Synthesis of barium titanate using supercritical CO2 drying of gels

BaTiO₃ powders from sol-gel derived gels were prepared using two different drying methods. In addition to the conventional drying of gels in air at 90°C the supercritical CO₂ drying method was also used. Results showed that the properties of BaTiO₃ powder produced by supercritical drying with CO₂ are better. The grain surface is less contaminated as a result of the supercritical drying and the microstructure development during sintering leads to a homogeneous fine-grained microstructure.     

Influence of the preparation methods on the microstructure and oxygen permeability of a CO2‐stable dual phase membrane

A CO₂‐stable dual phase membrane of the composition 40 wt % NiFe₂O₄‐60 wt % Ce_0.9Gd_0.1O_2‐δ (40NFO‐60CGO) was synthesized in three different ways: mixing of the starting powders (1) in a mortar and (2) in a ball‐mill as well as by (3) direct in situ one‐pot sol–gel powder synthesis. Backscattered scanning electron microscopy revealed that the direct one‐pot synthesis of 40NFO‐60CGO gives the smallest grains in a homogeneous distribution, compared with powder homogenization in the mortar or the ball‐mill. The smaller is the grains, the higher is the oxygen permeability. The permeation of the membrane can be improved by coating a porous La_0.6Sr_0.4CoO_3‐δ (LSC) layer on the surface of the air side. The dual phase membrane of 40NFO‐60CGO prepared by in situ synthesis shows a steady oxygen flux of 0.30 ml/(min cm²) over more than 100 h when pure CO₂ was used as sweep gas, which indicated that the dual phases membrane is CO₂‐resistant at least over this 5 days testing period. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

Sol–gel derived CeO2–Fe2O3 nanoparticles: Synthesis,characterization and solar thermochemical application

Synthesis of CeO₂–Fe₂O₃ nanoparticles via propylene oxide (PO) aided sol–gel method for the production of solar fuels via thermochemical H₂O/CO₂ splitting cycles is reported in this paper. For the synthesis of CeO₂–Fe₂O₃, cerium nitrate hexahydrate and iron nitrate nonahydrate were first dissolved in ethanol and then PO was added to this mixture as a proton scavenger to achieve the gel formation. Synthesized CeO₂–Fe₂O₃ gel was aged, dried, and then calcined in air to achieve the desired phase composition. Influence of different synthesis parameters on physico-chemical properties of sol-gel derived CeO₂–Fe₂O₃ was explored in detail by using various analytical methods such as powder x-ray diffraction (PXRD), BET surface area analyzer (BET), x-ray energy dispersive spectrometer (EDS), scanning electron microscopy (SEM), and high resolution transmission electron microscopy (HR–TEM). According to the findings, at all experimental conditions, phase/chemical composition of sol–gel derived CeO₂–Fe₂O₃ was observed to be unaltered. The SSA and pore volume was increased with the upsurge in the amount of PO used during sol–gel synthesis and decreased with the rise in the calcination temperature and dwell time. In contrast, the crystallite size was enlarged with the increase in the calcination temperature and dwell time. The nanoparticle morphology of the sol–gel derived CeO₂–Fe₂O₃ was verified with the help of SEM/TEM analysis. Thermochemical CO production ability of sol–gel derived CeO₂–Fe₂O₃ was investigated by performing thermogravimetric thermal reduction and CO₂ splitting experiments in the temperature range of 1000–1400 °C. Reported results indicate that the sol–gel derived CeO₂–Fe₂O₃ produced higher amounts of O₂ (69.134 μmol/g) and CO (124.013 μmol/g) as compared to previously investigated CeO₂ and CeO₂–Fe₂O₃ in multiple thermochemical cycles. It was also observed that the redox reactivity and thermal stability of sol–gel derived CeO₂–Fe₂O₃ remained unchanged as it produced constant amounts of O₂ and CO in eight successive thermochemical cycles.     

