Synthesis of silica aerogel blanket by ambient drying method using water glass based precursor and glass wool modified by alumina sol

Silica aerogel blankets have been synthesized by ambient drying technique using cheap water glass as the silica source and glass wool modified by alumina sol. One step solvent exchange and surface modification were simultaneously conducted by immersing the wet hydrogel blanket in EtOH/TMCS/hexane solution. The synthesized silica aerogel blanket was light with the density of 0.143-0.104 g/cm³ and 89.4-95% porosity. The microstructure of silica aerogel blanket exhibits a porous structure consisting of glass fibers of diameter ∼2.5 μm interconnected with solid silica clusters (5-20 μm).     

Microstructural and physical properties of the ambient pressure dried hydrophobic silica aerogels with various solvent mixtures

The experimental results on the microstructural and physical properties of the ambient pressure dried hydrophobic silica aerogels with various solvent mixtures have been reported. The aerogels were prepared with sodium silicate precursor, ammonium hydroxide catalyst, trimethylchlorosilane (TMCS) silylating agent, solvent mixture of methanol-isopropanol (MeOH/IPA) and various aprotic solvent mixtures namely, hexane and benzene (HB), hexane and toluene (HT), hexane and xylene (HX), heptane and benzene (HpB), heptane and toluene (HpT), heptane and xylene (HpX). The physical properties of the aerogels such as % of volume shrinkage, density, % of optical transmission, surface area, % of porosity, pore volume, thermal conductivity and heat capacities of the aerogels were studied. The hydrophobicity of the aerogels was studied by contact angle measurements. The HX and HpX aerogels have been found to be more hydrophobic (contact angle, θ > 155°) than the other aerogels. It has been observed that the % of weight increase is highest (1%) for the HT aerogels and lowest (0.25%) for HpX aerogels by keeping them at 70% humidity for 350 h. Further, the aerogels have been characterized by pore size distribution (PSD), Fourier transform infra red spectroscopy (FTIR) and thermogravimetric and differential thermal (TG-DGA) analysis and transmission electron microscopy (TEM) techniques. The results have been discussed by taking into account the surface tension, vapor pressure, molecular weight and chain length of the solvents. Low density (0.051 g/cc), hydrophobic (165°), transparent (85%), low thermal conductive (0.059 W/m K), low heat capacity (180 kJ/m³ K) and highly porous (97.38%) silica aerogels were obtained with HpX solvent mixture.     

Surface nature of nanoparticle gold/iron oxide aerogel catalysts

The aerogel catalysts investigated are constituted by two chemically different nanoparticle systems consisting of the gold phase and the iron oxide support. High-resolution transmission electronic microscopy (HRTEM) showed an increased surface roughness for aerogel particles with higher gold loading. X-ray photoelectron spectroscopy (XPS) revealed increases in the surface coverage of hydroxyl groups and the Fe²⁺/Fe³⁺ ratio due to the addition of gold, and showed the transition of gold from oxidized to metallic states due to calcination. In the presence of gold species, the Fe³⁺ satellite structure in XPS was not produced. The crystallinity of maghemite as the support was found quite stable with respect to gold addition and thermal treatment. The aerogels were evaluated for methanol oxidation carried out in an ambient flow reactor. The oxidation activity enhanced with decreasing catalyst pretreatment temperatures and with increasing gold loadings up to 5 wt%. A wide selectivity pattern formed between dimethyl ether and carbon dioxide products. The size of gold particles and the status of surface gold species played a crucial role in the catalytic conversion of methanol. The oxidized gold was more active than the metallic gold towards the total combustion to carbon dioxide. The surface nature has been proven to transform from strong Lewis acidic to high basic characters due to the formation of reactive hydroxyl groups near by the gold sites.     

Photo-chargeable titanium/vanadium oxide composites

Titanium and vanadium oxides were prepared by a sol-gel technique and supercritical drying and evaluated for light energy conversion and storage in a wet-type photoelectrochemical cell. Ultraviolet light irradiation to the nanocrystalline titania aerogel (anatase) produced significant photocurrents, and the maximum incident photon-to-current conversion efficiency (IPCE) attained 37.1%. From cyclic voltammetry, the vanadium oxide gel was shown capacitive for charge storage, associated with the shcherbinaite structure and V⁴⁺/V⁵⁺ redox pair. Photopotential responses revealed that coupled TiO₂/V₂O₅ composites not only were photo-chargeable but also exhibited a greater discharging capacity than the TiO₂ or V₂O₅ alone. The discharging capacity was remarkably reduced in the presence of dissolved oxygen. Results demonstrate that in the hybrid TiO₂/V₂O₅ system the V₂O₅ serves to accumulate photoelectrons generated by the illuminated TiO₂ during the photo-charging process. A schematic energy diagram that describes the band structure of the composite semiconductor is proposed.     

