Effects of silica aerogel particle sizes on the thermal–mechanical properties of silica aerogel – unsaturated polyester composites

Silica aerogels with a surface area as high as 773?m²?g^?1 and a density of 0.077?g?cm^?3 were produced from rice husk via sol–gel process and ambient pressure drying. A particulate composite material was prepared by adding silica aerogel particles of three different particle sizes (powder, granules and bead) to unsaturated polyester resin with a fixed volume fraction of 30%. Thermogravimetric and thermal conductivity studies revealed that silica aerogel composites were having higher thermal stability and thermal insulation than the neat resin. It was suggested that the preservation of aerogel pores from resin intrusion is important for better thermal properties. Larger silica aerogel particles have more porous area (unwetted region) which results in a lower degradation rate and lower thermal conductivity of the base polymer. However, the addition of silica aerogel into resin has reduced the tensile modulus of the polymer matrix where smaller particle size displayed higher toughness than those with bigger particle size.     

Synthesis of superhydrophobic core–shell mesoporous silica nanoparticles

Mesoporous silica nanoparticles (MSNPs) have been used in variety of applications due to their morphology and porous structure. This work reports the one-pot synthesis of ultrahydrophobic MSNPs using N-cetyl-n,n,n trimethyl ammonium bromide as a cationic surfactant template and ethanol (EtOH) as a cosolvent to form mesopores in the MSNPs. The effects of EtOH on the size and the pore structure of the MSNPs were studied by scanning electron microscopy and transmission electron microscopy. The results show that an addition of EtOH led to an enlargement of the MSNPs and a change in pore structure from a lamellar structure to a radially oriented structure. Co-condensation with two different types of fluoroalkyl silanes; trimethyl(fluoromethyl)silane, and trichloro(1H,1H,2H,2H-perfluorooctyl)silane provided low surface energy MSNPs with a core–shell structure. An assembly on the surface of these F-MSNPs generated nanostructure surface roughness rendering an improvement in surface wettability with water contact angle of 158.6°, which is a characteristic of oleophobic and ultrahydrophobic material.     

Synthesis and characterization of microporous silica–alumina membranes

The development of microporous ceramic thin layers is of prime interest for sensors or gas separation membranes working at high temperature. Microporous silica membranes can be easily prepared by the sol–gel process. However the microporosity of pure silica is rapidly modified by steam at high temperature. One way to improve hydrothermal stability is to use mixed-oxide membranes. In this work, microporous silica–alumina membranes were prepared by a simple and robust sol–gel method. Tetraethoxysilane was mixed with an acidic alumina hydrosol. Urea was added for preparing the alumina hydrosol, for controlling the mixed-oxide network polycondensation and also as porogen agent. FTIR and ²⁷Al NMR spectroscopic analyses showed that for Si/Al molar ratios up to 6/1, homogeneous mixed oxides were obtained with a random distribution of Al and Si atoms in the oxide lattice based on tetrahedral units. The derived supported layers were crack-free as demonstrated by scanning electron microscopy (SEM) observations. Their microporosity was investigated using ellipsoporosimetry (EP) with films supported on flat dense substrates. He, N₂ and CO₂ permeance measurements were performed for membranes deposited on porous tubular substrates. The measured values of He/N₂ and He/CO₂ ideal selectivities are in agreement with the microporous nature of the prepared layers.     

Selective photoepoxidation of propylene over hydroxyapatite–silica composites

Two types of hydroxyapatite (HAP)–silica composites were prepared from aqueous solutions of Ca(NO₃)₂ and (NH₄)₂HPO₄ in the presence of SiO₂ in a buffer (pH 7.5) and an alkaline condition. Photooxidation of propylene with oxygen was carried out over the composites at 303 K. The major product was propylene oxide which exceeded 80% among C3 oxygenated products. The conversion increased with an increase in HAP content, but the selectivity of propylene oxide decreased. This was caused by that propylene oxide was strongly adsorbed on HAP followed by consecutive photooxidation. The thin-layered HAP in the HAP–SiO₂ composite is more effective for photoepoxidation of propylene than the bulk HAP.     

Cobalt–silica interaction and the dehydrogenation of 2-propanol

The interaction between silica and cobalt was studied on supported catalysts with low silica loading. Below a threshold cobalt level of 0.41 wt%, the catalysts were inactive for dehydrogenation of 2-propanol at 450 K. Inactivity was attributed to irreducibility of cobalt ions. Samples that were impregnated at a level below the threshold, dried, calcined, then reimpregnated below the threshold level, redried and recalcined such that the total cobalt content exceeded the threshold, were inactive. These results are not consistent with a model in which a portion of the cobalt interacts with specific silica sites, forming an irreducible species. Rather, they suggest that strongly interacting cobalt ions are incorporated into the silica surface.     

