Control of pore structure during freeze casting of porous SiC ceramics by different freezing modes

The frozen moulds, including homogeneous, unidirectional and bidirectional freezing, were designed using materials with different thermal conductivities, and the temperature variations of the moulds and samples during the freezing process were simulated by finite element analysis. Highly porous SiC ceramics with significant differences in pore structure were fabricated by using the SiC/water slurries prepared via uniform or oriented freeze casting with various freezing modes, and porosity and compressive strength of the as-fabricated ceramics were investigated. The results showed that the pore structure of ceramics prepared by homogeneous freezing was relatively intricate and inconsistent, and had a higher compressive strength. In contrast, the pore structure of ceramics fabricated using bidirectional freezing mode was more ordered and higher porosity was observed. Moreover, porous ceramics prepared by unidirectional freezing mode exhibited a typical gradient structure with increased pore size from tens of micrometers in the bottom to hundreds of micrometers in the top.     

Preparation and properties of high-porosity ZrB2-SiC ceramics by water-based freeze casting

The development of novel cermet composites based on porous ceramics with high porosity, interconnected pore structure and good mechanical property has attracted considerable attention in engineering application. In this work, water-based freeze casting process was employed to fabricate ZrB₂-SiC porous ceramic with aligned lamellar-channels structure using PAA-NH₄ as the dispersant. The results revealed that the well-dispersed suspension with best rheological behavior was obtained using 1.0 wt% PAA-NH₄ at pH 9. The crack-free porous ceramic exhibited small volume shrinkage ranging from 2.59 % to 1.87 %. By varying the solid loading, the fabricated samples displayed a tailored porosity ranging from 76.12% to 59.37% and an excellent compressive strength of 7 MPa to 78 MPa. After oxidation, the samples displayed a decreased porosity and an increased compressive strength. The ZrB₂­SiC porous ceramic fabricated in this work will be a promising candidate for the framework of cermet composite.     

Structure control of hydroxyapatite ceramics via an electric field assisted freeze casting method

Using H₂O₂ aqueous solution as pore-forming agent, hydroxyapatite (HA) porous scaffolds with both lamellar and spherical pores were fabricated by a freeze casting method. The highest porosity was obtained in HA scaffolds prepared using 5 vol% H₂O₂ aqueous solution. The relationship between the electric field intensity and the properties of HA scaffolds was investigated. Results showed that when the electric field intensity was increased from 0 to 90 kV/m, the average diameters of lamellar and spherical pores of HA scaffold were increased from 460 μm to 810 μm, and from 320 μm to 420 μm, respectively. Vitro cellular assay indicated that HA scaffold with both the lamellar and the spherical pores has a better biocompatibility, compared with that with single pores.     

SiC porous structures obtained with innovative shaping technologies

SiC structures with porosities ranging between 20–60% have been fabricated using two methods emulsification and freeze casting. While emulsification results in foam-like isotropic materials with interconnected pores, freeze casting can be used to fabricate highly anisotropic materials with characteristic layered architectures. The parameters that control the pore size and final porosity have been identified (solid content in the initial suspensions, emulsification times or speed of the freezing front). We have found that liquid state sintering (suing Al₂O₃ and Y₂O₃ as additives) at 1800 °C on a powder (SiC/Al₂O₃) bed provides optimum consolidation for the porous structures. The mechanical strength of the materials depends on their density. Freeze casted materials fabricated with bimodal particle size distributions (a controlled mixture of micro and nanoparticles) exhibit higher compressive strengths that can reach values of up to 280 MPa for materials with densities of 0.47.     

Preparation of SiC/C composite sheet from polycarbosilane/carbon-based resin mixture

SiC/C composites were prepared from a mixture of polycarbosilane and phenolic resin with weight ratio of 2/1 and 1/1 using PVB as a binder. The two types of green bodies which were formed by mould pressing method were treated in the temperature range from 1,000‡C to 1,500‡C under nitrogen. X-ray diffraction patterns, density, flexural strength and fracture surfaces of the composite were examined. The flexural strength of the composites at room temperature increased with heattreatment temperature and showed a maximum value of 175 MPa at 1,300‡C. When the composite was heat treated at 1,400‡C, the flexural strength decreased rapidly due to the crystallization of SiC. The SiC/C composites showed good oxidation resistance up to 830‡C. The effective mixing ratio of PCS/phenolic resin to obtain improved mechanical property was 2/1.     

