Elastic modulus prediction based on thermal conductivity for silica aerogels and fiber reinforced composites

The speed of sound is a critical parameter in the test of mechanical and thermal properties. In this work, we proposed a testing method to obtain the elastic modulus of silica aerogel from the sound speed formulas. The solid thermal conductivity of the silica aerogel is experimentally measured for predicting the sound speeds, and then the elastic modulus is calculated based on the elasticity sound speed model. The experimental data of the solid thermal conductivity of silica aerogels with different densities are employed and the obtained elastic modulus is fitted as a power-law exponential function of the density. Two existing sound speed models and three groups of available experimental data are also employed to validate the present fitting relation, and good agreement is obtained for the silica aerogel in the density range of 150–350 kg/m³. The fitting formula can also be extended to estimate the elastic modulus of the glass fiber-reinforced silica aerogel composite. The results show that the elastic modulus of the aerogel composite is sensitive to the glass fiber volume fraction, while the thermal conductivity is weakly dependent on the glass fiber volume fraction at room temperature in the studied range of fiber volume fraction.     

A novel preparation of superhydrophobic silica aerogels via the combustion drying method

Silica aerogels with prominent physical, thermal, optical, and acoustic properties are considered to be highly promising materials. However, owing to the high cost and the complex production processes associated with existing drying technologies, the application of silica aerogels is limited in many fields. In this study, a novel combustion drying method (CDM) was successfully used in the synthesis of superhydrophobic silica aerogels for the first time. It was confirmed that silica aerogel prepared by CDM has a typical aerogel structure with low density, high porosity, high specific surface area, high total pore volume, superhydrophobicity and high thermal stability. Compared with supercritical fluid drying, freeze drying and ambient pressure drying, CDM possesses significant advantages in the drying efficiency and low-cost production due to its active drying mode. Finally, the mechanism of the combustion drying method is proposed based on the combustion of organic solvents. The results will be meaningful for the design and production of aerogel materials in the future.     

Improvement of thermal insulation performance of silica aerogels by Al2O3 powders doping

Silica aerogel is deemed as a kind of high-performance thermal insulation materials. However, the existence of macropores in the structure is always ignored in the research and application of aerogels. Thus the thermal insulation performance of silica aerogels could be further improved if the macropores are reduced. In this work, nano-sized Al₂O₃ powders are explored as nano fillers to reduce the macropore volume fraction in silica aerogels by filling the big voids among the silica aggregates, and further lower the thermal conductivity. The experimental results showed that the macropore volume fraction (${\mathrm{V}}_{\mathrm{MAC}}$) was dramatically reduced from 63.05% to 23.12% with the addition of Al₂O₃ powders ranging from 0.0 g to 1.0 g. This trend was also verified by the variation of (V_T*-V_BET) and (V_BET/V_T*). Accordingly, the thermal insulation performance was improved due to the reduction of macropores in aerogels. The lowest thermal conductivity of Al₂O₃-doped aerogels reached 7.41 mW/(m K) in contrast with that of pure silica aerogels (9.00 mW/(m K)), which was a significant decline for aerogel-based materials due to the gaseous heat transfer being further weakened. Moreover, the increment of thermal conductivity from 7.41 to 9.71 mW/(m K) with the Al₂O₃ powders increasing could be attributed to the enhancement of solid heat transfer in the system. The variation of experimental thermal conductivity was in good agreement with the result of theoretical calculation. This study proposed an innovative idea to improve the thermal insulation of aerogel under ambient conditions.     

