Isostructural phase transition (IPT) in CaMoO4 with Scheelite structure

The ceramic compound CaMoO₄ is synthesized via a solid-state reaction technique. Rietveld refinement studies were done on the powder X-ray diffraction data of CaMoO₄ and revealed that the compound is crystallized in the tetragonal Scheelite structure with I4₁/a space group. The differential scanning calorimetry (DSC) studies on CaMoO₄ divulged an anomaly around 440 °C. This anomaly is further probed using the temperature-dependent Raman and dielectric spectroscopic measurements and are corroborating with the results obtained from DSC. A detailed investigation on the temperature-dependent Raman spectroscopic data revealed that the A_1g mode of CaMoO₄ showed a soft phonon behavior up to the phase transition temperature. It is observed that the A_1g mode displayed phonon hardening behavior with further increasing the temperature. The anomaly is attributed to an isostructural phase transition (IPT), a rarely observed phenomenon in the compounds with Scheelite structure. The IPT in CaMoO₄ is elucidated with a phonon softening mechanism.     

(Cu1/3Nb2/3)4+ ionic substituting effects,low-temperature sintering behaviors,and improved temperature stability of Ba3Nb4Ti4O21 microwave dielectric ceramics

In this study, (Cu_1/3Nb_2/3)⁴⁺ complex cation and BaO–ZnO–B₂O₃ glass frit were adopted to solve the high sintering temperature and poor temperature stability of Ba₃Nb₄Ti₄O₂₁ ceramics. It is shown that pure Ba₃Nb₄Ti₄O₂₁ phase was formed when Ti site was partially replaced by (Cu_1/3Nb_2/3)⁴⁺ cation. The increasing number of dopants decreases the dielectric polarizability, correspondingly, the dielectric constant and temperature coefficient of the resonance frequency values are reduced consistently. The variation of the Q × f value is determined by internal ionic packing fraction and external sintering densification. The (Cu_1/3Nb_2/3)⁴⁺ cation effectively decreases the suitable sintering temperature from 1200 to 1050 °C while greatly improving the temperature stability. BaO–ZnO–B₂O₃ glass was used to further improve the low-temperature sintering characteristics of Ba₃Nb₄Ti₄O₂₁ ceramics. It is proven that the addition of glass frits effectively decreases the temperature to 925 °C with combinational excellent microwave dielectric properties: ε_r ～55.6, Q × f ～5700 GHz, τ_f ～3 ppm/^°C, making the Ba₃Nb₄Ti₄O₂₁ ceramics promising in the applications of low-temperature cofired ceramic technology.     

High Q×f values of Zn-Ni co-modified LiMg0.9Zn0.1-xNixPO4 microwave dielectric ceramics for 5G/6G LTCC modules

In this work, Zn-Ni co-modified LiMg_0.9Zn_0.1-xNi_xPO₄ (x = 0–0.1) microwave dielectric ceramics were fabricated using a solid state synthesis route. Rietveld refinement of the XRD data revealed that all ceramic samples have formed a single phase with olivine structure. SEM images showed that the samples have a dense microstructure, that agrees with the measured relative density of 97.73 %. Based on the complex chemical bond theory, Raman and infrared reflectance spectra, we postulate that ε_r is mainly affected by the ionic polarizability, lattice and bond energy, while P-O bond plays a decisive role in Q×f and τ_f value. Optimum properties of Q×f ~ 153,500 GHz, ε_r ~ 7.13 and τ_f ~ ?59 ppm/°C were achieved for the composition LiMg_0.9Zn_0.06Ni_0.04PO₄ sintered at 875 ℃ for 2 h. This set of properties makes these ceramics an excellent candidate for LTCC, wave-guide filters and antennas for 5 G/6 G communication applications.     

Annealing temperature-dependent structural and electrical properties of (Ta2O5)1-x - (TiO2)x thin films,x ≤ 0.11

(Ta₂O₅)_1-x- (TiO₂)_x (TTO_x) thin films, with x = 0, 0.03, 0.06, 0.08, and 0.11, were deposited using magnetron direct current (DC) sputtering method onto the P/boron-silicon (1 0 0) substrates by varying areas of Tantalum and Titanium metallic targets, in oxygen environment at ambient temperature. The as-deposited thin films were annealed at temperatures ranging from 500 to 800 °C. Generally, the formation of the Ta₂O₅ structure was observed from the X-ray diffraction measurements of the annealed films. The capacitance of prepared metal– oxide– semiconductor (MOS) structures of Ag/TTO_x/p-Si was measured at 1 MHz. The dielectric constant of the deposited films was observed altering with varying composition and annealing temperature, showing the highest value 71, at 1 MHz, for the TTO_x films, x = 0.06, annealed at 700 °C. With increasing annealing temperature, from 700 to 800 °C, the leakage current density was observed, generally decreasing, from 10^?5 to 10^?8 A cm^?2, for the prepared compositions. Among the prepared compositions, films with x = 0.06, annealed at 800 °C, having the observed value of dielectric constant 48, at 1 MHz; and the leakage current density 2.7 × 10^?8 A cm^?2, at the electric field of 3.5 × 10⁵ V cm^?1, show preferred potential as a dielectric for high-density silicon memory devices.     

