Structure and Properties of Silica Derived from Silicon Alkoxide Reacted with Tartaric Acid

The effects of tartaric acid that was used in sol–gel processing on specific surface area, pore-size distribution, and gel structure of sol–gel-derived silica gels were investigated. The specific surface area of silicas that were calcined at 450°C increased from ∼600 m²/g to ∼1200 m²/g as the amount of tartaric acid that was used increased. The pore-size distribution changed as the surface area increased, and only the gels that had a surface area of 930-990 m²/g showed a very sharp pore-size distribution in the mesopore range. The difference in gel structure and properties was explained in terms of the acidity of tartaric acid and the inhibition of condensation among primary particles through the coordination or adsorption of tartaric acid on the particle surface. From the thermal behavior of the gels with different features, it was concluded that gel properties are determined not only by the structure of the precursor gel but also by the surface activity. The gel with uniform mesopores gave a high surface area over a wide range of calcination temperatures.     

High surface area methyltriethoxysilane-derived aerogels by ambient pressure drying

In this paper we report the synthesis of methyltriethoxysilane (MTES) based aerogels by non-supercritical/ambient pressure drying. The alcogels have been aged in different concentrations of silane precursor solutions before drying and aerogels with low density and high porosity were obtained. The 60% vol silane aged aerogel shows a surface area of 416 m²/g with a pore volume of 0.99 cm³/g and a maximum surface area of 727 m²/g was obtained for 80% vol silane aged aerogel. The non-silane aged sample possess a surface area of 471 m²/g with a total pore volume of 0.83 cm³/g. The aerogels show broad pore-size distribution. The FT-IR studies reveal the retention of Si–C bond in the network and the formation of a hydrophobic gel. The ²⁹Si magic angle spinning nuclear magnetic resonance (²⁹Si MAS-NMR) studies were also employed to characterize the local environment around the silicon atoms and to obtain information on the condensation degree of the gel network. By varying the hydrolysis pH, highly flexible aerogels have also been successfully prepared. The porosity studies on the flexible aerogels are also presented here.     

Rearrangement of Porous CaO Aggregates During Calcite Decomposition in Vacuum

High-resolution SEM photographs, N₂ adsorption isotherms, Hg porosimetry, and micrometer measurements were used to characterize CaO particle shapes and pore-size distributions that result when calcite crystals are decomposed in vacuum at 686°C. The surface area of the CaO produced from large calcite crystals is constant at 116.4 m²/g independent of the extent of reaction. The volume occupied by a CaO aggregate is 98±2% that of the original calcite crystal. The ∼54% total porosity is comprised of 42% pores of ∼5 nm cross section and 12% pores of ∼10 μ m cross section. The duplex pore structure is formed by a diffusionless repacking of CaO particles that initially form with a more uniform distribution of particles and pores.     

Transformation, Microstructure Development, and Densification in α-Fe2O3-Seeded Boehmite-Derived Alumina

Addition of α-Fe₂O₃ seed particles to alkoxide-derived boehmite sols resulted in a 10-fold increase in isothermal rate constants for the transformation of γ- to α-Al₂O₃. Changes in porosity and surface area with sintering temperature showed no effect of seeding on coarsening of the transition alumina gels, but the 200-fold decrease in surface area associated with transformation to α-Al₂O₃ occurred ∼ 100°C lower in seeded gels compared with unseeded materials. As a result of high nucleation frequency and reduced microstructure coarsening, fully transformed seeded alumina retained specific surface areas >22 m²/g and exhibited narrow pore size distributions, permitting development of fully dense, submicrometer α-Al₂O₃ at ∼ 1200°C.     

Preparation of Mesoporous Silicon Nitride via a Nonaqueous Sol–Gel Route

A silicon diimide gel Si(NH) _x (NH₂) _y (NMe₂) _z was prepared by an acid-catalyzed ammonolysis of tris(dimethylamino)silylamine. Pyrolysis of the gel at 1000°C under NH₃ flow led to the formation of an amorphous silicon nitride material without carbon contamination. All of the gel and pyrolyzed products exhibited a mesoporous structure with a high surface area and narrow pore-size distribution. The effective surface area of the pyrolyzed silicon nitride residues decreases with increasing temperature, but the heating rate during pyrolysis has little influence on the surface area and pore-size distribution of the final mesoporous ceramic Si₃N₄ products because of the highly cross-linked structures of the precursor silicon diimide gel.     