Fabrication and characterization of photocurable inorganic-organic hybrid materials using organically modified colloidal-silica nanoparticles and acryl resin

Photocurable inorganic-organic hybrid materials were prepared from colloidal-silica nanoparticles synthesized through the sol-gel process and using acryl resin. The synthesized colloidal-silica nanoparticles had uniform diameters of around 20 nm and were organically modified, using methyl and methacryl functional silanes, for efficient hybridization with acryl resin. The organically modified and stabilized colloidal-silica nanoparticles could be homogeneously hybridized with acryl resin without phase separation. The successfully fabricated hybrid materials exhibit efficient photocurability and simple film formation due to the photopolymerization of the organically modified colloidal-silica nanoparticles and acryl resin upon UV exposure as well as an excellent optical transmission of above 90% in the visible region and an enhanced surface smoothness of around 1 nm RMS roughness. They likewise exhibit improved thermal and mechanical characteristics, much better than those of acryl resin. Lastly and most importantly, these photocurable hybrid materials fabricated through the synergistic combination of colloidal-silica nanoparticles with acryl resin are candidates for optical and electrical applications.     

Synthesis optimization of organic xerogels produced from convective air-drying of resorcinol-formaldehyde gels

Resorcinol-formaldehyde gels were produced at 50, 70 and 90 °C and with three different R/C ratios (500, 1000 and 2000). The effect of these variables combined with that of aging time was studied in order to optimize the synthesis conditions. The convective air-drying process was used, and the drying duration was studied with regard to the synthesis conditions. The aging time has no effect on the pore texture after 24 h at 90 °C or 48 h at 70 °C, whatever the R/C value. The synthesis-aging step can be shortened by increasing the temperature. Nevertheless, the pore size tends then to decrease, especially when R/C is high, but this can be counterbalanced by increasing R/C. Moreover, bubbles often appear in the gel at high synthesis temperature, which limits the temperature to about 70 °C in the case of monolithic parts. At 70 °C and with an air velocity of 2 m/s, the elimination of 90% of the solvent requires 1 h drying when the pore size reaches 400-600 nm, 2.5 h for 50 nm wide pores and 3 h when the pore size decreases to 15-20 nm. The drying duration does not exceed 8 h in all cases and could be shortened by increasing the temperature at the end of the process.     

Photosensitive defects in silica layers implanted with germanium ions

Ge-implanted silica layers have been investigated by high-power pulsed synchrotron-photoluminescence (PL), photoluminescence excitation spectroscopy (PLE), and optically stimulated electron emission (OSEE) with respect to association of excitation and absorption bands to respective emission bands and lifetimes of excited defect states. In this way singlet-singlet (4.35 eV) and triplet-singlet (3.18 eV) radiative transitions from excited states of oxygen-deficient centers (ODC) in Ge-doped silica glass are characterized by their absorption and emission bands as well as their lifetimes. The main channel for non-radiative relaxation of photoexcitation is electron emission by the OSEE effect. The OSEE shows non-radiative transitions of surface and bulk E′-centers found with concentrations of (2.7-3.4) × 10¹² cm⁻² and (2-4) × 10¹⁶ cm⁻³, respectively.     

Nanostructural damage associated with isostatic compression of silica aerogels

Isostatic compression of silica aerogels is known to allow densification of these highly porous materials. However, at the onset of compression, hydrophobic and consequently slightly reacting aerogels, exhibit a decrease in bulk modulus. This unusual behavior is associated with damage occurring at low pressures which recovers with further density increase. Damage development and healing are analyzed measuring elastic modulus and, for the first time, internal friction as a function of compression. It is proposed that the origin of damage and healing could be associated with the rupture of tenuous links between clusters of dense silica particles at low density levels, and with the creation of new links between the resulting arms and reacting species that are revealed at cluster interface under higher pressure.     

