Changing poisson’s ratio of mesoporous silica monoliths with high temperature treatment

The elastic moduli of mesoporous (fractal pore structure with a statistical pore size distribution with a maximum in the mesopore region) silica monoliths (silica aerogels) were measured in situ during calcination using the resonant beam technique. Above a temperature of approximately 573 K, a significant increase of the elastic moduli with increasing heat treatment temperature was observed, which was attributed to the rearrangement and completion of the network. Poisson’s ratio is close to zero up to this temperature and then increases to a positive value typical for isotropic bodies.     

Enhancing mechanical properties of silica aerogels

Low-density monolithic silica and hexylene-bridged polysilsesquioxane aerogels were chemical vapor deposition (CVD) treated with hexamethyldisilazane or hexachlorodisilane silylating agents producing TMS (trimethylsilane) or Si layers on the aerogel. Reinforcing the weak aerogels by controlled deposition process improved their compressive strength and preserved their properties characteristic of low-density aerogels. When the silica and hexylene-bridged polysilsesquioxane aerogels were CVD treated with hexamethyldisilazane, the compressive modulus more than doubled in some cases. However, when treating hexylene-bridged aerogels with hexachlorodisilane the compressive modulus increased six fold. Not only did CVD treatment of the aerogels improve the compressive modulus, but the low densities, high surface areas, high porosities, and the transparency of the aerogels were not significantly affected.     

Preparation, characterization and catalytic properties of singly and doubly titanium-modified mesoporous silica gel

A series of titanium-modified mesoporous silica gel have been synthesized using tetrabutyl titanate. The samples were characterized by nitrogen adsorption-desorption, FT-IR and Raman spectroscopy, as well as by solid state diffuse reflectance UV-VIS spectroscopy. Physicochemical characterization of the materials showed that Ti atoms were part of the framework of silica gel, and it was probably in a tetrahedral coordination for low Ti contents. The resulting titania modified the inner walls of the mesoporous silica gel after hydrolysis and calcination. Actually, the titanium precursor reacted and condensed with the active silanol groups on silica gel via Si-O-Ti bonds. In addition, the titanium-modified mesoporous silica gel showed distinct activity behavior in the catalytic oxidation of cyclohexene and styrene with hydrogen peroxide as oxidant.     

Adjusting the porous and structural properties of mesoporous silica by the addition of organic modifiers

The effects of the organic modifiers 2-cyanoethyltriethoxysilane and 3-aminopropyltriethoxysilane on the porous properties of silicates synthesised by co-condensation with tetraethyl orthosilicate were investigated. Materials were synthesised in aqueous solutions of cetyltrimethylammonium bromide or n-dodecylamine surfactants. Preparations using cetyltrimethylammonium bromide and sodium hydroxide gave MCM-48, with an average pore diameter of 25 Å, while addition of 10 mol% (of total silica) 2-cyanoethyltriethoxysilane improved the mesoporosity characteristics; the modified preparation gave a more intense X-ray diffraction pattern confirming a more ordered structure with a greater volume of regular mesopores. Disordered materials with pores 145 Å in diameter were formed using 2-cyanoethyltriethoxysilane modifier and ammonia as base. All preparations incorporating 3-aminopropyltriethoxysilane modifier were disordered and microporous. For silicates synthesised using n-dodecylamine surfactant, mesopores with diameter 118 Å were formed using 2-cyanoethyltriethoxysilane while preparations with 3-aminopropyltriethoxysilane and in the absence of a modifier were microporous. The particle sizes of the silicates displayed a clear correlation with the pore diameters: microporous silicates were 0.5–1 μm in particle diameter, MCM-48 phase (25/27 Å) were 1–2 μm, while relatively large mesoporous materials (>100 Å) had particle dimensions 10–100 μm.     

Photoluminescence characterization of aged and regenerated mesoporous silica

The investigation of the photoluminescence features of aged and regenerated mesoporous silica is reported. The emission spectrum of aged samples displays a blue band peaked at about 450 nm at room temperature with excitation channels at 250 and 200 nm. No UV emission band is detected. The regenerated samples recover the optical transparency of the samples, the vibrational properties in the 3000–3800 cm^? 1 but for the isolated silanols band and the UV-blue emission features. Indeed beside the blue band peaked around 450 nm a UV band centred at 340 nm is reported whose relative contribution depends on the excitation wavelength. The aging and regeneration processes are discussed in view of the attribution of the observed emission features to specific surface defects.     

