Design of a Sub-6 GHz Dielectric Resonator Antenna with Novel Temperature-Stabilized (Sm1-xBix)NbO4 (x = 0-0.15) Microwave Dielectric Ceramics.

Microwave dielectric ceramics exhibiting a low dielectric constant (εr), high quality factor (Q × f), and thermal stability, specifically in an ultrawide temperature range (from -40 to +120 °C), have attracted much attention. In addition, the development of 5G communication has caused an urgent demand for electronic devices, such as dielectric resonant antennas. Hence, the feasibility of optimizing the dielectric properties of the SmNbO4 (SN) ceramics by substituting Bi3+ ions at the A site was studied. The permittivity principally hinges on the contribution of Sm/Bi-O to phonon absorption in the microwave range, while the reduced sintering temperature results in a smaller grain size and slightly lower Q × f value. The expanded and distorted crystal cell indicates that Bi3+ doping effectively regulates the temperature coefficient of resonant frequency (TCF) by adjusting the strains (causing the distorted monoclinic structure) of monoclinic fergusonite besides correlating with the permittivity. Moreover, a larger A-site radius facilitates the acquisition of near-zero TCF values. Notably, the (Sm0.875Bi0.125)NbO4 (SB0.125N) ceramic with εr ≈ 21.9, Q × f ≈ 38 300 GHz (at ∼8.0 GHz), and two different near-zero TCF values of -9.0 (from -40 to +60 °C) and -6.6 ppm/°C (from +60 to +120 °C), respectively, were obtained in the microwave band. A simultaneous increase in the phase transition temperature (Tc) and coefficients of thermal expansion (CTEs) by A-site substitution provides the possibility for promising thermal barrier coating (TBC) materials. Then, a cylindrical dielectric resonator antenna (CDRA) with a resonance at 4.86 GHz and bandwidth of 870 MHz was fabricated by the SB0.125N specimen. The exceptional performance shows that the SB0.125N material is a possible candidate for the sub-6 GHz antenna owing to the advantages of low loss and stable temperature.

Structure and Microwave Dielectric Properties of Gillespite-Type ACuSi4O10 (A = Ca, Sr, Ba) Ceramics and Quantitative Prediction of the Q × f Value via Machine Learning.

Structure and dielectric properties of gillespite-type ceramics ACuSi4O10 (A = Ca, Sr, Ba) were investigated by crystal structure refinement, far-infrared reflectivity spectroscopy, and microwave dielectric measurements. A series of (CaxSr1-x)CuSi4O10 (0 < x < 1) ceramics with relative permittivities of 5.70-5.82, Q × f values of 20391-48794 GHz (@ ∼ 13.5 GHz), and τf of -46.3 to -38.9 ppm/°C were synthesized. By Ca2+ substitution for Sr2+ at the A-site, the rigid double-layered copper silicate framework remains stable, resulting in the nearly unchanged relative permittivity, while the [(Ca,Sr)O8] dodecahedron undergoes shrinkage and distortion, which is correlated to the changes in the Q × f and τf values. The normalized bond valence sums indicate that almost all ions are rattling, weakening the bond strengths and enlarging the molecular dielectric polarizability. The fitting of far-infrared reflectivity spectra reveals that the local structure changes suppress the intermediate and low-frequency vibrational modes significantly and improves the contribution from electronic polarization to permittivity. Symmetry breaking of the [(Ca,Sr)O8] dodecahedron conforms to the elevated restoring forces acting on the ions and improves the τf value. The large span in Q × f value may have intricate correlations to local structure changes and defects. Machine learning methods were introduced to explore the decisive structural factors for the Q × f value. A Q × f value prediction model correlated with the A-O2 bond length and the variance of A-O bond lengths was established. The Q × f values of isostructural (BaySr1-y)CuSi4O10 ceramics were predicted and verified by experiments.

