Hydrophobic and physical properties of the ambient pressure dried silica aerogels with sodium silicate precursor using various surface modification agents

The experimental results on the synthesis and physical properties of the ambient pressure dried hydrophobic silica aerogels in the presence of various surface modification (silylating) agents are presented. The silica aerogels were prepared with 1.12 specific gravity ion exchanged sodium silicate solution, 1N ammonium hydroxide, solvent exchanged with ethanol and hexane, and surface modification with 20% silylating agent in hexane followed by drying the modified gel up to 200 °C. The molar ratio of sodium silicate, water, ammonium hydroxide and silylating agent was kept at 1:45:4.3 × 10⁻²:5, respectively. The physical properties of the aerogels such as density, % of porosity, pore volume, thermal conductivity and contact angle measurements were studied by using various mono, di and tri alkyl or aryl silylating agents (SAs). The tri alkyl silylating agents produced low % of volume shrinkage (2%), low density (0.06 g/cm³), low refractive index (1.011), more pore volume (16.15cm³/g), high percentage of porosity (96.9%) and hydrophobic (contact angle >150°) silica aerogels. It was found from the Fourier transform infrared spectroscopic (FTIR) studies of the aerogels that the intensity of the bands related to the SiC and CH are more and the SiOH and OH are less with the tri than mono and di alkyl SAs. It was found from the TGA-DTA studies of the aerogels with increase in temperature above 325 °C, the % of weight decrease in TGA and exothermic peak in DTA are more with tri than the mono and di alkyl SAs. The SEM studies of the aerogels showed the large pore and particle sizes in the silica network with the tri alkyl SAs. The % of optical transmission of the aerogels is less with the tri alkyl SAs than the mono and di alkyl SAs. It was found from the contact angle and water adsorption studies that the hydrophobicity of the silica aerogel is more with tri alkyl than the di and mono alkyl silylating agents.     

Z箍缩准球形负载用TAC气凝胶的制备与表征

以三醋酸纤维素(TAC)为原料,并利用模具成型与溶胶凝胶方法,成功制备了Z箍缩准球形负载用球形及椭球形超低密度TAC气凝胶靶材料。研究了TAC溶胶凝胶化过程中光透过率随温度的变化,确定了球形与椭球形TAC气凝胶模具成型最佳凝胶化温度控制范围。TAC气凝胶微结构的扫描电子显微镜表征结果表明,该气凝胶材料结构为20~40nm的纤维丝交错形成具有纳米孔洞的三维网络微结构;TAC气凝胶的热分析结果表明,TAC气凝胶的热分解性能与其原料接近,热分解起始温度约为320℃。目前该材料已成功应用于Z箍缩准球形负载物理实验中。     

低密度SiO2气凝胶的结构与吸附特性研究

 低密度SiO₂气凝胶是一种新型纳米多孔材料,它不仅可作为惯性约束聚变的低温冷冻靶,还可作为HTO蒸汽的吸附剂用于放射性物质的环境监测。用SEM、TEM、BET、孔径分布等测试方法对低密度SiO₂气凝胶的微结构进行了研究;分别以水和苯作为吸附介质, 用吸附天平对其吸附特性进行了测试,并用BET吸附理论对其吸附结果进行了解释。     

Visible,near-infrared and infrared optical properties of silica aerogels

Silica aerogel is an excellent thermal insulation material with a low thermal conductivity and a high porosity and has attracted great concern in applications. This paper was to experimentally investigate the optical properties of optically thick silica aerogel in the visible, near-infrared and infrared spectrum region. The fiber-loaded silica aerogel sample was prepared through sol–gel technique and supercritical drying process. Silica fibers were added into the aerogel during the preparation procedure to strength the skeleton of aerogel. As a comparison with the fiber-load silica aerogel, a silica fiber composite sample with the same chemical component and different physical structure was also prepared. A simplified two-flux model neglecting the boundary effect was used to describe the radiation propagation characteristics inside the samples. The spectral normal-hemispherical reflectances, transmittances, and normal emittances of silica aerogel and silica fiber samples were measured and compared in the wavelengths of 0.38–15 μm. Then the spectral optical constants of samples were determined using the experimental data. The spectral absorption and scattering coefficients of silica aerogel were within (0.01 cm⁻¹, 31.0 cm⁻¹) and (1.4 cm⁻¹, 25.8 cm⁻¹). The results showed that the spectrum region where the scattering coefficient is low usually corresponds to a high absorption coefficient. In addition, the total radiation properties of samples were predicted at high temperatures. The analysis of optical properties of silica aerogel is necessary to provide valuable data in applications.     

