Preparation of Porous Mullite Ceramics Using Fly Ash Cenosphere as a Pore‐Forming Agent by Gelcasting Process

Porous mullite ceramics were fabricated from an industrial grade mullite powder by gelcasting process using fly ash cenospheres (FAC) as a pore‐forming agent. The influence of content of FAC and sintering temperature on the density and strength was evaluated. The microstructure showed that FAC can act as a sintering aid and a pore‐forming agent. When the sintering temperature at 1200°C, porous mullite ceramics with a relatively high porosity (48.1–72.2%), low density (0.84–1.64 g/cm³), low thermal conductivity (0.16–0.22 W/m · K), and high compressive strength (6.21–14.70 MPa) have been obtained.     

Fabrication of Highly Porous Silica Thermal Insulators Prepared by Gelation–Freezing Route

Highly porous silica thermal insulators were produced by gelation of a gelatin solution with dispersed silica particles, followed by freeze‐drying and heating at 800°C. The relationship between the ice‐template morphology and the parameters involved in gelation freezing was investigated, in addition to the effect of the microstructure on the thermal conductivity of the silica insulators. The porosity and thermal conductivity of the insulators ranged from 88 to 98 vol% and from 0.168 to 0.054 W (m·K)^?1, respectively, both of which could be controlled by changing the silica content in the gel stage. Gelation–freezing route was proved to be a feasible and promising route for the production of very highly porous, machinable insulators.     

Preparation of porous Y2SiO5 ceramics with high porosity and extremely low thermal conductivity for radome applications

It is well known that aqueous gel-casting is challenging to prepare high-porosity ceramics due to the considerable drying shrinkage, cracking, and deformation of green bodies during drying caused by the high surface tension of water. Porous Y₂SiO₅ ceramics with high porosity were prepared by introducing carbon fibers as a support material in the drying process of aqueous gel-casting to reduce shrinkage during drying. Burning out the carbon fibers after drying does not negatively affect the properties of the porous ceramic. As prepared green bodies by aqueous gel-casting have low shrinkages of 8.69%–6.81% during drying processes and high compressive strength of 13.73 ± 1.55–10.66～0.49 MPa. The higher compressive strength of the green body has a positive significance for processing porous ceramics into special-shaped structures. As prepared porous Y₂SiO₅ ceramics have high porosity of 73.94%–87.71%, lightweights of 1.16–0.55 g?cm³, extremely low thermal conductivities of 0.134 ± 0.006 to 0.051 ± 0.001 W?m^?1?k^?1, relatively low dielectric constants of 2.34–1.58, and tan δ are lower than 1.25 × 10^?3. Porous Y₂SiO₅ ceramics with excellent dielectric properties and thermal insulation properties meet the requirements of thermal insulation and wave transmission integration of radome materials. Aqueous gel-casting also enriches the preparation methods of high-porosity Y₂SiO₅ ceramics.     

Tubular solid oxide fuel cells fabricated by a novel freeze casting method

Freeze casting is an established method for fabricating porous ceramic structures with controlled porosity and pore geometries. Herein, we developed a novel freeze casting and freeze drying process to fabricate tubular anode supports for solid oxide fuel cells (SOFCs). Freeze casting was performed by injecting aqueous anode slurry to a dual-purpose freeze casting and freeze drying mold wrapped with peripheral coils for flowing a coolant. With the use of an ice barrier layer, proper control of the experimental setup, and adjustments in the drying temperature profile, complete drying of the individual anode tubes was achieved in 4 hours. The freeze-cast anode tubes contained radially aligned columnar pore channels, thus significantly enhancing the gaseous diffusion. SOFC single cells with conventional Ni/yttria-stabilized zirconia/strontium-doped lanthanum manganite materials were prepared by dip coating the thin functional layers onto the anode support. Single cell tests showed that the concentration polarization was low owing to the highly porous anode support with directional pores. With H₂/N₂ (1:1) fuel, maximum power densities of 0.47, 0.36, and 0.27 W/cm² were recorded at 800°C, 750°C, and 700°C, respectively. Our results demonstrate the feasibility of using freeze casting to obtain tubular SOFCs with desired microstructures and fast turn-around times.     

