Transient liquid phase diffusion process for porous mullite ceramics with excellent mechanical properties

Porous mullite ceramics were fabricated by the transient liquid phase diffusion process, using quartz and fly-ash floating bead (FABA) particles and corundum fines as starting materials. The effects of sintering temperatures on the evolution of phase composition and microstructure, linear shrinkage, porosity and compressive strength of ceramics were investigated. It is found that a large amount of quartz and FABA particles can be transformed into SiO₂-rich liquid phase during the sintering process, and the liquid phase is transient in the Al₂O₃-SiO₂ system, which can accelerate the mullitization rate and promote the growth of mullite grains. A large number of closed pores in the mullite ceramics are formed due to the transient liquid phase diffusion at elevated temperatures. The porous mullite ceramics with high closed porosity (about 30%) and excellent compressive strength (maximum 105?MPa) have been obtained after fried at 1700?°C.     

Joining of mullite ceramics with yttrium aluminosilicate glass interlayers

Pellets of yttrium aluminosilicate glass (Y₂O₃:Al₂O₃:SiO₂ = 30:20:50 mol%) powder were used as the filler interlayers (0.4 mm thick) to join two mullite substrates. The glass interlayer partially melted at joining temperature to bond the substrates and then crystallized during cooling to have better bonding strength. The results showed that joining could be performed at 1390–1420 °C for 1–5 h with applied pressure of 0.02 MPa. After joining, the thickness of glass layers varied between 250 μm and 80 μm, depending upon the temperatures. The glass interlayer crystallized into cristobalite, mullite and Y₂Si₂O₇. When joining mullite/3 mol%yttria–zirconia substrates using the same glass pellet, a layer of zircon/mullite was formed at the interface, indicating that reaction occurred between glass and substrates. The formation of zircon usually accompanied with cracks in the substrates. These cracks deteriorated the strength. The achievable three-point bending strengths were 139 MPa for joined mullite and 76 MPa for joined mullite/3 mol%yttria–zirconia.     

Low-temperature reaction-sintering of mullite ceramics with an Y2O3 addition

Mullite ceramics were fabricated at relatively low temperatures from powder mixtures of -Al₂O₃ and quartz, with an Y₂O₃ addition. The mullitization process was analyzed by X-ray diffraction. The densification behavior was investigated as a function of the Y₂O₃ content, sintering temperature and holding time as well as mullite seeds. It has been shown that mullitization occurs via a nucleation and growth mechanism within an yttrious aluminosilicate glass, but lattice and grain-boundary diffusion becomes important during the densification process. Moreover, the incorporation of mullite seeds was observed to enhance both mullitization and densification. At 1400°C for 5 h or 1450°C for 2 h, 15 mol% Y₂O₃-doped and 5 mol% mullite-seeded specimens can be sintered to almost full density.     

Properties and mechanism of mullite whisker toughened ceramics

High-strength ceramics were prepared from high alumina fly ash (HAFA) and activated alumina as raw materials with magnesia as a sintering additive. The growth kinetics and influence mechanism of secondary mullite whiskers were investigated. Meanwhile, the effects of the Al₂O₃/SiO₂ mass ratio (A/S) and the amount of magnesia on the content and morphology of mullite in the green body were investigated, so as to emphasize the effect of the liquid phase in the sintering process on the growth of secondary mullite whiskers. The results showed that the aspect ratio of secondary mullite whiskers increased significantly after adding activated alumina to increase the A/S ratio of raw materials. When 30 wt% activated alumina was added, the mullite content increased by 5.39%, and the whisker length increased from 1.36 μm to 4.18 μm. The addition of magnesia improved the liquid phase formed during the sintering process and the K value method was used to determine the sintering liquid phase content under various conditions. It was observed that increasing the magnesia level by 1 wt% could raise the liquid phase content by 5–7%. When the total liquid content of the system was 30–40%, the growth activation energy in the diameter direction of the whisker reduced significantly, promoting the growth of secondary mullite whiskers along the C axis. The morphology of mullite gradually developed from fibrous to long columnar crystal, making it combine more densely with the green body matrix. Furthermore, the staggered long columnar mullite crystal structure changes the fracture mode of ceramics from intergranular to transgranular fracture, which fully uses the high mechanical strength of mullite. As a result, the fracture energy and strength of ceramics are significantly improved.     

