Theoretical study on the effective thermal conductivity of silica aerogels based on a cross-aligned and cubic pore model

Aerogel nanoporous materials possess high porosity, high specific surface area, and extremely low density due to their unique nanoscale network structure. Moreover, their effective thermal conductivity is very low, making them a new type of lightweight and highly efficient nanoscale super-insulating material. However, prediction of their effective thermal conductivity is challenging due to their uneven pore size distribution. To investigate the internal heat transfer mechanism of aerogel nanoporous materials, this study constructed a cross-aligned and cubic pore model(CACPM) based on the actual pore arrangement of SiO_(2) aerogel. Based on the established CACPM, the effective thermal conductivity expression for the aerogel was derived by simultaneously considering gas-phase heat conduction, solid-phase heat conduction, and radiative heat transfer. The derived expression was then compared with available experimental data and the Wei structure model. The results indicate that, according to the model established in this study for the derived thermal conductivity formula of silica aerogel, for powdery silica aerogel under the conditions of T = 298 K, a_(2)= 0.85, D_(1)= 90 μm, ρ = 128 kg/m^(3), within the pressure range of 0–10^(5)Pa, the average deviation between the calculated values and experimental values is 10.51%. In the pressure range of 10^(3)–10^(4)Pa, the deviation between calculated values and experimental values is within 4%. Under these conditions, the model has certain reference value in engineering verification. This study also makes a certain contribution to the research of aerogel thermal conductivity heat transfer models and calculation formulae.

Mechanical Properties of Silica Aerogels Prepared from a Mixture of TEOS and Organo-alkoxysilanes of Type R_1SiX_3

Silica aerogels were prepared from a mixture of tetraethylorthosilicate and organo- alkoxysilanes. The effects of organo-alkoxysilanes on the mechanical properties of the silica aerogels were studied. The flexibility of silica aerogels was significantly improved by incorporation of organo-alkoxysilanes. When MTES and TEOS were combined as precursors of silica areogels, with the increased amount of MTES, the apparent elastic modulus and apparent compressive strength monotonously rose. At the same organo- alkoxysilanes to TEOS ratio, the size of alkyl groups of the organo-alkoxysilanes had little effect on the mechanical properties. In series of MTES and TEOS, the lowest elastic modulus of silica skeleton and the highest compressive strength of silica skeleton were observed at MTES to TEOS ratio of around 50：50. At a certain organo-alkoxysilanes to TEOS ratio, the elastic modulus of silica skeleton increased and the compressive strength of silica skeleton decreased with the size increase of the alkvl grouns.

Preparation and Properties of PMMA Modified Silica Aerogels from Diatomite

Diatomite was used as raw material to prepare sodium silicate with a modulus of 3.1 by alkali dissolution method and the resulted sodium silicate solution was employed as a precursor. Methyl methaerylate monomers were introduced in wet gels through solution-immersion, and upon heating at 70 ℃, the mesoporous surfaces throughout the skeletal framework were coated with the polymer layer. PMMA modified silica aerogels were successfully synthesized via ambient pressure drying. The properties were investigated by FT- IR, NMR, TGA, nitrogen adsorption-desorption, FESEM and nano-indentation, etc. Results indicate that with the increasing of PMMA incorporated into silica aerogels, the bulk density and the BET surface area increase, the porosity decreases. Through the observation of FESEM, it is found that the interconnecting pores and the big pores add, the pore size distribution expands from 5-17 to 28-150 urn. By comparison, the PMMA modified silica aerogels achieve a 52-fold increase in hardness and a 10-fold increase in modulus.

Synthesis and Characterization of Multi-walled Carbon Nanotube Doped Silica Aerogels

Multi-walled carbon nanotube doped silica aerogels（MWCNT-SAs） were synthesized from a wet gel of well-dispersed MWCNT by one-step solvent exchange/surface modification and ambient pressure drying（APD）. Waterglass was employed as a precursor to prepare wet gel. The content of MWCNT varied from 0 to 15% volume by wet gel. The surface group, thermal stability and microstructure of pure silica aerogel and MWCNT-SAs were investigated by FTIR, DTA, and TEM. Experimental results show that MWCNT-SAs are hydrophobic when the temperature is below 400 ℃, MWCNT-SAs exhibit a mesoporous network structure, and they achieve the largest scale with least shrinkage and lowest density when doped with 5 vol% MWCNT.