High specific surface area TEOS-based aerogels with large pore volume prepared at an ambient pressure

The experimental results on the synthesis of tetraethoxysilane (TEOS)-based silica aerogel with high specific surface area and large pore volume, via ambient pressure drying (APD) route, are reported. The silica aerogels were prepared by the acid-base sol-gel polymerization of TEOS precursor followed by the drying of the alcogels at an ambient pressure. The solvent present in the alcogel (i.e. ethanol) was replaced by a non-polar solvent such as hexane prior to the surface modification step. In order to minimize the drying shrinkage, the surface of the gels was modified using trimethylchlorosilane (TMCS) before the APD. The FTIR spectra of the surface modified aerogels showed Si-CH₃ peaks at 2965 and 850 cm⁻¹. The effect of the base catalyst (NH₄OH) addition to the sol, at different time intervals (T), on the physical and textural properties of the resulting aerogels has been investigated. It has been observed that the surface area and the cumulative pore volume of the aerogels enhanced considerably from 819 to 1108 m² g⁻¹ and 2.65 to 4.7 cm³ g⁻¹, respectively with an increase in the T value from 6 to 48 h. Silica aerogels with very low bulk density (0.06 g cm⁻³), extremely high specific surface area (1108 m² g⁻¹) and large cumulative pore volume (4.7 cm³ g⁻¹) could be synthesized by drying the alcogels at the ambient pressure. The aerogels were mesoporous solids with the average pore size ranging from 12 to 17 nm. The results have been discussed by taking into consideration the hydrolysis and condensation reactions during the sol-gel polymerization of the TEOS precursor.     

Electrical and infrared dielectrical properties of silica aerogels and of silica-aerogel-based composites

In this contribution we have studied the key electrical parameters of silica aerogels and of silica-aerogel-based composites, namely the dielectric constants , the dielectric losses tan (at 1 kHz), and the breakdown fields E _b (at 50 Hz). For low-density bulk silica aerogels we find =1.25 and tan =0.0005. E _b is about 500 kV/cm in quasi-homogeneous fields, and of the order of MV/cm in strongly inhomogeneous fields. The dielectric constants of partially densified aerogels increase linearly with density; their dielectric losses are relatively large and their breakdown fields are comparativiely low. The same results are found for aerogels in the form of settled materials, i.e. aerogel granules and powders in air. Acrylate-based aerogel composites with volume fractions larger than 70% have low dielectric constants but their losses are at least 10 times higher than those of low-density aerogels. These materials sustain high local fields in the MV/cm region, while in quasihomogeneous fields, breakdown occurs at about 100 kV/cm. Based on the present results and the interplay with other physical properties (low mechanical resistance, low thermal conductivity, adsorption of water, etc.), silica aerogels and silica aerogel-acrylate-based composites are predicted to have a low potential for electrical insulation.     

改性SiO2气凝胶制备及其在ICF实验中的应用

 以正硅酸乙酯（TEOS）为前驱体，采用酸碱两步催化法制备了SiO₂醇凝胶。醇凝胶分别经过TEOS母液、甲基三乙氧基硅烷（MTEOS）处理后，以六甲基二硅胺烷（HMDSA）为疏水改性试剂，制备了改性SiO₂醇凝胶，醇凝胶经溶剂交换后以CO₂作为干燥介质，采用超临界干燥法制备了密度在30～100 mg/cm³的SiO₂气凝胶。用傅里叶变换红外光谱仪（FTIR）对疏水性SiO₂气凝胶进行了研究。研究结果表明,经过改性的气凝胶在潮湿环境中具有极好的尺寸稳定性和疏水性。采用精密车床加工得到了满足惯性约束聚变（ICF）物理试验要求的微柱。     