Preparation and characterization of ordered mesoporous silica membrane

Hexagonal mesoporous silica (MCM-41) membranes were prepared at air-water interface by means of an interfacial silica-surfactant self-assembly process. The free-standing and oriented mesoporous silica membranes with pore size ≈2.9-3.8 nm were synthesized at room temperature in acidic media and were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM) observations. Small-angle X-ray diffraction (SAXRD) patterns of membranes clearly indicated that as-synthesized membranes were typical of MCM-41 materials with a periodic hexagonal structure with the channels parallel to the surface. SEM images showed that the as-synthesized membrane was continuous and crack-free. In this paper, some novel findings are reported.     

Atomic layer deposition of TiO2 on mesoporous silica

Ultra-thin layers of titanium dioxide are conformally grown within the pores of an ordered mesoporous silica, SBA-15, using atomic layer deposition, reducing the pore size from the original value of 67 Å to a final value of 32 Å. Analysis of the nitrogen isotherms indicated a conformal growth process in which both the internal surface area of the mesoporous material and the external surface was coated.     

Micron scale and nanoscale structure of mesoporous silica thin films

Ordered mesoporous silica thin films have been prepared on silicon substrates by spin-coating technique using poly(alkaline oxide) triblock copolymers EO₂₀PO₇₀EO₂₀ (P123) as structure-directing agent. The X-ray diffraction and transmission electron microscopy investigations show that the obtained mesoporous silica thin films have an ordered pore array structure in nanoscale. The atomic force microscopy analysis reveals that the obtained mesoporous silica thin films exhibit a tile arrangement structure in micron scale.     

Synthesis of cubic mesoporous silica and carbon using fly ash

A supernatant solution of silicate species extracted from coal fly ash in a power plant by alkali fusion was used under acidic conditions to prepare a mesoporous silica, SBA-16. SBA-16 was used as a template for the synthesis of a mesoporous carbon using sucrose as a carbon source. These mesoporous silica and carbon materials were characterized by XRD, N₂ adsorption-desorption, SEM, and TEM. Textural properties of the silica and carbon samples prepared using fly ash were found to be comparable to those prepared by pure chemicals, successfully demonstrating the feasibility of recycling fly ash for the synthesis of high quality porous materials.     

Rod-like nano-composite of inorganic nanowires encapsulated by mesoporous silica solid

A novel rod-like praseodymium-containing inorganic nanowire encapsulated by mesoporous silica, was synthesized via a self-assembly method. The specific surface area of the composite was 1198m²g^− 1. The nanowires with 4-5 nm in diameter and 100 nm in length were encapsulated at the center of mesoporous solid showed by TEM images. The quantum size effects of the sample can be noted. The controversial absorption band at 960 cm^− 1 in Fourier-transform infrared (FT-IR) spectra was proved to be not the evidence of the introduction of heteroatom. On the basis of the absorption spectra and select area electron diffraction (SEAD) pattern, the nano-composite was known as an amorphous phase containing praseodymium element, in which the praseodymium was trivalent. The absorption spectra indicated the 4f² electronic configuration of Pr³⁺ ions. Four energy bands were attributed to the transitions from the ground state ³H₄ to the excited levels ³P₂, ³P₁, ³P₀ and ¹D₂, respectively.     

Thermal properties of vitreous silica with He impurities

The specific heat and thermal conductivity of vitreous silica (Suprasil W) doped with He at 420°C and 200 bar has been measured at low temperatures (0.5 K to 8 K). While with respect to an undoped sample the specific heat shows an excess contribution which varies as T^1.7, no effect of doping on the thermal conductivity is observed. This shows that the coupling to phonons of the excitations introduced by He doping is weak compared to that of intrinsic low energy excitations common to glasses. The excess specific heat can be attributed to excitations of He atoms in cavities.     