Effect of Heat Treatment on Silica Aerogels Prepared via Ambient Drying

Silica aerogels were prepared at ambient drying by using ethanol/trimethylchlorosilane （TMCS）/heptane solution as pore water exchange and surface modification of the wet gel before drying. The obtained silica aerogels exhibit a sponge-like structure with uniform pore size distribution. The effects of heat-treatment on the hydrophobicity, specific surface area and other properties were investigated. The results indicated that the hydrophobicity of silica aerogels could be maintained up to 350℃. With increasing heating temperature, hydrophobicity decreased, and became completely hydrophilic after heat-treatment at 500℃. Brunaueremmitt-teller （BET） surface area results indicated that the specific surface area of silica aerogels increased with increasing heating temperature in the range of 150-500℃. The effects of heat-treatment on the morphology and chemical bonding state of silica aerogels were investigated by scanning electron microscopy （SEM）, differential temperature analysis （DTA） and Fourier-transform infrared spectroscopy （FT-IR）.

Synthesis and Characteristics of Mesoporous Silica Aerogels with One-step Solvent Exchange/Surface Modification

The synthesis procedures and physical properties of the ambient dried hydrophobic silica aerogels by using different contents of ethanol （EtOH）/trimethylchlorosilane （TMCS）/n-Hexane as surface modification agent were investigated. One-step solvent exchange and surface modification were simultaneously progressed by immersing silica hydrogels in EtOH/TMCS/n-Hexane solution. It is found that microstructures as well as properties of silica aerogels like porosity, specific density and specific surface area are affected by the contents of surface modification agent in the sol from the results of SEM, TEM morphology, FT-IR chemical structure, BET surface area and BJH pore size analyses. The volume of TMCS is of 10% and 20% of hydrogels, and the final product is hydrophilic xerogels. When TMCS＇s percent （v/v） is elevated to 75 %-100%, hydrophobic silica aerogels with good performance are synthesized, the porosities of aerogels are in the range of 93.5%-95.8% and the average pore size diameter is less than 20 nm.

Preparation and Characterization of Silica Aerogels Derived from Ambient Pressure

Silica aerogels were prepared by sol-gel technique from industrial silicon derivatives （polyethoxydisiloxanes, E40）, followed by silylation and drying under ambient pressure. The specific surface area, pore size distribution and thermal conductivity of the silica aerogels were investigated and the results showed that the diameter of the silica particles is about 6 nm and the average pore size of the silica aerogels is 14.7 nm. The specific surface area of which is about 1000 m^2.g^-1 and the thermal conductivity is about 0.014 wm^-l.K^-1 at room temperature and pressure of 1.01×10^5 Pa. The Si-CH3 groups were also detected on the internal surface of the silica aerogels, which show hydrophobic. Silica aerogels derived by this technique is low cost and have wide applications.

Influence of Drying Methods on Fractal Geometric Characteristics of Mesoporous Silica Aerogels

Chemical modification/ambient drying method and freeze drying method were introduced to research the synthesis of mesoporous silica aerogels. By analyzing N2 gas adsorption/desorption isotherms, the fractal geometric characteristics of gels were focused. The overall surface fractal dimensions were determined by analyzing N2 gas adsorption branch and a Frenkel-Halsey-Hill （FHH） equation was empolyed to determine surface fractal dimension Df It is found that, during ambient drying process, VTMCS/VWetgel ratio plays a crucial role in the changes of geometric feature, the key point is 50%, when the ratio is lower, and surface roughness increases with the ratio, when it exceeds 50%, the surface is almost unaffected by the modification. While freeze drying always tends to get larger Df freeze drying process could cause a rough surface of the gels. Compared with traditional porosity and specific surface area analyses, fractal geometry may be expected to be favorable for mesoporous structural analyses of materials.

Effect of sodium bicarbonate solution on methyltrimethoxysilane-derived silica aerogels dried at ambient pressure

Here we present an economical ambient pressure drying method of preparing monolithic silica aerogels from methyltrimethoxysilane precursor while using sodium bicarbonate solution as the exchanging solvent.We prepared silica aerogels with a density and a specific surface area of 0.053 g·cm^(-3) and 423 m^(2)·g^(-1) respectively.The average pore diameter of silica aerogels is 23 nm as the pore specific volume is 1.11 cm^(3)·g^(-1),Further,the contact angle between water droplet and the surface of silica aerogels in specific condition can be as high as 166°,which indicates a super-hydrophobic surface of aerogels.

