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.     

A viable approach to prepare 3C-SiC coatings by thermal MOCVD using commercial grade precursors

A series of 3 C-SiC coatings were prepared by organometallic chemical vapor deposition (MOCVD) using precursor solution containing a varying proportion of commercial-grade hexamethyldisiloxane (HMDSO) and n-hexane. The phase composition, bonding state, and microstructure of 3 C-SiC coatings were studied in detail by grazing incidence X-ray diffraction (GIXRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM). The microstructure and mechanical properties of the optimal 3 C-SiC coating were characterized by scanning transmission electron microscopy (STEM) and nanoindentation, respectively. Our results revealed that the amount of undesired graphite phase can be significantly reduced in the 3 C-SiC coating by introducing hydrogen gas in the reaction chamber alongside increasing the ratio of HMDSO/n-hexane in the precursor mixture. The STEM results revealed that the optimal coating was predominantly composed of nano-crystalline 3 C-SiC grains alongside a small amount of amorphous graphite. The hardness and elastic modulus of the optimal coating were 38.19 GPa and 363.2 GPa, respectively.     

Observation of table-like magnetocaloric effect and large refrigerant capacity in Nd6Fe13Pd1–xCux compounds

The table-like magnetocaloric effect is significant for the magnetic refrigeration applications above 20 K based on the Ericsson cycle. Herein, we prepared a series of Nd₆Fe₁₃Pd_1–xCu_x (x = 0.05, 0.1, 0.15) compounds by the arc-melting method. These compounds show the single crystalline phase in the tetragonal Nd₆Fe₁₃Si-type structure with the space group I4/mcm. A magnetic phase transition from ferromagnetism to antiferromagnetism and a metamagnetic transition from the antiferromagnetic state to the ferromagnetic state are observed in each of the compounds. The compounds exhibit table-like magnetocaloric effects with large refrigerant capacities. A constant ΔS_M in a temperature span of 40 K in the Nd₆Fe₁₃Pd_0.85Cu_0.15 compound are observed. For a field change of 0–5 T, the peak values of –ΔS_M for the Nd₆Fe₁₃Pd_0.95Cu_0.05, Nd₆Fe₁₃Pd_0.90Cu_0.10, and Nd₆Fe₁₃Pd_0.85Cu_0.15 compounds are estimated to be 4.8, 4.6 and 4.4 J/(kg·K) with corresponding refrigerant capacity values of 323, 331 and 316 J/kg, respectively. The obtained table-like magnetocaloric effects with large refrigerant capacities as well as fairly small thermal and magnetic hysteresis deem these series of compounds good candidates for single-phase magnetic refrigeration based on the Ericsson cycle.     

Ultra-high temperature ceramics based on ZrB2 obtained by pressureless sintering with addition of Cr3C2, Mo2C,and WC

ZrB₂-MeC and ZrB₂-19 vol% SiC-Me_xC_y where Me=Cr, Mo, W were obtained by pressureless sintering. The capability to promote densification of ZrB₂ and ZrB₂-SiC matrices is the highest for WC and lowest for Cr₃C₂. The interaction between the components results in the formation of new phases, such as MeB (MoB, CrB, WB), a solid solution based on ZrC, and a solid solution based on ZrB₂. The addition of Cr₃C₂ decreases the mechanical properties. On the other hand, the addition of Mo₂C or WC to ZrB₂-19 vol% SiC composite ceramics leads increased mechanical properties. Long-term oxidation of ceramics at 1500 °C for 50 h showed that, in binary ZrB₂-Me_xC_y, a protective oxide scale does not form on the surface thus leading to the destruction of the composite. On the contrary, triple composites showed high oxidation resistance, due to the formation of dense oxide scale on the surface, with ZrB₂-SiC-Mo₂C displaying the best performance.     

Hematite crystal growth in high-temperature lead-free multicomponent alkali borosilicate glass frit for red overglaze enamels

To elucidate the crystal growth process of hematite in high-temperature lead-free multicomponent alkali borosilicate glass, which is essentially important to control the color of red overglaze enamels, frit and hematite mixture is heat-treated and subjected to microscopic observations. Hematite particles slightly grew due to sintering at low temperature. Once the glass matrix formed near the softening point of frit, hematite dissolved into glass fluid. Hematite crystal growth concomitantly ensued with decrease in the number of hematite particles via Ostwald ripening as the temperature increased. The grown particles exhibited an anisotropic morphology with straight outlines reflecting crystal planes, the morphology of which is completely different from those grown by sintering and particles prior to heating. These results suggest that comprehensive understanding of frit and hematite from the perspectives of glass science and chemistry as well as powder technology are important to truly control the color of red overglaze enamels.     