Effect of mullite phase formed in situ on pore structure and properties of high-purity mullite fibrous ceramics

Porous mullite ceramics are potential advanced thermal insulating materials. Pore structure and purity are the main factors that affect properties of these ceramics. In this study, high performance porous mullite ceramics were prepared via aqueous gel-casting using mullite fibers and kaolin as the raw materials and ρ-Al₂O₃ as the gelling agent. Effects of addition of mullite fibers on the pore structure and properties were examined. The results indicated that mullite phase in situ formed by kaolin, and ρ-Al₂O₃ ensured the purity of mullite samples and mullite fibers bonded together to form a nest-like structure, greatly improving the properties of ceramic samples. In particular, the apparent porosity of mullite samples reached 73.6%. In the presence of 75% of mullite fibers, the thermal conductivity was only 0.289 W/m K at room temperature. Moreover, the mullite samples possessed relatively high cold compressive strength in the range of 4.9–9.6 MPa. Therefore, porous mullite ceramics prepared via aqueous gel-casting could be used for wide applications in thermal insulation materials, attributing to the excellent properties such as high cold compressive strength and low thermal conductivity.     

Transient liquid-phase sintering of AlN ceramics with CaF2 additive

Transient liquid-phase (TLP) sintering of CaF₂ additive on the densification behaviors and microstructural development of AlN ceramics are investigated. It is found that 1 wt% CaF₂ can effectively promote densification process. Increasing content of CaF₂ results in finer grain size and slower densification during intermediate sintering stage. XRD results show that grain-boundary phase of CaAl₄O₇ is formed at 1150 °C from reactions of AlN–CaF₂–Al₂O₃. With further temperature increasing, the grain-boundary phases of CA2 and CaAl₁₂O₁₈, which were formed from the reaction between CaF₂ and oxide layers, experienced transformations firstly into CaAl₄O₇ above 1600 °C and into CaAl₂O₄ at higher temperature. SEM and TEM results show that formed grain-boundary phases can evaporate from sintering bodies during further soaking, leaving clean grain boundaries. The efficiency of TLP sintering mechanism is further manifested by the preparation of transparent AlN ceramics with good combination properties.     

Preparation of self-reinforcement of porous mullite ceramics through in situ synthesis of mullite whisker in flyash body

Self-reinforced porous mullite ceramics were fabricated by a starch consolidation method with flyash, different aluminium sources (Al(OH)₃ and Al₂O₃) and the additive AlF₃ as raw materials. The reinforcement mechanism of needle-like mullite whiskers through in situ synthesis in ceramic body was investigated. The bulk density, apparent porosity and bending strength of the samples were tested. Phase compositions and microstructures of the sintered samples were measured by XRD and SEM, respectively. It showed that AlF₃ as additive was helpful to the formation of mullite whiskers at a low temperature. As the aluminium sources, Al(OH)₃ was more suitable for the preparation of mullite whiskers than Al₂O₃. The in situ synthesized mullite whiskers formed an interlocking structure, which enhanced the mechanical strength of the porous mullite ceramics. Porous mullite ceramics with bending strength of about 100 MPa and apparent porosity of about 55% were made at 1550 °C.     

烧结点火炉用莫来石质浇注料的研制与应用

针对烧结点火炉的使用工况要求,保持特级矾土骨料占70%(质量分数,下同)、结合剂纯铝酸钙水泥占5%、活性α-Al2O3微粉占4%不变,其余21%的细粉为不同组成的莫来石细粉、SiO2微粉、添加剂(分别为蓝晶石粉、碳化硅粉、硅线石粉),同时外加0.15%的三聚磷酸钠研制了莫来石质浇注料,并研究了SiO2微粉加入量(分别为0、1%、2%、3%、4%)和各添加剂加入量(分别为1%、2%、3%、4%、5%)对浇注料烘干或烧后(1 350℃3 h)性能的影响.结果发现,加入3%的SiO2微粉,同时加入3%的蓝晶石和4%的碳化硅时,研制的莫来石质浇注料性能较优良.该浇注料在几家钢厂的烧结点火炉上实际使用寿命目前已超过4年,证明使用效果较好.     

