Extrusion-based 3D printing alumina-silica inks: Adjusting rheology and sinterability incorporating waste derived nanoparticles

The nanoparticle (NP) exhibits numerous distinctive and extraordinary properties than micron level and up. The inclusion of NP effects in the rheological and densification behavior of extrusion-based (direct ink writing (DIW)) inks has been extensively investigated. The aqueous-based alumina-silica inks were first designed using waste rice husk ash (RHA) derived nano-silica (NS) (0–10 wt%) and found that the solid-to-liquid ratio reduces continuously with NS addition for printable rheology. For functionalization of NS, dispersant requirement is increased that improve the solids loading of inks. Second, the optimized inks are printed via DIW technique and sintered at a temperature of 1400–1650 °C. The NS has remarkably enhanced the shrinkage, density, and morphology of sintered DIW specimens and 7.5 wt% RHA NS reduces the sintering temperature ∼150 °C. Incorporating NP in the 3D printing ink is a clean approach to filling pores generated by binder-burnout and fabricating a dense ceramic at a low temperature.     

Temperature-induced changes in morphology and microstructure of electrospun mullite nanofibers fabricated from a hybrid mullite sol

Mullite nanofibers with small diameter and high surface area are an ideal candidate as the reinforcements in composite materials, and have promising applications in the fields of catalysis, filtration, thermal storage and so forth. In this work, electrospun mullite nanofibers were successfully synthesized using a hybrid mullite sol. The morphology and microstructure of fibers calcined at different temperatures were investigated. The morphology of fibers synthesized at 900 °C is porous with coarse surface, and after crystallization it becomes compact with smooth surface. The densities of fibers increase with the increasing temperatures. At 1200 °C the surface of fibers becomes coarse again, as a result of the grain growth of mullite. The crystallization path of fibers was revealed that the Al-rich mullite (4Al₂O₃·SiO₂) together with amorphous silica formed at 1000 °C, changed into mullite with higher silica contents as temperature further increased, and finally transformed into a stable 3Al₂O₃·2SiO₂ phase at 1200 °C. During this crystallization process, the flow of amorphous silica phase and the formation of mullite crystal structure benefit the densification of fibers, leading to the resultant fibers with fine and compact microstructure. The present findings can provide a guideline for the preparation of the promising high-mechanical mullite nanofibers and the synthesized nanofibers display great potential as reinforcements in structural ceramic composites.     

EQUILIBRIUM STUDIES IN THE SYSTEM FeO-AI2O3,-SiO2*

Equilibrium relationships on the liquidus surface in the system Fe0-Al₂O₃SiO₂ have been established by a modified quenching procedure. The crystal phases which separate from melts heated in iron crucibles are fayalite (2FeO·SO₂), hercynite (FeO·Al₂O₃), tridymite and cristobalite (SiO₂), mullite (3Al₂O₃·2SiO₂), corundum (Al₂O₃), and wastite (approximately FeO). A considerable portion of this system is liquid at 1400°C. Diagrams show the isotherms and the index of refraction of the glasses formed. Two quintuple points have been established in this investigation. One point is at the composition, SiO₂ 42% by weight, Al₂O₃13%, and FeO 45%, and is a eutectic involving the phases fayalite, hercynite, and tridymite at 970°C. ± 200C. The preferred composition of the second quintuple point is 48% of SO₂, 23% of Al₂O₃, and 29% of FeO; it is a peritectic, and the crystal phases are mullite, hercynite, and tridyrnite. Crystallization from this melt without a change in the weight composition calls for the resorption of mullite at a temperature of 1100°C. ±20°C.     

Electrospinning preparation and microstructure characterization of homogeneous diphasic mullite ceramic nanofibers

In this work, diphasic mullite (3Al₂O₃·2SiO₂) nanofibers with good homogeneity were prepared by electrospinning method. Aluminum nitrate (AN) and aluminum isopropoxide (AIP) were used as alumina sources, commercial colloidal silica as silica source, and polyvinyl alcohol (PVA) as polymer additive. Precursor nanofibers with continuous and uniform structures were acquired at mass ratio of PVA to precursor sol from 0.06 to 0.09. γ-Al₂O₃ phase was obtained at 878 ^°C and mullite phase formed at 1322 ^°C upon heating of the precursor under air atmosphere. Calcined samples suggested mullite as dominant phase at 1300 ^°C and amorphous SiO₂ could even exist at 1400 ^°C. As-prepared nanofibers possessed continuous structures with subequal average diameters at 900–1200 °C. However, such morphological characteristics were lost at temperatures above 1300 ^°C due to rapid growth of crystal grains. Al and Si elements were uniformly distributed in fibers and mixed at nanoscale, confirming homogeneity and diphasic features of nanofibers.     