High‐Temperature Aging of Plasma Sprayed Quasi‐Eutectoid LaYbZr2O7–Part II: Microstructure & Thermal Conductivity

LaYbZr₂O₇ ceramic thermal barrier coatings (TBC) of meta‐stable structure were prepared by an air plasma spraying process. Their microstructure and associated thermal transport properties evolution during high‐temperature annealing at 1300°C were characterized. The as‐sprayed LaYbZr₂O₇ TBCs underwent a fast crystallization and a quasi‐eutectoid transformation during annealing, resulting in a biphase composite consisting of La‐rich pyrochlore phase and Yb₂Zr₂O₇ fluorite phase with coherent phase boundaries. Due to the diffusion barriers between the two phases as well as the low interface energy of the coherent boundaries, sintering and grain growth of materials was significantly refrained. Therefore, a final thermal dynamically stable microstructure with a grain size of ~300 nm and a total porosity about 5% could be maintained even after long‐term aging at a high temperature of 1300°C. Resulting from this stable microstructure, an ultralow thermal conductivity of 1.3 W·(m·K)^?1 could be obtained even after 216 h high‐temperature aging, which is much lower than that of the state‐of‐art 7 wt% yttria‐stabilized zirconia TBCs. Both the high phase and microstructure stability and the extremely low thermal conductivities could be particularly beneficial for TBC material in gas turbine applications.     

Porous yttria‐Stabilized Zirconia Ceramics Fabricated by Nonaqueous‐Based Gelcasting Process with PMMA Microsphere as Pore‐Forming Agent

Porous yttria‐stabilized zirconia (YSZ) ceramics were fabricated using tert‐butyl alcohol (TBA)‐based gelcasting with monodisperse polymethylmethacrylate (PMMA) microspheres as both pore‐forming agent and lubricant agent. The TBA‐based slurry of 50 vol% solid loading with excellent rheological properties appropriate for casting was successfully prepared by using a commercial polymer dispersant DISPERBYK‐163 as both dispersant and stabilizer. The distribution of the spherical pores made from PMMA microspheres was very homogeneous. Their average diameter decreased from 16.9 to 15.7 μm when the sintering temperature was increased from 1350°C to 1550°C. The compressive strength increased from 14.57 to 142.29 MPa and the thermal conductivity changed from 0.17 to 0.65 W/m·K when the porosity decreased from 71.6% to 45.1%. The results show that this preparation technology can make all the main factors controllable, such as the porosity, the size and shape of pores, the distribution of pores, and the thickness and density of pore walls. This is significant for fabricating porous ceramics with both high compressive strength and low thermal conductivity.     

New Sintered Li2O–Al2O3–SiO2 Ultra‐Low Expansion Glass‐Ceramic

We developed a new Li₂O–Al₂O₃–SiO₂ (LAS) ultra‐low expansion glass‐ceramic by nonisothermal sintering with concurrent crystallization. The optimum sintering conditions were 30°C/min with a maximum temperature of 1000°C. The best sintered material reached 98% of the theoretical density of the parent glass and has an extremely low linear thermal expansion coefficient (0.02 × 10^?6/°C) in the temperature range of 40°C–500°C, which is even lower than that of the commercial glass‐ceramic Ceran^® that is produced by the traditional ceramization method. The sintered glass‐ceramic presents a four‐point bending strength of 92 ± 15 MPa, which is similar to that of Ceran^® (98 ± 6 MPa), in spite of the 2% porosity. It is white opaque and does not have significant infrared transmission. The maximum use temperature is 600°C. It could thus be used on modern inductively heated cooktops.     

Enhancing the thermal insulating properties of lanthanum zirconate porous ceramics via pore structure tailoring

The potentially useful role of lanthanum zirconate (La₂Zr₂O₇, LZO) porous bulk ceramics has been rarely explored thus far, much less the optimisation of its pore structure. In this study, LZO porous ceramics were successfully fabricated using a tert-butyl alcohol (TBA)-based gelcasting method, and the pore structures were tailored by varying the initial solid loading of the slurry. The as-prepared ceramics exhibited an interconnected pore structure with high porosity (67.9 %–84.2 %), low thermal conductivity (0.083–0.207 W/(m·K)), and relatively high compressive strength (1.56–7.89 MPa). The LZO porous ceramics with porosity of 84.2 % showed thermal conductivity as low as 0.083 W/(m·K) at room temperature and 0.141 W/(m·K) at 1200 °C, which is much lower than the counterparts fabricated from particle-stabilized foams owing to its unique pore structure with a smaller size, exhibiting better thermal insulating performance.     