Oxygen Storage Capacity, Specific Surface Area, and Pore-Size Distribution of Ceria–Zirconia Solid Solutions Directly Formed by Thermal Hydrolysis

The oxygen storage capacity (OSC) of CeO₂–ZrO₂ solid solutions that were directly formed as nanocrystals by thermal hydrolysis of acidic aqueous solutions of (NH₄)₂Ce(NO₃)₆ and ZrOCl₂ at 150°C increased from 94 μmol of O₂/g for pure CeO₂ to >400 μmol of O₂/g for compositions of CeO₂/ZrO₂ with molar ratios (C/Z) from 74.1/25.9 to 41.7/58.3 (maximum value of 431 μmol O₂/g was reached at the composition C/Z = 51.7/48.3) and then decreased with increased ZrO₂ content in the solid solutions. As compared with pure CeO₂, the CeO₂–ZrO₂ solid solutions that contained <84.8 mol% ZrO₂ maintained high specific surface area and large pore volume with nanosized pores (pore size at maximum pore volume) <10 nm in diameter after heat treatment at 700°C.     

New Uniformly Porous CaZrO3/MgO Composites with Three-Dimensional Network Structure from Natural Dolomite

Porous CaZrO₃/MgO composites with a uniform three-dimensional (3-D) network structure have been successfully synthesized using reactive sintering of highly pure mixtures of natural dolomite (CaMg(CO₃)₂) and synthesized zirconia powders with LiF additive. Equimolar dolomite and zirconia powders doped with 0.5 wt% LiF were cold isostatically pressed at 200 MPa and sintered at 1100–1400°C for 2 h in air. Through the liquid formation via LiF doping, strong necks were formed between constituent particles before completion of the pyrolysis of dolomite, resulting in the formation of a 3-D network structure. During and after the formation of the network structure, CO₂ was given off to form a homogeneous open-pore structure. The pore-size distribution was very narrow (with pore size ∼ 1 μm), and the porosity was controllable (e.g., ∼30%–50%) by changing the sintering temperature. The porous composites can be applied as filter materials with good structural stability at high temperatures.     

Synthesis of Ultrafine Ceria Powders by Mechanochemical Processing

The synthesis of ultrafine cerium dioxide (CeO₂) powders via mechanochemical reaction and subsequent calcination was studied. Anhydrous CeCl₃ and NaOH powders, along with NaCl diluent, were mechanically milled. A solid-state displacement reaction—CeCl₃+ 3NaOH → Ce(OH)₃+ 3NaCl—was induced during milling in a steady-state manner. Calcination of the as-milled powder in air at 500°C resulted in the formation of CeO₂ nanoparticles in the NaCl matrix. A simple washing process to remove the NaCl yielded CeO₂ particles ∼10 nm in size. The particle size was controlled in the range of ∼10–500 nm by changing the calcination temperature.     

Synthesis of Cerium(IV) Oxide Ultrafine Particles by Solid-State Reactions

CeO₂ ultrafine particles were prepared by solid-state reactions at room temperature. These particles were found to have very fine particle sizes (∼3 nm) with a fluorite structure ( a = 5.42 Å). BET measurements showed that the surface area of the particles was 96.2 m²/g. The use of two different precursors was found to affect the size of the CeO₂ particles. We discuss the effect of calcination at different temperatures on the morphology, size, and BET surface area of CeO₂ particles. A salt byproduct coating prevented agglomeration of the CeO₂ particles.     

CO2-Catalyzed Surface Area and Porosity Changes in High-Surface-Area CaO Aggregates

The changes in surface area and mesoporosity in aggregates of ∼0.01 μm cross-section CaO particles when heated in CO₂at 686°C were determined from N₂ adsorption isotherms. Initially, the surface area decreases rapidly with little change in porosity. When the surface area has decreased below ∼90 m²/g, surface area and porosity variations become consistent with expectations for coarsening by grain-boundary or bulk diffusion. The initial rapid decrease in surface area must result from CO₂-catalyzed surface diffusion, but the data suggest that surface diffusion is not rate-limiting. The rate-limiting step may be reaction of CO₂ to form surface CO₃^2- ions or decomposition of these ions to O^2- ions and CO₂ gas.     