Effect of different trimethyl silylating agents on the hydrophobic and physical properties of silica aerogels

An essential feature of the ambient pressure dried aerogel manufacturing process is the end-capping of the reactive silanol groups in the silica wet gel. In this report, we have presented the effect of two different trimethyl silylating agents viz. trimethylchlorosilane (TMCS) and hexamethyldisilazane (HMDZ) on the hydrophobic and physical properties of ambient pressure dried silica aerogels. The hydrogels were prepared by sol-gel processing of sodium silicate precursor (Na₂SiO₃) in the presence of acetic acid catalyst followed by vapour passing treatment and different solvent exchanging steps. The silylating agent in hexane was used for end-capping of the silanols present on the silica surface of the gel. To study silylation behavior silylating agent/Na₂SiO₃ molar ratio was varied from 2.4 to 5.6. The aerogels have been characterized by density, % of volume shrinkage, porosity, % of optical transmission, Fourier Transform Infrared Spectroscopy (FTIR), Scanning Electron Microscopy (SEM), Thermo-gravimetric and Differential Thermal Analysis (TG-DTA) and contact angle measurements.     

浸渍过程对纳米纤维素/二氧化硅复合气凝胶结构与性能研究

纳米纤维素(CNF)气凝胶兼具传统气凝胶的优异特性和自身优良的生物相容性和可降解性,在很多领域应用前景广阔。然而纤维素自身的超亲水性严重限制了其更广泛的应用,为改善纤维素气凝胶的亲水性能,提高其综合应用性能,采用简单浸渍法在纤维素气凝胶基体中引入二氧化硅(SiO₂)颗粒制备纳米纤维素/二氧化硅复合气凝胶,利用傅里叶红外光谱仪(FTIR)分析纤维素气凝胶和复合气凝胶的化学结构;用扫描电镜(SEM)观察气凝胶的微观结构;测定气凝胶的物理、力学性能和接触角。结果表明,复合气凝胶在3 340 cm-1处-OH吸收峰较纤维素气凝胶均有所减弱,表明SiO₂的引入促使Si-OH形成,也降低了气凝胶的亲水性,同时有Si-CH₃和Si-O-Si吸收振动峰出现,表明三甲基氯硅烷(TMCS)的改性作用以及纤维素与SiO₂颗粒之间形成稳定化学键连接。浸渍时间影响硅含量,进而影响气凝胶的密度、比表面积和孔隙率。当浸渍时间为10 min时制备的复合气凝胶性能较好,其微观结构分布均匀,具有疏水性能,接触角可达152°,同时气凝胶仍具有较好的力学性能和较低密度,其压缩模量和压缩性能分别为5.91和1.38 MPa,密度为0.1 g·cm-3。     

A molecular model of adsorption in a dilute semiflexible porous network

A Monte Carlo simulation study has been made of adsorption and desorption of a gas in a semiflexible porous network with a porosity of over 95%, which is comparable with that of silica aerogels. Although dilute, the network has substantial effects on the properties of confined fluids. Network flexibility is shown to make a significant difference to both the adsorption/desorption isotherms and the fluid phase coexistence when compared with the case where the network is rigid. For one of the systems studied the solid volume changes by as much as 30% during desorption. This is qualitatively similar to an effect seen in nitrogen adsorption/desorption in some silica aerogels.     

Effect of drying technique on the physicochemical properties of sodium silicate-based mesoporous precipitated silica