Compositional design,structure stability,and microwave dielectric properties in Ca3MgBGe3O12 (B = Zr,Sn) garnet ceramics with tetravalent cations on B-site

Two garnet-structured Ca₃MgBGe₃O₁₂ (B = Zr, Sn) ceramics with tetravalent cations at B-site were prepared by conventional solid state reaction. The crystal structure, microstructure evolution, and microwave dielectric performance were investigated using X-ray powder diffraction, Rietveld refinement, scanning electron microscopy, Raman spectroscopy, and infrared spectroscopy techniques. Dense Ca₃MgZrGe₃O₁₂ and Ca₃MgSnGe₃O₁₂ ceramics were obtained at sintering temperatures of 1420 and 1400 °C, respectively. The dielectric constant, unloaded quality factor, and temperature coefficient of resonance frequency of Ca₃MgZrGe₃O₁₂ were 10.80 ± 0.2; 79,600 ± 1000 GHz (f = 12.61 GHz); and ?66.8 ± 1 ppm/°C, respectively, and the corresponding values for Ca₃MgSnGe₃O₁₂ were 9.68 ± 0.2; 83,400 ± 1000 GHz (f = 14.19 GHz); and ?57.9 ± 1 ppm/°C, respectively. The dielectric performances of the two ceramics were compared by analyzing the ionic polarizability, packing fraction, and bond valence. The intrinsic dielectric properties were predicted by fitting the infrared reflectivity spectra.     

Effect of annealing atmosphere on the structure and dielectric properties of unfilled tungsten bronze ceramics Ba4PrFe0.5Nb9.5O30

Unfilled tungsten bronze ceramics with the nominal formula Ba₄PrFe_0.5Nb_9.5O₃₀ were synthesized via the standard solid-state sintering route, and the effects of oxygen vacancies on the dielectric and electrical properties were investigated in addition to the structure. Room-temperature X-ray diffraction showed that the N₂-annealed sample had the largest cell volume. Low-temperature spectrum showed that N₂ annealing rendered the dielectric constant and dielectric loss more frequency dispersive, whereas O₂ annealing inhibited the frequency dispersion. The dc conductivity of all the samples originated from the electrons produced in the second ionization of oxygen vacancies and was most likely controlled by a mixed conduction mechanism of the electron and oxygen-vacancy ions. The N₂-annealed sample has the highest dc conductivity owing to its high concentration of oxygen vacancies. The broadening of the Raman lines and the decrease of Raman intensity for the N₂-annealed sample originated from a significant structural disorder. X-ray photoelectron spectra demonstrated that the increased oxygen vacancies caused by the change of valences of Fe and Pr ions contributed to the structural disorder.     

Toward nanograined gadolinia doped ceria via two-step sintering at ultralow temperature and its electrical conductivity

Highly dense (>98%) and nanograined (∼60 nm) gadolinia doped ceria are obtained from ultrafine powders by adopting two-step sintering (TSS) procedure at an ultralow temperature of 750 °C with a dwell time of 20 h, which is the lowest sintering temperature for ceria family without sintering aids up to now. Electrochemical impedance spectroscopy investigations suggest that the electrical conductivities of densified electrolytes are closely related to sintering temperature and grain size, and GDC900-750 exhibits the highest total electrical conductivity of 3.640 S m⁻¹ at 700 °C in air. Fitting calculation indicates partial grain-size dependence of oxygen vacancy association enthalpy and grain-size independence of oxygen ion migration enthalpy. Grain boundary maturity influences on grain boundary conductivity to some extent, and younger grain boundary endues the densified electrolytes with higher grain boundary conductivity.     

Chemical bond characteristics and infrared reflectivity spectrum of a novel microwave dielectric ceramic CaIn2O4 with near-zero τf

Orthorhombic-structured CaIn₂O₄ ceramics with a space group Pca2₁ were synthesized via a solid-state reaction method. A high relative density (95.6 %) and excellent microwave dielectric properties (ε_r ～11.28, Qf = 74,200 GHz, τ_f ～ ?4.6 ppm/°C) were obtained when the ceramics were sintered at 1375 °C for 6 h. The dielectric properties were investigated on the basis of the Phillips–Van Vechten–Levine chemical bond theory. Results indicated that the dielectric properties were mainly determined by the InO bonds in the CaIn₂O₄ ceramics. These bonds contributed more (74.65 %) to the dielectric constant than the CaO bonds (25.35 %). Furthermore, the intrinsic dielectric properties of the CaIn₂O₄ ceramics were investigated via infrared reflectivity spectroscopy. The extrapolated microwave dielectric properties were ε_r ～10.12 and Qf = 112,200 GHz. Results indicated that ion polarization is the main contributor to the dielectric constant in microwave frequency ranges.     

Pressure-less joining of alumina ceramics by the reaction-bonded aluminum oxide (RBAO) method

The present work demonstrates a pressure-less and reliable joining technique for alumina ceramics through a reaction-bonded aluminum oxide (RBAO) method. Effective joining relies on the RBAO mechanism, in which Al particles are converted to alumina through oxidation and bond with alumina particles from the parts to be joined upon sintering. Alumina ceramics in a green state were successfully joined with the use of an Al/Al₂O₃ powder mixture as an interlayer. The oxidation behavior of the Al particles was confirmed by thermogravimetry and X-ray diffraction analyses. Joining was performed in ambient air at 1650 °C for 2 h without applying any external pressure. Microstructural observations at the joining interfaces indicated a compact joining. The joining strengths were assessed by determining the biaxial strengths at room temperature, and the joined samples exhibited no fractures at the joining interfaces. Moreover, the joints had a strength of almost 100 % when compared with those of the parent alumina ceramics.