Internal Relations between Crystal Structures and Intrinsic Properties of Nonstoichiometric Ba1+ xMoO4 Ceramics.

Ba1+ xMoO4 (-0.03 ≤ x ≤ 0.03) ceramics were fabricated by a conventional two-step sintering technique. X-ray diffraction patterns show that there appeared new diffraction peaks when x > 0, which were identified as Ba2MoO5. The Rietveld refinement results indicate that the unit cell volume is the largest at x = -0.02, because it has the lowest packing fraction and covalency. The far-infrared reflectivity (IR) spectra were fitted and analyzed for calculating the intrinsic properties, which comply well with the data obtained from microscopic polarizabilities and damping coefficient angle. The proportion of each mode in the dielectric response demonstrates that the Ba-O8 polyhedra have a decisive role on the dielectric properties. And based on the Raman modes, the internal relations of the structural-properties were revealed with the changes of Ba2+ content.

Structure, Intrinsic properties and Vibrational Spectra of Pr(Mg1/2Sn1/2)O3 Ceramic Crystal.

Pr(Mg1/2Sn1/2)O3 (PMS) ceramic was prepared through a conventional solid-state reaction method. Crystal structure was investigated through X-ray diffraction (XRD), which certificates that the main phase is PMS with monoclinic P2 1/n1 symmetry. Lattice vibrational modes were obtained through Raman scattering spectroscopy and Fourier transform far-infrared reflection spectroscopy. The Raman spectrum active modes were assigned and illustrated, respectively, and then fitted with Lorentzian function. The four modes within the range of 110-200 cm-1 are derived from the F 2g vibrations (A-site cations), and the other three modes (300-430 cm-1) are derived from the F 2g vibrations (B-site cations).The mode with highest frequency above 650 cm-1 is attributed to A 1g -like mode that corresponds to the symmetric breathing of oxygen octahedral. The far-infrared spectrum with seven infrared active modes was fitted using four-parameter semi-quantum models to calculate intrinsic properties (permittivity and loss). F 2u(2) yielded the greatest contribution to dielectric constant and loss, which is mainly performed as the inverted translational vibration of Pr-MgO6 octahedron.

Phase Evolution, Crystal Structure, and Microwave Dielectric Properties of Water-Insoluble (1 - x)LaNbO4-xLaVO4 (0 ≤ x ≤ 0.9) Ceramics.

In the present work, a series of low-temperature firing scheelite structured microwave dielectric in water-insoluble La2O3-Nb2O5-V2O5 system was prepared via the traditional solid-state reaction method. Backscattering electron diffraction, X-ray diffraction (XRD), energy-dispersive analysis, and Rietveld refinements were performed to study the phase evolution and crystal structure. In the full composition range of (1 - x)LaNbO4-xLaVO4 (0 ≤ x ≤ 0.9) ceramics, at least four typical phase regions including monoclinic fergusonite, tetragonal sheelite, B-site ordered sheelite, and composite of monoclinic LaVO4 and tetragonal sheelite phases can be detected according to XRD analysis. The variations of relative dielectric constant εr, quality factor Q × f, and resonant frequency τf could be attributed to Nb/V-O bond ionicity, lattice energy, and the coefficient of thermal expansion. Infrared reflectivity spectra analysis revealed that ion polarization contributed mainly to the permittivity in microwave frequencies ranges. Furthermore, the 0.7LaNbO4-0.3LaVO4 ceramic sintered at 1160 °C possessed excellent microwave dielectric properties with an εr of ∼17.78, a Q × f of ∼75 940 GHz, and a τf of ca. -36.8 ppm/°C. This series of materials might be good candidate for microwave devices.

Influence of W substitution on crystal structure, phase evolution and microwave dielectric properties of (Na0.5Bi0.5)MoO4 ceramics with low sintering temperature.