Structural characteristics of silica sonogels prepared with different proportions of TEOS and TMOS

Sonohydrolysis of mixtures of tetraethoxysilane (TEOS) and tetramethoxysilane (TMOS) with different TMOS/(TMOS + TEOS) molar ratio R was carried out to obtain ∼2.0 × 10⁻³ mol SiO₂/cm³ and ∼86%-volume liquid phase wet gels. Aerogels were obtained by supercritical CO₂ extraction in autoclave. The samples were analyzed by small-angle X-ray scattering (SAXS) and nitrogen adsorption. The structure of the wet gels can be described as a mass fractal structure with fractal dimension D ∼ 2.2 and characteristic length ξ increasing from ∼4.6 nm for pure TEOS to ∼6.4 nm for pure TMOS. A fraction of the porosity is eliminated with the supercritical process. The fundamental role of the TMOS/(TMOS + TEOS) molar ratio on the structure of the aerogels is to increase the porosity and the pore mean size as R changes from pure TEOS to pure TMOS. The supercritical process increases the mass fractal dimension and shortens the fractality domain in the mesopore region. A secondary structure appearing in the micropore region of the aerogels can be described as a mass/surface fractal structure with correlated mass fractal dimension D_m ∼ 2.6 and surface fractal dimension D_s ∼ 2.3.     

Photoluminescence characterization of sol–gel prepared low density silica samples

By exciting with synchrotron radiation in the 4–10 eV range the emission properties of sol–gel synthesized porous silica at room temperature and at 8 K are investigated. The modifications of the ultraviolet emission in the range 3.7–4.2 eV excited at different energies (5.64, 6.20, 6.53, and 6.89 eV) support the hypothesis of the contribution of two emitting centers. In particular the two emissions are spectrally resolved when exciting at 5.64 eV and a blue shift of the emission peak is reported as the excitation energy increases. The analysis of the decay times indicates that the two centers are temporally resolved with the 5.64 eV excitation both at room temperature and at 8 K and allows to estimate lifetimes of about 3 and 18 ns. When exciting at 6.53 eV, the larger relative contribution of the 4.0 eV band does not allow to efficiently resolve the two decay times and the estimated life time of the 3.8 eV band is shortened.     

Structural evolutions of hydrothermally prepared mesostructured MCM-48 silica using differently manufactured amorphous silica powders

The hydrothermal synthesis of Si-MCM-48 mesoporous molecular sieves was carried out using a ternary SiO₂:CTAOH:H₂O system wherein differently manufactured amorphous silica powders such as fumed silica (FMDS), spray dried precipitated silica (SDPS) and flash dried precipitated silica (FDPS) were used as silica source materials. The changes in structural/textural properties were evaluated using powder XRD, N₂ adsorption-desorption and scanning electron microscopy techniques. Studies on the progressive development of MCM-48 mesophases revealed that, the reactivity of the silica source follow the trend: FMDS > SDPS > FDPS. MCM-48 synthesized using low cost FDPS has exhibited thicker pore walls but poorer orderness, while MCM-48 prepared from relatively expensive FMDS has thinner pore walls and more ordered structure. Moreover, the extent of contraction caused by calcinations, agglomerate size and structural stability were found to depend on the reactivity of the silica source used.     

Silica aerogels prepared via rapid supercritical extraction: Effect of process variables on aerogel properties

We have examined experimentally the effects of rapid supercritical extraction (RSCE) process variables and their resulting pressure and temperature characteristics on aerogel properties. We employ an RSCE process that uses a hydraulic hot press to seal and heat a contained mold until the aerogel precursors reach a supercritical state. After a short stabilization period the hot press restraining force is lowered and the supercritical fluid is allowed to escape, leaving behind an aerogel monolith. The entire process can be accomplished in fewer than 3 h. To control the process, we set the restraining force, the maximum temperature, the heating and cooling rates, the pressure release rate and the mold volume fill ratio (related to the amount of initial precursor material). To investigate the effects of these variables we made silica aerogels from a TMOS-based recipe. We varied the volume of precursor material from 10 to 15 mL (60-97% fill volume), the restraining force from 43 to 111 kN, the temperature heat rate from 0.7 to 4.2 °C/min, the maximum temperature from 288 to 371 °C and the pressure release rate from 0.23 to 0.66 MPa/min. The RSCE process is robust. We were able to make transparent, monolithic aerogels under almost all conditions with little effect on the resulting aerogel properties. Typical density measurements yielded values of approximately 0.065 g/mL (bulk) and 1.9 g/mL (skeletal). The samples were translucent and transmitted 70% of the light at 800 nm (for 5-mm thick samples). The BET surface areas ranged from 517 to 590 m²/g. Maximum temperature was the only variable found to have a significant effect on the aerogels’ properties. As the maximum temperature increased from 288 to 371 °C the surface area decreased from 560 to 395 m²/g and average pore diameter (BJH desorption) increased from 21 to 32 nm.     