Hydrophobic titania–silica aerogels: epoxidation of cyclic compounds

Topics in Catalysis - Titania–silica mixed oxides with covalently bound methyl or phenyl groups were prepared from the corresponding alkyltrimethoxysilane and tetramethoxysilane using a...     

Cyclic fatigue of silica refractories – effect of test method on failure process

Silica refractories serving in high temperature industrial installations fail due to thermo-mechanical cyclic loads. The failure process was investigated by performing cyclic fatigue tests of several methods. In uni-axial compression the samples were tested either with constant force or displacement amplitude or with fixed upper displacement limit. In bending constant displacement amplitude tests were done. The investigation was supported by monotonic loading tests and microstructural analysis. It was determined that the fatigue failure occurs due to the degradation of interlocking in the crack wake. Cracking of larger grains is important for the crack initiation. The test set-up and the loading procedures significantly influence the potential to resist the crack propagation. Cyclic loading produces less brittle failure than monotonic loading. The displacement controlled method allows more gradual, less brittle, failure than the force controlled method. The potential of the crack arrest is less developed in bending than in compression.     

Brønsted acidity of silica silanol groups induced by adsorption of acids

Surface silanol groups of silica, which never revealed any Brønsted acidity, are shown to donate protons to adsorbed basic molecules, such as ammonia, pyridine or 2,6-dimethylpyridine, after addition of acids such as SO₂ or NO₂. The latter, when coadsorbed with bases, interact with the oxygen atoms of silanols leading to OH acidity increase and to protonation. Bases, in turn, enhance chemisorption of SO₂ or NO₂, and strongly held coadsorption products are formed as a result. The proposed mechanism of induced Brønsted acidity could account for the promoting effect of acidic gases in reactions catalysed by metal oxides.     

Stability of cenospheres in lightweight cement composites in terms of alkali–silica reaction

This paper presents an experimental study on characteristics and stability of cenospheres used in lightweight cement composites. ASTM C227 and C1260 tests were used to evaluate if cenospheres are potentially deleterious due to alkali–silica reaction (ASR). Natural sand was used as control. Examination by scanning electron microscope with energy-dispersive X-ray spectroscopy and analyses by X-ray diffractometer and thermogravimetry were conducted on samples with cenospheres after 9-month C227 and C1260 tests to better understand the behavior of cenospheres exposed to high alkaline environments and higher temperatures in these tests. Results indicate that cenospheres are not potentially deleterious due to ASR. Expansion of the mortar specimens tested to ASTM C227 and C1260 seems to be affected by the pozzolanic reactivity of cenospheres. Fine cenospheres showed limited pozzolanic reactivity at 28–30 °C and 38 °C, but exhibited significant pozzolanic reactivity at 80 °C with aluminum tobermorite [Ca₅Si₅Al(OH)O₁₇? 5H₂O] identified as the main reaction product.     

Preparation of transparent ultrahydrophobic silica film by sol�Cgel process

Transparent ultrahydrophobic films were synthesized by sol–gel process with organic silicones modified into silica sol and cured under UV irradiation. The effects of hydrolysis temperature, hydrolysis time, molar ratio of organic silicone to silica sol, and surface morphology on the hydrophobicity of the films were discussed in detail using FTIR spectroscopy, scanning electron microscopy (SEM), AFM, optical transmission, and contact angle measurement, respectively. The AFM and SEM images indicated that the surface roughness enhanced the hydrophobicity of the films. The results revealed that methyl-trimethoxysilane (MTMS)-modified silica film prepared at 50°C for 2 h with an MTMS/silica sol molar ratio of 1:10 had a very high contact angle (130°). However, the higher hydrolysis temperature and longer reaction time might have accelerated the self-condensation of silanol and decreased the contact angle of the films.     