In this work, the (Na0.5Bi0.5)(Mo1-xWx)O4 (x = 0.0, 0.5 and 1.0) ceramics were prepared via solid state reaction method. All the samples can be well densified at sintering temperature about ~720 °C. Dense and homogeneous microstructure with grain size lying between 2~8 µm can be observed from scanning electron microscopy (SEM). Microwave dielectric permittivity of the (Na0.5Bi0.5)(Mo0.5W0.5)O4 ceramic was found to be temperature-independent in a wide range between 25~120 °C with a temperature coefficient of frequency (TCF) ~-6 ppm/°C, a permittivity ~28.9, and Qf values 12,000~14,000 GHz. Crystal structure was refined using Rietveld method and lattice parameters are a = b = 5.281 (5) Å and c = 11.550 (6) Å with a space group I 41/a (88). The (Na0.5Bi0.5)(Mo1-xWx)O4 ceramics might be good candidate for low temperature co-fired ceramics (LTCC) technology.

Crystal Structure, Infrared Spectra, and Microwave Dielectric Properties of Temperature-Stable Zircon-Type (Y,Bi)VO4 Solid-Solution Ceramics.

A series of (Bi1-x Y x )VO4 (0.4 ≤ x ≤ 1.0) ceramics were synthesized using the traditional solid-state reaction method. In the composition range of 0.4 ≤ x ≤ 1.0, a zircon-type solid solution was formed between 900 and 1550 °C. Combined with our previous work (scheelite monoclinic and zircon-type phases coexist in the range of x < 0.40), a pseudobinary phase diagram of BiVO4-YVO4 is presented. As x decreased from 1.0 to 0.40, the microwave permittivity (εr) of (Bi1-x Y x )VO4 ceramics increased linearly from 11.03 to 30.9, coincident with an increase in the temperature coefficient of resonant frequency (TCF) from -61.3 to +103 ppm/°C. Excellent microwave dielectric properties were obtained for (Bi0.3Y0.7)VO4 sintered at 1025 °C and (Bi0.2Y0.8)VO4 sintered at 1075 °C with εr ∼ 19.35, microwave quality factor (Qf) ∼ 25 760 GHz, and TCF ∼ +17.8 ppm/°C and εr ∼ 16.3, Qf ∼ 31 100 GHz, and TCF ∼ -11.9 ppm/°C, respectively. Raman spectra, Shannon's additive rule, a classical oscillator model, and far-infrared spectra were employed to study the structure-property relations in detail. All evidence supported the premise that Bi-based vibrations dominate the dielectric permittivity in the microwave region.

Crystal structure and microwave dielectric behaviors of ultra-low-temperature fired x(Ag(0.5)Bi(0.5))MoO4-(1 - x)BiVO4 (0.0 ≤ x ≤ 1.0) solid solution with scheelite structure.

x(Ag(0.5)Bi(0.5))MoO4-(1 - x)BiVO4 (0.0 ≤ x ≤ 1.0) ceramics were prepared by using the solid-state reaction technique. Ceramics with x < 0.10 had a monoclinic scheelite structure, while those with ≥0.10 were tetragonal scheelite solid solutions. This indicates that the phase transformation temperature of BiVO4 was lowered through the formation of a solid solution. The thermal expansion data of the x = 0.08 sample showed that the thermal expansion coefficient was increased suddenly from +8 to +15 ppm/°C at about 60.6 °C due to the phase transition. Similarly, a maximum value of microwave dielectric permittivity was revealed at about 65 °C for the x = 0.08 sample. All of the ceramics could be well sintered below 700 °C. Good microwave dielectric behaviors, with relative permittivity >75 and Q(f) > 9000 GHz, were obtained in ceramics with compositions near x = 0.10. Both the THz data and the infrared spectra were used to study the intrinsic dielectric behavior of the materials at microwave frequencies.

Structure-property relationships of novel microwave dielectric ceramics with low sintering temperatures: (Na(0.5x)Bi(0.5x)Ca(1-x))MoO(4).

