Transient liquid phase sintering of high-purity mullite for high-temperature structural ceramics

High-purity mullite ceramics, promising engineering ceramics for high-temperature applications, were fabricated using transient liquid phase sintering to improve their high-temperature mechanical properties. Small amounts of ultrafine alumina or silica powders were uniformly mixed with the mullite precursor depending on the silica-alumina ratio of the resulting ceramics to allow for the formation of a transient liquid phase during sintering, thus, enhancing densification at the early stage of sintering and mullite formation by the reaction between additional alumina and the residual glassy phase (mullitization) at the final stage of sintering. The addition of alumina powder to the silica-rich mullite precursor resulted in a reaction between the glassy silica and alumina phases during sintering, thereby forming a mullite phase without inhibiting densification. The addition of fine silica powder to the mullite single-phase precursor led to densification with an abnormal grain growth of mullite, whereas some of the added silica remained as a glassy phase after sintering. The resulting mullite ceramics prepared using different powder compositions showed different sintering behaviors, depending on the amount of alumina added. Upon selecting an optimum process and the amount of alumina to be added, the pure mullite ceramics obtained via transient liquid phase sintering exhibited high density (approximately 99%) and excellent high-temperature flexural strength (approximately 320 MPa) at 1500 °C in air. These results clearly demonstrate that pure mullite ceramics fabricated via transient liquid phase sintering with compositions close to those of stoichiometric mullite could be a promising process for the fabrication of high-temperature structural ceramics used in an ambient atmosphere. The transient liquid phase sintering process proposed in this study could be a powerful processing tool that allows for the preparation of superior high-temperature structural ceramics used in the ambient processing atmosphere.     

Ion migration behavior and its interaction with sintering environment in cation conductor during flash sintering

Flash sintering has been reported in various ceramics. Nevertheless, anion and cation conductors exhibit different flash-sintering behaviors, and the interaction mechanism between the conductive species and the sintering environment has remained unclear. Herein, we report the flash-sintering phenomena of a typical cation conductor, Na₃Zr₂(SiO₄)₂(PO₄) with anode region surrounded by air and NaNO₃ environments. The results prove that the ionic behavior and joule heating distribution can be controlled by changing the electrode environment. Four possible scenarios describing the ion migration behavior and interaction with the environment are proposed for providing a guidance for controlling the ion interaction behavior during flash sintering.     

Influence of α′‐/α‐crystal polymorphism on properties of poly(l‐lactic acid)

Poly(l ‐lactic acid) (PLLA) is a biodegradable and biocompatible thermoplastic polyester produced from renewable sources, widely used for biomedical devices, in food packaging and in agriculture. It is a semicrystalline polymer, and as such its properties are strongly affected by the developed semicrystalline morphology. As a function of the crystallization temperature, PLLA can form different crystal modifications, namely α′‐crystals below about 120 °C and α‐crystals at higher temperatures. The α′ modification is therefore of special importance as it may be the preferred polymorph developing at processing‐relevant conditions. It is a metastable modification which typically transforms into the more stable α‐crystals on annealing at elevated temperature. The structure, kinetics of formation and thermodynamics of α′‐ and α‐crystals of PLLA are reviewed in this contribution, together with the effect of α′‐/α‐crystal polymorphism on the properties of PLLA. © 2018 Society of Chemical Industry     

Facile synthesis of MgO–Mg2SiO4 composite ceramics with high strength and low thermal conductivity

The recycling of solid waste is a win-win solution for humans and nature. For this purpose, magnesite tailings and silicon kerf waste were employed to prepare MgO–Mg₂SiO₄ composite ceramics by solid-state reaction synthesis in the present work. Then, effects of sintering temperature and raw material ratio on as-prepared ceramics were systematically studied. As-prepared ceramics showed improvement in their relative density (from 47.55%–68.12% to 90.96%–95.25%) and cold compressive strength (from 7.34–118.66 MPa to 303.39–546.65 MPa) with the increase in sintering temperature from 1300 to 1600 °C. In addition, it was found that Si promoted synthesis process of Mg₂SiO₄ phase through transient liquid phase sintering and Fe₂O₃ accelerated sintering process through activation sintering. Consequently, the presence of Mg₂SiO₄ phase effectively improved the density and strength of MgO–Mg₂SiO₄ composite ceramic, while reducing its thermal conductivity. This work provides a potential reutilization strategy for magnesite tailings, and as-prepared products are expected to be applied in fields of construction, metallurgy, and chemical industry.     

Effects of (Li0.5Sm0.5)/W co-substitution and sintering temperature on the structure and electrical properties of ultrahigh Curie temperature piezoceramics,Ca0.92(Li0.5Sm0.5)0.08Bi2Nb2-xWxO9

With co-substitution of (Li_0.5Sm_0.5) at A site and W at B site, the electrical properties of modified Ca_0.92(Li_0.5Sm_0.5)_0.08Bi₂Nb_2-xW_xO₉ [(CLS)BN-xW, x = 0, 0.015 and 0.03] piezoceramics with ultrahigh Curie temperature (T_C) of > 930 °C were enhanced dramatically. The increased resistivity induced by the co-substitution ensure them to be polarized under an enough high field. Combined with the increase of spontaneous ferroelectric polarization (P_S), the significant enhancements in the piezoelectric, dielectric and ferroelectric properties can be obtained in the composition x = 0.015. Furthermore, the piezoelectric activity (d₃₃) and bulk resistivity (ρ_b) of (CLS)BN-0.015 W can be further enhanced at an appropriate sintering temperature. This optimum composition sintered at 1170 °C shows ultrahigh T_C of ～948 °C, d₃₃ of ～17.3 pC/N and ρ_b of ～6.9 MΩ cm at 600 °C, which are comparable to those of the reported high-temperature Aurivillius piezoceramics with T_C > 850 °C.     