Influences of heat-treatment on the microstructure and properties of silica–titania composite aerogels

Silica–titania composite aerogels were synthesized via ambient pressure drying by using water glass and titanium tetrachloride as raw materials. The influences of heat-treatment at different temperature with different heating rate on the microstructure and properties of the composite aerogels were investigated by differential thermal analyzer, Fourier transform infrared spectrometer, X-ray diffraction, nitrogen adsorption–desorption, scanning electron microscope and transmission electron microscope analysis. The results indicate that the silica–titania composite aerogels heat-treated at 250 °C exhibited highest specific surface area, pore volume and average pore diameter. When the heat-treatment temperature was higher than 450 °C, the –CH₃ groups on the surface of silica–titania composite aerogels would transform into –OH groups gradually, and in the meantime, the composite aerogels network structure would be destroyed gradually and the crystallinity of TiO₂ would be improved with the increase of heat-treatment temperature. Particularly, heat-treatment at temperatures above 750 °C would cause serious damage to the network structure of the composite aerogels. The adsorption/photocatalytic activity experiments showed that the composite aerogels heat-treated at 550 °C exhibit highest darkroom adsorption efficiency, and the 650 °C-heat-treated samples exhibited highest efficiency for removing the Rhodamine B from water.     

Preparation and characterization of PLLA–ESO/surface-grafted silica nanocomposites

Various amounts of surface-grafted silica (g-SiO₂) and un-grafted (SiO₂) nanoparticles were solution blended with a copolymer of l-lactide and epoxidized soybean oil (PLLA–ESO) or PLLA. Chemical reaction between the low molecular weight (LMW) PLLA and surface of silica nanoparticles is confirmed by FTIR and TGA analyses. The amount of grafted LMW PLLA investigated by thermal gravimetric analysis (TGA) was about 14.9%–28.2% in weight. g-SiO₂ nanoparticles can be easily dispersed into PLLA–ESO matrix to form a uniform PLLA–ESO/g-SiO₂ composite. Thermal properties of PLLA–ESO/g-SiO₂ and PLLA/g-SiO₂ nanocomposites were subsequently investigated by the differential scanning calorimeter measurements (DSC). DSC analyses indicated that g-SiO₂ nanoparticles can serve as a nucleating agent for the crystallization of PLLA–ESO in the composites, while the melting temperature (T _m) and the glass transition temperature (T _g) of PLLA–ESO/g-SiO₂ nanocomposites seemed to be independent of loading of g-SiO₂ particles. The DSC curves of PLLA/g-SiO₂ nanocomposite obviously showed double melting peaks, while that of PLLA–ESO/g-SiO₂ nanocomposites only a single melting peak. PLLA–ESO/g-SiO₂ composites exhibited a higher tensile strength and elongation than that of PLLA–ESO/SiO₂ composites.     

Thermally activated sintering–coarsening–coalescence-polymerization of amorphous silica nanoparticles

An onset sintering–coarsening–coalescence-polymerization (SCCP) event of amorphous SiO₂ nanoparticles (ca. 40–100 nm in size) by isothermal firing in the 1150–1300 °C range in air was characterized by an N₂ adsorption–desorption hysteresis isotherm coupled with X-ray diffraction and vibrational spectroscopy. The apparent activation energy of such a rapid SCCP process was estimated as 177±32 kJ/mol, based on 30% reduction of a specific surface area with an accompanied change of medium range orders, i.e. forming Si₂O₅ while retaining the Si–2ndO yet losing the Si–2ndSi without appreciable crystallization. The minimum temperature of the SCCP process, as of concern to industrial silica applications and sedimentary/metamorphosed sandstone formation, is 1120 °C based on the extrapolation of steady specific surface area reduction rates to null.     

Sol–gel incorporation of silica nanofillers for tuning the anti-corrosion protection of acrylate-based coatings

The aim of the present work is to synthesize through sol–gel approach new hybrid polymeric nanocomposites to be used as coating materials. An acrylic-based polymer was prepared by free-radical copolymerization of two monomers widely used for coatings, namely 2-ethylhexylacrylate (EHA) and glycidyl methacrylate (GMA) bearing epoxy moieties, in which silica nanoparticles were incorporated by in situ acid hydrolysis and subsequent condensation of tetraethoxysilane (TEOS). Glycidoxypropyl trimethoxysilane (GPTS) was used as coupling agent to fine-tune the compatibility between organic and inorganic phases. The morphology, mechanical properties and corrosion resistance of thin films applied on aluminum alloys were optimized by varying the content of silica nanoparticles whose properties were strongly affected by the TEOS/GPTS ratios. Performances of the obtained hybrid materials were scrutinized by atomic force microscopy (AFM), differential scanning calorimetry (DSC), thermal gravimetric analysis (TGA), and electrochemical impedance spectroscopy (EIS). Thus it was evidenced that an optimum amount of silica nanoparticles with a precise morphology and composition in term of TEOS/GPTS ratio is needed to maintain good coating barrier properties. Outstanding anti-corrosion protection was reached by using optimized hybrid films.     