A novel series of microwave dielectric ceramics (Na0.5xBi0.5xCa1-x)MoO4 (0 ≤ x ≤ 0.6) was synthesized by the solid state reaction method. The crystal structures, microstructures, dielectric responses, and vibrational properties were investigated using X-ray diffraction, scanning electron microscopy, a microwave network analyzer, and terahertz, Raman and infrared spectroscopies. All the samples could be sintered well below 850 °C and a scheelite solid solution could be formed without any secondary phase. At x = 0.5 and x = 0.6, low-firing (750-775 °C) high performance microwave dielectric materials were obtained with permittivities of 19.1-21.9, Q × f values of 20 660-22 700 GHz, and near-zero temperature coefficients. The factors affecting microwave dielectric properties were discussed based on the vibrational data. As revealed by Raman spectroscopy, the disorder degree grows with x rising, which might increase the permittivities and decrease the Q × f values. The infrared spectra were analyzed using the classical harmonic oscillator model, and the complex dielectric responses gained from the fits were extrapolated down to the microwave and THz range. It is believed that the external vibration modes located at low frequencies dominate the main dielectric polarization contributions, especially the Na-O/Bi-O translational mode. This result indicates that the microwave dielectric properties of (Na0.5xBi0.5xCa1-x)MoO4 ceramics mainly depend on the behavior of AO8 polyhedra.

Structure, phase evolution, and microwave dielectric properties of (Ag0.5Bi0.5)(Mo0.5W0.5)O4 ceramic with ultralow sintering temperature.

In the present work, the microwave dielectric ceramic (Ag0.5Bi0.5)(Mo0.5W0.5)O4 was prepared by using the solid-state reaction method. (Ag0.5Bi0.5)(Mo0.5W0.5)O4 was found to crystallize in the scheelite structure, in which Ag(+) and Bi(3+) occupy the A site randomly with 8-coordination while Mo(6+) and W(6+) occupy the B site with 4-coordination, at a sintering temperature above 500 °C, with lattice parameters a = b = 5.29469(2) Å and c = 11.62114(0) Å, space group I4(1)/a (No. 88), and acceptable Rp = 9.38, Rwp = 11.2, and Rexp = 5.86. High-performance microwave dielectric properties, with permittivity ∼26.3, Qf value ∼10,000 GHz, and temperature coefficient ∼+20 ppm/°C, were obtained in the sample sintered at 580 °C. Its chemical compatibility with aluminum at its sintering temperature was revealed and confirmed by both X-ray and energy dispersive spectrometer analysis. This ceramic could be a good candidate for ultralow-temperature cofired ceramics.

Phase evolution and microwave dielectric properties of xBi(2/3)MoO4-(1 -x)BiVO4 (0.0 ≤ x ≤ 1.0) low temperature firing ceramics.

In the present work, a full range of compositions of xBi(2/3)MoO4-(1 -x)BiVO4 (0.0 ≤ x ≤ 1.0) was prepared by the solid state reaction method. All the ceramic compositions could be readily densified to below 850 °C. As the x value increased, the monoclinic scheelite structure continuously changed to a tetragonal structure at x = 0.10, which means the ferroelastic phase transition temperature was lowered to near room temperature. In the compositional range 0.50 ≤ x < 0.70, a novel ordered scheelite phase was formed, most likely through A-site vacancy ordering. For compositions x ≥ 0.70, a composite two-phase region consisting of the ordered scheelite and Bi(2/3)MoO4 phases was formed. High microwave permittivity around 75 and Qf values around 8000 GHz could be obtained in the compositions near the phase boundaries between monoclinic and tetragonal scheelite phases. The intrinsic microwave dielectric properties were extrapolated from the far infrared reflectivity spectra, and it was found that the polarization was dominated by the Bi-O stretches when x ≤ 0.10.

Influence of Ce substitution for Bi in BiVO4 and the impact on the phase evolution and microwave dielectric properties.