Two-step sinter-crystallization of K2O–CaO–P2O5–SiO2 (45S5-K) bioactive glass

Bioactive glasses and glass-ceramics (GCs) effectively regenerate bone tissue, however most GCs show improved mechanical properties. In this work, we developed and tested a rarely studied bioactive glass composition (24.4K₂O-26.9CaO-46.1SiO₂-2.6P₂O₅ mol%, identified as 45S5-K) with different particle sizes and heating rates to obtain a sintered GC that combines good fracture strength, low elastic modulus, and bioactivity. We analyzed the influence of the sintering processing conditions in the elastic modulus, Vickers microhardness, density, and crystal phase formation in the GC. The best GC shows improved properties compared with its parent glass. This glass achieves a good densification degree with a two-step viscous flow sintering approach and the resulting GC shows as high bioactivity as that of the standard 45S5 Bioglass®. Furthermore, the GC elastic modulus (56 GPa) is relatively low, minimizing stress shielding. Therefore, we unveiled the glass sintering behavior with concurrent crystallization of this complex bioactive glass composition and developed a potential GC for bone regeneration.     

Phase formation,structure and properties of light-weight aluminosilicate proppants based on clay-diabase and clay-granite binary mixes

One of the drawbacks of fusible clays is the narrow sintering interval due to a sharp increase in the amount of iron-silicate melt at a temperature of 1000–1100 °C, which hardens in the form of a glass phase upon cooling. This leads to a relatively low mechanical strength of the calcined samples and causes the danger of melting the granular material surface from such clays during the firing process. To increase the strength of samples of fusible clays, the influence of diabase and granitoid rocks was considered. It was found that the strengthening effect of diabase and granitoid rock additives in an amount of 20–50% in a mixture with fusible clay is due to an increase of total content of the crystalline phase (mullite, cristobalite and residual quartz) from 18–20% in clays without additives to 22–28 % - in mixtures with diabase and to 28–34% - with granitoid additives) at a temperature of 1050–1100 °C. This increase is due to the activation of synthesis processes of secondary mullite and crystallization from alkali-rich feldspar melt of amorphous silica, released from the structure of clay minerals. The established influence of the igneous rocks used made it possible to develop compositions and propose process flow sheet for producing aluminosilicate proppants based on fusible clays. The use of granitoid and diabase rocks in an amount of 20–70% with fusible clays produces lightweight aluminosilicate proppants with bulk density of 1.40–1.46 g/cm³ at temperature range of 1050–1100 °C, which can endure destructive pressures up to 34.5–52 MPa.     

Synthesis of nanopowders with low agglomeration by elaborating Φ values for producing Gd2O3-MgO nanocomposites with extremely fine grain sizes and high mid-infrared transparency

Refining ceramic microstructures to the nanometric range to minimize light scattering provides an interesting methodology for developing novel optical ceramic materials. In this work, we reported the fabrication and properties of a new nanocomposite optical ceramic of Gd₂O₃-MgO. The citric acid sol-gel combustion method was adopted to fabricate Gd₂O₃-MgO nanocomposites with fine-grain sizes, dense microstructures and homogeneous phase domains. Nanopowders with low agglomeration and improved sinterability can be obtained by elaborating Φ values. Further refining of the microstructure of the nanocomposites was achieved by elaborating the hot-pressing conditions. The sample sintered at 65 MPa and 1300 °C showed a quite high hardness value of 14.3 ± 0.2 GPa, a high transmittance of 80.3 %–84.7 % over the 3?6 μm wavelength range, due mainly to its extremely fine-grain size of Gd₂O₃ and MgO (93 and 78 nm, respectively) and high density.     

Pelletization and sintering of New Zealand titanomagnetite ironsand

Direct reduction (DR) of iron ore with hydrogen is a potential route for near-zero CO₂ steelmaking, but vertical shaft DR reactors require that iron ore fines must first be pelletized. This study reports an investigation of the pelletization and subsequent sintering behaviour of titanomagnetite (TTM) ironsand, which is the main iron ore feedstock for New Zealand’s steel industry. Initially green pellets were bound with bentonite and carboxymethyl-cellulose (Peridur), using an average ironsand particle size of 65 µm. The compressive strength of these pellets after sintering at 1200 °C in air for 2 hr was measured to be 976 N, meeting the expected feedstock requirements for a shaft reactor. This strength was attributed to interparticle bonding arising from extensive recrystallisation of titanohematite grains from oxidation of TTM, as well as the formation of a liquid bonding phase due to melting and diffusion of the binders. Building on these results, alternative binders were then explored in order to lower the required sintering temperature. A combination of both organic and inorganic binders was found to deliver optimum performance, wherein carboxymethyl-cellulose based binders provided strength in the green pellets, whilst inorganic binders, such as calcium borate or ground glass, promoted high sintered strengths.