Mechanical and thermal properties of SiO2–PMMA monoliths

Organic–inorganic hybrid monoliths of cross-linked polymethylmethacrylate (PMMA) and silica (SiO₂) were prepared by sol–gel, using tetraethoxysilane (TEOS) and methylmethacrylate (MMA) as precursors and 3-(trimethoxysilyl) propylmethacrylate (TMSPM) to make compatible the organic and inorganic components. Two types of monoliths were prepared, H1-type using a molar ratio composition of 16:1:4 for water:TEOS:ethanol and 1:0.1:0.1 for TEOS:TMSPM:MMA and H2-type using 6.3:1:2.52 for water:TEOS:ethanol and 1:0.25:0.25 for TEOS:TMSPM:MMA. Semi-transparent monoliths were obtained in both cases after the gelation–solidification and drying processes, which took about seven days. Thermal properties of the samples were obtained by applying thermal lens spectroscopy and their mechanical properties were measured by depth sensing indentation and Vickers microhardness. FTIR spectroscopy measurements were performed to complement the characterization. We found that the hardness of the hybrid monoliths have values between those of commercial PMMA and a sol–gel SiO₂ monolith. This result is a consequence of the reinforcement produced by the SiO₂ component in the organic–inorganic hybrid matrix. The thermal diffusivity of the hybrid monoliths shows an appreciable increasing in the hybrid system with respect to the pure SiO₂ monolith. Mechanical behavior of monoliths is strong influenced by the SiO₂–PMMA ratio or changing the water:TEOS:ethanol contents.     

Simulation of the microstructural evolution of a polymer crosslinked templated silica aerogel under high-strain-rate compression

Surfactant-templated mesoporous silica aerogels (or nanofoams) with their entire skeletal framework nanoencapsulated conformally by a thin polyurea layer are emerging as materials with high specific strength and high energy absorption. In this paper a modified split Hopkinson pressure bar was used to investigate their mechanical behavior under dynamic compression at high strain rates. The evolution of the mesoporous structure under such dynamic impact conditions was simulated using the Material Point Method (MPM). The material point model was generated from X-ray micro-computed tomography whereas each voxel was converted to a material point corresponding to the local skeletal density of the material. Simulation results agree well with the experimental data, indicating that the MPM can effectively model the compression of complex mesoporous structures. Simulations indicate a nearly uniform deformation at all three stages of compression: the elastic region, compaction and the final densification due to the low ratio of pore size to wall thickness and random distribution of the pores. Simulations have also indentified the function of the conformal polymer coating as a reinforcing factor, showing that different porosities, obtained by varying the skeletal wall thickness, affect the local stress distribution. Eventually, simulations confirm that the stress-strain behavior of aerogels under compression follows a power-law relationship with the initial bulk density, consistent with experimental results.     

Influence of synthesis temperature on the structural characteristics of mesoporous silica

The characteristics of mesoporous silica prepared at different temperatures and the behavior of this system relating to the microencapsulation of a model drug were investigated. The preparation of mesoporous materials was initiated with the dissolution of a surfactant in distilled water and strong acid medium. After this, tetraethyl orthosilicate was added under agitation. The mixture was heated for 24 h at the synthesis temperature (60 °C, 80 °C, 100 °C and 130 °C) under static conditions. The surfactant was removed by calcination, which was carried out by increasing the temperature to 550 °C for 5 h. Atenolol was used as a model drug to study the kinetics of drug delivery. It could be observed that aging materials at higher temperatures presents no microporosity, and this influences the control of the release of the model drug.     

Preparation and properties of silica films with higher-alkyl groups

Silica films with various types of alkyl groups were grown from the liquid phase, at room temperature, using alkyl tri-alkoxy silane compounds. From Fourier transform infrared (FTIR) absorption measurements, a majority of Si-alkyl bonds in the source molecules were found to remain in the grown film, while Si-alkoxy bonds were completely removed. Electrical and thermal properties have been measured comparatively for various films having dense alkyl groups. The films with the methyl group are promising for silicon production in ultra large-scale integrated circuits (Si-ULSIs) and the film having the vinyl group for non-heat-tolerant compound-semiconductor large-scale integrated circuits (LSIs).     