The conventional drying (oven drying) method used for the preparation of precipitated mesoporous silica with low surface area (>300 m²/g) and small pore volume is often associated with a high production cost and a time consuming process. Therefore, the main goal of this study was to develop a cost-effective and fast drying process for the production of precipitated mesoporous silica using inexpensive industrial grade sodium silicate and spray drying of the precipitated wet-gel silica slurry. The precipitated wet-gel silica slurry was prepared from an aqueous sodium silicate solution through the drop-wise addition of sulfuric acid. Mesoporous precipitated silica powder was prepared by drying the wet-gel slurry with different drying techniques. The effects of the oven drying (OD), microwave drying (MD), and spray drying (SD) techniques on the physical (oil, water absorption, and tapping density), and textural properties (specific BET surface area, pore volume, pore size, and % porosity) of the precipitated mesoporous silica powder were studied. The dried precipitated mesoporous silica powders were characterized with field-emission scanning electron microscopy; Brunauer, Emmett and Teller and BJH nitrogen gas adsorption/desorption methods; Fourier-transform infrared spectroscopy; thermogravimetric and differential analysis; N₂ physisorption isotherm; pore size distribution and particle size analysis. There was a significant effect of drying technique on the textural properties, such as specific surface area, pore size distribution and cumulative pore volume of the mesoporous silica powder. Additionally, the effect of the microwave-drying period on the physicochemical properties of the precipitated mesoporous silica powder was investigated and discussed.     

超低密度SiO2气凝胶的制备及成型研究

 以正硅酸乙酯(TEOS)为硅源，采用酸碱二步催化溶胶-凝胶法，结合超临界干燥技术制备了超低密度SiO₂气凝胶,最低密度为3.4 mg/cm³；进一步结合成型工艺，在解决了模具设计和脱模技术后制备了具有不同密度的柱状和微型套筒样品，密度10～50 mg/cm³。研究了水、催化剂、稀释剂对二步溶胶-凝胶过程的影响，获得了制备低密度SiO₂气凝胶的最佳条件。利用扫描电镜、孔径分布及比表面积测试仪等对SiO₂气凝胶微结构进行了研究。结果表明，获得的超低密度SiO₂气凝胶具有较好的纳米网络，平均孔径18.9 nm，还具有高比表面积898 9 m²/g。     

低密度Cu掺杂SiO_2复合气凝胶的制备及表征

分别以正硅酸甲酯、醋酸铜为硅源和铜源,通过溶胶凝胶法及CO2超临界干燥技术制备了一系列Cu掺杂SiO2复合气凝胶。采用红外谱仪(FTIR)、扫描电镜(SEM)、X射线能谱仪(EDS)、比表面积和孔隙度分析仪(BET)、动态热机械分析仪(DMA)对样品进行了表征。结果表明随着铜含量的增加,复合气凝胶密度增加,比表面积降低,平均孔径增加,实际掺杂比与理论掺杂比对应增加。该复合气凝胶具有三维网状结构,密度低(40mg/cm3),比表面积高(390m2/g),成型性较好,有望应用于惯性约束聚变(ICF)实验。     

掺杂C60的SiO2气凝胶的制备及荧光特性研究

利用“化学掺杂”方法，制备掺杂C₆₀-SiO₂气凝胶，对掺杂C₆₀-SiO₂气凝胶的红外吸收光谱、飞行时间质谱的测试表明C₆₀分子被成功地掺入SiO₂气凝胶中．室温条件下，在Ar⁺激光（488nm）激发下，观察到掺杂C₆₀-SiO₂气凝胶有很强的可见发光现象，发光峰位较纯C₆₀发光明显蓝移 关键词：     

The sol-gel glass transformation of silica

Abstract

Large monolithic xerogel silica glasses were successfully made from tetramethyl-orthosilicate and distilled water using the combination of an acidic drying control chemical additive (DCCA) and a specially designed drying chamber. The acidic DCCA increases the gel strength by formation of a fibrillar ultrastructure, and the drying chamber reduces the catastrophic capillary forces inside the wet gel body.

Partially densified monolithic gels up to 850°C were routinely made for physical property tests and compared to commercial fused silicas. Although the mechanical properties of the porous gel-silica monoliths such as microhardness, Young's modulus, toughness, flexural strength, density are relatively lower than fused silica, the optically transparent porous gel silica has a UV cut-off ranging from 250–300 nm. Such a porous gel with excellent optical transmission and a highly uniform pore radius of 10–50 Å offers a unique, chemically stable matrix for impregnation with a second phase of optically active organic or inorganic compounds.

