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).     

Preparation and properties of mullite-bonded porous fibrous mullite ceramics by an epoxy resin gel-casting process

Porous fibrous mullite ceramics with a narrow range of pore size distribution have been successfully prepared utilizing a near net-shape epoxy resin gel-casting process by using mullite fibers, Al₂O₃ and SiC as raw materials. The effects of sintering temperatures, different amounts of fibers and Y₂O₃ additive on the phase compositions, linear shrinkage, apparent porosity, bulk density, microstructure, compressive strength and thermal conductivity were investigated. The results indicated that mullite-bonded among fibers were formed in the porous fibrous mullite ceramics with a bird nest pore structure. After determining the sintering temperatures and the amount of fibers, the tailored porous fibrous mullite ceramics had a low linear shrinkage (1.36–3.08%), a high apparent porosity (61.1–71.7%), a relatively high compressive strength (4.4–7.6 MPa), a low thermal conductivity (0.378–0.467 W/m K) and a narrow range of pore size distribution (around 5 µm). The excellent properties will enable the porous ceramics as a promising candidate for the applications of hot gas filters, thermal insulation materials at high temperatures.     

Microstructure and properties of lightweight fibrous porous mullite ceramics prepared by vacuum squeeze moulding technique

A novel fibrous porous mullite network with a quasi-layered microstructure was produced by a simple vacuum squeeze moulding technique. The effects of organic binder content, inorganic binder and adsorbent on the microstructure and the room-temperature thermal and mechanical properties of fibrous porous mullite ceramics were systematically investigated. An anisotropy microstructure without agglomeration and layering was achieved. The fibrous porous mullite ceramics reported in this study exhibited low density (0.40 g/cm³), low thermal conductivity (~0.095 W/(m K)), and high compressive strength (~2.1 MPa in the x/y direction). This study reports an optimal processing method for the production of fibrous porous ceramics, which have the potential for use as high-temperature thermal insulation material.     

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.     

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.     

Preparation and characterization of mullite microspheres based porous ceramics with enhancement of in-situ mullite whiskers

High-strength insulating ceramic materials were prepared using lightweight mullite microspheres with dense surfaces and high internal porosity as the main raw material and silica sol as a binder. The effects of AlF₃·3H₂O content on the in situ formation and growth of mullite whiskers were analyzed by X-ray diffraction and scanning electron microscopy. The obtained results showed that mullite whiskers were formed in large quantities at 1200 °C using AlF₃·3H₂O and V₂O₅ as additives; their optimal growth was observed at 4 wt% AlF₃·3H₂O and 1 wt% V₂O₅. The apparent porosity of the produced specimens was 39%; the MOR and CCS of the specimens were 31 and 152 MPa, respectively; the HMOR at 1300 °C was 11.32 MPa; and the thermal conductivity at 900 °C was 0.783 W m⁻¹ K⁻¹. The staggered whisker network structure formed between mullite microspheres not only improved the mechanical properties of the material, but also refined its pore size, reduced the thermal conductivity, and enhanced the thermal insulation properties.     

Influence of ZrO2 and WO3 doping additives on the thermal properties of porous mullite ceramics

Porous mullite-corundum refractory ceramics were produced by a patented slurry slip casting method from compositions based on commercially available α-Al₂O₃ and γ-Al₂O₃, fused SiO₂ and kaolin. Pores were formed as a result of a chemical reaction of aluminium with water. The influence of usage of raw materials and doping additives such as micro-size ZrO₂ and WO₃ on the sintering temperature, formation of crystalline phases, linear thermal expansion, thermal conductivity and thermal shock resistance of mullite-corundum ceramic was studied. The best thermal shock resistance and, simultaneously, lower thermal conductivity was achieved for the samples doped with WO₃. This was due to the influence of micro-sized WO₃ on the change in γ-Al₂O₃ modification to α-Al₂O₃ and on the structure of mullite ceramics.     

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.     

Theoretical and experimental analyses of thermal properties of porous polycrystalline mullite

This paper examined experimentally and theoretically the thermal diffusibility (α), heat capacity (C_P1) at a constant pressure (1 atm, 101.33 kPa) and thermal conductivity (κ=C_P1α) for the porous mullite ceramics with 0–55% porosity in a wide temperature range from 298 to 1073 K. The change in the κ values with temperature or porosity for the porous mullite was similar to the temperature dependence or porosity dependence of the α values, which were greatly reduced by the air included in the pores. The κ values for the porous mullite were theoretically analyzed with two model structures of pore–dispersed mullite continuous phase system (A model) and mullite–dispersed pore continuous phase system (B model). The measured κ values at 0–23% porosity agreed well with the κ values calculated for model A structure. In the high porosity range from 33% to 55%, the measured κ values deviated from the κ curve calculated for model A structure and approached the κ value curve for model B structure with increasing porosity. The real microstructure of 30–60% porosity is equivalent to the mixed microstructure of model A and model B for the thermal conductivity measurement.     