Porous asymmetric microfiltration membranes shaped by combined alumina freeze and tape casting

An assembled asymmetric alumina microfiltration membrane with high performance was prepared by combining freeze and tape casting techniques followed by two sintering steps. Freeze casting was used for manufacturing of the porous support layer with a highly interconnected pore network. Tape casting was applied on the top layer to form a pre-membrane with smaller pore size and controlled thickness, which was set on the sintered support. Morphology influences were investigated for different solid loadings, additives content and the assembled layer membrane structures. No delamination among the layers was observed. The assembled ceramic membrane had an average pore size between 30 and 50 μm together with a top surface layer around 0.35 μm, which is suitable to the microfiltration separation process. Porosity in the range of 26–50 % and water flux of 11–32 m³ m^?2 h^?1 bar^?1 were reached for samples prepared with two sintering steps at 1600 and 1300 °C for 2 h.     

Protecting nuclear graphite from liquid fluoride salt and oxidation by SiC coating derived from polycarbosilane

Modification process has been conducted on commercial nuclear graphite IG-110 (Toyo Tanso Co., Ltd., Japan) by impregnation and pyrolysis of polycarbosilane (PCS) solution for getting the modified IG-110 (M-IG-110) coated by dense SiC coating for molten salt reactor. The microstructure and properties of graphite were systematically investigated and compared before and after the modification process. Results indicated that the M-IG-110 possessed of more excellent integrated properties including molten salt barrier property and oxidation resistance than bare IG-110 due to the filling effect of SiC particles in the pores of M-IG-110 and dense SiC coating adhering to the surface of M-IG-110. The fluoride salt infiltration amount of M-IG-110 under 5 atm was only 1.1 wt%, which was much less than 14.9 wt% for bare IG-110. The SiC coating derived from PCS exhibited remarkable compatibility with graphite substrate under high temperature and gave rise to excellent oxidation resistance of M-IG-110.     

Processing,properties and microstructure of SiC foam derived from epoxy-modified polycarbosilane

SiC foams having controlled porosity were fabricated using epoxy modified polycarbosilane (EMPCS). The EMPCS was synthesized by refluxing adequate amount of epoxy and polycarbosilane (PCS) in THF solution at 150 °C. The EMPCS having epoxy content of 0%, 10% and 20% by weight were termed as PCS, 10EMPCS and 20EMPCS respectively. Thermal foaming of the EMPCS was carried out at 1000 °C under inert atmosphere followed by ceramization at 1200, 1400 and 1600 °C under vacuum. The cell size of the ceramized SiC foam was found to be varying between 100 and 700 µm. The ceramized SiC foams were characterized for their density, porosity and compressive strength. Total porosity was found to be 81.8 ± 3.9, 87 ± 4.1 and 90.6 ± 4.6% for the PCS, 10EMPCS and 20EMPCS based SiC foams while their bulk densities were found to be 0.6 ± 0.03, 0.4 ± 0.02 and 0.3 ± 0.01 g/cc respectively. Compressive strength was found to be the highest for the SiC foams ceramized at 1600 °C for all the types of EMPCS. The compressive strength of the 10EMPCS is found to be 2.2 ± 0.2 MPa, 2.5 ± 0.2 MPa and 3.8 ± 0.3 MPa for the foams pyrolyzed at 1200 °C, 1400 °C and 1600 °C respectively while the strength was 1.9 ± 0.1 MPa, 2.1 ± 0.2 MPa and 2.9 ± 0.2 MPa for the 20EMPCS based SiC. The 20EMPCS based SiC foam of thickness 10 mm was exposed to oxy-acetylene flame for 120 s, back face temperature was found to be around 300 °C. Microstructure and phase analysis was carried out to understand the effect of epoxy content and ceramization temperature on physical, mechanical and thermal properties of different types of the SiC foams.     

Modification of polycarbosilane as a precursor with high ceramic yield for oxygen-free SiC fibers

Polycarbosilane (PCS) was modified by addition of 1 wt% polyborazine and subsequent heat treatment at 70-400 °C. The modified PCS exhibited highly improved ceramic yield from original 63% to 78% by heating at 70 °C for 10 h. The molecular weight of the PCS modified at higher temperatures markedly increased, then was rendered infusible but soluble PCS in organic solvent on heating at 300 °C. H-NMR indicated that original PCS was enhanced by dehydrocoupling reaction between Si-H groups. Solution of the modified PCS was hand-drawn to fibers, followed by direct pyrolysis up to 1,400 °C without air-curing step to convert into oxygen-free SiC fibers. The morphology and crystalline phase were determined by SEM and XRD analysis, respectively. Presented at the Int’l Symp. on Chem. Eng. (Cheju, Feb. 8-10, 2001), dedicated to Prof. H. S. Chun on the occasion of his retirement from Korea University. Mr. Cao worked at CNU under co-advisor system.     