The processing and properties of Types I and II fused quartz optics and Types III and IV synthetic fused silica optics are compared with the new organometallic sol-gel derived gel-silica optics. Fully dehydrated and densified gel-silica has excellent transmission from 165 nm to 4400 nm with no OH absorption peaks. This optical transmission is equivalent to the best Type IV fused silica. The other physical properties and structural characteristics of the dehydrated dense gel-silica are similar to fused quartz and fused silica. However, the dense gel-silica has a lower coefficient of thermal expansion of 2.0 × 10^?7 cm/cm compared with 5.5 × 10^?7 cm/cm for standard vitreous silicas. The CTE value is temperature independent from 80 K to 500 K. Sol-gel silica optics can be made as complex shapes by casting of the sol into inexpensive plastic molds.     

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.     

Imperviousness of the hydrophobic silica aerogels against various solvents and acids

The experimental results on the imperviousness of the silica aerogels against various organic solvents and acids, are reported. Various types of hydrophobic silica aerogels were prepared using methyltrimethoxysilane (MTMS); tetraethoxysilane (TEOS) with ethyltriethoxysilane (ETES) and phenyltriethoxysilane (PTES) as co-precursors. The organic solvents used were: methanol, ethanol and acetone, and the acids used were: hydrochloric acid (HCl), nitric acid (HNO₃) and sulphuric acid (H₂SO₄). The imperviousness of the aerogels against these solvents and acids were tested with the variation of the percentage of organic solvents and acids in water from 10 to 100% and was characterized by the contact angle measurements. It was observed that in all the cases, the contact angle decreased with an increase in the percentage of solvent in water. While there was no absorption of the solvent up to 20% in water by the ETES and PTES modified aerogels, the MTMS-based aerogels showed the imperviousness up to 60% of the solvent in water. The MTMS aerogels were also impervious against all the three acids up to 100%, while the ETES and PTES modified aerogels could withstand only up to 80% of acids in water.     

Sol–gel synthesis and luminescent properties of SiO2/Zn2SiO4 and SiO2/Zn2SiO4:V composite materials

Undoped and vanadium-doped Zn₂SiO₄ particles embedded in silica host matrix were prepared by a simple solid-phase reaction after the incorporation of ZnO and ZnO:V nanoparticles, respectively, in silica monolith using the sol–gel method with supercritical drying of ethyl alcohol in two steps. After supercritical drying and annealing in the temperature range between 1423 and 1473 K in an air atmosphere, the photoluminescence (PL) measurements show a band centered at about 760 nm in the case of non-doped Zn₂SiO₄ which is attributed to energy transfer from Zn₂SiO₄ particles to NBOHs interface defects. In the case of vanadium doped Zn₂SiO₄, the PL reveals a band centered at about 540 nm attributed to the vanadium in the interfaces between Zn₂SiO₄ particles and SiO₂ host matrix. Photoluminescence excitation (PLE) measurements show different origins of the emission bands. The PLE band (～240–350 nm) may be understood as an energy transfer process from O^2? to V⁵⁺ which occurs intrinsically in the vanadyl group.     

种子法制备金掺杂二氧化硅气凝胶

 采用羟胺种子法合成了金掺杂二氧化硅气凝胶。采用紫外 可见光分光光度计研究了还原过程中体系的变化情况。使用透射电镜（TEM）研究了气凝胶的微观结构，气凝胶的比表面积和孔径分布由BET-BJH方法测试。结果表明通过种子法可以制备金掺杂质量分数0.01%~1.00%，密度25～50 mg／cm³，比表面积达800 m²/g以上的SiO₂气凝胶样品。     

Mössbauer studies on ultraporous Fe-Oxide/SiO2 aerogel

Magnetic aerogels with very low volume density of ～0.2 g/cm³ were prepared by sol-gel method and supercritical drying. The resulting materials were monolithic and displayed high surface area. By X-ray diffraction and Mössbauer spectroscopy the crystalline phase formed inside the mesopores of the SiO₂ matrix was identified as a spinel iron oxide. Comparison of the magnetic measurements with Mössbauer spectra at various temperatures contributed to the elucidation of the magnetic state of this nanocomposite system with restricted magnetic interactions, in particular its transition to a superparamagnetic state.