Effect of ammonia treatment on laser-induced damage of nano-porous silica film

The sol-gel monolayer silica films on K9 glass substrates were prepared with the dip method, and then treated in saturated ammonia gas. The laser-induced damage threshold (LIDT) of silica films with and without ammonia treatment was measured. Properties of the films were analyzed by using Stanford photo-thermal solutions (SPTS), ellipsometry, atomic force microscopy (AFM), and optical microscopy to study the effect of ammonia treatment on laser-induced damage of sol-gel monolayer silica film under laser irradiation. The experimental results showed that compared with the as-grown silica film, the silica film with ammonia treatment had larger absorption and smaller porous ratio, and it had smaller LIDT. Considering the improved abrasion resistance of films with ammonia treatment, a trade-off is always needed between abrasion resistance and LIDT in practice.     

Effects of ultrasonic treatment on zeolite NaA synthesized from by-product silica

The synthesis of zeolite NaA from silica by-product was carried out in the presence of 20 kHz ultrasound at room temperature. Zeolites obtained in this type of synthesis were compared to zeolites obtained by performing conventional static syntheses under similar conditions. The sonication effects on zeolite NaA synthesis were characterized by phase identification, crystallinity etc. The effects of different parameters such as crystallization time and initial materials preparation methods on the crystallinity and morphology of the synthesized zeolites were investigated. The final products were characterized by XRD and FT-IR. It was possible to obtain crystalline zeolite NaA from by-product silica in the presence of ultrasound.     

Photoluminescence and growth mechanism of amorphous silica nanowires by vapor phase transport

Amorphous silica [SiO_x (1<x<2)] nanowires were fabricated on silicon substrate in an acidic environment by heating the mixture of ZnCl₂, and VO₂ powders at 1100 °C. The length of SiO_x nanowires ranges from micrometers to centimeters, with uniform diameters of 10–500 nm depending on substrate temperature. Room-temperature photoluminescence spectra of the SiO_x nanowires showed two strong luminescence peaks in the red and green region, respectively. The photoluminescence was suggested to originate from nonbridging oxygen hole center (red band), and hydrogen-related species in the structure of SiO_x (green band). The study on chemical reactions and growth of the SiO_x nanowires revealed the formation process of silica nanowires in acidic environment was closely related to the vapor–solid–liquid mechanism.     

Structure study of rare earth doped vitreous silica by molecular dynamics simulation

A series of erbium doped vitreous silica, with erbium concentration as low as 0.25 per cent up to 5 per cent, has been modeled, using molecular dynamics. It has been found that as the Er content decreases, the percentage of erbium ions in pairs remains almost constant until very low concentration, when pairing is the only clustering mechanism and those that are not in pairs are isolated.     

Fabrication of superhydrophobic cotton fabrics by silica hydrosol and hydrophobization

Superhydrophobic cotton fabrics were prepared by the incorporation of silica nanoparticles and subsequent hydrophobization with hexadecyltrimethoxysilane (HDTMS). The silica nanoparticles were synthesized via sol-gel reaction with methyl trimethoxy silane (MTMS) as the precursor in the presence of the base catalyst and surfactant in aqueous solution. As for the resulting products, characterization by particle size analyzer, scanning electron microscopy (SEM), scanning probe microscopy (SPM), X-ray photoelectron spectroscopy (XPS), and thermal gravimetric analysis (TGA) were performed respectively. The size of SiO₂ nanoparticles can be controlled by adjusting the catalyst and surfactant concentrations. The wettability of cotton textiles was evaluated by the water contact angle (WCA) and water shedding angle (WSA) measurements. The results showed that the treated cotton sample displayed remarkable water repellency with a WCA of 151.9° for a 5 μL water droplet and a WSA of 13° for a 15 μL water droplet.     

