Mingwei Yan

Morphology of α-Si3N4 in Fe–Si3N4 prepared via flash combustion

The state and formation mechanism of α-Si3N4 in Fe–Si3N4 prepared by flash combustion were investigated by X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. The results indicate that α-Si3N4 crystals exist only in the Fe–Si3N4 dense areas. When FeSi75 particles react with N2, which generates substantial heat, a large number of Si solid particles evaporate. The product between Si gas and N2 is a mixture of α-Si3N4 and β-Si3N4. At the later stage of the flash combustion process, α-Si3N4 crystals dissolve and reprecipitate as β-Si3N4 and the β-Si3N4 crystals grow outward from the dense areas in the product pool. As the temperature decreases, the α-Si3N4 crystals cool before transforming into β-Si3N4 crystals in the dense areas of Fe–Si3N4. The phase composition of flash-combustion-synthesized Fe–Si3N4 is controllable through manipulation of the gas-phase reaction in the early stage and the α→β transformation in the later stage.

Formation mechanism of calcium hexaluminate

To investigate the formation mechanism of calcium hexaluminate (CaAl12O19, CA6), the analytically pure alumina and calcia used as raw materials were mixed in CaO/Al2O3 ratio of 12.57:137.43 by mass. The raw materials were ball-milled and shaped into green specimens, and fired at 1300–1600°C. Then, the phase composition and microstructure evolution of the fired specimen were studied, and a first principle calculation was performed. The results show that in the reaction system of CaO and Al2O3, a small amount of CA6 forms at 1300°C, and greater amounts are formed at 1400°C and higher temperatures. The reaction is as follows: CaO·2Al2O3 (CA2) + 4Al2O3 → CA6. The diffusions of Ca2+ in CA2 towards Al2O3 and Al3+ in Al2O3 towards CA2 change the structures in different degrees of difficulty. Compared with the difficulty of structural change and the corresponding lattice energy change, it is deduced that the main formation mechanism is the diffusion of Ca2+ in CA2 towards Al2O3.

Reaction behavior of trace oxygen during combustion of falling FeSi75 powder in a nitrogen flow

To explore the reaction behavior of trace oxygen during the flash combustion process of falling FeSi75 powder in a nitrogen flow, a flash-combustion-synthesized Fe-Si3N4 sample was heat-treated to remove SiO2. The samples before and after the treatment were investigated by X-ray diffraction, scanning electron microscopy, and transmission electron microscopy, and the formation mechanism of SiO2 was investigated. The results show that SiO2 in the Fe-Si3N4 is mainly located on the surface or around the Si3N4 particles in dense areas, existing in both crystalline and amorphous states; when the FeSi75 particles, which are less than 0.074 mm in size, fell in up-flowing hot N2 stream, trace oxygen in the N2 stream did not significantly hinder the nitridation of FeSi75 particles as it was consumed by the surface oxidation of the generated Si3N4 particles to form SiO2. At the reaction zone, the oxidation of Si3N4 particles decreased the oxygen partial pressure in the N2 stream and greatly reduced the opportunity for FeSi75 particles to be oxidized into SiO2; by virtue of the SiO2 film developed on the surface, the Si3N4 particles adhered to each other and formed dense areas in the material.

Influence of Microstructure on Formation of Deterioration Layer in Periclase-Hercynite Bricks

The microstructure of the original layer and the cement melt-penetrated layer of a used periclase-hercynite brick from a cement rotary kiln with a daily output of 5000 tons for 12 months was studied by XRD, SEM, EDS, and a mercury porosimeter. The results show that the cation diffusion between hercynite and periclase particles in the brick at high temperatures decreases the pore size of the brick. The pore size in the original layer is located mainly in the range of 4 – 20 μm; the decreased pore size increases the penetration resistance of the cement melt to the inside of the brick and makes the cement melt react with the pore walls better. The components of the matrix pore walls such as MgO and Al2O3 dissolve in the cement melt, enhancing the hot properties of the penetrated melt, decreasing the penetration depth, and slowing the formation of the deterioration layer. The pore structure and the element distribution endow the brick with good thermal shock resistance.