Structural study of mullite based ceramics derived from a mica-rich kaolin waste

Mullite-based ceramics have been synthesized by reactive sintering of a mixture containing kaolin and a mica-rich kaolin waste. Samples fired in the temperature range from 1300 to 1500 °C were characterized by X-ray diffraction (XRD). The quantitative phase analysis and unit cell parameters of the mullite were determined by Rietveld refinement analysis of the XRD data. Mullite-based ceramics with 1.2 wt% quartz, 56.3 wt% glass (amorphous phase), 2.64 g/cm³ of apparent density, and 35±1.2 MPa of flexural strength were obtained after firing at 1500 °C. A liquid phase sintering mechanism activated by a total mica content of 13.3 wt% allowed to increase the mullite content to 47.6 wt% (2.3 wt% quartz and 50.1 wt% glass phase) and improve the flexural strength (70±3.9 MPa) after firing at 1400 °C.     

Fabrication of porous forsterite-spinel-periclase ceramics by transient liquid phase diffusion process for high-temperature thermal isolation

Porous forsterite-spinel-periclase ceramics with low thermal conductivity were synthesized via a transient liquid phase diffusion process by using pre-synthesized pellets and fused magnesia powder. The effects of sintering temperature on the pore formation, phase composition, sintering behavior, and properties of the resulting porous ceramics were investigated. The pre-synthesized pellets had a porous structure and contained a large amount of cordierite and enstatite. During the sintering progress, the pellets were converted into a transient liquid phase, which diffused into the solid MgO matrix. The liquid phase diffusion reaction promoted forsterite and spinel formation, which resulted in the in-situ formation of large pores. At elevated temperatures, the liquid phase disappeared and a large number of well-developed grains were simultaneously precipitated from the liquid phase. Porous ceramics with thermal conductivities of 0.42–0.48 W/(m·K) and refractoriness under load values of 1588 °C and 1624 °C were obtained after sintering at 1600 °C for 3 h.     

High-temperature diametral compression strength of microwave-sintered mullite

The mechanical strength of mullite materials sintered by the conventional route or by microwave was evaluated by diametral compression at room temperature and 1400 °C. Crack patterns and fracture mechanisms were analyzed and the results were discussed in terms of the final microstructures. The conventional and microwave sintered materials showed similar densification degrees and homogeneous microstructures with small equiaxial grains. Independent of the sintering route, the fracture strength did not change as the temperature increased. However, the mechanical strength of microwave sintered mullite was always higher than the conventionally sintered materials. Moreover, in both mullite materials, microcracks produced by the effects of thermal expansion and/or elastic anisotropies during sintering and/or mechanical testing were critical defects. In the early steps, microcracks occurred in transgranular mode. However, upon approaching the critical condition, their propagation was more intergranular until they coalesced and the specimen failed, generally in a triple-cleft fracture.     

Transient liquid phase bonding of alumina to alumina via boron oxide interlayer

Alumina bulks coated with 3 μm boron oxide layer were bonded at various temperatures and times in air. The joining strength, interfacial compounds and morphologies of cross-sections and fracture surfaces were investigated by means of four-point bending, X-ray diffraction and scanning electron microscopy. The maximum bending strength is 71 MPa for alumina bonded at 800 °C for 15 h. The layered metastable phase of 3Al₂O₃---B₃O₃ forms at the beginning of joining at temperature above 700 °C. This interlayer transforms into a whisker structure consisting of 2Al₂O₃---B₃O₃ and 9Al₂O₃---2B₃O₃ with increasing temperature and time. Models for the growth and morphology of these interfacial compounds are proposed.     

Effects of in situ synthesized mullite whiskers on compressive strength of mullite fiber brick

