Low-temperature firing and microwave dielectric properties of MgNb2-xVx/2O6-1.25x ceramics

MgNb_2-xV_x/2O_6-1.25x (0.1≤x≤0.6) ceramics with orthorhombic columbite structures were prepared at low-temperature by a solid-phase process. The phase component, microscopic morphology, low-temperature sintering mechanism and microwave dielectric performance of MgNb_2-xV_x/2O_6-1.25x ceramics were comprehensively investigated. Low-temperature sintering densification of dielectric ceramics was achieved via the nonstoichiometric substitution of vanadium (V) at the Nb-site. In contrast to pure MgNb₂O₆ ceramics, the sintering temperature of MgNb_2-xV_x/2O_6-1.25x (x = 0.2) ceramics was reduced by nearly 300 °C owing to the liquid-phase assisted sintering mechanism. The liquid phase arises from the autogenous low-melting-point phase. Meanwhile, MgNb_2-xV_x/2O_6-1.25x (x = 0.2) samples with nonstoichiometric substitution could achieve a more than 900% improvement in the Q × f value, compared with stoichiometrically MgNb_2-xV_xO₆ (x = 0.1, 0.2) ceramics. Finally, MgNb_2-xV_x/2O_6-1.25x dielectric ceramics possess outstanding microwave dielectric properties: ε_r = 20.5, Q × f = 91000, and τ_f = -65 ppm/°C when sintered at 1030 °C for x = 0.2, which provides an alternative material for LTCC technology and an effective approach for low-temperature sintering of Nb-based microwave dielectric ceramics.     

Low temperature fired CaF2-based microwave dielectric ceramics with enhanced microwave properties

Low-temperature-fired microwave ceramics are key to realizing the integration and miniaturization of microwave devices. In this study, a facile wet chemical method was applied to synthesize homogenous nano-sized CaF₂ powders for simultaneously achieving low-temperature sintering and superior microwave dielectric properties. Pure CaF₂ ceramics sintered at 950 °C for 6 h with good microwave dielectric properties (ε_r = 6.22, Q×f = 36,655 GHz, and τ_f = ?102 ppm/°C) was achieved. The microwave dielectric properties of the CaF₂ ceramics were further improved by introducing LiF as a sintering aid. The sintering temperature of CaF₂-based ceramics was effectively lowered from 950 °C to 750 °C with 10 wt% LiF doping, and excellent microwave dielectric properties (ε_r = 6.37, Q×f = 65,455 GHz, and τ_f = ?71 ppm/°C) were obtained.     

Synthesis of a low-firing BaSi2O5 microwave dielectric ceramics with low dielectric constant

In this study, BaSi₂O₅ ceramics with an orthorhombic structure were synthesized by using a traditional solid-state method at a low temperature by doping with Li₂O–B₂O₃–CaO–CuO (LBCC) glass. The phase composition, mechanism of low-temperature sintering, microwave dielectric properties, and changes in the mesophase during the heating of low-temperature sintered BaSi₂O₅ ceramics were examined by performing an X-ray diffraction analysis. A compact matrix of BaSi₂O₅ can be wetted by the liquid phase of the formed LBCC glass. Therefore, LBCC glass with different doping percentages can effectively reduce the sintering temperature of BaSi₂O₅. The microwave dielectric properties of BaSi₂O₅ ceramics sintered at 900 °C at 4 wt% of LBCC glass were determined: ε_r = 7.32, Q × f = 19,002 GHz, and τ_f = ?35.8 ppm/°C. The chemical compatibility of the samples with Ag was studied at 4 wt% doping with LBCC glass, and the samples were fired for 4 h at 900 °C.     

Crystallographic characteristics and microwave dielectric properties of Ni-modified MgTa2O6 ceramics

Ni²⁺ modified MgTa₂O₆ ceramics with a trirutile phase and space group P4₂/mnm were obtained. The correlations between crystallographic characteristics and microwave dielectric performance of MgTa₂O₆ ceramics were systematically studied based on the chemistry bond theory (PVL theory) for the first time. The results indicate that the introduction of Ni²⁺ causes a change in polarizability and the Mg–O bond ionicity, which contributes to the variation of dielectric constant. Moreover, the lattice energy, and packing fraction, full width at half maximum of the Raman peak of Ta–O bond, as the quantitative characterization of crystallographic parameters, regulate the dielectric loss of MgTa₂O₆ ceramics in GHz frequency band. In addition, the study of sintering behavior shows that the densification and micromorphology are the crucial factors affecting the microwave dielectric performance. Typically, Ni²⁺ doping on the A-site of MgTa₂O₆ can effectively promote the Q × f values to 173,000 GHz (at 7.43 GHz), which ensures its applicability in 5G communication technology.     