The devitrification kinetics of silica powder heat-treated in different conditions

In the present paper, the devitrification kinetics of silica powder heat-treated in air and in nitrogen were investigated. The heat-treated powders were confirmed to partially crystallize into cristobalite by X-ray diffraction analysis. The devitrification kinetics data of silica powder fitted the Avrami equation very well. The measured value of n was ascertained to be 1.63 and 1.60 when the silica powder was heat-treated in air and in nitrogen, respectively, corresponding to activation energies of 408 kJ/mol and 529 kJ/mol, respectively. The effect of phenolic resin-derived carbon on crystallization of silica powder was also studied. By adding phenolic resin into silica powder, the devitrification of silica powder was fully restrained up to 1500 °C in flowing nitrogen. High concentrations of oxygen vacancies may retard the nucleation of cristobalite on the surface of silica powder. Phenolic resin-derived pyrolysis carbon restrained the nucleation of cristobalite, because it prevented the reactions of oxygen vacancies with H₂O and O₂ molecules.     

Production of CN(BΣ) state from dissociative excitation reaction of BrCN with microwave discharge flow of Ar

The mechanism of the dissociative excitation reaction of BrCN with the microwave discharge flow of Ar was investigated based on the CN(B²Σ⁺-X²Σ⁺) emission-spectroscopic and the electrostatic-probe measurements. By passing Ar and BrCN through P₂O₅, the contamination of H₂O molecules into the reaction region was reduced to ≈30%, being confirmed by monitoring the reduction of the OH(A²Σ⁺-X²Π) emission intensity. The variation of the CN(B²Σ⁺-X²Σ⁺) emission intensity on the pressure of Ar, P_Ar, of 0.1-0.3 Torr was compared with that of the density of electrons whose kinetic energy was lower than the ionization energy of BrCN, 11.9 eV. The dissociation of BrCN was found to proceed predominantly via the charge transfer from Ar⁺ followed by the BrCN⁺ − e⁻ recombination. When the contamination of H₂O molecules in the reaction region was not reduced, the dissociation via the energy transfer from metastable Ar atoms became significant. The present study shows that the contamination of H₂O molecules in the reaction system makes significant effect onto the gas-phase plasma process.     

Improvement in optical transmission of the ambient pressure dried hydrophobic nanostructured silica aerogels with mixed silylating agents

The experimental results on the preparation of transparent and hydrophobic silica aerogels based on ion exchanged sodium silicate (Na₂SiO₃) using mixed silylating agents of trimethylchlorosilane (TMCS), hexamethyldisiloxane (HMDSO) and hexamethyldisilazane (HMDZ) are reported. Hydrogels were prepared with ion exchanged Na₂Si0₃ of 1.10 specific gravity with 1 N ammonium hydroxide (NH₄OH). The resulted gels were exchanged with methanol solvent followed by silylation using HMDZ + HMDSO or TMCS + HMDZ or TMCS + HMDSO mixture in methanol and hexane and dried the gels at room temperature for 24 h, at 50 and 200 °C for 1 h each. It has been observed that the percentage of the silylating agent in the mixture, time interval of addition of one agent followed by another and volume of silylating mixture have an effect on density, % of optical transmission, % of porosity, porevolume, thermalconductivity and refractive index of the aerogels. Hydrophobicity of the aerogels was studied by contact angle measurements. The TMCS + HMDSO aerogels have been found more hydrophobic (contact angle > 150°) than the other aerogels. Further, aerogels have been characterized by pore size distribution, Fourier Transform Infra Red Spectroscopy (FTIR), Transmission Electron Microscopy (TEM) and thermogravimetric analysis and differential thermal analysis (TGA–DTA) techniques. It has been found that the weight increase is the highest (325%) for HMDSO + HMDZ aerogels and lowest (1.2%) for HMDSO + TMCS aerogels by keeping the aerogels in the atmosphere over a period of 18 months. Low density (0.042 g/cc) transparent (85%), low thermal conductive (0.047 W/m K), low refractive index (1.0088) and hydrophobic (152°) silica aerogels were obtained with equivolume TMCS + HMDSO mixture of 10 ml, time interval of addition of 12 h between the two reagents prior addition of TMCS followed by HMDSO for 24 h of silylation period. It was found from the TGA–DTA of the aerogels that hydrophobicity of the aerogels remained up to the temperature of 425 °C.     