In the present work, the (Bi1-xCex)VO4 (x ≤ 0.6) ceramics were prepared via a solid-state reaction method and all the ceramic samples could be densified below 900 °C. From the X-ray diffraction analysis, it is found that a monoclinic scheelite solid solution can be formed in the range x ≤ 0.10. In the range 0.20 ≤ x ≤ 0.60, a composite region with both monoclinic scheelite and tetragonal zircon solid solutions was formed and the content of the zircon phase increased with the calcined or sintering temperature. The refined lattice parameters of (Bi0.9Ce0.1)VO4 are a = 5.1801(0) Å, b = 5.0992(1) Å, c = 11.6997(8) Å, and γ = 90.346(0)° with the space group I112/b(15). The VO4 tetrahedron contracts with the substitution of Ce for Bi at the A site, and this helps to keep the specific tetrahedron chain stable in the monoclinic structure. The microwave dielectric permittivity was found to decrease linearly from 68 to about 26.6; meanwhile, the quality factor (Qf) value increased from 8000 GHz to around 23900 GHz as the x value increased from 0 to 0.60. The best microwave dielectric properties were obtained in a (Bi0.75Ce0.25)VO4 ceramic with a permittivity of ∼47.9, a Qf value of ∼18000 GHz, and a near-zero temperature coefficient of ∼+15 ppm/°C at a resonant frequency of around 7.6 GHz at room temperature. Infrared spectral analysis supported that the dielectric contribution for this system at microwave region could be attributed to the absorptions of structural phonon oscillations. This work presents a novel method to modify the temperature coefficient of BiVO4-type materials. This system of microwave dielectric ceramic might be an interesting candidate for microwave dielectric resonator and low-temperature cofired ceramic technology applications.

[Synchrotron radiation-based FTIR microspectroscopy study of 6-hydroxydopamine induced Parkinson's disease cell model].

SH-SY5Y cell line treated with 6-hydroxydopamine (6-OHDA) is a classical Parkinson's disease (PD). In the present study, synchrotron-based Fourier transform infrared (FTIR) microspectroscopy was used to analyze the biochemical composition of SH-SY5Y cell line treated with 6-OHDA. The detailed spectral analyses show the significant changes in cellular compositions such as lipids, proteins and nucleic acids in SH-SY5Y cells treated with 6-OHDA compared to control SH-SY5Y cells. As a result, the unsaturation levels of phospholipids decrease in SH-SY5Y cells treated with 6-OHDA compared to control cells, the analysis of protein secondary structure shows the significantly higher ratio of beta-sheet in PD cells compared to that of control cells, and the content of nuclear acid is highly decreased compared to that of control cells, suggesting that 6-OHDA induces the serious oxidative damage in SH-SY5Y cells. These findings suggest that SR-FTIR is an effective and precise technical tool to probe the biochemical changes of cells and then evaluate the pathological damage in cells.

[Synchrotron radiation-based FTIR microspectroscopy study of the hippocampus of 6-hydroxydopamine-lesioned rats].

Synchrotron radiation based-Fourier transform infrared microspectroscopy (SR-FTIR) was used to preliminarily investigate the biochemical composition of the hippocampal neurons for 6-hydroxydopamine-lesioned rats and normal rats. Spectral analysis showed that in PD samples, the CH2 asymmetric and symmetric vibrational absorption of integral area at 2 924 and 2 850 cm(-1) and the intensity of C=O vibrational absorption at 1 736 cm(-1) (assigned to the lipid functional group) increase compared to normal samples, which indicate that lipid content increased in PD sample; the PO2 asymmetric and symmetric vibrational absorption decrease compared to normal samples (assigned to the nucleic acid functional group; However no clear difference of the vibrational fingerprinting of protein between PD and normal samples was noticed. The present results suggest that the changes in biochemical composition in hippocampal neurons in PD rats probed by synchrotron radiation based-FTIR may contribute to the elucidation of PD pathology.