A low-firing melilite ceramic Ba2CuGe207 and compositional modulation on microwave dielectric properties through Mg substitution

A melilite Ba2CuGe2O7 ceramic was characterized by low sintering temperature and moderate microwave dielectric properties.Sintered at 960℃,the Ba2CuGe2O7 ceramic had a high relative density 97%,a low relative permittivity(εr)9.43,a quality factor(Q×f)of 20,000 GHz,and a temperature coefficient of resonance frequency(τf)-76 ppm/℃.To get a deep understanding of the relationship between composition,structure,and dielectric performances,magnesium substitution for copper in Ba2CuGe2O7 was conducted.Influences of magnesium doping on the sintering behavior,crystal structure,and microwave dielectric properties were studied.Mg doping in Ba2CuGe2O7 caused negligible changes in the macroscopic crystal structure,grain morphology,and size distribution,while induced visible variation in the local structure as revealed by Raman analysis.Microwave dielectric properties exhibit a remarkable dependence on composition.On increasing the magnesium content,the relative permittivity featured a continuous decrease,while both the quality factor and the temperature coefficient of resonance frequency increased monotonously.Such variations in dielectric performances were clarified in terms of the polarizability,packing fraction,and band valence theory.

The melilite-type compound (Sr_(1-x),A_x)_2MnGe_2S_6O(A=K,La) being a room temperature ferromagnetic semiconductor

The seeking of room temperature ferromagnetic semiconductors, which take advantages of both the charge and spin degrees of freedom of electrons to realize a variety of functionalities in devices integrated with electronic, optical, and magnetic storage properties, has been a long-term goal of scientists and engi- neers. Here, by using the spin-polarized density functional theory calculations, we predict a new series of high temperature ferromagnetic semiconductors based on the melilite-type oxysulfide Sr2MnGe2S60 through hole （K） and electron （La） doping. Due to the lack of strong antiferromagnetic superexchange between Mn ions, the weak antiferromagnetic order in the parent compound Sr2MnGe2S60 can be sup- pressed easily by charge doping with either p-type magnetic order. At a doping concentration of or n-type carriers, giving rise to the expected ferro- 25%, both the hole-doped and electron-doped compounds can achieve a Curie temperature （To） above 300 K. The underlying mechanism is analyzed. Our study provides an effective approach for exploring new types of high temperature ferromagnetic semiconductors.

Sol-gel approach to low-temperature synthesis of single-phase metastable La_(2)Ga_(3)O_(7.5) melilite with enhanced grain-boundary oxide ionic conductivity via a kinetically favorable mechanism

Starting with the stoichiometric and highly homogeneous gel-precursor,single-phase metastable melilite La_(2)Ga_(3)O_(7.5),as the end-member of solid solution La_(1+x)Sr_(1−x)Ga_(3)O_(7+x/2)(0≤x≤1),has been synthesized by solid-state reaction at 700℃ for 2 h via a kinetically favorable mechanism and characterized by X-ray diffraction(XRD),Raman,X-ray photoelectron spectroscopy(XPS),field emission scanning electron microscopy(FESEM),transmission electron microscopy(TEM),AC impedance spectroscopy,etc.It has been revealed that the as-synthesized melilite La_(2)Ga_(3)O_(7.5) shows an orthorhombic symmetry with crystal cell parameters a=11.4690(1)A,b=11.2825(4)A,and c=10.3735(4)A,while has more Raman active modes than LaSrGa_(3)O_(7) with a tetragonal structure,which was also synthesized under the same conditions for comparison,but tends to slowly decompose into perovskite LaGaO_(3) and Ga2O_(3) when annealed at 700℃ for over 20 h driven by its meta-stability.Moreover,the metastable La2Ga3O7.5 shows a higher XPS binding energy for the excess oxide ions in the crystal structure than those at normal lattice sites.Its intrinsic grain oxide ion conductivity can reach as high as 0.04 and 0.51 mS·cm^(-1) at 550 and 700℃,respectively,characterized by a simple Arrhenius relationship ln(σT)-1/T with invariable activation energy,E_(a)=1.22 eV,over the temperature range from 300 to 700℃,along with an apparent grain boundary conductivity that is about double that from the grains thanks to the clean grain boundaries.This paper provides a new strategic approach to the synthesis of complex oxides that may be of high performance but are difficultly achieved by the conventional ceramic method at high temperatures.