Facile joining of SiC ceramics with screen-printed polycarbosilane without pressure

Joining of SiC ceramics was successfully achieved at a relatively low temperature of 1500 °C without any pressure using pure polycarbosilane (PCS) as the joining material, which was distributed homogenously on the surface of SiC monolith through a screen printing method. The XRD pattern shows that the pyrolysis product of PCS is single-phase SiC. The interlayer thickness of the SiC joint is approximately 2 μm. This ultra-thin interlayer with lower possibility of the existence of defects contributes to the average shear strength of 105.8 ± 10.4 MPa, higher than that of other works using other preceramic polymers to the best of our knowledge. Due to the simplicity, low cost and high joining strength, the screen printing method using PCS as the joining material has good practicality in SiC ceramics joining.     

Preparation of porous TiO2 by a novel freeze casting

Highly porous and open interconnected pore structural TiO₂ were prepared by a novel freeze casting method. In the experiment, the well-dispersed aqueous slurries were first frozen, and then dried at a reduced vacuum. Since the sublimation of ice crystals developed in the freezing process, the green bodies with highly porous were obtained. The phase composition and the microstructure of the sintered samples were characterized by XRD, SEM, porosity and the pore size distribution was measured by mercury porosimetry. The results demonstrated that the PVA concentration in the slurries remarkably affect the microstructure of TiO₂ ceramics. The pore morphology of TiO₂ ceramics with 3 wt.% polyvinyl alcohol (PVA) addition was dendritic, and however, the pore morphology of TiO₂ ceramics with 6 wt.% PVA addition changed into columnar. The reason for the variation of the pore morphology was ascribed to the effect of the PVA gelation on the growth behavior of the ice crystals.     

The controllable microstructure of porous Al2O3 ceramics prepared via a novel freeze casting route

In traditional aqueous slurry freezing casting processing, the growth method of ice crystals is hard to control, resulting in the uncontrollable pore's morphologies of the porous ceramics. In the experimental, the pure Al₂O₃ sol was used to substitute water as a medium for preparing ceramic slurry. With Al₂O₃ sol addition, it becomes easy to control the microstructure and pore's morphologies of the porous Al₂O₃ ceramics via adjusting of the solid loading, composition of the ceramic slurries, as well as the cooling methods. The SEM micrographs showed that the sol-contained ceramic slurry combined with freeze casting processing can easily prepare the porous Al₂O₃ ceramics with different pore sizes and different morphologies. The porous Al₂O₃ ceramics prepared from 70 wt.% to 90 wt.% solid loading sol-contained Al₂O₃ slurries and sintered at 1500 °C for 2 h have open porosities from 81.7% to 64.6%.     

A new approach for the net-shape fabrication of porous Si3N4 bonded SiC ceramics with high strength

In this study, Si₃N₄ bonded porous SiC ceramics with high strength had been net-shapely fabricated by a new approach. In this approach, we proposed a two-step processing route composed of freeze casting and carbothermal reduction reactions in which carbon aerogels, derived from sol infiltration and pyrolysis, involved. The phase components, microstructures and properties of the prepared ceramics were investigated. The results showed that carbon aerogels with high apparent surface area had been completely reacted and new SiC and Si₃N₄ grains had been produced. The porous ceramics with flexural strength of 164.3 MPa at 33% porosity and 80.5 MPa at 46% porosity were obtained, whose linear shrinkages were only 1.06% and 1.94% during the whole processing respectively.     