The method of in situ synthesis of mullite whiskers by gas-phase deposition and reaction was applied to improve the compressive strength of the mullite fiber brick. During the preparation process, silica sol, Al(NO₃)₃ solution and NH₄F solution were introduced into the fibrous brick in the form of ions or sol through vacuum impregnation and freeze drying, and the silica sol, Al(NO₃)₃ and NH₄F served as the silica sources, aluminum source and catalyst, respectively. Effects of process parameters (concentration of impregnation solutions, holding time, sintering temperature) on compressive strength and elastic modulus of the fibrous brick during the in situ toughening process were analyzed. SEM and XRD analysis results demonstrated that the mullite whiskers were synthesized on the surface of mullite fibers based on the reaction of AlOF and SiF₄. What is more, the whiskers on adjacent fibers intersected with each other and formed many unfixed lap-jointing points, resulting in the increase of compressive strength and elastic modulus. Although the density and thermal conductivity of the sample after the generation of mullite whiskers fabricated with the optimum process were 0.406 g/cm³ and 0.1262 W/(m K), respectively, which were slightly higher than that of the raw fibrous brick (0.375 g/cm³ density and 0.1069 W/(m K) thermal conductivity, respectively), the corresponding compressive strength and elastic modulus of the sample reinforced with the whiskers increased to 1.45 MPa and 42.03 MPa, respectively, which were much higher than that of the raw fibrous brick (0.39 MPa compressive strength and 6.5 MPa elastic modulus).     

Effect of MgO sintering additive on mullite structures manufactured by fused deposition modeling (FDM) technology

An optimized recipe for 3D printing of Mullite-based structures was used to investigate the effect of MgO sintering additive on the processing stages and final ceramic properties. To achieve dense 3:2 mullite, ceramic filaments were prepared based on an alumina powder, a methyl silicone resin, EVA elastomeric binder and MgO powder. Using 1 wt% MgO and a dwell time of 5 h at 1600 °C, a dense mullite structure could be obtained from filaments with a diameter of 1.75 mm. Ceramic structures with and without sintering additive were printed in vertical and horizontal direction, to investigate the effect of printing direction on mechanical strength after sintering. Using four-point bending test, it was demonstrated that by using MgO, the printing orientation did not affect the mechanical strength significantly anymore. The low Weibull modulus could be explained by the closed porosity that emerge during the degassing of the preceramic polymer due to cross-linking.     

Ultrafast high-temperature sintering of barium titanate ceramics with colossal dielectric constants

Application of Ultrafast High-temperature Sintering (UHS) technique to rapidly densify barium titanate ceramics has been explored for the first time. Bulk ceramic with ~94% density was obtained by UHS at ~1340 °C for 60 seconds. The densification process was accompanied with progressive sample discolouration from light to dark grey. Further analysis indicates that oxygen vacancy and its associated Ti-rich phase Ba₄Ti₁₂O₂₇ are present in the ceramics. Their roles in ultrafast densification and sample discoloration are discussed. Due to the presence of oxygen vacancies, the UHSed ceramics generally exhibit a colossal dielectric constant of ~ 15–30k at 1 kHz, with dielectric loss of ~0.07–0.10, while the ceramics without oxygen vacancy retain a dielectric constant of ~3000–6000 and dielectric loss of ~ 0.06 at 1 kHz which are comparable to that of the conventionally sintered ceramics. Furthermore, the challenges in applying UHS to sinter thick BT ceramics are discussed, aided by thermal simulations.     

Isothermal sintering of barium-zinc-titanate ceramics

Mixtures of BaCO₃-ZnO-TiO₂ were mechanically activated using high-energy planetary ball mill during 20, 40 and 80 min. As the time of mechanical activation increased, the decrease in particle size was observed. The effect of milling on microstructure was investigated by scanning electron microscopy, as well. Sintering process was performed in air at 1100 and 1200 °C for 2 h. Various phases are present within mixtures sintered at 1100 and 1200 °C, and almost pure BaZn₂Ti₄O₁₁ phase was obtained after 80 min of milling and sintering at 1200 °C for 2 h.     

Effects of mixing state of composite powders on sintering behavior of cathode for solid oxide fuel cells

For efficient development of high-performance composite electrodes for solid oxide fuel cells (SOFCs), it is crucial to precisely tailor the microstructural features of the electrodes, such as their grain size, phase connectivity, and pore structure. Herein, we report the effects of the mixing state of component powders of a composite cathode composed of Sr-doped LaMnO₃ (LSM) and yttria-stabilized zirconia (YSZ) on its sintering behavior. LSM-YSZ composite powders were synthesized by a particle-dispersed glycine-nitrate process using YSZ particles as inclusions in the LSM precursor solution. The dispersion state of the YSZ particles in the solution was varied from a well-dispersed state to a highly flocculated state through adjustment of the amount of adsorbed polyethylene glycol. The dispersion state of the component powders was found to strongly impact the densification behavior of the composite, which was explained by the formation of a continuous network of the “slow-sintering” inclusion particles. A highly porous structure with phase connectivity and sufficient triple phase boundaries could be achieved by enhancing the mixing homogeneity and optimizing the mixing scale. The proposed concept provides new insights into the microstructural evolution of composites in constrained sintering, and it could potentially enable development of the ideal electrode structure for SOFCs.     