The Effect of La2O3 Addition on Sol–Gel Derived Mullitization

Monophasic gel with stoichiometric 3Al₂O₃·2SiO₂ composition and gels with 0.99, 1.96, and 2.91 mol% La₂O₃ added were sol–gel derived. The crystallization path, structure evolution, microstructure, and morphology of calcined premullite powders and sintered ceramic bodies have been investigated as a function of La₂O₃ content and sintering temperature. In addition to mullite, spinel phase at about 980°C, and α‐alumina at above 1000°C were determined; however, neither La₂O₃ nor La‐related compounds had crystallized. The La₂O₃ predominately incorporated into the glassy phase, enhanced with La₂O₃ level, which affected both mullite structure and composition, as confirmed by electron microscopy, Rietveld structure refinement, determination of unit cell parameters, electron microscopy, and achieved density of the sintered bodies. Increased thermal treatment changes the alumina/silica ratio in mullite (towards 3:2 below 1200°C, and toward 2:1 above), and decreases the mullite/amorphous ratio. Sintered dense ceramic bodies revealed a positive densification effect and increased sinterability as a result of the lanthanum‐induced increase in glassy phase.     

Thermal evolution and structural study of 2:1 mullite from monophasic gels

Single phase mullite gels with composition 2Al₂O₃·SiO₂ (2:1) were prepared by the slow hydrolysis method using aluminium nitrate nonahydrate and tetraethylorthosilicate as reagents. The evolution to mullite from gels was studied by infrared (IR) spectroscopy and X-ray diffraction (XRD). Gels thermally treated under fast schedules showed mullite formation below 900 °C. Compositional and microstructural changes in 2:1 mullites through the range of temperature from 900 to 1600 °C were determined by the measurement of lattice parameters and field emission scanning electron microscopy. The alumina-rich mullites formed at low temperatures become almost the nominal 2:1 at 1600 °C. This result is consistent with available thermodynamic data for mullite formation from alumina and silica. Microstructural examination indicated an almost constant grain size for mullite from 900 to 1600 °C.     

Preparation and properties of porous mullite-based ceramics fabricated by solid state reaction

In this study, the effect of the alumina particle size on the formation of mullite using a silica gel powder and micro- and nano-scale Al₂O₃ powders as raw materials was investigated. The optimized Al₂O₃ source was then reacted with the silica gel to prepare porous mullite-based ceramics. The results revealed that the highly reactive nano-Al₂O₃ powder could form mullite at a relatively low firing temperature. Therefore, the nano-Al₂O₃ powder was used to prepare porous mullite-based ceramics by firing at 1600 °C, 1650 °C and 1700 °C. The pore size of the prepared porous mullite-based ceramics ranges from tens to hundreds of micrometres, with the apparent porosity being 42.8–58.0%. Further, the mullite content in the samples increased with increasing firing temperature, and a higher firing temperature promoted sintering, resulting in improved strength of the sample. After calcination at 1700 °C, the mullite content in the sample reached 81.8%, and the sample showed excellent thermal shock resistance. The strengths of the samples before and after thermal shock were found to be 23.6 and 15.58 MPa, with the residual strength ratio being 66%.     

Mechanical properties of in situ synthesized mullite-based composite ceramics with three-dimensional network structure

Needle-like nanocrystalline mullite powders were prepared through the molten salt process at the temperature of 900°C using coal gangue as raw material. Then, mullite-based composite ceramics were prepared by a conventional solid-state reaction between in situ synthesized mullite and Al₂O₃ powders. Effects of Al₂O₃ content and sintering temperatures on phase compositions, microstructure, and mechanical properties of the mullite-based composite ceramics were also studied. The results show that mullite content productivity increase from 72% to 95%, as the sintering temperature increased from 1480°C to 1580°C, which led to the improvement in the bulk density and flexural strength of the samples. The three-dimensional interlocking structure for mullite-based composite ceramics was obtained by the in situ solid-state reaction process. The maximum bulk density, flexural strength, and fracture toughness for the sample with 15 wt% Al₂O₃ content are 2.48 g/cm³, 139.79 MPa, and 5.62 MPa··m^1/2, respectively, as it was sintered at the temperature of 1560°C for 3 h. The improved mechanical properties of mullite-based composite ceramics maybe ascribed to good densification and increased mullite phase content, as well as to the in situ three-dimensional network structure. Therefore, the results would provide new ideas for high-value utilization of coal gangue.     