Transparent SiO2 aerogels prepared by ambient pressure drying with ternary azeotropes as components of pore fluid

Transparent SiO₂ aerogels were prepared by two-step sol–gel processing followed by ambient pressure drying at temperatures from 70 to 250 °C. The wet gels were synthesized via acid–base catalysis using tetraethyl orthosilicate as a silica precursor and isopropanol as a solvent. Isopropanol was exchanged with n-butanol, and the gel surface was modified using a trimethylchlorosilane solution in n-butanol. Next, the solvent was exchanged in several steps with saturated hydrocarbon in order to obtain pore fluids containing azeotropic mixtures of water, n-butanol and a corresponding hydrocarbon (hexane, heptane, octane, nonane). Ambient pressure drying was performed in two steps, at the boiling points of the ternary azeotropes and hydrocarbons, respectively. In this way, transparent, crack-free aerogels of different shapes, with a specific surface area of 1000 m²/g, average pore diameter of ～40–55 Å and density in the range 0.4–0.57 g/cm³ were obtained.     

Fluorinated silica glass ablated with ArF excimer laser at low fluence

Amorphous SiO₂ (a-SiO₂) was formed by liquid-phase deposition (LPD) at room temperature. As a result of one shot of ArF excimer laser irradiation, LPD-formed a-SiO₂ shows a threshold fluence for ablation of below than 200 mJ/cm², which is much lower than the threshold fluence (∼1 J/cm²) of a-SiO₂ formed by thermal oxidation of silicon. Raman scattering spectroscopy revealed that two sharp lines at 495 cm⁻¹ and 606 cm⁻¹, respectively, labeled D₁ and D₂, had disappeared, and the main band at 430 cm⁻¹ was sharpened in LPD-formed a-SiO₂. It is presumed that the fluorine broke the silica network, relaxing the Si-O-Si bond angle and dramatically reducing the threshold energy for ablation of a-SiO₂.     

Preparation of amorphous composites with polymer-derived silicon nitride matrix reinforced by three-dimensional silica fiber

Perhydropolysilazane, a low viscosity preceramic polymer with good infiltration efficiency and high char yield, was used to prepare amorphous composites with polymer-derived silicon nitride matrix reinforced by three-dimensional silica fiber, and the mechanical properties and microstructures were investigated. The composites without fiber coating showed a typical brittle fracture behavior with a smooth fracture surface, and a flexural strength of just 33.5 MPa. While the composites with fiber coating exhibited a non-brittle fracture behavior with distinct fiber pull-out in the fracture surface, and a high flexural strength of 144.9 MPa. It was the controlled fiber/matrix interface by precoating treatment that contributed to the high mechanical property of the composites.     

Characterization of HF-catalyzed silica gels doped with Degussa P25 titanium dioxide

SiO₂/TiO₂ composites were synthesized by adding Degussa P25 TiO₂ to a liquid sol that was catalyzed by HNO₃ and HF acids. Various composites were synthesized by altering the mass loading of TiO₂ and concentration of HF added to the liquid sol before gelation. The resulting materials were characterized by SEM, nitrogen adsorption-desorption, streaming potential, XRD, diffuse reflectance and TiO₂ surface area analyses. Approximate characteristics include an isoelectric point of 3, TiO₂ particle size of 30 nm, and a band gap energy of 3.2 eV. Small variations in these properties were noted for the different composites. Physical characteristics were largely affected by HF concentration and TiO₂ loading. Nitrogen adsorption-desorption isotherms were type IV for all materials and exhibited trends of decreased pore volume with an increase in TiO₂ loading and an increase in pore diameter with increased HF concentration. Surface areas of the composites ranged from 167 to 630 m²/g. Available TiO₂ surface area of the composite was also dependent upon TiO₂ loading and increased as the mass composition of TiO₂ increased but was not largely affected by HF concentration.