The synergy of supercritical CO2 and supercritical N2 in foaming of polystyrene for cell nucleation

This study examines the foaming behaviour of polystyrene (PS) blown with supercritical CO₂–N₂ blends. This is achieved by observing their foaming processes in situ using a visualization system within a high-temperature/high-pressure view-cell. Through analyzing the cell nucleation and growth processes, the foaming mechanisms of PS blown with supercritical CO₂–N₂ blends have been studied. It was observed that the 75% CO₂–25% N₂ blend yielded the highest cell densities over a wide processing temperature window, which indicates the high nucleating power of supercritical N₂ and the high foam expanding ability of supercritical CO₂ would produce synergistic effects with that ratio in batch foaming. Also, the presence of supercritical CO₂ increased the solubility of supercritical N₂ in PS, so the concentration of dissolved supercritical N₂ was higher than the prediction by the simple mixing rule. The additional supercritical N₂ further increased the cell nucleation performance. These results provide valuable directions to identify the optimal supercritical CO₂–N₂ composition for the foaming of PS to replace the hazardous blowing agents which are commonly used despite their high flammability or ozone depleting characteristics.     

Methods and Approaches of the Sol–Gel Technology for the Surface Modification of Aluminum Oxide Powders

The results of studies, sol–gel synthesis, and the sedimentation stability of complex multicomponent sol–gel systems of the “silica sol modified with Co(NO₃)₂ · 6H₂O, Al(NO₃)₃ · 9H₂O with α-Al₂O₃ or γ-Al₂O₃ as highly dispersed filler” type are generalized. The physical–chemical processes accompanying the formation of modifying layers on the powder oxide particles are examined. The promising prospects of applying α-Al₂O₃ powders modified with a silicate layer of the composition (wt %) 1.2K₂O · 3Al₂O₃ · 3.2CaO · 12.5Na₂O · 28.1B₂O₃ · 52SiO₂ in the fabrication of ceramic materials with improved strength characteristics are demonstrated.     

Activation of lipase by sol–gel coating with hydrophobic alkyl‐substituted silicates in supercritical carbon dioxide

BACKGROUND: Sol–gel entrapment of lipases is usually performed in an aqueous solution. A novel method of sol–gel coating of lipase in supercritical carbon dioxide (SC‐CO₂) is proposed. RESULTS: Crude lipase powder (Rhizopus oryzae) coated with hydrophobic silicates, derived from dimethyldimethoxysilane and tetramethoxysilane in SC‐CO₂ at 35 °C and 15 MPa, exhibited 5–7 times higher esterification activity than that prepared via an aqueous sol–gel route. Lipase immobilized in a methyl‐substituted silica monolith was also highly activated by sol–gel coating using the same silica precursors in SC‐CO₂. CONCLUSION: Sol– gel coating in SC‐CO₂, of lipases in powder and immobilized forms with hydrophobic alkyl‐substituted silicates provides an efficient tool for the enhancement of enzymatic activities in non‐aqueous media. Copyright © 2009 Society of Chemical Industry     

A Fourier-transform infrared study of CO2 and CO2/H2 interactions with caesium-doped copper catalysts

FTIR spectra are reported of CO₂ and CO₂/H₂ on a silica-supported caesium-doped copper catalyst. Adsorption of CO₂ on a “caesium”/silica surface resulted in the formation of CO₂ ⁻ and complexed CO species. Exposure of CO₂ to a caesium-doped reduced copper catalyst produced not only these species but also two forms of adsorbed carboxylate giving bands at 1550, 1510, 1365 and 1345 cm⁻¹. Reaction of carboxylate species with hydrogen at 388 K gave formate species on copper and caesium oxide in addition to methoxy groups associated with caesium oxide. Methoxy species were not detected on undoped copper catalyst suggesting that caesium may be a promoter for the methanol synthesis reaction. Methanol decomposition on a caesium-doped copper catalyst produced a small number of formate species on copper and caesium oxide. Methoxy groups on caesium oxide decomposed to CO and H₂, and subsequent reaction between CO and adsorbed oxygen resulted in carboxylate formation. Methoxy species located at interfacial sites appeared to exhibit unusual adsorption properties.     