Preparation,mechanical, dielectric and microwave absorption properties of hierarchical porous SiCnw-Si3N4 composite ceramics

Herein, hierarchical porous SiC_nw-Si₃N₄ composite ceramics with good electromagnetic absorption properties were prepared. A porous Si₃N₄ matrix with different pore structures was first prepared by gelcasting-pressureless sintering (G-PLS) and gelcasting combined with particle stabilized foam-pressureless sintering (G-PSF-PLS). SiC_nw was then introduced by catalytic chemical vapor deposition (CCVD). An increase in solid loading (25–40 vol%) decreased apparent porosity (47.7–41.3%) and improved flexural strength (142.19–240.36 MPa) and fracture toughness (2.25–3.68 MPa·m^1/2). The addition of foam stabilizer propyl gallate (PG, 0.5–1.0 wt%) significantly increased apparent porosity (73.2–86.4%) and realized large-sized spherical pores, reducing flexural strength (58.23–38.56 MPa) and fracture toughness (0.75–0.41 MPa·m^1/2). High apparent porosity and large-sized pores facilitated the introduction of SiC_nw. The 25 vol% sample exhibited a reflection loss of ? 14.67 dB with an effective absorption bandwidth of 3.47 GHz, suggesting a development potential in the electromagnetic wave absorption field.     

Freeze‐drying of aqueous solution frozen with prebuilt pores

To save drying time and increase productivity, a novel idea was proposed for freeze‐drying of liquid materials by creating an initially unsaturated frozen structure. An experimental investigation was carried out aiming at verifying the idea using a multifunctional freeze‐drying apparatus. Mannitol was selected as the primary solute in aqueous solution. Liquid nitrogen ice‐cream making method was used to prepare the frozen materials with different initial porosities. Results show that freeze‐drying can be significantly enhanced with the initially unsaturated frozen material, and substantial drying time can be saved compared with conventional freeze‐drying of the initially saturated one. Drying time was found to decrease with the decrease in the initial saturation. The drying time for the initially unsaturated frozen sample (S₀ = 0.28 or 0.69 of initial porosity) can be at best 32% shorter than that required for the saturated one (S₀ = 1.00 or zero porosity). This unique technique is easy to implement and improves the freeze‐drying performance of liquid materials. © 2015 American Institute of Chemical Engineers AIChE J, 61: 2048–2057, 2015     

Superior hydrophobicity of nano-SiO2 porous thermal insulating material treated by oil-in-water microemulsion

Nano-SiO₂ porous thermal insulating material (TIM) has drawn tremendous research interests due to its advantages of low density, high porosity and low thermal conductivity. However, its long-term stability in humid environment can be severely deteriorated by the high hydrophilicity resulting from tetrahedral coordination of oxygen and capillary effect of porous structure. It is still a great challenge to cost-effectively fabricate bulk TIM with superior hydrophobicity and consequent remarkable self-cleaning capability. Herein, via an oil-in-water microemulsion treatment, we have proposed a new strategy to construct 3D superior hydrophobic nano-SiO₂ porous TIM. The polymethylhydrosiloxane-modified TIM exhibits a large water contact angle of 166°, and corresponding excellent self-cleaning characteristic while maintaining low thermal conductivity of 0.031 W/m·K. Moreover, our high hydrophobicity of TIM exhibits excellent durability under high temperature up to 400 °C, high humidity of 100%, and chemical erosions. Detailed knowledge of the physical chemistry basis of the superior hydrophobic nano-SiO₂ porous TIM can provide great opportunity to fabricate advanced self-cleaning and heat insulating devices especially targeted for harsh environments.     