二氧化硅气凝胶的气相热导率模型分析

气凝胶是一种超级隔热材料,具有极低的整体热导率。气凝胶的纳米多孔网络结构极大限制了气体分子热运动,使得气凝胶中的气相热导率低于自由气体的气相热导率。本文介绍并讨论了气凝胶气相热导率的基本理论和模型,考察了孔径尺度和气凝胶固相骨架对气相热导率的影响。结果表明,气凝胶气相热导率随气压和孔径的减小而迅速降低,随气凝胶密度的增大而降低。当压力极低时,气凝胶的气相热导率远低于常压下大空间的静止空气。气凝胶纳米固体网格对气相热导率存在重要影响,在(0.01～100)×10⁵ Pa的压力范围内影响尤其显著。     

View cell investigation of silica aerogels during supercritical drying: Analysis of size variation and mass transfer mechanisms

We report the synthesis and supercritical drying of silica aerogels made via a sol–gel process. Tetramethylortosilicate has been used as precursor. Hydrolysis and poly-condensation steps were followed by carbon dioxide supercritical drying (T = 45 °C; P = 10.5 MPa). The complete supercritical drying step was video recorded in order to study the evolution of the size of the gels, concluding that a noticeable shrinkage only takes place during the decompression of CO₂ at the end of the drying process, being the total shrinkage of 3–4%. The mass transfer mechanisms during drying have also been studied through analysis of the evolution transparency of the aerogels along the supercritical drying process. The mass transfer processing during drying was observed to be dominated by convection in the earliest stages, where a direct relationship between drying rate and CO₂ flow were found. In the later stages, diffusion of the remaining organic solvent through the alcogel determined the mass transfer process.     

Facile synthesis of hydrophobic,thermally stable,and insulative organically modified silica aerogels using co-precursor method

Silica aerogels have low density and high specific surface area, but there are restrictions regarding their durability and commercialization owing to their fragile nature and the strong moisture absorbing behavior of the siloxane network. To overcome these restrictions, this study evaluated hybrid organically modified silica (ORMOSIL) aerogels by employing 3-(trimethoxysilylpropyl) methacrylate (TMSPM) in tetraethyl orthosilicate (TEOS) through a two-step sol-gel co-precursor method. The methacrylate organic groups were incorporated into the silica networks via reactions between the Si-OH moieties in silica aerogels, resulting in ORMOSIL aerogels. The properties of the ORMOSIL aerogels were strongly affected by the amount of TMSPM co-precursor. The highest concentration of TMSPM (30 wt%) resulted in ORMOSIL aerogels with improved characteristics when compared with the pristine TEOS-based silica aerogels, such as hardness (0.15 GPa), Young's modulus (1.26 GPa), low thermal conductivity (0.038 W/m K), high water contact angle (140°), and high thermal stability (350 °C).     

Requirements of organic gels for a successful ambient pressure drying preparation of carbon aerogels

In this paper, we investigated the requirements of organic gels for a successful ambient pressure drying by analyzing the role of the strength, the pore size and the surfactant of organic gels in decreasing the drying shrinkage of organic aerogels. Experimental results showed the effect of the decrease of the surface tension, resulting from the surfactant, on the drying shrinkage was very small and negligible. The drying shrinkage depended strongly on the strength and the pore size. Subsequently, the respective role of the strength and the pore size was evaluated. It can be found that the strength plays a greater role than the pore size.     

二氧化硅气凝胶常压干燥工艺的研究进展

二氧化硅气凝胶因具有低密度、高比表面积、稳定的物理化学性质等特性在吸附分离、隔热保温等领域表现出巨大的应用潜力。但长耗时、高成本的制备工艺限制了它的发展,尤其是湿凝胶向气凝胶转变的干燥工艺。本文介绍了二氧化硅气凝胶在常压干燥的过程中面临的主要难点及解决方法,虽然常压干燥方法工艺简单、过程安全、对设备要求低且可连续制备,成为近年来的研究热点,但也存在制备周期长、体积收缩大、需要消耗大量有机溶剂和改性剂等不足。文中从凝胶基体增强与优化、降低毛细管力与减少不可逆收缩两种角度,介绍了二氧化硅气凝胶常压干燥的改进方法及其发展现状,分析归纳了不同改进方法的优缺点,总结了二氧化硅气凝胶常压干燥目前面临的技术挑战。并且,立足于目前二氧化硅气凝胶基体增强和表面改性技术发展的趋势,对今后二氧化硅气凝胶常压干燥过程中结构可控、成本降低以及产品多功能化的发展路线进行了展望。     