Microstructures and mechanical properties of high-performance nacre-inspired Al-Si/TiB2 composites prepared by freeze casting and pressure infiltration

The nacre-inspired Al-Si/TiB₂ composites were successfully prepared by freeze casting and pressure infiltration. The microstructures and mechanical properties of nacre-inspired Al-Si/TiB₂ composites were studied by optical microscopy (OM), scanning electron microscopy (SEM), X-ray diffraction (XRD) and mechanical testing. The results show that the high performance of Al-Si/TiB₂ composites can be attributed to the clean interfaces between TiB₂ and Al and several toughening mechanisms, such as crack blunting, crack branching, crack deflection, plastic deformation of Al layer, and bridging of the uncracked fracture process zone. Specifically, the compressive strength, three-point bending strength and K_IC of composites corresponding to LS were 640–710 MPa, 629 MPa, and 16.4 MPa m^1/2, respectively. The fracture behaviors of the Al-Si/TiB₂ composites have been discussed in detail in this work. It was found that single cracks were accompanied by the propagation of multiple micro-cracks in the layered composites. The precipitation of Si particles at the TiB₂/α-Al interface and the Al phases infiltrated in the TiB₂ layers play a great role in the formation of single crack fractures and multiple micro-cracks fractures, respectively, in the nacre-inspired Al-Si/TiB₂ composites.     

Porous SiC/SiCN composite ceramics fabricated by foaming and reaction sintering

Porous SiC/SiCN composite ceramics with heterogeneous pore structure and rod-like SiCN grains were fabricated by foaming and reaction sintering. The mixture slurry containing SiC and silicon as raw materials, cornstarch as binder, Y₂O₃ as sintering additive and an electrosteric dispersant was stirred with foams derived from pre-foaming using foaming agent. The casted green body was sintered at 1650 °C under nitrogen atmosphere. The results demonstrated that the porous SiC/SiCN ceramics exhibited hierarchical vias ranging from 1 μm to 1 mm and the rod-like crystalline SiCN grains generated in the SiC matrix.     

Mullite rod-enhanced porous SiC ceramics prepared at low temperature from photovoltaic waste

In this paper, porous SiC ceramics (PSCs) were fabricated from photovoltaic waste at low temperatures. The effects of different additives and sintering temperatures on PSCs were studied in detail. The temperature of PSCs preparation can be reduced to 850?°C by adding MoO₃ as catalyst. The PSCs are reinforced by mullite rods grown in-situ, they also have a high permeability coefficient due to their network structure. From 850?°C to 1200?°C, the open porosity of PSCs changed slightly, and was within 45.32?±?0.6%. The PSCs produced at 1000?°C had the highest gas permeability coefficient of 8.24?×?10^–11?m² and the highest flexural strength of 50.17?MPa. However, the same PSCs could not be fabricated at 850?°C when Y₂O₃ or CeO₂ were used as sintering aids. This study provides an environment-friendly method for reusing photovoltaic waste and reducing the cost of preparing PSCs.     

Dendritic porous alumina with high porosity by directional freeze casting using a binary solution for bacterial removal

High-porosity dendritic porous alumina was fabricated by using tertiary butanol (TBA) hydrate crystals combined with directional freeze casting. The porosity of this porous alumina approximated 80 %, and its high porosity resulted in high water flux. Dendritic pores improved the physical interception capability of porous ceramics due to the intrinsic moving paths and intercepts from the pore structure. Changes in the TBA content (from 70 vol.% to 85 vol.%) caused a change in pore size from 36.58 μm to 11.54 μm and pore structure (change order: snowflake, dendritic, rod-like, and needle-like), which are important factors affecting water flux and interception capability. The interception and removal of Escherichia coli by 7 mm-height porous ceramics with dendritic structure and an average pore size of 27.90 μm reached 100 % at pH 7.2. This study provides a simple and low-cost method for the effective removal of bacteria.     

Influence of chemical composition on sintering ability of ZTA ceramics consolidated from freeze dried granules

Dense zirconia-toughened alumina (ZTA) ceramic composites with ZrO₂ = 0, 5, 10, 15, 20, 30, 60 and 100 wt.% have been prepared by sintering green compacts obtained by dry powder pressing of freeze dried granules consisting of α-alumina and a yttria partially stabilized zirconia (YPSZ) at various temperatures ranging from 1450 to 1650 °C for 1-2 h. The characteristics of sintered products were determined by X-ray diffraction (XRD), scanning electron microscopy (SEM), Archimedes principle, Vickers indentation method and by 3-point bend test. Characterization results revealed that adding YPSZ increased the 3-point bend (flexural) strength, fracture toughness and homogeneity of the microstructure, but slightly decreased the hardness and the sintering ability of alumina. A 20 wt.% YPSZ was sufficient to increase the fracture toughness and flexural strength of specimens sintered for 2 h at 1600 °C from 2.5 to 4.6 MPa m^1/2 and 150 to 400 MPa, respectively. The XRD results revealed that there is no solid-solution formation between zirconia and alumina constituents of ZTA ceramic composites upon sintering.