The fabrication of porous mullite ceramics based on the different sizes of aluminum hydroxide

In this research, for studying the influence of size and heat treatment temperature of initial Al(OH)₃ on the physical properties of porous mullite ceramics, porous mullite ceramics were prepared by in situ reaction sintering of amorphous silica and treated Al(OH)₃. The transition phases χ-Al₂O₃, к-Al₂O₃, and stable phase α-Al₂O₃ can be obtained in turn when the treatment temperature of raw Al(OH)₃ is 500, 1000, and 1500°C, respectively. The coarser the raw Al(OH)₃, the higher the strength of porous mullite ceramics. When the sintering temperature is 1500°C, the bending strengths of PS500-C, PS1000-C, and PS1500-C (PSx-C represents that the specimen was prepared by the coarse grade Al(OH)_3, which was previously treated at x°C) are 40.3 ± 2.1, 54.9 ± 5.2, and 64.8 ± 4.8 MPa, respectively. In addition, although the activated Al₂O₃ can decrease the formation temperature (∼100°C) of porous mullite ceramics, the strength and density of porous mullite ceramics prepared by activated Al₂O₃ will decrease at the same sintering temperature. It is believed that the increase of defects and pores during the phase transformation should be responsible for this phenomenon.     

High temperature single crystal properties of mullite

Extensive neutron diffraction and Rietveld studies of dense, hot pressed mullite (3Al₂O₃·2SiO₂) have been conducted up to 1650 °C in air, yielding a complete set of lattice parameters and axial thermal expansion coefficients. Unconstrained powders of the same stoichiometric composition were also analyzed by X-ray diffraction and Rietveld techniques up to 900 °C in air, from which lattice parameters and thermal expansion coefficients were obtained. An earlier reported structural discontinuity was confirmed by XRD to lie in the temperature range 425 to 450 °C. Single-crystalline mullite fibers of composition 2·5Al₂O₃·SiO₂ were grown from the melt by a laser-heated, float zone method. A partial set of the single-crystal elastic moduli were determined from various sections of fiber, by Brillouin spectroscopy, from room temperature up to 1400 °C. They indicated a roughly 10% reduction in stiffness over that temperature range.     

Solid-state synthesis of mullite from spent catalysts for manufacturing refractory brick coatings

This paper shows the results of the solid-state synthesis of mullite from spent catalysts discarded from fluid catalytic cracking (FCC); the catalysts are mainly composed of silica and alumina but are polluted with SO_X, forming a non-crystalline network. The synthesized mullite was used as a feedstock to thermally spray a coating onto a silica-alumina refractory brick, and its chemical resistance at high temperature was subsequently evaluated by contact with K₂CO₃ at 950 °C. Initially, the spent catalyst was thermally treated for 2 h at 600, 900, and 1200 °C to eliminate the SO_X pollutant. The heat treatment at 1200 °C completely removed the SO_X in the sample. Additionally, four thermal processes were performed by heating the spent FCC catalyst in an electrical furnace to 1500 and 1600 °C and by using an oxyacetylene flame to synthesize mullite. Thermal treatments at 1500 °C were performed with and without alumina added to the spent FCC catalyst, whereas those conducted at 1600 °C and using a flame were performed using only added alumina. In the powders thermally treated at 1500 °C, silica-rich mullite (3Al₂O₃.2SiO₂) accompanied by an excess of alumina or silica was obtained with or without alumina added, respectively. In contrast, the materials treated at 1600 °C formed alumina-rich mullite (2Al₂O₃.SiO₂), which was accompanied by an excess of alumina. Mullite was not synthesized in the flame-heated powder. The silica-rich mullite accompanied by an excess of alumina was used as feedstock powder to modify the surface of a refractory brick, improving its resistance to chemical attack by K₂CO₃ at high temperature.     

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.     