Mechanical and dielectric properties of polyimide/silica nanocomposite films

Polyimide/silica (PI/silica) nanocomposite films were successfully prepared via in situ dispersive polymerisation and thermal imidisation. In order to obtain homogeneous nanoscale dispersibility and good compatibility with the PI matrix, hydrophobic aerosil was selected as the nanosilica precursor. 4,4-Bis(3-aminophenoxy)biphenyl (4,3-BAPOBP) was used as diamine to improve the processability of PI. The PI/silica nanocomposite films were characterised using Fourier transform infrared spectroscopy, scanning electron microscopy and differential scanning calorimetry. The mechanical and dielectric properties of the films were also measured. The results demonstrate that the tensile strength and breakdown strength of films can be markedly improved by the addition of appropriate amounts of silica to the PI matrix. At a silica content of 4.0?wt-%, the tensile strength and the breakdown strength of the films increased by 21 and 13%, respectively, compared with the neat PI. Thus, it is feasible to use nanosilica to improve the properties of PI.     

The unusually formation of porous silica nano-stalactite structure by high temperature heat treatment of SiO2 aerogel synthesized from rice hull

The SiO₂ aerogel has attracted the attention of many researchers in recent years in terms of energy saving due to its properties such as very low density, high porosity, and superior insulation. The primary purpose of this study was to synthesize SiO₂ aerogel. For this purpose, the sodium silicate obtained from rice hull ash was used as pre-initiator and dried at ambient pressure and SiO₂ aerogel was synthesized. BET surface area of the obtained SiO₂ aerogel was found as 241 m²/g. The difference of this study is the structures obtained after this stage. After obtaining SiO₂ aerogel, it was subjected to heat treatment at a high temperature to increase the BET area of aerogel and after examining under SEM, it was noticed that some uncommon structures that have not seen before formed. After observing nano-stalactite type structures in the sample, the study was expanded on the causes of the formation of these structures. It was seen that this structure forming after heat treatment was a stalactite composed of SiO₂ nanoparticles having a crystal structure. This study examined the formation mechanism and some properties of this structure which was not encountered in previous studies. Brunauer-Emmett-Teller (BET), Transmission electron microscopy (TEM), Scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) analysis were conducted in order to determine the physical and chemical properties of both synthesized SiO₂ aerogel and nano-stalactite type structure.     

Core@double-shell structured fillers for increasing dielectric constant and suppressing dielectric loss of PVDF-based composite films

High dielectric constant polymer dielectrics have attracted a great deal of attention in flexible electronics. However, it appears to be a paradox for polymer dielectrics that the enhancement of their dielectric constant often comes along with the increase of dielectric loss. Hence, we reported core@double shell structured filler/poly(vinylidene fluoride) (PVDF) composites to overcome this paradox. The hybrid filler with BaTiO₃ (BT) as the core, conductive carbon as the inner shell, and insulating polydopamine (PDA) as the outer shell was synthesized. As a result, the BT@C@PDA/PVDF composites at the filler content of 11 vol% exhibit an outstanding dielectric performance with a dielectric constant of 45 and a dielectric loss of 0.053 at 10³ Hz. This phenomenon can be attributed to the increased interfacial polarization induced by the inner carbon shell and the conductive paths blockade caused by the outside PDA shell inside the BT@C@PDA/PVDF composites. This work reveals that rational design of core@double shell structured hybrid fillers maybe a promising way to optimize the overall dielectric performance of the PVDF-based composites.     

表面修饰对常压干燥SiO2气凝胶的研制

以正硅酸乙酯为硅源,采用溶胶-凝胶法常压下制备S iO2气凝胶。用比表面测定仪(BET),多功能衍射仪(XRD)和透射电镜(TEM)研究表明,S iO2气凝胶具有高比表面积和非晶纳米多孔结构;激光粒度分析仪表明,S iO2气凝胶平均粒子尺寸不足20μm,为介孔结构;表面化学修饰由傅里叶变换红外光谱仪(FTIR)进行确定;疏水性气凝胶(TG-DTA)的热稳定性测定从25—1 200℃进行了研究,研究表明:气凝胶的疏水性能维持到500℃;吸水性能分析结果进一步表明S iO2气凝胶具有非常好的疏水性。     