利用氟硅烷提高溶胶-凝胶SiO2增透膜的疏水性

 以正硅酸乙酯为前驱体，氨水为催化剂，采用溶胶 凝胶法制备了二氧化硅增透膜；通过自组装技术，用氟硅烷对膜层进行表面修饰，制得了疏水增透膜，克服了常规增透膜亲水的缺点。采用红外光谱、分光光度计、扫描探针显微镜和静滴接触角测量仪等测试手段分析了薄膜的特性。结果表明：疏水增透膜的峰值透光率为99.7％，疏水角为110°；氟硅烷自组装改性不影响二氧化硅增透膜的光学性能。     

Magnetic properties of Co-impregnated zeolites

The structure and magnetic properties of Co-containing zeolites prepared by wet impregnation were investigated. The samples were calcined and then reduced in flowing H₂. The samples studied have large saturation magnetization due to the presence of cubic Co particles over a wide range of sizes. The zero field cooling-field cooling curves show a sharp magnetization peak with a blocking temperature around 7 K followed by an exponential decay and two other peaks—of much lower amplitude—around 160 and 280 K. The low temperature peak is analyzed considering first, at T_crit, thermal relaxation toward equilibrium over an energy barrier, with increasing viscosity S with T. Above T_crit relaxation does not occur and viscosity abruptly goes to zero. The behavior of the smallest Co particles is unusual above the blocking temperature.     

Development of porous silica production by hydrothermal method

Abstract

A new process for porous silica production has been developed using a hydrothermal method. Hydrothermally synthesized calcium silicate was used as the starting material in this study, which was produced from a mixture of Ca(OH)₂ and amorphous silica (white carbon) under hydrothermal conditions of 140°C and 0.4 MPa, for 8 hours. The calcium silicate was subsequently treated with an acid solution, facilitating the leaching of Ca ions. After washing with pure water, the multant Ca²⁺ -free silica powder was allowed to dry. The Ca²⁺ -free silica powder was found to have an amorphous structure, with 0.9 ml/g pore volume, up to 610m²/g BET specific surface area, and an average 5 ～ 8 nm pore size. Our hydrothermal process is simple and low cost, and is anticipated to have numerous applications to the petrochemical industry.     

EPR investigation of two types of Syrian's natural zeolites

Two different samples of natural zeolite have been investigated by X-band electron paramagnetic resonance (EPR) spectroscopy. The observed EPR spectra are typical to those observed for Fe³⁺ and Mn²⁺ ions. The lines, related to the iron, are observed, respectively at g≈4.3 and g≈2. The observed six lines, at g≈2, are the hyperfine structure due to the Mn²⁺ ions. The simulation of the experimental EPR spectra suggests that both of the manganese and the iron are present in more one site. The temperature dependence of the EPR spectra has been also investigated. The nature of the different sites involved in the EPR absorption is discussed.     

Study on the silica hollow spheres by experiment and molecular simulation

This paper presents the synthesis, characterization and molecular simulation of the silica hollow spheres (SHSs). The SHSs have been prepared using a double-template method, in which the calcium carbonate nanoparticles (CaCO₃) serve as core templates and the cetyltrimethyl-ammonium bromide (CTAB) as wall structure-directing agents. The TEM, XRD, and nitrogen adsorption have been employed to characterize morphologies and structures of the SHSs. The experimental results indicate that the as-prepared sample has an average external diameter of about 85 nm and has occurrence of disordered mesopores in the walls. In the simulation, the SHSs have been modeled as cylindrical pore with pore size distribution according to the experimental data. A combined method of grand canonical Monte Carlo (GCMC) simulation and statistics integral equation (SIE) has been carried out to determine the pore size distribution (PSD) of the SHSs based on the experimental adsorption data of nitrogen at 77 K. The results show that the PSD simulated data are in a good agreement with the experiment, which means that the proposed model for the SHSs is reliable and the combined method of GCMC and SIE is powerful for evaluation of the PSD of the silica hollow spheres.     

The effects of heat treatment on microfluidic devices fabricated in silica glass by femtosecond lasers

We fabricated complex microfluidic devices in silica glass by water-assisted femtosecond laser ablation and subsequent heat treatment.The experimental results show that after heat treatment,the diameter of the microchannels is significantly reduced and the internal surface roughness is improved.The diameters of the fabricated microchannels can be modulated by changing the annealing temperature and the annealing time.During annealing,the temperature affects the diameter and shape of the protrusions in microfluidic devices very strongly,and these changes are mainly caused by uniform expansion and the action of surface tension.     

Preparation and optical properties of UV dye DMT-doped silica films

UV dye DMT-doped silica films were prepared by sol-gel process with dioxane as the cosolvent. Luminescence quenching was not observed even if the DMT concentration in the visibly transparent silica film is as high as 1.26×10⁻² M. The emission peaks centered at ∼375 nm for the films show red-shift of 35-45 nm, comparing with that of the cyclohexane solution of DMT. The fluorescence quantum efficiency of the films centered at ∼590 nm are larger than those at ∼375 nm.     