Synthesis of Pt-containing mesoporous silica using Pt precursor as a pore-forming agent

We synthesized Pt nanoparticle-containing mesoporous silica in a one-pot process using tetraammineplatinum(II) hydroxide (TPH) precursor as a pore-forming agent and silica nanospheres as a silica source. The TPH precursor was added into as-prepared colloidal silica sol with silica nanospheres (SN) of about 8 nm in particle diameter, to obtain the SN–TPH sol. During drying process of the SN–TPH sol, an amorphous SN–TPH nanocomposite was formed via hydrogen-bonding interaction between silanol groups and amine groups of the TPH precursor. The hydrogen-bonding interaction was confirmed by thermal gravimetry and differential thermal analysis (TG–DTA) profiles and Fourier transform infrared (FTIR) spectra. Using the TPH precursor as a pore-forming agent, incorporation of the Pt nanoparticles into the mesoporous silica can be simultaneously achieved with the synthesis of the mesoporous silica in a one-pot process. In addition, Pt nanoparticle size and pore diameter of the mesoporous Pt/silica were simultaneously controlled by simply varying the concentration of the TPH precursor. The pore diameter of the mesoporous silica was easily controlled from 3.2 nm to 6.5 nm with an increase in the TPH concentration.     

Synthesis of bulky mesoporous silica (FSM) by hydrothermal hot-pressing method

In this study, we successfully synthesized the bulk of dense mesoporous silica (FSM) bodies by a short-term hydrothermal hot-pressing (HHP) method. It was thought that these dense bodies were achieved by solution/precipitation mechanism during HHP. Bulk pieces with the dimension in the range of centimeters in diameter possessed a high surface area of over 1000 m²/g and sharp distribution of mesopores with an average diameter of approximately 2.4 nm. This successful synthesis of bulky mesoporous silica will expand the capabilities of application to various fields, for example, gas separation (CO₂ and H₂ etc.) and catalysis.     

Enhancement of structural stability of mesoporous silica via infiltration of SnCl4 vapor

Sn-infused MCM-41 was prepared using a pre-mixing method and two different vapor phase methods. The sample prepared by the pre-mixing method showed lower hydrothermal stability than pure silica MCM-41. MCM-41 prepared by vapor phase treatment with SnCl₄ before calcination showed higher structural stability in water and hexane at 423 K than the sample treated with SnCl₄ vapor after calcination. The pore size and pore volume of MCM-41 treated with SnCl₄ vapor before calcination were larger than those of pure silica MCM-41. With SnCl₄ vapor treatment after calcination, the SnCl₄ vapor must have reacted with silanol groups around the pore entrance and partly plugged the pore mouth of MCM-41. On the other hand, SnCl₄ also penetrated into the pore wall and uniformly dispersed into the silicate network. Thus, SnCl₄ vapor treatment before calcination was more effective in enhancing the structural stability in water and hexane.     

Fabrication of mesoporous polymer/silica hybrid using surfactant-mediated sol–gel method

A mesoporous polymer/silica hybrid was fabricated by a surfactant-mediated sol–gel method. Under our experimental conditions, acrylonitrile (AN) monomer was located at the exterior of micelles and the sol–gel reaction of tetraethoxyorthosilicate (TEOS) proceeded concurrently with the polymerization reaction of the AN monomer. In other words, the micelle/polyacrylonitrile/silica precursor was synthesized through the radical polymerization accompanied with a hydrolysis/condensation single reaction in a reaction system. This is a unique characteristic of our methodology, which embraces the concept of ‘micelle templating’. The pore diameter of the mesoporous polymer/silica hybrid could be tuned by varying the spacer length and concentration of surfactants. Furthermore, compared with conventional mesoporous carbons, the carbonized mesoporous polymer/silica hybrids displayed an enhanced electrical performance favorable for use as a supercapacitor.     

Acidity-dependent mesostructure transformation of highly ordered mesoporous silica materials during a two-step synthesis

Highly ordered mesoporous silica materials have been synthesized under mildly acidic conditions by templating with a nonionic triblock copolymer (Pluronic P104) in a two-step process. It was found that a transformation from the SBA-15 type 2-dimensional (2D) hexagonal channel mesostructure (p6mm symmetry) to the MSU-X type 3-dimensional (3D) worm-like mesostructure could be induced by varying the pH whilst keeping all other conditions constant. The transformation between two types of mesoporous silica materials can be attributed to the effect of varying proton concentration on the interaction between organic micelles and inorganic species. Both types of mesoporous materials have high surface areas, large pore volumes, thick pore walls, large mean pore sizes, and narrow pore size distribution.