Enhanced dielectric constant and breakdown strength in dielectric composites using TiO2@HfO2 nanowires with gradient dielectric constant

To investigate the influence of modification of ceramic fillers on the dielectric properties of polymer-based composites, TiO₂ and core-shell structured TiO₂@HfO₂ nanowires were synthesized, and investigated in this study. TiO₂ nanowires/polyvinylidene fluoride (PVDF) and TiO₂@HfO₂ nanowires/PVDF nanocomposites were prepared using the solution casting method. The experimental results showed that the TiO₂@HfO₂ nanowires/PVDF composites had improved dielectric properties compared with that of the TiO₂ nanowires/PVDF composites. Owing to the enhanced interfacial polarisation by the multilevel interface, the composites with 10 wt % TiO₂@HfO₂ nanowires achieved the highest permittivity of 12.56 at 1 kHz, which was enhanced by ～72% compared to the PVDF matrix. The electric field was evenly distributed by building the fillers with a gradient dielectric constant. The characteristic breakdown strength of the composite with 5 wt % TiO₂@HfO₂ reached 377.76 kV/mm, compared with that of 334.37 kV/mm for the composite with 5 wt % TiO₂ nanowires. This study initiated a novel strategy for preparing dielectrics with high dielectric constant and improved breakdown strength.     

The relationship between the silica wet-gels relative optical transmittance at 500 nm and structural features of silica aerogels

Aerogels are usually synthesized from supercritical drying of wet-gels. High quality aerogels are usually characterized with high specific surface area (measured by BET method here) and high degree of polymerization of silicate (characterized by ²⁹Si NMR here). The quality of the aerogels depends highly on the quality of the corresponding wet-gels because the skeletal structure in the wet-gels changes only slightly in the supercritical drying process. Here we present a simple method to predict the quality of the desired silica aerogels before the supercritical drying. We found that the relative optical transmittance of the silica wet-gels at 500 nm had good linear correlation with the specific surface area and the degree of silicate polymerization in the corresponding aerogels. We can assess the quality and screen out the low-quality wet-gels from supercritical drying operation, and greatly reduce the cost for aerogel production.     

Signature of rigidity percolation effect in dielectric behavior of germanium containing multi-component chalcogenide glasses (ChGs)

To develop new chalcogenide glasses (ChGs) as dielectric materials having a high dielectric constant and low dielectric loss, some quaternary glasses have been prepared from a novel third-generation Se–Te–Sn-Ge (STSG) system. This study reveals the effect of Ge addition on the dielectric relaxation and thermally activated a.c. conduction in a ternary ChG of Se–Te–Sn (STS) system. The compositional variation of the various dielectric and electrical parameters in the present STSG chalcogens rich non-oxide glasses Se_78-yGe_yTe₂₀Sn₂ (0 ≤ y ≤ 6) has been investigated. The results show that Ge plays a potential role in improving the dielectric properties of the parent STS glass.The dielectric relaxation and thermally assisted a.c. conduction have been investigated by examining the frequency/temperature dependence of dielectric constant/loss. The absence of the dielectric relaxation for the higher concentration of Ge indicates that the relationship of microstructure and dielectric properties can be explained in terms of the stiffness transition followed by the self-organization of the corner sharing and the edge-sharing arrangements of GeSe₄ phase.     

Effect of supercritical drying conditions in ethanol on the structural and textural properties of silica aerogels

Research on the preparation and characterization of silica aerogels has focused mainly on transparency and monolithicity. In this paper, we address the effect of supercritical drying conditions in ethanol on the shrinkage and porous texture of aerogels. The variables studied included the initial amount of ethanol added to the reactor, initial pressure of N₂, heating rate and stabilization time above supercritical conditions. The starting material was an alcogel obtained by the sol–gel process in acidic media. All aerogels were amorphous. In general, skeletal density increased when the initial amount of ethanol added into the body of the autoclave was decreased and the volume fraction of porosity was above 91%. According to infrared spectra, skeletal SiO₂ network was independent of supercritical drying conditions. N₂ adsorption isotherms identify the macroporous character of aerogels, which was confirmed by SEM and TEM. Specific surface area significantly increased when the initial volume of ethanol added to the reactor was increased and the stabilization time above supercritical conditions decreased, whereas surface area decreased when autoclave pre-pressurization was increased.     