X-ray photoelectron spectroscopic analysis of the surface chemistry of silica nanowires

A thorough analysis of the surface chemistry of silica nanowires has been performed by X-ray photoelectron spectroscopy to investigate unexpected surface changes. Examination of the Si 2p, O 1s, and C 1s core level states before and after exposure of the nanowires to various liquid media showed that silica nanowires are capable of much higher surface hydroxyl concentrations than planar native oxides. It is further demonstrated that the nanowire surface hydroxyl concentration corresponds to the pH of the aqueous media to which the nanowires are exposed. Spectral feature changes due to water exposure similar to those observed for fibronectin binding suggests that fibronectin binding is competitively inhibited by slow changes in surface chemistry resulting from water exposure.     

Sonochemical effect and pore structure tuning of silica xerogel by ultrasonic irradiation of semi-solid hydrogel

Silica xerogels were prepared by the sol-gel method under ultrasonic irradiation, using tetraethylorthosilicate (TEOS) as the starting material. Hexamethyldisiloxane (HMDSO) was used as the hydrophobizing agent. When preparing silica xerogel, it is necessary to perform aging and hydrophobization to suppress shrinkage during ambient pressure drying, however, such treatments are time-consuming. In this study, the semi-solid hydrogel was irradiated with ultrasonic for the first time in order to accelerate aging and hydrophobic treatment, and the effect of ultrasonic frequency on structure was investigated. Firstly, ultrasonic irradiation was performed at frequencies of 100 kHz and 500 kHz, followed by hydrophobic treatment at a frequency of 500 kHz, in order to promote aging. The results identify optimum conditions for ultrasonic irradiation to promote aging and hydrophobization reactions, and it was found to be possible to prepare silica xerogels in less than 1/5 of the conventional time. The silica xerogels had a low density and the shrinkage was suppressed. In this study, it was found that ultrasonic irradiation of semi-solid hydrogel was very effective for promoting the reaction.     

Facile ultrasound-assisted grafting of silica gel by aminopropyltriethoxysilane for aldol condensation of furfural and acetone

This work focuses on the development of a simple method to prepare heterogeneous catalysts with tunable basicity and stability for aldol condensation of furfural and acetone. Silica gel was grafted by aminopropyltriethoxysilane (APTES) with 20, 30, 40 and 50 wt. % of APTES using probe-type ultrasonicator with a power of 130 W and a frequency of 20 kHz. The grafted samples were studied by XRD, SEM, N₂ sorption, FTIR, XPS, CHN and TG analysis, and CO₂-TPD. The sonication facilitated the bond formation between APTES and the silica gel with less pore blocking than the conventional grafting method. The basicity of the samples was tunable with the quantity of APTES loading. The grafted samples were active catalysts for aldol condensation between furfural and acetone at 60 °C. The catalyst with 30 wt. % APTES grafting (30APS-U) provided a nearly complete furfural conversion and high furfurylbutenone selectivity. The conversion and selectivity increased with time and reached the highest values at 24 h. Thus, the catalysts with tunable basicity prepared by ultrasound-assisted grafting of silica with various APTES amounts were effective in furfural valorization.     

Surface chemical modification of TEOS based silica aerogels synthesized by two step (acid-base) sol-gel process

The present paper describes the comparative studies on the hydrophobic and physical properties of the tetraethoxysilane (TEOS) based silica aerogels prepared by two step sol-gel process followed by supercritical drying. Silica alcogels were prepared by keeping the molar ratio of TEOS:methanol (MeOH):H₂O (acidic):H₂O (basic) constant at 1:33:3.5:3.5 with oxalic acid and ammonium hydroxide concentrations fixed at 0.001 and 1 M, respectively. In all, nine different co-precursors (CP) of the type R_nSiX_4 − n, have been used. The aerogels have been characterized by density, porosity, percentage of volume shrinkage, optical transmission, contact angle and thermal conductivity measurements. The surface chemical modification of silica aerogels was confirmed by the presence of CH and SiC peaks at 2900, 1450 and 840 cm⁻¹, respectively, from the Fourier transform-infrared spectroscopy (FT-IR). The microstructure of the aerogels was studied using transmission electron microscopy (TEM) and scanning electron microscopy (SEM) techniques. In addition to these studies, the stability of the hydrophobic aerogels against an organic impurity (methanol, in the present studies) in water has also been studied.     