Fabrication of porous SiC ceramics having pores shaped with Si grain templates

SiC porous ceramics were prepared by heating mixtures of Si powder and carbon black at 900 °C for 24 h in Na vapor. The grains of the Si powder were not only the source of Si for SiC but also served as templates for the pores in the SiC porous ceramics. Angular-shaped pores with sizes of 2-10, 10-150 and 50-150 μm were formed by angular Si grains with sizes of ≤10, ≤50 and ≤150 μm, respectively. The porosity of the SiC porous ceramics was around 55-59%. Spherical pores were also formed when spherical Si grains were used. A bending strength of 14 MPa was measured for the SiC porous ceramics prepared with the Si grains (≤50 μm).     

Development of cordierite/mullite composites using industrial wastes

Ceramics containing cordierite and mullite as their principal phases are promising for many applications, due to properties such as a low coefficient of thermal expansion, high durability, low dielectric constant, resistance to thermal shock, and refractoriness. The objective of this study was to produce ceramic composites suitable for use as refractory materials. The raw materials were subjected to chemical characterization and the formulations to physical, chemical, and mineralogical characterization. The specimens were formed by pressing, dried at 110°C, and sintered from 1150°C to 1300°C for 2 hours. The following properties were then determined: linear shrinkage, water absorption, apparent porosity, and flexural modulus of rupture. The phases formed, crystal morphology, and coefficient of thermal expansion were evaluated. The cordierite and mullite phases were observed in all formulations at 1250°C and 1300°C. The results obtained from the formulations with a higher content of fine kaolin residue suggest that these formulations have the potential to be used for the manufacture of refractory materials such as furnace rollers and supports.     

Seed assisted in-situ synthesis of porous anorthite/mullite whisker ceramics by foam-freeze casting

Porous anorthite/mullite whisker ceramics with both high strength and low thermal conductivity have been successfully prepared by combining seed-assisted in situ synthesis and foam-freeze casting techniques. The addition of mullite seed was conducive to a reduction in the sintering shrinkage, pore size, and anorthite grain size. This increased the high aspect ratio of mullite whiskers, which enhanced the strength and diminished the thermal conductivity. Mullite whiskers overlapped to form a stable three-dimensional network structure similar to the bird's nest, which was also beneficial to heighten the mechanical properties of the prepared porous ceramics. Through this method, the prepared materials had a high apparent porosity of 87.7–90.2%, a low bulk density of 0.29–0.36 g/cm³, a high compressive strength of 0.65–3.31 MPa, and low thermal conductivity of 0.067–0.112 W/m·K. The results indicated that the method described here can fabricate porous ceramics with excellent properties for further thermal insulating applications.     

Effect of sintering temperature on compressive strength of porous yttria-stabilized zirconia ceramics

Porous yttria-stabilized zirconia (YSZ) ceramics were fabricated by tert-butyl alcohol (TBA)-based gel-casting method for potential applications in heat-insulation materials. The effect of sintering temperature on compressive strength of porous YSZ ceramics was investigated on the basis of measurements linear shrinkage, porosity and pore size. As the sintering temperature increased from 1350 to 1550 °C, a decrease of porosity from 77 to 65%, a decrease of average pore size from and an increase of linear shrinkage from 15.4 to 31.8% were observed. The compressive strength increased remarkably from 3 to 27 MPa with increasing sintering temperature from 1350 to 1550 °C, which was related to the corresponding change of linear shrinkage, porosity, pore size and microstructure. A remarkable decrease of compressive strength with increasing porosity was observed. The compressive strength decreased also with increasing pore size.     

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.     

Microstructure and property of porous mullites with a whiskers framework obtained by a sol–gel process

Porous mullites with a whiskers framework and high porosities were fabricated by the reaction sintering (1100 to 1600 °C, 1 h, in an airtight container) of an aerogel block shaped by the sol–gel transition of a mullite precursor composed of SiO₂ sol, Al₂O₃ and AlF₃ powders (as reaction catalyst). The effect of heating temperatures on porosity, whisker formation, microstructure feature and compressive strength of the porous mullites was determined by XRD, SEM and compressive test. The results indicate that after heating at temperatures from 1100 to 1600 °C, the porosities of the mullites varied within the range of 84.1–80.2%. The whiskers in the framework well lap-jointed each other to form the large space and became elongated and smooth at high temperatures due to the accelerated vapor–solid reaction rate. A maximum compressive strength of 16.1 MPa was obtained for the whiskers framework heated at 1600 °C; this strength was attributed to the strong bonding among the smooth whiskers.     