Molten salt synthesis of La2Zr2O7 ultrafine powders

Ultrafine powders of pyrochlore-type La₂Zr₂O₇ were synthesized via a simple molten salt mediated process using zirconium oxide and lanthanum oxide as raw materials, and sodium chloride, potassium chloride and sodium fluoride to form a reaction medium. The effects of reaction temperature, salt/reactant ratio and salt type on the La₂Zr₂O₇ formation were investigated. Among the three attempted salt assemblies (KCl–LiCl, Na₂CO₃–K₂CO₃, and NaCl–KCl–NaF), NaCl–KCl–NaF showed the best accelerating effect on the La₂Zr₂O₇ formation. At a given temperature, the La₂Zr₂O₇ content in the final products increased with the increase in the salt amount. Phase pure submicron sized La₂Zr₂O₇ ultrafine powders were obtained after 3 h firing at 1100 °C with the salt/reactant weight ratio of 5:1 or at 1200 °C with salt/reactant weight ratio of 3:1. The synthesis temperature (1100 °C) was much lower than that required by the conventional solid-state mixing method or a wet chemical method. The “dissolution–precipitation” mechanism had dominated the synthesis process.     

Synthesis and encapsulation of yttria stabilized zirconia particles in supercritical carbon dioxide

Nanocrystalline oxide powders synthesized in supercritical CO₂ (SC-CO₂) generally consist in nanoparticle agglomerates, which are difficult to handle. In this work a particle encapsulation method in SC-CO₂ was developed to overcome this problem. By performing both the synthesis and encapsulation steps in the supercritical fluid, the agglomeration of particles can be limited, their handling can be improved and the powder behavior can be modified depending on the selected encapsulation agent. Poly(dimethylsiloxane)-graft-polyacrylate (PDMS-g-PA) phase separation method and methylmethacrylate (MMA) polymerization on particle surface are typical encapsulation processes usable in batch mode, with SC-CO₂ as a solvent, for ceramic powder encapsulation. This paper describes preliminary results concerning the synthesis of yttrium stabilized zirconia (YSZ) in SC-CO₂ and its encapsulation with PDMS-g-PA or PMMA in SC-CO₂. It has been shown that both phase separation and polymerization allow coating of the oxide particles, and clearly modify their properties. On the other hand, the use of a surfactant like PDMS-g-PA allows anchoring of MMA monomer and promotes polymerization on the particle surface. The choice of the surfactant is considered as a key parameter for a successful encapsulation process. This preliminary work offers new perspectives for synthesis and encapsulation of ceramic powders in SC-CO₂.     

Preparation by sol–gel and solid state reaction methods and properties investigation of double perovskite Sr2FeMoO6

Double perovskite Sr₂FeMoO₆ was prepared by two ways consisting in sol–gel technique and solid-state reaction method. The resulting powders from gel and mixed oxides precursors showed microstructures consisting of very fine grains (0.5–0.8 μm) and a crystalline perovskite structure. The structural and microstructural properties of the double perovskite Sr₂FeMoO₆ powders as-prepared and ceramics were compared. Tetragonal Sr₂FeMoO₆ pellets were prepared from the two powders by spark plasma sintering at: 1000, 1100 and 1200 °C and then annealing at 1200 °C, 2 h in 5%H₂/Ar. The pellets presented different magnetic characteristics. The saturation magnetization of the samples prepared by sol–gel is close to those prepared by conventional synthesis method.     

On-line extraction-reaction of canola oil using immobilized lipase in supercritical CO2

Lipase-catalyzed hydrolysis of canola oil in supercritical CO₂ (SCCO₂) was studied as a model reaction to develop an on-line extraction–reaction process to extract oil from oilseeds and convert the oil to other valuable products using SCCO₂. Immobilized lipase from Mucor miehei was used as the catalyst and the process was carried out at 24 MPa and 35°C. Product composition was analyzed using supercritical fluid chromatography. The effect of enzyme load, CO₂ flow rate and canola flake load on the amount of product and its composition was investigated. Hydrolysis occurred to a larger extent to free fatty acids and glycerol with an increase in enzyme load, a decrease in CO₂ flow rate or a decrease in canola load. On-line extraction-reaction process using SCCO₂ shows great potential for new process design to obtain products from agricultural commodities for use as ingredients in food and other industries.     