Microstructure and magnetic properties of tubular cobalt–silica nanocomposites

Co-based (Co and Co₃O₄) nanoparticles were self-integrated into SiO₂ nanotubes with a methodology based on the use of a Co salt as a template structure for the formation of SiO₂ nanotubes. Within the confinement of tubular matrix of SiO₂, the nanofibres of cobalt precursor, i.e., [Co(NH₃)₆](HCO₃)(CO₃)·2H₂O, were treated in a H₂ atmosphere with different parameters. With a sufficient reduction on the cobalt precursor, sphere-like Co-based nanoparticles are obtained, being well aligned in the interior space of the SiO₂ nanotubes. With an insufficient reduction, platelet-like Co-based nanoparticles are formed, being arranged in a random manner inside the SiO₂ nanotubes. The sufficiently reduced Co–SiO₂ nanocomposite exhibits an open hysteresis loop in the low field region (<3 kOe) and a paramagnetic response in high field (>3 kOe) at 300 K. An observed wide separation between the zero-field-cooling (ZFC) and field-cooling (FC) curves over the whole temperature region has demonstrated a characteristic feature of ferromagnetism with a magnetically anisotropic barrier diverting the easy axis from the axis of the applied field. The predominant factor leading to this anisotropic potential barrier is attributed to the shape anisotropy native to the one-dimensional arrangement of Co-based nanoparticles within the tubular matrix, i.e. SiO₂ nanotubes.     

Preparation of silica nanowires using porous silicon as Si source

This very paper is focusing on the preparation of silica nano-wires via annealing porous silicon wafer at 1200 °C in H₂ atmosphere and without the assistant metal catalysts. X-ray diffraction, X-ray energy dispersion spectroscopy, scanning electron microscopy, high-resolution transmission electron microscopy and selected area diffraction technology have been employed for characterizing the structures, the morphology and the chemical components of the nano-wires prepared, respectively. It is found that the diameter and the length of the nano-wires were about 100 nm and tens micron, respectively. Meanwhile, it is also necessary to be pointed out that silica NWs only formed in the cracks of porous wafers, where the stress induced both by the electro-chemical etching procedure for the porous silicon preparation and nanowires growth procedure is believed to be lower than that at the center of the island. Therefore, a stress-driven mechanism for the NWs growth model is proposed to explain these findings.     

Preparation and atomic oxygen erosion resistance of silica film formed on silicon rubber by sol-gel method

Based on the characteristic that silicon coupling agents have the capability to develop ‘molecular bridge’ in the interface of organic materials and inorganic materials, silica films were prepared on the surface of flexible silicon rubber by sol-gel method and the optical transmittance of the sample before and after atomic oxygen irradiation was tested. The surface morphology and structure of silica films were investigated by scanning electronic microscope (SEM) and Fourier transformed infrared spectroscopy (FTIR). The results indicated that the silica sol could easily form a uniform thin film on the surface of silicon rubber pretreated by high concentration silicon coupling agents, and the inorganic silica films could combine with organic silicon rubber without obvious delamination on the interface.     

Reinforced silver-embedded silica matrix from the cheap silica source for the controlled release of silver ions

In this study, a reinforced silver-embedded silica matrix was designed by utilizing the interaction between the [AlO₄]⁻ tetrahedral and the Ag⁺ in sol-gel process using sodium silicate as a silica precursor. The Ag⁺ mole ratio in each sample was significantly varied to examine the influence of silver concentration on the properties of the final product. Aluminium ions were added to reinforce and improve the chemical durability of silver-embedded silica. A templated sample at Al/Ag = 1 atomic ratio was also synthesized to attempt a possibility of controlling porosity of the final product. Also, a sample neither embedded with silver nor templated was synthesized and characterized to serve as reference. The material at Al/Ag = 1 was found to have a desirable properties, compared to its counterparts, before and even after calcination up to 1000 °C. The results demonstrate that materials with desirable properties can be obtained by this unprecedented method while utilizing sodium silicate, which is relatively cheap, as a silica precursor. This may significantly boost the industrial production of the silver-embedded silicas for various applications.