Cold sintering assisted CaF2 microwave dielectric ceramics for C-band antenna applications

A cold sintering process is adopted to pre-densify CaF₂ ceramics from 85.7% at 300 MPa to 91.7% at 750 MPa. Subsequent post-annealings at 1000–1150 °C lead to further improvements in densification, where great enhancements of grain size and crystallinity are also observed from the scanning and transmission electron micrographs. Significant advances in Qf values are achieved in the post-annealed CaF₂ ceramics. The optimum Qf value (80,522 GHz) is achieved after cold sintering at 750 MPa and post-annealing at 1000 °C, which is three times higher than the conventional sintered one at 1000 °C (26,448 GHz). Moreover, the obtained low-ε_r (5.9–6.5) of CaF₂ ceramics suggests broad application prospects in the high-band microwave communications. A microstrip patch antenna is fabricated using the CaF₂ ceramics as the substrate, which operates at 7.89 GHz in the C-band, with an S₁₁ of ?13.4 dB, simulated high gain and efficiency of 6.41 dBi and ?0.56 dB, respectively.     

Microwave dielectric properties of Ca1-xBaxMgSi2O6 ceramics

Ca_1-xBa_xMgSi₂O₆(x = 0–0.4) ceramics were prepared through a traditional solid-state reaction sintering route with various sintering temperatures. The effects of substituting Ba²⁺ for Ca²⁺, the relative density, phase composition, crystal morphology, and microwave dielectric properties of Ca_1-xBa_xMgSi₂O₆ (x = 0–0.4) ceramics were thoroughly studied. X-ray diffraction patterns indicate a single phase was formed in the samples when x ≤ 0.2, and the second phase BaMg₂Si₂O₇ appeared at x = 0.4. As the amount of Ba²⁺ substitution increases, the Q×f value first increases and then decreases due to the combined effects of FWHM of peak v₁₁ and atomic packing density, and the ${\epsilon }_r$ value was increased continuously which was closely corrected with the relative density and molecular polarization. The ${\tau }_f$ value improved slightly with the substituting Ba²⁺ for Ca²⁺. Typically, the Ca_0.88Ba_0.12MgSi₂O₆ ceramic can be well sintered at 1275 °C for 4 h with a maximum relative density of 99.3%, and possesses optimal microwave dielectric properties: ${\epsilon }_r=7.49$, $Q\times f=64310$ GHz, ${\tau }_f=-44.02$ ppm/°C.     

0.73ZrTi2O6–0.27MgNb2O6 microwave dielectric ceramics modified by Al2O3 addition

0.73ZrTi₂O₆–0.27MgNb₂O₆ ceramics with various Al₂O₃ contents (0‐2.0 wt%) were prepared by conventional ceramic route. The effects of Al₂O₃ on the phase composition, microstructure, conductivity, and microwave dielectric properties were systematically investigated. The coexistence of a disordered α–PbO₂‐type phase and a rutile second phase was found in all compact ceramics with low Al₂O₃ contents (x = 0, 0.5, and 1.0 wt%), while a corundum phase was detected when Al₂O₃ additive increased to 1.5 and 2.0 wt% based on X‐ray diffraction results. With the addition of Al₂O₃, the decreased grain size of the matrix phase was observed using field‐emission scanning electron microscope, accompanied with increased resistivity and band‐gap energy. Additionally, Al₂O₃ additives efficiently improved the quality factor of the ceramics. After sintering at 1360°C for 3 hours, the ceramic with 1.0 wt% Al₂O₃ exhibited excellent microwave dielectric properties: a dielectric constant of 43.8, a quality factor of 33 900 GHz (at 6.6 GHz), and a near‐zero temperature coefficient of resonant frequency (3.1 ppm/^°C).     

Synthesis and microwave dielectric properties of BaO-Sm2O3-5TiO2 ceramics with NdAlO3 additions

BaO-Sm₂O₃-5TiO₂ (BST5) ceramics with NdAlO₃ additions of up to 15 wt% were produced with a solid state reaction method, and their structural and microwave dielectric properties were determined. Experimental results showed that NdAlO₃ neither merged nor altered the orthorhombic tungsten bronze structure of the main phase of the produced ceramics (except for a shrinkage in the crystal lattice), but it was segregated in distinct grains in the microstructure of the produced ceramics. However, the amount of NdAlO₃ strongly influenced the densification and the microstructure (i.e. grain shape and size) of the produced ceramics. Analysis of the experimental results suggests that the microstructural features can be correlated to the dielectric properties of these ceramics. Accordingly, the dielectric constant (ε_r) and the temperature coefficient of resonant frequency (τ_f) of the produced BLT5 ceramics can be tuned with the amount of NdAlO₃ additions and the sintering process parameters. The best dielectric properties were achieved for BaO-Sm₂O₃-5TiO₂ ceramics with 7.5% NdAlO₃ (ε_r=73.22, Q×f =10,300 GHz, and τ_f=−1.05 ppm/°C).     