Porous acicular mullite ceramics fabricated with in situ formed soot oxidation catalyst obtained from waste MoSi2

Porous acicular mullite (3Al₂O₃·2SiO₂) ceramics containing Cu₃Mo₂O₉ as a soot oxidation catalyst was fabricated by a novel approach using commercial powders of Al₂O₃ and CuO, and powder obtained by controlled oxidation of ground waste MoSi₂. The obtained material consisted of elongated mullite grains which are known to be effective in carbon soot removal from diesel engine exhaust. The presence of in situ created Cu₃Mo₂O₉ was found to catalyze the carbon burnout which is an extremely important feature when it comes to filter regeneration, i.e., the captured soot removal. The carbon burnout temperature in the sample containing 12 wt% CuO was by 90 °C lower than that in the sample without CuO. Effect of sintering temperature as well as the effect of amount of CuO additive on mullite properties were studied. It was found that the increase in amount of CuO in samples sintered at 1300 °C decreased porosity and increased compressive strength of the porous mullite ceramics. The addition of 12 wt% CuO increased the strength of the porous mullite ceramics up to 70 MPa, whereas the porosity was reduced from 62% in the mullite without CuO to 44% in the mullite ceramics containing 12 wt% CuO. Although affected by the amount of CuO, the microstructure still consisted of elongated mullite grains.     

Characterization and sintering of gels in the system MgO–Al2O3–SiO2

Cordierite aerogels, made by supercritical drying, and xerogels, formed by ambient pressure drying, have been prepared by combining two different recipes. The chemical composition of the gels varied from stoichiometric cordierite 2MgO·Al₂O₃·5SiO₂ to 0·5MgO·1·4Al₂O₃·5SiO₂ due to different procedures for washing of the gels. The crystallization of nearly stoichiometric cordierite gels was shown to be relatively complex involving the formation of several metastable phases such as μ-cordierite (Mg₂Al₄Si₅O₁₈), spinel (Al₆Si₂O₁₃) and sapphirine (Mg₄Al₈Si₂O₂₀) before the equilibrium phase composition was obtained at around 1350°C. On the other hand, during crystallization of gels with stoichiometry close to 0·5MgO·1·4Al₂O₃·5SiO₂ the equilibrium phases mullite, cristobalite and α-cordierite were the major phases formed during heat treatment. A lower densification rate was observed for aerogels compared to xerogels due to a larger pore size. A lower crystallization temperature in aerogels probably due to heterogeneous nucleation reduced the densification. For gels with a composition near 0·5MgO·1·4Al₂O₃·5SiO₂ nucleation and densification occur simultaneously and large differences in the densification behavior was observed. ©     

Manufacturing of nano mullite-silicon carbide filters by in situ reaction bonding

In the present study, the effect of silica nanoparticles on the formation of nano-mullite phase for use in the manufacture of silicon carbide based ceramic foam filters has been investigated. Polyurethane foam filters were impregnated with nanosilica particles by slip casting. In this method, the effect of different percentages of nanosilica particles in the slurry on compressive strength, density and porosity of ceramic foam filters was investigated. The effect of silica nanoparticles on viscosity of slurry was studied using rheometric test. So, sample S₁₅ was selected to proceed. For thermal treatment of ceramic foams, different sintering temperatures were investigated and the best temperature was reported at 1250 °C. Compressive strength results showed that with increasing nano-silica content, CCS increased. XRD results from the samples showed that the nano-mullite phase was formed at 1250 °C along with silicon carbide and alumina phases. Scanning electron microscope images (SEM) showed that the mullite phase was formed in nano-dimensions in ceramic foam bodies. The formation of mullite phase in the microstructure of the filters is one of the factors of strengthening and increased refractory characteristics. EDS analysis by the scanning electron microscopy of the filter which passed ductile iron melt showed that cast iron inclusions and impurities were mostly consisted from FeO, MnO, SiO₂, Al₂O₃, MgO and CO, which were trapped inside the ceramic filter.     

Mechanical properties of reinforced porcelain slabs with mullite whiskers introduced by aluminum silicate fiber

Mullite whiskers (3Al₂O₃·2SiO₂) reinforced porcelain slabs with high bending strength and fracture toughness were successfully prepared by calcining a kaolin-potash feldspar-albite mixture with aluminum silicate fibers (ASF, Al₂O₃·SiO₂). Effects of ASF content on the properties of porcelain slabs were investigated. Bending strength and fracture toughness of the samples reach the peak values, 39% and 19% higher than that of the blank samples when the amount of ASF is 5 wt%. The elongated and needle-like mullite whiskers are obtained in the substrates with ASF fiber addition, differing from the rod-shaped mullite whiskers in the blank ones. During the sintering process, ASF provides growth environment and ingredient for elongated mullite whiskers. The in-situ generated elongated mullite whiskers link the porcelain slabs substrate as a bridge and consume more energy before the fracture occurred. Therefore, mullite whiskers induced by ASF can offer reliable opportunity for preparation of porcelain slabs with good mechanical properties.     