Fabrication of Mullite Ceramics With Ultrahigh Porosity by Gel Freeze Drying

Porous mullite (3Al₂O₃·2SiO₂) ceramics with an open porosity up to 92.9% were fabricated by a gel freeze-drying process. An alumina (Al₂O₃) gel mixed with ultrafine silica (SiO₂) was frozen and sublimation of ice crystals was carried out by drying the frozen body under a low pressure. Porous mullite ceramics were prepared in air at 1400°–1600°C due to the mullitization between Al₂O₃ and SiO₂. A complex and porous microstructure was formed, where large dentritic pores with a pore size of ∼100 μm contained small cellular pores of 1–10 μm on their internal walls. Owing to the complete mullitization, a relatively high-compressive strength of 1.52 MPa was obtained at an open porosity of 88.6%.     

Fabrication and Microstructure Characterization of Continuous Porous TiO2/Al2O3 Composite Membrane

Using a multipass extrusion process, continuous porous Al₂O₃ body (∼41% porosity) was produced and used as a substrate to fabricate continuous porous TiO₂/Al₂O₃ composite membrane. The diameter of the continuous pores of the porous Al₂O₃ body was about 150 μm. The TiO₂ nanopowders dip coated on the continuous pore-surface Al₂O₃ body existed as rutile and anatase phases after calcination at 520°C in air. However, after aging of the fabricated continuous porous TiO₂/Al₂O₃ composite membrane in 20% NaOH at 60°C for 24 h, a large number of TiO₂ fibers frequently observed on the pore surface. The diameter of the TiO₂ fibers was about 150 nm having a high specific surface area. However, after 48-h aging period, the diameter of the TiO₂ fibers increased, which was about 3 μm. Most of the TiO₂ fibers had polycrystalline structure having nanosized rutile and anatase crystals of about 20 nm.     

Formation and Pore Structure of Boron Nitride Aerogels

Gels containing a poly(borazinyl amine) and tetrahydrofuran were processed by CO₂ supercritical drying techniques followed by pyrolysis. The resulting BN ceramic aerogels are highly porous, and the microstructure, porosity, and surface area characteristics have been examined. The aerogels show excellent thermal stability exhibiting surface areas in excess of 350 m²/g and porosities greater than 0.8 even when heated in argon at 1500°C for 8 h. By removing solvent via evaporation before supercritical drying, the mean pore radius can be varied between 3.6 and 10 nm.     

酸碱催化剂浓度对柔性硅气凝胶性能和结构的影响

以甲基三甲氧基硅烷(MTMS)和正硅酸乙酯(TEOS)作为混合硅源,甲醇为溶剂,十六烷基三甲基溴化铵(CTAB)为表面活性剂,通过酸碱两步催化溶胶凝胶法制备醇凝胶,经超临界干燥可以制备高弹性疏水块状硅气凝胶。分别采用0.1 mol·L^-1 和0.01 mol·L^-1 的草酸作为酸催化剂,5 mol·L^-1 和10 mol·L^-1 的氨水作为碱催化剂,研究不同酸碱催化剂浓度对其网络结构的影响。发现高浓度酸和高浓度碱以及低浓度酸和低浓度碱作为催化剂合成的硅气凝胶的网络结构更加均匀,孔径分布更窄。其中,在草酸浓度为0.01 mol·L^-1、氨水浓度为5mol·L^-1 时,所得硅气凝胶密度为0.135 g·cm^-3、比表面积为807 m²·g^-1、孔隙率约为93%,凝胶最大可压缩至其起始长度的60%,压缩回弹率为100%。     

Preparation of freestanding and crack-free titania–silica aerogels and their performance for gas phase, photocatalytic oxidation of VOCs

Freestanding and crack-free titania–silica aerogels with high titanium content (i.e., Ti/Si = 1) were successfully prepared by adjusting the hydrolysis of the two alkoxide precursors to a comparable rate during the sol–gel processing. Two titania–silica aerogels were prepared by ethanol and CO₂ supercritical drying methods. Well-dispersed, nanometer-sized anatase crystal domains (ca. 10 nm) were crystallized by high temperature, ethanol supercritical drying. The crystalline domains were solidly anchored to the aerogel network by Ti–O–Si bonds. Titania–silica aerogels prepared by CO₂ supercritical drying method were devoid of TiO₂ crystals. A molecular-level mixing was achieved and anatase TiO₂ was only crystallized with difficulty by high temperature calcination (1073 K). Both aerogels were mesoporous and displayed similar open pore structure that is readily accessible to reactant molecules. However, only the titania–silica aerogel with anatase TiO₂ prepared by ethanol supercritical drying was active for the gas phase, photocatalytic oxidation of volatile organic compounds (i.e., isopropanol and trichloroethylene). Catalysts prepared from Degussa P25 TiO₂ displayed lower activity under similar reaction conditions.     