Morphology characterization of periclase–hercynite refractories by reaction sintering

A periclase-hercynite brick was prepared via reaction sintering at 1600°C for 6 h in air using magnesia and reaction-sintered hercynite as raw materials. The microstructure development of the periclase-hercynite brick during sintering was investigated using X-ray diffraction, X-ray photoelectron spectroscopy, and scanning electron microscopy in combination with energy-dispersive X-ray spectroscopy. The results show that during sintering, Fe2+, Fe3+ and Al3+ ions in hercynite crystals migrate and react with periclase to form (Mg1-xFex)(Fe2-yAly)O4 spinel with a high Fe/Al ratio. Meanwhile, Mg2+ in periclase crystals migrates into hercynite crystals and occupies the oxygen tetrahedron vacancies. This Mg2+ migration leads to the formation of (Mg1-uFeu)(Fe2-vAlv)O4 spinel with a lower Fe/Al ratio and results in Al3+ remaining in hercynite crystals. Cation diffusion between periclase and hercynite crystals promotes the sintering process and results in the formation of a microporous structure.

In situ reaction mechanism of MgAlON in Al–Al2O3–MgO composites at 1700°C under flowing N2

The Al–Al2O3–MgO composites with added aluminum contents of approximately 0wt%, 5wt%, and 10wt%, named as M1, M2, and M3, respectively, were prepared at 1700°C for 5 h under a flowing N2 atmosphere using the reaction sintering method. After sintering, the Al–Al2O3–MgO composites were characterized and analyzed by X-ray diffraction, scanning electron microscopy, and energy-dispersive X-ray spectroscopy. The results show that specimen M1 was composed of MgO and MgAl2O4. Compared with specimen M1, specimens M2 and M3 possessed MgAlON, and its production increased with increasing aluminum addition. Under an N2 atmosphere, MgO, Al2O3, and Al in the matrix of specimens M2 and M3 reacted to form MgAlON and AlN-polytypoids, which combined the particles and the matrix together and imparted the Al–Al2O3–MgO composites with a dense structure. The mechanism of MgAlON synthesis is described as follows. Under an N2 atmosphere, the partial pressure of oxygen is quite low; thus, when the Al–Al2O3–MgO composites were soaked at 580°C for an extended period, aluminum metal was transformed into AlN. With increasing temperature, Al2O3 diffused into AlN crystal lattices and formed AlN-polytypoids; however, MgO reacted with Al2O3 to form MgAl2O4. When the temperature was greater than (1640 ± 10)°C, AlN diffused into Al2O3 and formed spinel-structured AlON. In situ MgAlON was acquired through a solid-solution reaction between AlON and MgAl2O4 at high temperatures because of their similar spinel structures.

A new synthetic route to MgO–MgAl2O4–ZrO2 highly dispersed composite material through formation of Mg5Al2.4Zr1.7O12 metastable phase: synthesis and physical properties

Mg5Al2.4Zr1.7O12 metastable phase was successfully synthesized from analytical-grade MgO, α-Al2O3, MgAl2O4, and ZrO2 under an N2 atmosphere. The sintering temperature was varied from 1650 to 1780°C, and the highest amount of Mg5Al2.4Zr1.7O12 appeared in the composite material when the sintering temperature was 1760°C. According to our research of the formation mechanism of Mg5Al2.4Zr1.7O12, the formation and growth of MgAl2O4 dominated when the temperature was not higher than 1650°C. When the temperature was higher than 1650°C, MgO and ZrO2 tended to diffuse into MgAl2O4 and the Mg5Al2.4Zr1.7O12 solid solution was formed. When the temperature reached 1760°C, the formation of Mg5Al2.4Zr1.7O12 was completed. The effect of MgAl2O4 spinel crystals was also studied, and their introduction into the composite material promoted the formation and growth of Mg5Al2.4Zr1.7O12. A highly dispersed MgO–MgAl2O4–ZrO2 composite material was prepared through the decomposition of the Mg5Al2.4Zr1.7O12 metastable phase. The as-prepared composite material showed improved overall physical properties because of the good dispersion of MgO, MgAl2O4, and ZrO2 phases.