Immobilization and enzymatic activity of β-glucosidase on mesoporous SBA-15 silica

The mesoporous silicate SBA-15 has shown to be a good support for the immobilization of β-glucosidase from almonds, an enzyme with high molecular weight (ca. 130 kDa for the dimer). An enzyme loading of 430 mg per gram of support (3.2 ± 0.2 μmol g⁻¹ of SBA-15) was achieved at 7 h. The optimum pH for the immobilization was 3.5. The electrostatic interactions between the surface of SBA-15 and the enzyme molecules were the driving force of the adsorption process. The immobilized β-glucosidase presented enzymatic activity on the hydrolysis of the 4-nitrophenyl-β-d-glucopyranoside at 3.5 pH. The catalytic activity was similar to the free enzyme for reaction time of 30 min. When the reaction pH was higher (5.5 pH) the enzyme was desorbed.     

Sol–gel preparation of PTMS modified hydrophobic and transparent silica coatings

Wettability of solid surfaces is an important property, which depends on both the surface chemistry and surface roughness. The present paper describes the room temperature synthesis of dip coated water repellent silica coatings on glass substrates using phenyltrimethoxysilane (PTMS) as a co-precursor with two-step sol–gel process. Silica sol was prepared by keeping the molar ratio of tetraethylorthosilicate precursor, methanol solvent, acidic water (0.001 M oxalic acid) and basic water (12 M NH₄OH) constant at 1:11.03:0.17:0.58 respectively, throughout the experiments and the PTMS weight percentage was varied from 0 to 15 %. It was found that with an increase in wt% of PTMS, the roughness and hydrophobicity of the films increased. However, the optical transmission decreased from 93 to 82 % in the visible range. The hydrophobic silica films retained their hydrophobicity up to a temperature of 386 °C and above this temperature the films became hydrophilic. The hydrophobic silica thin films were characterized by taking into consideration the surface roughness studies, Fourier transform infrared spectroscopy, percentage of optical transmission, scanning electron microscopy, thermogravimetric–differential thermal analysis and contact angle measurements.     

Synthesis of composite insulation materials—expanded perlite filled with silica aerogel

The aim of this paper is to synthesis a new type of insulation material (EPA), which fill the aerogels into the expanded perlite (EP). EP is a kind of lightweight filler, its application is constrained by the character of absorbing water easily. The silicic acid is inhaled into the expanded perlite at ?0.1 MPa, aging 24 h, it becomes aerogel after solvent exchanging/surface modifying and drying. The pores of EP are filled with aerogel which affects thermal conductivity of expanded perlite little and makes it hydrophobic. EPA has a wider use than EP for its hydrophobic character. A new recipe to synthesize aerogel, filled into EP, with the thermal conductivity of 0.034 W/m?K in ambient pressure drying is found in this experiment. The time and reagents dosage for synthesizing EPA are less than large block of aerogel, while the thermal conductivity is close to it. The scanning electron microscopy is used to analyze EPA’s micro structure. The thermal conductivity tester is used for testing the thermal conductivity of silica aerogel, expanded perlite and EPA.     

Influence of β-Si3N4 whiskers on sintering and crystallization of fused silica ceramics

Fused silica ceramics are widely applied for radome materials, crucibles, and vanes, but the mechanical properties were deteriorated due to the cristobalite crystallization. The fused silica ceramics added with by β-Si₃N₄ whiskers were prepared by a slip-casting method to retard the cristobalite crystallization. The influences of the sintering environments and the β-Si₃N₄ whiskers on the microstructure and phase structure were investigated. The silanol (Si-(OH)_n) and oxygen vacancies (V_O) in the fused silica in formed in different conditions were studied by Fourier Transform Infra-Red (FT-IR) and X-ray photoelectron spectroscopy (XPS), and the results indicated that the ball-milled produced a large amount of the silanol groups onto the surface of the fused silica particles. The fused silica heated in the vacuum created the maximum oxygen vacancies (24.2%) on the surfaces. Silanol groups reacted with the β-Si₃N₄ whiskers, and the O atoms in the silanol groups were fixed into the bulk materials. And the crystallization kinetics and the activation energy of Si₃N_4w/SiO₂ ceramics at the temperature ranging from 1200 to 1400°C were calculated based on the JMA(Johnson-Mehl-Avrami) model. The activation energy of the fused silica ceramics with the addition of the β-Si₃N₄ is 506.2 kJ/mol, increased by 23.6% than that of the pure fused silica ceramic.