Improvement of microwave dielectric properties for Ba(Ni1/3Nb2/3)O3 ceramics by Zr-substitution

Effects of Zr-substitution on the structure, microstructure and microwave dielectric properties of Ba(Ni_1/3Nb_2/3)O₃ ceramics have been investigated. A small amount of Zr-substitution facilitates the densification of Ba(Ni_1/3Nb_2/3)O₃ ceramics. Within x≤0.05, the densification temperature decreases with increasing x in Ba[(Ni_1/3Nb_2/3)_1−xZr_x]O₃, while it turns to increase for x>0.05. With increasing x, the grains become more homogeneous and closely contacted, and significantly increase in size for x=0.15–0.20. The B-site cations 1:2 ordering is destroyed by Zr-substitution, and only stabilizes for x≤0.04. B-site cations 1:1 ordering starts to form in x=0.04, and the 1:1 ordering degree first increases and then decreases with increasing x. Qf value decreases slightly in x=0.01 and then increases monotonously with x increasing from 0.02 to 0.20. The destroyed 1:2 ordering structure is responsible for the decreased Qf value in x=0.01, while the improved grain configuration dominates the increase of Qf value for x=0.02–0.20. The dielectric constant ε_r increases monotonously with increasing x, due to the higher polarizability of Zr ion than the average value of Ni/Nb ions. The temperature coefficient of resonant frequency τ_f shifts from negative to positive through zero with increasing x, which is ascribed to the highly positive τ_f value of the end member BaZrO₃. The significant improvement of microwave dielectric properties has been achieved for x=0.10, higher ε_r, higher Qf as well as near zero τ_f value have been obtained: ε_r=31.8, Qf=36,100 GHz, τ_f=7.8 ppm/°C.     

Influence of Cr3+ substitution for Mg2+ on the crystal structure and microwave dielectric properties of CaMg1-xCr2x/3Si2O6 ceramics

The CaMg_1-xCr_2x/3Si₂O₆ (0?≤?x?≤?0.1) microwave dielectric ceramics were synthesized via conventional solid state reaction. In this study, the effects of Cr³⁺ substituting for Mg²⁺ on morphology, crystal structure and microwave dielectric properties of CaMg_1-xCr_2x/3Si₂O₆ ceramics were explored. XRD diffraction patterns exhibited that the CaMg_1-xCr_2x/3Si₂O₆ ceramics possessed the pure phase of CaMgSi₂O₆ when x?≤?0.06 and a small amount of secondary phase Ca₃Cr₂(SiO₄)₃ for 0.08?≤?x?≤?0.1. SEM micrographs revealed that the substitution of Mg²⁺ with Cr³⁺ could decrease the grain size. The apparent density was affected by the concentration of Mg vacancies. The correlation between crystal structure and microwave dielectric properties was investigated through the Rietveld refinement and Raman analysis. The microwave dielectric properties were mainly dependent on relative density, ionic polarizabilities, internal strain ?, disordered structure and MgO₆ octahedron distortions. Finally, CaMg_1-xCr_2x/3Si₂O₆ (x?=?0.02) ceramics sintered at 1270?°C for 3?h exhibited excellent microwave dielectric properties of ε_r?=?8.06, Q?×?f?=?89054?GHz, τ_f?=??44.92182?ppm/ºC.     

Novel temperature stable NiSnTa2O8 microwave dielectric ceramics with trirutile structure

A novel low-loss and temperature stable NiSnTa₂O₈ ceramic with trirutile structure was prepared using traditional solid-state method. The structure-performance relationships were investigated by Rietveld refinement, chemical bond theory and far-infrared spectrum. The results show that the relative densities play a dominant role in the change of dielectric constant. Theoretical dielectric constant calculated via bond theory, Clausius-Mossotti equation and fitted result of far-infrared spectrum are close to experimental value. Ta–O bonds with greatest bond ionicity and bond energy have the primary contributions to dielectric polarizabilities and dielectric loss. The optimal microwave dielectric performances of NiSnTa₂O₈ ceramics were obtained: ε_r ∼21.04, Q×f ∼31328 GHz and τ_f = −2.63 ppm/^°C at 1425 °C.     