Preparation and properties of porous BaTiO3 nanostructured ceramics produced from cuboidal nanocrystals

The preparation and properties of BaTiO₃ nanostructured ceramics with porosity level in the range of percolation limit (33% and 37% porosity) produced by partial sintering of cubic nanoparticles are presented. Hydrothermally synthesized cuboid-like particles were produced by using Field-Assisted Sintering Technique facility in which temperature and pressure were selected to ensure the consolidation of mechanically stable porous nanoceramics, while preserving as much as possible the starting grain shape. Nanosized grains in the range of (10–40) nm and multiscale porosity ranging from a few nm to hundreds of nm were observed in the sintered ceramics. The dielectric constant of porous nanoceramics assumes low values of ~280–320 and shows a flat thermal response typical to nanostructured ceramics, without a net ferroelectric-paraelectric peak, followed by a Curie-Weiss dependence in the paraelectric state, with negative Curie Weiss temperatures and lowered Curie constant, as result of porosity and ultrafine grain size. A strong conductivity relaxation around room temperature related to air-ceramic interface phenomena indicated a possible sensitivity of these ceramics for gas sensing. Preliminary qualitative tests with saturated acetone vapours have shown a good response of both resistive and reactive components of such porous BaTiO₃ nanoceramics and possible gas sensing interface-related mechanisms were discussed.     

Preparation and characterization of mullite whisker reinforced ceramics made from coal fly ash

Ceramics with mullite whiskers were prepared from coal fly ash and Al₂O₃ raw materials, with AlF₃ used as an additive. The phase structures and microstructures of the ceramics were identified via X-ray diffraction and scanning electron microscopy, respectively. The results show that pickling of coal fly ash is an effective method for enhancing the flexural strength of ceramics. Sintering temperature and AlF₃ addition were also key factors influencing the creation of ideal ceramics. The ceramic made from pickled coal fly ash, 6?wt% AlF₃, and sintered at 1200?°C, exhibited the highest flexural strength of 59.1?MPa, and had a bulk density of 1.32?g/cm³ and porosity of 26.8%. The results show that ceramic materials made under these conditions are ideal candidates for manufacturing ceramic proppants for the exploitation of unconventional oil and gas resources.     

Lightweight porous silica-alumina ceramics with ultra-low thermal conductivity

Thermal protection has always been an important issue in the energy, environment and aerospace fields. Porous ceramics produced by the particle-stabilized foaming method have become a competitive material for thermal protection because of their low density and low thermal conductivity. However, the study of porous ceramics for composite systems using particle-stabilized foaming method was relatively rare. Here, silica-alumina composite porous ceramics were prepared by particle-stabilized foaming method, which was achieved by tailoring the surface charges of silica and alumina through adjustment of the pH. Porous ceramics exhibited porosity as high as 97.49% and thermal conductivity (25 °C) as low as 0.063 W m^?1 K^?1. The compressive strength of porous ceramics sintered at 1500 °C with a solid content of 30 wt% could reach 0.765 MPa. Based on the light weight and excellent thermal insulation properties, the composite porous ceramic could be used as a potential thermal insulation material in the spacecraft industry.     

Corrosion behavior of porous silicon nitride ceramics in different atmospheres

The corrosion behavior of silicon nitride (Si₃N₄) ceramics with a porosity of 46% at 1200–1500 °C under different conditions including dry O₂, O₂ containing 20 vol% H₂O and Ar containing 20 vol% H₂O is compared. The results show that porous Si₃N₄ ceramics exhibit good oxidation resistance up to 1200 °C. Their corrosion behavior varies depending on the temperature and atmosphere. Water vapor can obviously affect the morphology of the reaction product and thus accelerate the corrosion rate due to its specific inward diffusion mechanism and devitrified effect at high temperature. In view of the reaction kinetics, it proceeds in a diffusion-controlled manner in dry O₂ while follows the parabolic-linear law at water-containing atmosphere. Furthermore, a new model considering both oxidation and volatilization reactions is established. These provide a baseline for expanding the application fields of non-oxide porous ceramics such as Si₃N₄ and silicon carbide (SiC) etc.