Studies of the chemical and pore structures of the carbon aerogels synthesized by gelation and supercritical drying in isopropanol

The carbon aerogels prepared by a new method through gelation and supercritical drying in isopropanol were characterized by X‐ray photoelectron spectroscopy (XPS), scanning electron microscopy, and a surface area analyzer. Their chemical structure, morphology, and pore structure are discussed. We found that all of these carbon aerogel (CA‐IPA) samples have almost the same carbon and oxygen elemental states, as well as similar oxygen‐containing groups. The curve fitting of the C1s XPS spectra of the samples for characterizing oxygen‐containing surface groups can be performed by assuming the peak type to be a Gaussian–Lorentzian Cross Product, but we cannot obtain good results using a Gaussian lineshape. When the mass density of the CA‐IPA decreases, the mesopores and macropores of the samples are found to grow, but the size and the shape of individual carbon nanoparticles in various CA‐IPA samples do not apparently change. The micropore volume of the CA‐IPA samples increases with a decrease in the mass density, while the mesopore volume has a maximum at a certain mass density. The CA‐IPA samples have a very narrow micropore distribution at about 0.5 nm. The mesopore distribution of the CA‐IPA is widened and the average pore size increases as the mass density of the sample decreases. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 3060–3067, 2004     

Influence of interphase and moisture on the dielectric spectroscopy of epoxy/silica composites

Epoxy/silica composites have been used widely as the electronics packaging materials. This paper tested the thermal properties, moisture absorption and dielectric properties of pure epoxy and epoxy composites with micron-sized silica and nano-sized silica. The master curve of the dielectric loss factor was obtained by time-temperature superposition principle. Results showed that the nano-composite had a much higher loss factor, lower glass transition temperature and higher moisture absorption than other samples. By the analysis of the origin of the dielectric response in epoxy/silica composite, the reason for the different dielectric relaxation behaviors of the nano-composite, the micron-composite, and the pure epoxy was discussed.     

Elastic anomalies in tridymite- and cristobalite-based silica materials

Cristobalite and tridymite are the main SiO₂ phases in silica bricks, a widespread refractory product. The elastic properties of cristobalite at room temperature have been extensively studied, because it is known for auxetic behavior, i.e. negative Poisson ratios, whereas the elastic properties of tridymite are essentially unknown. Here we show that silica brick materials, consisting almost entirely of tridymite and cristobalite, exhibit remarkable anomalies in the temperature dependence of the Young modulus: in the intermediate temperature range between approximately 50 and 250 °C these materials become very compliant, with stiffness minima of around 60% of the room temperature values, with a broad transition region at the low-temperature end, a sharp transition at the high-temperature end and a precisely reproducible hysteresis during heating and cooling. Furthermore, it is shown that Young's moduli at around 800 °C can be more than three times as high as the room temperature values.     

Analysis of fluorescence properties of novel Eu3+-doped ZnAl2O4-based ceramic aerogels for high-power optical device applications

A novel series of ZnAl₂O₄:Eu³⁺ aerogels (ZAE) and mullite ceramic phase reinforced ZnAl₂O₄:Eu³⁺ aerogels (MZAE) with high fluorescence thermal stability have been firstly synthesized for the encapsulation of high-power optical devices. However, due to the intrinsic structural brittleness of the aerogel, the structure of ZAE tends to collapse during the heat treatment and the fluorescence performance falls short of expectations. To this end, we propose a simple and effective strategy to enhance the structural rigidity of fluorescent aerogels by introducing the mullite ceramic phase into the network structure of ZAE. This can effectively suppress the agglomeration of Eu³⁺ caused by the collapse of the structure during the heat treatment, thus enhancing the optical properties of the aerogel. Compared with ZAE, MZAE has higher fluorescence thermal stability. The fluorescence intensity of MZAE at 498 K is still 75 % of that at 298 K, and the chromaticity shift is only 22 × 10⁻³.