Structure,far-infrared reflectance spectra,and microwave dielectric properties of Ba2MGa11O20 (M = Bi,La) ceramics

Ba₂MGa₁₁O₂₀ (M = Bi, La; called BBG and BLG, respectively) ceramics with monoclinic space group I2/m were prepared through a solid-state reaction method. BBG ceramic sintered at 1150 °C for 6 h has the best microwave dielectric properties with low ε_r = 10.68, Q × f = 41,756 GHz, and negative τ_f = ?61.3 ppm/°C. BLG ceramic sintered at 1440 °C for 6 h exhibits ε_r = 13.94, Q × f = 45,592 GHz, and near-zero τ_f = ?16.3 ppm/°C. The large deviation between ε_r and ε_th was ascribed to the “rattling” effect of the cations and the existence of lone pair ions of Bi³⁺. The difference in Q × f of the two ceramics was discussed in terms of packing fraction, and the τ_f of BLG was closer to zero than that of BBG due to the smaller τ_ε value. Their intrinsic dielectric properties were analyzed through far-infrared reflectivity spectroscopy.     

Synthesis,lattice energy and microwave dielectric properties of BaCu2-xCoxSi2O7 ceramics

BaCu_2-xCo_xSi₂O₇ solid solutions with orthorhombic structure (Pnma) were prepared by solid-state reaction method. The phase synthesis process, structural evolution and microwave dielectric properties of BaCu_2-xCo_xSi₂O₇ ceramics were investigated. Single BaCu₂Si₂O₇ phase was obtained when calcined at 950 °C for 3 h and was decomposed into BaCuSi₂O₆ phase when calcined at 1075 °C for 3 h. The sintering process was effectively promoted when Cu²⁺ was replaced by Co²⁺ and the maximum solubility of BaCu_2-xCo_xSi₂O₇ was located between 0.15 and 0.20. P-V-L complex chemical bond theory and Raman spectra were used to explain the structure-property correlations of BaCu_2-xCo_xSi₂O₇ ceramics. The corrected dielectric constant (ε_r-corr) of BaCu_2-xCo_xSi₂O₇ ceramics decreased monotonously with the susceptibility (Σχ^μ) and ionic polarizability of primitive unit cell. The quality factor (Q × f) increased with bond strength and lattice energy (U_cal), especially the lattice energy of the Si-O bond. The temperature coefficient of resonant frequency (τ_f) was determined by the susceptibility and lattice energy of the Cu/Co-O bond. The following optimum microwave dielectric properties were obtained at x = 0.15 when sintered at 1000 °C for 3 h: ε_r = 8.45, Q×f =58958 GHz and τ_f = -34.4 ppm/°C.     

Weak ferroelectricity and low-permittivity microwave dielectric properties of Ba2Zn(1+x)Si2O(7+x) ceramics

Ba₂Zn_(1+x)Si₂O_(7+x) ceramics were prepared using the conventional solid-state method at 1200 °C for 3 h in air. Apart from the previously reported Ba₂Zn_(1+x)Si₂O_(7+x) (x = 0) with a monoclinic structure (C 2/c), the end-member compositions at x = −1 and 1 exhibit single-phase β-BaSiO₃ with an orthorhombic structure (P2₁2₁2₁) and BaZnSiO₄ with a hexagonal structure (P6₃), and possess a coexistence of weak ferroelectricity and low-permittivity microwave dielectric properties. A reduction in Zn²⁺ content mainly decreases the intensity of the ε_r anomaly peak at lower temperature and increases the ε_r (or frequency) stability against temperature. The Zn²⁺-rich BaZnSiO₄ phase has a τ_f value of −181 ppm/°C, whereas the τ_f value of Zn²⁺-free BaSiO₃ phase decreases to −35.4 ppm/°C. The Zn²⁺ deficiency in Ba₂ZnSi₂O₇ composition could inhibit the presence of BaZnSiO₄ phase and improve the τ_f value, whereas excessive Zn²⁺ cations prompt the formation of the BaZnSiO₄ phase to deteriorate significantly the τ_f value.     