Mineralogical and dielectric properties of mullite and cordierite ceramics produced using wastes

In this work technical ceramics containing industrial inorganic wastes was carried out. Ceramic formulations prepared with clay, magnesium oxide and residues of kaolin and alumina as raw materials, were formed in a disk-shaped specimens using the uniaxial pressing process and sintering at temperatures from 950°C to 1400°C. The mineralogical, physical and dielectric characteristics of the fired samples were investigated. The dielectric properties, the relative dielectric constant (ε_r) and the loss tangent (tan δ) were evaluated at frequencies of 0.1, 1, 10, and 100?kHz at room temperature. Mullite and cordierite were present as major phases at the highest temperatures. Relative dielectric constant values closest to that of mullite (ε_r = ~ 5 to ~ 6) and cordierite (ε_r =?~ 4 to ~ 6) at 1?kHz. On the other hand, the lowest dielectric losses (tan δ ~ 0.06 to ~ 0.04) were observed for the formulations containing the mullite major phase, and tan δ ~ 0.009 to ~ 0.003 for formulations that showed cordierite as main phase. It was verified that an increase in temperature promoted a reduction of porosity, a property that had a direct influence on the dielectric properties of the formulations. The materials obtained from the residues presented low dielectric constants and loss tangents, which make them suitable for use in electrical and electronic systems.     

Mechanical and fracture properties of zircon–mullite composites obtained by direct sintering

Refractory materials based on zircon (ZrSiO₄) are applied in high temperature applications (1400–1500 °C). They are demonstrated to have an excellent chemical attack resistance, such as corrosion or degradation due to molten glass or metals. On the other hand mullite (3Al₂O₃2SiO₂) is important both in traditional and advanced ceramics. Although multi-phase ceramic materials were always used, nowadays composite materials have an important industrial and technological development, to enlarge the designing capability of the manufacturer in properties and behaviors. The objective of the present work is to study the influence of the starting composition on the mechanical and fracture properties of zircon–mullite composites obtained by direct sintering of consolidated samples by slip cast of concentrated aqueous suspensions in plaster molds. Zircon–mullite composites using 15–45 wt% mullite were prepared and compared with pure zircon material obtained in the same conditions. Flexural strength (σ_f), dynamic elastic modulus (E), toughness (K_IC) and initiation fracture surface energy (γ_NBT) were evaluated. The results were explained by microstructure and the XRD analysis. The presence of mullite increased the zircon thermal dissociation. The ZrO₂ was a product of this reaction and also influence the mechanical and fracture properties of these materials through several combined mechanisms.Zircon composites prepared with 45 wt% of mullite in the starting powder showed a higher fracture toughness and initiation energy than ceramics derived from pure zircon. Microstructure consisting in mullite as a continuous predominant phase in which zircon and zirconia grains were distributed improved almost all the mechanical and fracture properties.     

Normal sintering of (K, Na)NbO3-based lead-free piezoelectric ceramics

Lead-free piezoelectric ceramics have received more attention due to the environmental protection of the earth. (K, Na)NbO₃-based ceramics are one of the most promising candidates. Normal sintering of un-doped and Li/Ta co-doped (K, Na)NbO₃ ceramics was investigated to clarify the optimal sintering condition for densification, microstructure and electrical properties. It was found that density increased greatly within a narrow temperature range but turned to decrease when the sintering temperature slightly exceeded the optimal one. Piezoelectric properties also showed similar relationship between the density and sintering temperature, but the highest piezoelectric strain coefficients were obtained at the temperatures lower than that for the highest density. The grain growth and property change as a function of sintering temperature were discussed on basis of the formation of liquid-phase and the composition deviation caused by the volatilization of alkali components during sintering.