Preparation and characteristics of highly porous BN-Si3N4 composite ceramics by combustion synthesis

Nitride based ceramics are considered as a kind of promising material for structural and functional integration due to their robust structure, extreme environmental resistance and electromagnetically transparency. It is still challenging to prepare nitride based ceramics with homogeneous and controllable microstructure because of their low self-diffusion coefficient and difficulty in sintering. Here, we developed a gelcasting-SHS process by combining gelcasting forming and self-propagating high temperature synthesis (SHS) for the preparation of porous BN-Si₃N₄ composite ceramics. First, carbon residue problem in the gelcasting -SHS process was studied. Based on the result, porous BN-Si₃N₄ composite ceramics with high porosity (69.42 ~ 86.48%), high strength (21.7 ~ 81.0 MPa) and low dielectric constants (1.42 ~ 2.87) were synthesized. In addition, the thermal shock resistance of porous BN-Si₃N₄ composite ceramics until 1000 ℃ was evaluated.     

Low-temperature preparation of high-performance porous ceramics composed of anorthite platelets

Platelet-like anorthite based porous ceramics with improved mechanical strength were fabricated via direct gelcasting and firing at 1223-1473 K using CaCO₃, Al(OH)₃, and SiO₂ powders as the raw materials, along with H₃BO₃ and melamine sintering/crosslinking agents. Based on density functional theory calculations, H₃BO₃ promoted the formation of platelet-like anorthite at a relatively low temperature via covering the {130} facet of anorthite and reducing the corresponding adsorption energy, which led to the preferential growth along the a- and b-axes. The optimal amount of H₃BO₃ for the anorthite platelet formation was 0.9 wt%. The porous anorthite sample with an original solid content of 22.0 wt%, after firing at 1373 K, contained 71.0% porosity and exhibited a compressive strength as high as 5.7 MPa, which were comparable or even superior to those of porous anorthite ceramics prepared previously at a much higher temperature (1573-1723 K), indicating that the preparation strategy reported in this paper is feasible in fabricating high-performance porous anorthite ceramics at a much milder condition. The thermal conductivity of the porous anorthite sample at 1073 K was as low as 0.266 W/(m·K), much lower than that (0.645 W/(m·K)) of the control sample, suggesting that the former could be potentially used for thermal insulation at high temperatures.     

Electronically conductive porous TiN ceramics with enhanced strength by aqueous gel‐casting

In this paper, we report on a study of electronically conductive porous TiN ceramics prepared by aqueous gel‐casting. The effects of solid loading, sintering temperature, and sintering aids on the phase composition, microstructure, and volume fraction of porosity of the prepared porous TiN ceramics are studied. The SEM results show that porosity is uniformly distributed in all of the samples studied. With increasing solid loading and sintering temperature, the volume fraction of porosity decreases slowly. Moreover, the relationship between volume fraction of porosity and mechanical and electrical properties has also been investigated. Our results show that adding Y₂O₃‐TiO₂ as combined sintering aids results in a sharp decrease in the volume fraction of porosity, and the volume fraction range changes from 42%‐60% to 28%‐52%. Moreover, adding sintering aids results in an increase in flexural strength and electrical conductivity with a change in maximum value from 34.6 MPa and 2.3 × 10⁴ S?m^?1 to 101.6 MPa and 5.1 × 10⁴ S?m^?1, respectively.     

Preparation and properties of porous ceramics from nickel slag by aerogel gelcasting

To further resource industrial solid waste, porous ceramics with high porosity were prepared by a gelcasting method using nickel slag and kaolin as raw materials and hydrophilic nontoxic SiO₂ aerogel as a gelling agent. The effects of nickel slag content, dispersant and solid content on the properties and microstructure of porous ceramics were investigated in detail in terms of density, compressive strength, porosity, phase composition and micromorphology. The results confirmed that a certain amount of nickel slag can effectively improve the porosity of porous ceramics, while the addition of dispersant can promote the flow of the slurry, enhanced the denseness of the raw billet and significantly improved the compressive strength. However, its excessive use had a negative effect on the ceramic density and porosity. At the same time, the solid content played a key role in the performance of porous ceramics prepared by gelcasting, and too much solid content was also not conducive to the generation of pores. When the nickel slag content was 55%, the amount of dispersant was 2%, and the solid content was 60 vol%, the porous ceramic had a better overall performance, the density of the porous ceramic was 510 kg/m³, the compressive strength was 1.3 MPa, and the porosity reached 80.1%. The major crystalline phases of porous ceramics prepared by nickel slag were cordierite and anorthite.     