Novel non-equimolar SrLa(Al0.25Zn0.125Mg0.125Ga0.25Ti0.25)O4 high-entropy ceramics with excellent mechanical and microwave dielectric properties

Novel non-equimolar high-entropy SrLa(Al_0.25Zn_0.125Mg_0.125Ti_0.25Ga_0.25)O₄ (SLAZMTG) ceramics with a layered perovskite structure have been prepared via the standard solid-state reaction method. The high-entropy composition belongs to the tetrahedral structure with a space group of I4/mmm, which is confirmed by the XRD and TEM analyses. Excellent microwave dielectric properties with a suitable dielectric constant (ε_r = 22.5), high quality factor (Qf = 83,003 GHz), and near-zero τ_f value of −1.7 ppm/°C are obtained in SLAZMTG ceramics sintered at 1400 °C. Meanwhile, a significant enhancement in compressive strength was achieved due to the improvement of configuration entropy, 912 MPa for SLAZMTG compared to 578 MPa in the pure SrLaAlO₄ composition. Additionally, the high-entropy engineering in the present work suggests great potential in achieving low thermal conductivities. SLAZMTG ceramics exhibit low thermal conductivities ranging from 2.86 W/m•K at 323 K to 1.99 W/m•K at 673 K, much lower than those of SrLaAlO₄ and other perovskite ceramics.     

Structure,bond characteristics and Raman spectra of CaMg1-xMnxSi2O6 microwave dielectric ceramics

The CaMg_1-xMn_xSi₂O₆(x = 0–0.08)ceramics were reported here for the first time. The relationships among structural characteristics, vibrational modes and dielectric properties for the ceramics were researched based on complex chemical bond theory and Raman vibrational spectroscopy. The formation of a single phase with clinopyroxene structure when x = 0 to 0.08 was detected by X-ray diffraction. The monotonous increase of ${\epsilon }_r$ is ascribed to the average bond covalency, polarizability and Raman shift. The $Q\times f$ value is influenced by total lattice energy and full width at half maximum of Raman spectra which are both connected with the intrinsic loss. The variation of ${\tau }_f$ is related to thermal expansion coefficient and M1-site bond valence. Furthermore, the CaMg_0.98Mn_0·02Si₂O₆ ceramic sintered at 1300 °C possessed optimal microwave dielectric properties of ${\epsilon }_r$ = 8.01, $Q\times f$ = 83469 GHz and ${\tau }_f$ = −45.27 ppm/°C.     

Mg3B2O6 microwave dielectric ceramics fabricated by combining cold sintering with post-annealing process

It is difficult to get pure-phase Mg₃B₂O₆ (abbreviated as MBO) ceramics by the traditional high-temperature solid-state reaction method. In this paper, pure-phase MBO ceramics were successfully densified and obtained by combining the cold sintering and post-annealing process. The relative density of MBO ceramics was ∼80% cold sintered at 150°C/90 min/800 MPa, which was further improved to ∼91% by post-annealing at 900°C, 400°C lower than that of the traditional high-temperature sintering process (∼1300°C). X-ray powder diffraction (XRD), scanning electron microscopy (SEM), and Raman results demonstrated that the secondary phase of MgO was effectively eliminated, and dense microstructure was observed by the cold-sintering process plus post-annealing treatment. Finally, the microwave dielectric properties of MBO were evaluated with ε_r: 5.15–6.37, Q×f: 5942–16 686 GHz, τ_f: −48.45–69.72 ppm/°C.     

The effect of co-substitution on the microwave dielectric properties of Ba6-3xNd8+2xTi18O54(x=2/3) ceramics

In this work, the microwave dielectric properties of Ba₄(Nd_1-yBi_y)_28/3Ti_18-x(Al_1/2Ta_1/2)_xO₅₄(0≤x≤2, 0.05≤y≤0.2) ceramics co-substituted by A/B-site were studied. Firstly, (Al_1/2Ta_1/2)⁴⁺ was used for substitution at B-site. At 0≤x≤1.5, the above mentioned ceramic was found to exist in single-phase tungsten bronze structure, but at x = 2.0, the secondary phase appeared. Although the dielectric constant decreased by doping the (Al_1/2Ta_1/2)⁴⁺, but the quality factor was observed to improve by 40% and the temperature coefficient of resonant frequency decreased by 75%. Based on the above results, Bi³⁺ was introduced to Ba₄Nd_28/3Ti₁₇(Al_1/2Ta_1/2)O₅₄. The introduction of Bi³⁺ reduced the sintering temperature, greatly improved the dielectric constant, and ultimately decreased the temperature coefficient of resonant frequency, but it led to deterioration of quality factor. At last, with appropriate site-substitution content control (x = 1.0,y = 0.15), excellent comprehensive properties (ε_r = 89.0, Q × f = 5844 GHz @ 5.89 GHz,TCF = +8.7 ppm/°C) were obtained for the samples sintered at 1325 °C for 4 h.