Cold sintered,temperature-stable CaSnSiO5-K2MoO4 composite microwave ceramics and its prototype microstrip patch antenna

Dense (1-x)wt%CaSnSiO₅-xwt%K₂MoO₄ (CSSO-KMO) composite ceramics were fabricated by the cold sintering process at 180 °C under 400 MPa for 60 min. X-ray diffraction, Energy dispersive X-ray and Raman spectroscopy confirmed that CSSO and KMO coexisted without intermediate phases. As KMO weight fraction increased, relative permittivity (ε_r) and temperature coefficient of resonant frequency (τ_f) decreased and the microwave quality factor (Q×f, where f is resonant frequency) increased. Near-zero τ_f (-0.5 ppm/°C) was obtained for 65 wt%CSSO-35 wt%KMO with ε_r ～ 9.2 and Q×f ～ 6240 GHz. No chemical reaction between ceramic composites and silver was observed, demonstrating potential for cofiring with Ag-paste. A prototype antenna was fabricated from 65 wt%CSSO-35 wt%KMO composite ceramic with a bandwidth of 144 MHz @ -10 dB, a gain of 5.7 dBi and a total efficiency of 88.4 % at 5.2 GHz, suitable for 5 G mobile communication systems.     

Good dielectric performance and broadband dielectric polarization in Ag,Nb co-doped TiO2

Due to the demand of miniaturization and integration for ceramic capacitors in electronic components market, TiO₂-based ceramics with colossal permittivity has become a research hotspot in recent years. In this work, we report that Ag⁺/Nb⁵⁺ co-doped (Ag_1/4Nb_3/4)_xTi_1−xO₂ (ANTOx) ceramics with colossal permittivity over a wide frequency and temperature range were successfully prepared by a traditional solid–state method. Notably, compositions of ANTO0.005 and ANTO0.01 respectively exhibit both low dielectric loss (0.040 and 0.050 at 1 kHz), high dielectric permittivity (9.2 × 10³ and 1.6 × 10⁴ at 1 kHz), and good thermal stability, which satisfy the requirements for the temperature range of application of X9R and X8R ceramic capacitors, respectively. The origin of the dielectric behavior was attributed to five dielectric relaxation phenomena, i.e., localized carriers' hopping, electron–pinned defect–dipoles, interfacial polarization, and oxygen vacancies ionization and diffusion, as suggested by dielectric temperature spectra and valence state analysis via XPS; wherein, electron-pinned defect–dipoles and internal barrier layer capacitance are believed to be the main causes for the giant dielectric permittivity in ANTOx ceramics.     

Optimized Biocatalytic Synthesis of 2-Selenopyrimidine Nucleosides by Transglycosylation**

Selenium-modified nucleosides are powerful tools to study the structure and function of nucleic acids and their protein interactions. The widespread application of 2-selenopyrimidine nucleosides is currently limited by low yields in established synthetic routes. Herein, we describe the optimization of the synthesis of 2-Se-uridine and 2-Se-thymidine derivatives by thermostable nucleoside phosphorylases in transglycosylation reactions using natural uridine or thymidine as sugar donors. Reactions were performed at 60 or 80 °C and at pH 9 under hypoxic conditions to improve the solubility and stability of the 2-Se-nucleobases in aqueous media. To optimize the conversion, the reaction equilibria in analytical transglycosylation reactions were studied. The equilibrium constants of phosphorolysis of the 2-Se-pyrimidines were between 5 and 10, and therefore differ by an order of magnitude from the equilibrium constants of any other known case. Hence, the thermodynamic properties of the target nucleosides are inherently unfavorable, and this complicates their synthesis significantly. A tenfold excess of sugar donor was needed to achieve 40−48 % conversion to the target nucleoside. Scale-up of the optimized conditions provided four Se-containing nucleosides in 6–40 % isolated yield, which compares favorably to established chemical routes.     

冷低压分离器油相系统铵盐垢下腐蚀风险的模拟预测

为探究某加氢装置高压换热器管束腐蚀泄漏原因，利用Aspen Plus工艺模拟软件计算了冷低压分离器油相（简称冷低分油）中水质量分数分别为1%,2%,3%时，冷低分油系统的露点温度、氯化铵结晶温度、氯化铵潮解点温度和相对湿度。结果表明：相较于经验的露点温度预测方法，通过引入潮解点、划分系统“湿环境”温度范围判断氯化铵垢下腐蚀风险区域的方法与实际腐蚀案例更为切合；在3种油相含水条件下，换热器管束存在氯化铵垢下腐蚀的“湿环境”温度范围分别为：50~103 ℃,50~161 ℃,50~176 ℃；随着油相中含水量的提高，“湿环境”腐蚀区域逐渐向高温部位迁移，预计铵盐导致的垢下腐蚀将会愈加严重。     

Investigation of the microwave dielectric properties of the Li4x/3Zn2−2xTi1+2x/3O4 system by P–V–L theory and vibration spectroscopy

Li_4x/3Zn_2–2xTi_1+2x/3O₄ microwave dielectric ceramics with a spinel phase were prepared via a high-temperature solid-phase method. P–V–L theory, vibration spectra, and XPS were utilized to establish the links between the intrinsic and extrinsic factors and the microwave dielectric properties. According to the characterization, the change in permittivity (ε_r) was ascribed to the increase in the average bond ionicity of Ti–O(Af_iTi-O) and the polar mode of the lattice vibration; the change in quality factor(Q × f) resulted from the change in the Ti–O lattice energy (AU_Ti-O) and existence of oxygen vacancy; the increase in temperature coefficient of the resonance frequency (τ_f) was triggered by the increase in the Ti–O bond energy. The Li_0.6Zn_1.1Ti_1.3O₄ ceramics (x = 0.45) sintered at 1125 °C finally obtained optimal microwave dielectric constants of ε_r = 17.3, Q × f = 76,318 GHz and τ_f = -58 ppm/°C.