Evaluation of a new On-Stream Supercritical Fluid Deposition process for sol–gel preparation of silica-based membranes on tubular supports

A novel “On-Stream Supercritical Fluid Deposition” (OS-SFD) process has been investigated in this work coupling the sol–gel chemistry and a filtration/compression operation in supercritical CO₂ (sc-CO₂), for the production of uniform membranes on/in porous ceramic tubular supports. The versatility of this process allows both the direct formation of thin coatings on porous tubular membrane supports but also their internal modification. An attractive on-line control of the deposition process was operated by recording the transmembrane pressure evolution during membrane formation. Silica membranes were directly deposited on macroporous supports (155 mm long α-Al₂O₃, with 200 nm pore sizes) from TEOS derived sols dissolved in sc-CO₂ and transported to the tubular support where the condensation/gelation and deposition occurred. The deposition mechanism has been correlated with the sol–gel transition in sc-CO₂ conditions and the impact of the deposition temperature, sol formulation and sc-CO₂ flow rate on the membrane characteristics (morphology, weight increase and single gas permeance) have been discussed. Supersaturation and precipitation of transported clusters followed by their condensation and gelation were found as key parameters controlling the silica-based membrane design and microstructure/compacity of the silica network.     

The Assembly of TiO2 Nanoparticles into Micrometer‐Sized Structures,Photocatalytically Active Under UV and Vis Light

Micrometer‐sized structures consisting of TiO₂ nanoparticles were prepared using the sol–gel technique in combination with the structure‐directing agent triethanolamine (TEA). The interaction of the TEA with the hydrolyzed sol–gel products led to the formation of TEA titanate complexes, which then enabled the assembly of sol–gel‐precipitated nanosized powders. A subsequent thermal treatment of these powders resulted in the formation of micrometer‐sized structures consisting of TiO₂ anatase and rutile nanoparticles. To characterize the prepared powders, FTIR spectroscopy, XRD analysis, the Brunauer‐Emmett‐Teller method (s_BET), UV–Vis spectrometry and electron microscopy (FE‐SEM, and TEM) were employed. The photocatalytic degradation of the azo dye known as methylene blue was monitored under UV and Vis irradiation and showed that the micrometer‐sized structures consisting of TiO₂ nanoparticles exhibited a similar photocatalytic activity to submicrometer‐sized structures consisting of TiO₂ nanoparticles prepared without TEA.     

SPS densification and microstructure of ZrB2 composites derived from sol–gel ZrC coating

A technique for densifying ultra high temperature ceramic composites while minimising grain growth is reported. As-purchased ZrB₂ powder was treated with a zirconia-carbon sol–gel coating. Carbothermal reduction at 1450 °C produced 100–200 nm crystalline ZrC particles attached on the surface of ZrB₂ powders. The densification behaviour of the sol–gel coated powder was compared with both the as-purchased ZrB₂ and a compositionally similar ZrB₂–ZrC mixture. All three samples were densified by spark plasma sintering (SPS). The ZrB₂ reference sample was slow to densify until 1800 °C and was not fully dense even at 2000 °C, while the sol–gel modified ZrB₂ powder completed densification by 1800 °C. The process was studied by ram displacement data, gas evolution, SEM, and XRD. The sol–gel coated nanoparticles on the ZrB₂ powder played a number of important roles in sintering, facilitating superior densification by carbothermal reduction, nanoparticle coalescence and solid-state diffusion, and controlling grain growth and pore removal by Zener pinning. The sol–gel surface modification is a promising technique to develop ultra-high temperature ceramic composites with high density and minimum grain growth.     

Controlled Synthesis of Statistical Polycarbonates Based on Epoxides and CO2

The controlled synthesis of terpolymer structures is often limited by the intrinsic reactivities of the monomers. For the synthesis of a statistical terpolymer from cyclohexene oxide (CHO) and propylene oxide (PO) with CO₂, an instrumental solution is demanded. Implementing a setup where one monomer can be added to the reaction mixture over the whole course of the reaction, the random distribution of the epoxides over the whole chain is realized. The successful terpolymerization can be determined with diffusion-ordered nuclear magnetic resonance spectroscopy and gel permeation chromatography measurements while the statistical microstructure of the generated polymers is indicated in NMR spectroscopy and differential scanning calorimetry measurements. Furthermore, the concept is transferred to the terpolymerization of limonene oxide with PO and CO₂ underlining the versatility of the setup.     

