ceramics

Dense MgO–12% TiO₂(w) ceramics containing 12 wt% TiO₂, which were doped with Li₂CO₃–Bi₂O₃ composite sintering aids, were prepared at a low sintering temperature of 950 °C in this study. The effects of sintering additives on the sintering characteristics, phase composition, microstructure, and dielectric and mechanical properties of the ceramic samples were systematically investigated, and the influences of their phase composition and microstructure on the dielectric and mechanical properties were examined. The introduction of sintering aids produced a new Bi₄Ti₃O₁₂ phase in the sample structure, while the residual Bi₂O₃ mixed with the newly formed Mg₂TiO₄ and Bi₄Ti₃O₁₂ phases distributed at MgO grain boundaries formed a structure surrounding MgO grains. This structure filled the pores in the ceramic sample, which increased its density and enhanced the mechanical properties. At a Li₂CO₃–Bi₂O₃ content of 15 wt%, the density, flexural strength, and Vickers hardness of the ceramic samples reached their maximum values of 3.4 g/cm³, 218.9 MPa, and 778.7 HV, respectively. However, the further increase in the Li₂CO₃–Bi₂O₃ content deteriorated their dielectric properties although the dielectric constant and dielectric loss remained below 13.4 and 2.1 × 10⁻³, respectively. The findings of this work indicate that Li₂CO₃–Bi₂O₃ sintering aids can significantly lower the sintering temperature of MgO–12% TiO₂(w) ceramics and control their dielectric and mechanical properties through microstructural changes.     

Effects of ion polarizability and oxygen vacancy on microwave dielectric properties of fluorite-structured Ce1−xCaxO2−x

X-ray diffractometer with Rietveld refinement and Raman spectroscopy were used for phase analysis. Ca doping results in decreased ε_r (24.09–21.52), Q × f (68 914–40 110 GHz), and τ_f (−50.0 ppm/°C to −60.2 ppm/°C) all decrease, which obviously does not conform to the mutual constraint relationship among the three parameters of microwave dielectric properties. The ε_r of Ce_1−xCa_xO_2−x ceramics is affected by the ion polarizability and the Ce rattling and valence states, among which the rattling of Ce cations plays a dominant role. The presence of oxygen vacancies in Ce_1−xCa_xO_2−x ceramics explains the decrease in Q × f. The τ_ε, ε_r, and α_L are responsible for the decrease in τ_f, especially for the τ_αm-3α_L values.     

Synthesis and microwave dielectric properties of pseudobrookite-type structure Mg5Nb4O15 ceramics by aqueous sol–gel technique

Pseudobrookite-type Mg₅Nb₄O₁₅ ceramics were prepared by aqueous sol–gel process and microwave dielectric properties were investigated. Highly reactive nanosized Mg₅Nb₄O₁₅ powders were successfully synthesized at 600 °C in oxygen atmosphere with particle sizes of 20–40 nm firstly and then phase evolution was detected by DTA-TG and XRD. Sintering characteristics and microwave dielectric properties of Mg₅Nb₄O₁₅ ceramics were studied at different temperatures ranging from 1200 °C to 1400 °C. With the increase of sintering temperature, density, ?_r and Q·f values increased, and then saturated at 1300 °C. Excellent microwave properties of ?_r ～11.3, Q·f ～43,300 GHz and τ_f ～?58 ppm/°C, were obtained finally. The sintering temperature of Mg₅Nb₄O₁₅ ceramics was significantly reduced by aqueous sol–gel process compared to conventional solid-state methods.     

Phase structure,band gap and microwave dielectric properties of Ba8Ti3Nb4−xSbxO24 ceramics

High dielectric constant and low loss ceramics in the Ba₈Ti₃Nb_4?xSb_xO₂₄ (x=0–2) system were prepared by conventional solid-state ceramic route. As x increased from 0 to 1.5, a single phase with hexagonal 8H perovskite structure was formed and the band gap values increased from 3.38 to 3.47 eV. However, the Sb₂O₃ secondary phase was detected as the x reached 2. The optimum sintering temperature was reduced from 1460 to 1380 °C, the quality factors (Q×f) were effectively enhanced from 22,900 to 38,000 GHz and τ_f was significantly lowered from 110 ppm/°C to 2 ppm/°C, whereas the dielectric constant decreased from 49 to 35. A good combined microwave dielectric properties with ε_r=37.5, Q×f=38,000 GHz, τ_f=15 ppm/°C were obtained for x=1.5.