Melilite-derived mineral inclusions in chromite from the Gaositai complex: Implications for an extensional tectonic setting in Early Permian at the north North China Craton

The Early Permian mafic-ultramafic concentrically zoned Gaositai intrusion at Chengde, on the northern margin of the North China Craton(NCC), is a cumulative complex emplaced along a giant fracture that penetrates deeply into the continental lithosphere. Melt inclusions are present in chromite crystals from the inner dunite and chromitite zones of the Gaositai complex. The melt inclusions have experienced post-trap crystallization and resulted in multiple mineral phases, including melilite, garnet, phlogopite, magnesite and apatite, which can indicate the liquidus minerals of the primitive magma. The characteristics of the melilite+melanite+clinopyxene assemblage indicate that the primary parental magma was highly undersaturated and derived from an alkali-rich mantle source. The crystallization of phlogopite, magnesite and apatite suggests a primary magma rich in K, H_2O and CO_2. When compared with experimental data, the primary magma of the Gaositai intrusion is concordant with a kamafugite magma originating from partial melting of enriched mantle with H_2O and CO_2 at pressures greater than 2.7 GPa. This magmatic process would have been related to extensional thinning of the continental lithosphere. The Gaositai primary magmas have high Nb/La ratios, which are similar to those of ocean island basalts, but different from arc-related magmas. This suggests that the northern margin of the NCC was not an active continental margin of the Paleo-Asian Ocean subduction zone during the Early Permian: an extensional tectonic setting during the emplacement of the Gaositai intrusion is more likely.

Effects of Y_(2)O_(3) and transition-metal nitrates on phase,microstructures and PL properties of N-containing Ce_(2)Si_(2.5)Al_(0.5)O_(3.5)N_(3.5) melilite

N-containing Ce_(2)Si_(2.5)Al_(0.5)O_(3.5)N_(3.5)(CeSiAlON) melilite was synthesized at 1550 and 1600℃ for 5 h from CeO_(2),Si,Al,and Al_(2)O_(3) in nitrogen by using Y_(2)O_(3) and transition-metal nitrates(Co(NO_(3))_(2)·6 H_(2) O and Ni(NO_(3))_(2)·6 H_(2)O) as additives.The effects of Y_(2)O_(3) and transition-metal nitrates on the phase,microstructures and photoluminescence properties of CeSiAlON melilite were studied.The incorporation of Y_(2)O_(3) can promote the reaction of raw materials to a low degree,and results in a unit cell shrinkage of CeSiAlON due to the smaller radius of Y atom than that of Ce atom.The transition-metal nitrates can accelerate the reaction clearly and facilitate the formation of CeSiAlON fibers.The photoluminescence(PL) properties of CeSiAlON melilite presents a board violet emission band because of the 5 d-4 f transitions of Ce^(3+),and the additives can enhance the PL emission intensities of specimen significantly.

Mechanism of phase separation in BFS (blast furnace slag) glass phase

XRD,TEM,ED,and NMR analyzed four types of blast furnace slags (BFS) with different structures in this paper. The composition requirement for phase separation in BFS glass phase was then put forward,that is the composition of slag locates in the coexisting phase region of melilite and any silicate mineral with Q0 units. The special structure of melilite units,a 5-membered ring with high degree of polymerization (DOP),plays a key role in the formation of phase separation. In BFS system,one with chemical composition of larger ratio of (CaO + MgO/(SiO2 + Al2O3) would be more promising to meet the requirement for phase separation.