Microstructure and Grain-Boundary Effect on Electrical Properties of Gadolinium-Doped Ceria

The microstructural evolution and grain-boundary influence on electrical properties of Ce_0.90Gd_0.10O_1.95 were studied. The nanoscale powders synthesized from a semibatch reactor exhibited 50% green density and 92% sintering density at 1200°C (∼200°C lower than previous studies). Impedance spectra as a function of temperature and grain size were analyzed. The Ce_0.90Gd_0.10O_1.95 with finest grain size possessed highest overall grain-boundary resistance; this contribution was eliminated at temperatures >600°C, regardless of grain size. The grain conductivity was independent of grain size and was dependent on temperature with two distinct regimes, indicative of the presence of Gd'_Ce− V _o^∘∘ complexes that dissociated at a critical temperature of ∼580°C. The activation energy for complex dissociation was ∼0.1 eV; the value for the grain-boundary was ∼1.2eV, which was size independent.     

Pressureless Sintering of SiC-Whisker-Reinforced Al2O3 Composites: I, Effect of Matrix Powder Surface Area

Pressureless sintering of SiC-whisker-reinforced Al₂O₃ composites was investigated. In Part I of the study, the effect of the matrix (Al₂O₃) powder surface area on densification behavior and microstructure development is reported. Compacts prepared with higher surface area Al₂O₃ powder showed enhanced densification at lower whisker concentrations (5 and 15 vol%). Samples with 15 vol% whiskers could be pressureless sintered to ∼97% relative density with zero open porosity and ∼1.6-μm matrix average grain intercept size.     

Low-Temperature Synthesis of Praseodymium-Doped Ceria Nanopowders

Praseodymium-doped ceria (CeO₂) nanopowders have been synthesized via a simple but effective carbonate-coprecipitation method, using nitrates as the starting salts and ammonium carbonate as the precipitant. The precursors produced in this work are ammonium rare-earth double carbonates, with a general formula of (NH₄)_0.16Ce_{1− x} Pr _x (CO₃)_1.58·H₂O (0 < x ≤ 0.20), which directly yield oxide solid solutions on thermal decomposition at a very low temperature of ∼400°C. Praseodymium doping causes a gradual contraction of the CeO₂ lattice, because of the oxidation of Pr³⁺ to smaller Pr⁴⁺, and suppresses crystallite coarsening of the oxides during calcination. Dense ceramics have been fabricated from the thus-prepared nanopowders via pressureless sintering for 4 h at a low temperature of 1200°C.     

CeO2−CoO Phase Diagram

Phase equilibria in the CeO₂−CoO system at temperatures above 1500°C were investigated. The microstructures and the phase compositions of the DTA (differential thermal analysis) samples and the quenched solid pellets were analyzed using SEM (scanning electron microscope), EDX (energy dispersive X-ray), and WDX (wavelength dispersive X-ray). A eutectic reaction was found at 1645 ± 5°C. The eutectic point was calculated to be at 82 ± 1.5 mol% CoO. The eutectic phases were the CeO₂-rich phase (containing <5 mol% CoO) and the CoO-rich phase (containing ∼0.5 mol% CeO₂). At 1580°C, the solubility of CoO in CeO₂ was ∼3 mol%.     

Microporous Glass-Ceramics in NASICON-Type Copper(II) Titanium Phosphate

A novel porous glass-ceramic with a skeleton of a NASICON-type copper(II) titanium phosphate was prepared via the controlled crystallization of a glass and the subsequent chemical leaching of the resulting dense glass-ceramic. A volume-crystallized dense glass-ceramic comprised of CuTi₂(PO₄)₃ and Cu₃(PO₄)₂, whose surface was covered by a thin layer of CuO, was prepared by reheating a glass with a nominal composition of 50CuO20TiO₂30P₂O₅ (in mol%) in air. When the resulting glass-ceramic was leached with dilute HCl, the Cu₃(PO₄)₂ and CuO phases were dissolved out selectively, and a cuprous NASICON crystal of CuTi₂(PO₄)₃ was converted to its cupric type, CuTi₄(PO₄)₆, which was left as a skeleton of the porous materials. The specific surface area and the average pore radius of the porous glass-ceramic obtained were ∼70 m²/g and ∼7 nm, respectively. The porous glass-ceramic showed high catalytic activities for the dehydration of 2-propanol.