Mechanochemical reaction in the K2CO3–Nb2O5 system

We studied the mechanochemical synthesis of KNbO₃, starting from a powder mixture of K₂CO₃ and Nb₂O₅. The milling experiments were designed with different ball-impact energies in order to investigate the mechanochemical reactions. X-ray diffraction, thermogravimetric analysis, infrared spectroscopy, Raman spectroscopy and transmission electron microscopy were used to characterize the samples. Based on the results, we propose a mechanism for the mechanochemical reaction between K₂CO₃ and Nb₂O₅. The first stage of the reaction is characterized by the formation of an amorphous carbonato complex, which decomposes after prolonged milling at higher ball-impact energy giving rise to the crystallization of KNbO₃ and other niobate phases with a molar ratio K/Nb < 1. The reaction course is discussed and compared with the Na₂CO₃–Nb₂O₅ system.     

Sol-Gel synthesis and characterization of SiC–B4C nano powder

In the present research, SiC–B₄C nano powders were synthesized through sol–gel process in water–solvent–catalyst–dispersant system. In order to evaluate the formation mechanism of the product during sol-gel process, TEM, SEM, DTA/TG, BET, XRD, FTIR and DLS analysis methods were employed. The nanometric size of precursor was controlled by dispersing agents and controlling pH inside the sol. DLS analysis revealed that the particles of the precursor inside the sol were below 10 nm. FTIR results indicated that the (Si–O–B) bonds were formed in the dried gel powder, due to hydrolysis and condensation reactions. DTA analysis confirmed that the synthesis temperature was lower than 1400 °C. XRD results implied the presence of cubic β-SiC and the rhombohedral B₄C phases, which were formed simultaneously in the SiC–B₄C nanopowder. BET analysis indicated a high surface area for the particles of about 171.42 m²/g, and that the surfaces of these particles were meso porous. SEM analysis exhibited that SiC– B₄C particle size was in the range of 20–40 nm with homogenous morphology. Ultimately, the TEM/EDS microstructural analysis showed that B₄C and SiC particles were formed simultaneously and uniformly in the final product.     

Control of H2O generated during the CO2 hardening process in a casting mold

An additive reagent was introduced into a water glass binder system for enhancing the mechanical properties and dimension stability of a casting mold, and for improving the surface quality of a cast product. Two different processes with three different additive reagents were employed to investigate the relation between fracture strength of the mold and water (H₂O) existed in the mold. In processes I and II, the mold samples were coated with a water glass binder, and then dipped into different solutions with additive reagent after and before carbon dioxide (CO₂) hardening, respectively. The fracture strength of the mold was enhanced by reducing H₂O content in the mold, achieved by a hydrolysis reaction of additive reagents. In process I, the H₂O movement was restricted in the mold by the solid phase, converted from the water glass during CO₂ hardening. When employing process II, especially in the TEOS used as additive reagent, the fracture strength was significantly increased due to the effective reduction of H₂O content in the mold and the homogeneous generation of glass phase by a sol–gel reaction of the additives.     

Particle formation and agglomeration of an alumina-zirconia powder synthesized an supercritical CO2 method

Alumina - 20 vol% zirconia doped with 2 mol% yttria composites were prepared by a supercritical CO₂ method. The powder characteristics were examined through control of the supercritical conditions; temperature and pressure. The agglomeration degrees (N) for powders were changed from 1.2 and 5.4. As the value N become smaller or close to unity, powder agglomerates tend to approach their primary powder size. The sintered sample had hardness of 12.5 GPa. SEM and TEM characterization were used to characterize the microstructure and morphology of the prepared powders.     

Micronization and characterization of drug substances by RESS with supercritical CO2

A RESS (rapid expansion of supercritical solution) process for the preparation of ultra-fine drug particles with no organic solvent has been developed with supercritical CO₂. Three drug substances with different solubility in supercritical CO₂ were used, and orifice disks and capillary tubes were adapted as an expansion device. The solubilities of drug substances in supercritical CO₂ and the effects of various operating parameters on the characteristics of the particles prepared by RESS process were experimentally investigated. The solubility of the drug substance in supercritical CO₂ had a major effect on the average diameter of the particle prepared by RESS process, and the particle diameter decreased with the solubility for all the drugs and operating conditions. The particle diameter also decreased with preexpansion temperature and increased with the hole diameter of the orifice nozzle and aspect ratio (L/D) of the capillary tube.