Advanced ceramics from a preceramic polymer and nano-fillers

A commercial silicone resin (“silicone”) filled with ceramic nanoparticles has been employed for the preparation of mullite and β-SiAlON ceramics. Dense, pure, crack free mullite were prepared by the heating in air of a mixture of silicone resin and alumina nanoparticles in the temperature range 1200–1550 °C. The high reactivity of Al₂O₃ towards silica, coupled with nanometric size, led to a large volume fraction of mullite crystals even at low firing temperatures (1250 °C). β-SiAlON ceramics were prepared by the heating of a mixture of silicone resin and fillers consisting of Al₂O₃ nanoparticles and Si₃N₄ and AlN microparticles, in the temperature range 1450–1550 °C in nitrogen atmosphere. The formation of SiAlON was found to be preceded by the formation of intermediate alumino-silicate phases like mullite and sillimanite, successively reduced (due to the carbon content of the ceramic residue of silicone resins) and nitrided. Although some oxide contamination was still present after the high temperature treatment, a high β-SiAlON yield (about 80%) was achieved. The use of nano-filled silicones provides a promising route for the fabrication of advanced ceramic components by exploiting polymer processing techniques, with the achievement of complex shapes.     

In situ reaction synthesis of Al2O3–SiC nanostructure using different carbon sources

Abstract

The formation of Al₂O₃–SiC nanostructure was studied using three different carbon sources (charcoal activated, graphite and carbon black) mixed with colloidal silica and aluminium nitrate. All mixtures were heated at 1500°C for duration of 30, 45 and 60 min. The results showed that Al₂O₃–SiC powders with an average diameter of ～220 nm and almost equiaxial geometry with aspect ratio of 1–1·2 could only be synthesised from the mixture containing carbon black (30 wt-%) at low heating time (30 min). It was found that the intensity of SiC peaks was the highest in samples containing graphite which was attributed to the higher initial density of this sample.     

Thermodynamic properties of aluminum titanate-mullite composite ceramics containing heat stabilizer

Using Al₂O₃ and TiO₂ as raw materials, adding MgO as heat stabilizer and mullite as enhancer, aluminum titanate-mullite multiphase ceramics were successfully prepared by solid phase synthesis. The effects of MgO and mullite were systematically studied on the phase composition, microstructure, thermal stability, sintering properties, and mechanical properties of aluminum titanate ceramics. The results showed that the introduction of Mg²⁺ can partially replace Al³⁺ to form Mg_xAl_2(1-x)Ti_(1+x)O₅ solid solution, improved the thermal stability of aluminum titanate ceramics, and promoted the formation and growth of grains, which reduced the sintering temperature. The crack deflections caused by mullite particles improved the mechanical properties. The filling effect of mullite particles and the formation of silica in mullite raw materials were conducive to ceramic densification. The statistics of Mg4M10 sample were as follows: the porosity was only 2.9%, the flexural strength was as high as 64.15 MPa, and the thermal expansion coefficient was 1.35 × 10⁻⁶ K⁻¹ (RT-700°C), encouraging the application of ceramics with high thermal mechanical properties.     

Anisotropic grain growth of mullite in high-energy ball milled powders doped with transition metal oxides

Dense mullite ceramics with anisotropic grains were derived from the high-energy ball milled mixtures of Al₂O₃ and amorphous silica with the presence of transition metal oxides (FeO_1.5, CoO and NiO). The mullitization and grain growth behavior of the unmilled mixture without the addition of the transition metal oxides and the undoped system of Al₂O₃ and amorphous silica with and without milling were also investigated and compared. The mullitization temperature was about 1200 °C in the milled systems, 100 °C lower than that required by the conventional solid-state reaction process. The lowered mullitization temperature, as well as the anisotropic grain growth, was attributed to the refined structure of the oxide powders, as a result of the high-energy ball milling. The experimental results have been explained by a dissolution-precipitation mechanism.