Carbothermal reduction synthesis of high porosity and low thermal conductivity ZrC-SiC ceramics via an one-step sintering technique

In this work, porous ZrC-SiC ceramics with high porosity and low thermal conductivity were successfully prepared using zircon (ZrSiO₄) and carbon black as material precursors via a facile one-step sintering approach combining in-situ carbothermal reduction reaction (at 1600 °C for 2 h) and partial hot-pressing sintering technique (at 1900 °C for 1 h). Carbon black not only served as a reducing agent, but also performed as a pore-foaming agent for synthesizing porous ZrC-SiC ceramics. The prepared porous ZrC-SiC ceramics with homogeneous microstructure (with grain size in the 50–1000 nm range and pore size in the 0.2–4 µm range) possessed high porosity of 61.37–70.78%, relatively high compressive strength of 1.31–7.48 MPa, and low room temperature thermal conductivity of 1.48–4.90 W·m^?1K^?1. The fabricated porous ZrC-SiC ceramics with higher strength and lower thermal conductivity can be used as a promising light-weight thermal insulation material.     

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.     

SiC junction enhanced carbon nanofiber aerogels with extremely high specific strength and ultra-low thermal conductivity

C/SiC aerogels with both ultra-low thermal conductivity and extremely high strength were fabricated by freeze casting. SiC junctions originated from pyrolysis of polycarbosilane (PCS) were formed between carbon nanofibers (C_f) to enhance the strength of aerogels. The effects of PCS content and total solid content on the phase composition, pore structure, thermal conductivity and compressive property were studied. The fabricated aerogels possess hierarchical pore structure. In the micro-scale, it contains circular pores with size of about 15 µm, while it is mesoporous and macroporous in the nano-scale. Both thermal conductivity and compressive strength increase with the increase in PCS content. Through tailoring PCS content and total solid content, C_f/SiC aerogels with porosity of 99.5%, thermal conductivity of 33 mW·m⁻¹·K⁻¹ and compressive strength of 7.14 MPa can be obtained. The specific strength of the fabricated C_f/SiC aerogels is up to 467.6 MPa/(g/cm³), which is the highest value for ceramic aerogels.     

Low thermal conductivity in porous SiC–SiO2–Al2O3–TiO2 ceramics induced by multiphase thermal resistance

The introduction of multiple heterogeneous interfaces in a ceramic is an efficient way to increase its thermal resistance. Novel porous SiC–SiO₂–Al₂O₃–TiO₂ (SSAT) ceramics were fabricated to achieve multiple heterogeneous interfaces by sintering equal volumes of SiC, SiO₂, Al₂O₃, and TiO₂ compacted powders with polysiloxane as a bonding phase and carbon as a template at 600 °C in air. The porosity could be controlled between 66% and 74% by adjusting the amounts of polysiloxane and the carbon template. The lowest thermal conductivity (0.059 W/(m·K) at 74% porosity) obtained in this study is an order of magnitude lower than those (0.2–1.3 W/(m·K)) of porous monolithic SiC, SiO₂, Al₂O₃, and TiO₂ ceramics at an equivalent porosity. The typical specific compressive strength value of the porous SSAT ceramics at 74% porosity was 3.2 MPa cm³/g.     

Preparation of calcium hexaluminate porous ceramics by gel-casting method with polymethyl methacrylate as pore-forming agent

Calcium hexaluminate (CA₆) porous ceramics were prepared by gel-casting method, with α-Al₂O₃ and CaCO₃ as raw materials and polymethyl methacrylate (PMMA) microspheres as pore-forming agent. The effects of the amount of pore-forming agent PMMA microspheres on the phase composition, bulk density, apparent porosity, flexural strength, microstructure, thermal shock stability and thermal conductivity of CA₆ porous ceramics were systematically studied. The pores of CA₆ porous ceramics are mainly formed by the burning loss of PMMA microspheres and the decomposition of organic matter. Adding an appropriate amount of PMMA microspheres as pore-forming agent has a positive effect on the thermal shock stability of CA₆ porous ceramics. When the amount of pore-forming agent is 15 wt%, the volume density of CA₆ porous ceramics is 1.33 g/cm³, the porosity is 63%, the flexural strength is 13.9 MPa, the thermal shock times can reach 9 times, and the thermal conductivity is 0.293 W/(m·K), which can meet the application in refractory, ceramics or high temperature cement industries.