Nano silica aerogel-induced formation of an organic/alloy biphasic interfacial layer enables construction of stable high-energy lithium metal batteries

Lithium metal batteries represent promising candidates for high-energy-density batteries, however, many challenges must still be overcome,e.g., interface instability and dendrite growth. In this work, nano silica aerogel was employed to generate a hybrid film with high lithium ion conductivity(0.6 mS cm^(-1)at room temperature) via an in situ crosslinking reaction. TOF-SIMS profile analysis has revealed conversion mechanism of hybrid film to Li–Si alloy/Li F biphasic interface layer, suggesting that the Li–Si alloy and Li F-rich interface layer promoted rapid Li+transport and shielded the Li anodes from corrosive reactions with electrolyte-derived products. When coupled with nickel-cobalt-manganese-based cathodes, the batteries achieve outstanding capacity retention over 1000 cycles at 1 C. Additionally the developed film coated on Li enabled high coulombic efficiency(99.5%) after long-term cycling when coupled with S cathodes. Overall, the results presented herein confirm an effective strategy for the development of high-energy batteries.

Application of Silica Aerogel Carrier via Supercritical Drying for Fragrance Controlled-release

Silica aerogel with different hydrophilicities were prepared from tetramethoxysilane,Methymethoxysilane,tetramethoxysilane-propyltrimethoxysilane,or tetramethoxysilane-phenyltrimethoxysilane mixtures via supercritical drying process(labelled as TMOS-AG Me-TMOS-AG,Pr-TMOS-AG,or Ph-TMOS-AG,respectively).Three fragrances,including geraniol,ethyl vanillin,and menthol,were loaded to TMOS-AG.The thermal analysis confirmed all loading fragrances are stable until over 200℃.And among all fragrances,geraniol presented the maximum loading contents(L_(m)).Concentration dependences indicated the geraniol was mono layer absorbed.Py-GC/MS of geraniol in TMOS-AG under both N_(2)and mimic air atmosphere(90%N_(2)and 10%O_(2))confirmed that loaded geraniol could be thermally controlled-released beginning at 200℃.As N_(2)absorption confirmed,even absorption/desorption equilibrium constant(k)was determined mainly by hydrophilicity of silica aerogels,and the maximum loading contents(L_(m))were influenced more by the pore size.Due to mono layered absorption,bigger pores usually give less specific areas and less absorbing sites for geraniol,and then present lower L_(m).

SiO_2 Aerogels Prepared with Ambient Pressure Drying and Its Properties

SiO2 aerogels were produced from tetraethyl orthosilicate （TEOS） as silicon resources,ethanol as solvent and watery HCl or ammonia by sol-gel method and surface modification at ambient pressure.Scanning electronic microscopy,Fourier transform infrared spectrometer （FT-IR）,pore size distribution measurement,packing density and some other experiment methods were used to characterize the morphology and pore structure and other properties of the silica aerogels.The results show that the silica aerogels have a typical nano-porous microstructure with hydrophobic property.It was discovered that SiO2 aerogels have better properties when the preparation condition is as following the watery HCl concentration is 1%,the aging reagent is CH3CHOHC4H9,the aging time is 20 d,the volume concentration of trimethylchlorosilane （TMCS） in hexane is 6% and the surface modification time is 24 h.

Mechanism of low thermal conductivity of xonotlite-silica aerogel nanoporous super insulation material

In an effort to incorporate the low thermal conductivity of the silica aerogel and the superior structure strength of the xonotlite,a composite material of these two was produced. It was synthesized under vacuum condition and dried by supercritical drying technique. The thermal conductivity of the new material,which is at 298K with the gas pressure ranging from 1.01×10^5 to 1×10^-2 Pa,was measured using the transient hot-strip method. The mechanism of the low thermal conductivity was studied. The results indicate that the low thermal conductivity mainly results from the significant decrease of gaseous thermal conductivity of the new material due to the restriction of the motion of gas molecules in its fine structures. The formation of the fine structures is because the new material takes the pore structure of the silica aerogel which consists of mainly nanometer-sized pores.

Synthesis and Thermal Insulation Performance of Silica Aerogel from Recycled Coal Gangue by Means of Ambient Pressure Drying

Silica aerogel materials are well recognized for their superinsulation performance and are regarded as one of the hot candidates to revolutionize building insulation. To date, high production cost related to exorbitant precursors as well as cumbrous multi-step hydrophobization process has often narrowed the field of applications. In this work, granular silica aerogel materials were synthesized by extracting Si O2 from recycled rich silicon coal gangue, followed by one-step hydrophobization and ambient pressure drying. Lightweight(about 0.16 g/cm3) and nanostructural aerogels were obtained through this route. They exhibit a 3D open porous microstructure with around 600 cm2/g surface area and 20 nm of the average pore diameter, thermal conductivity of 4-5 mm packed granules is 20-25 m W/(m·K), which was proved by both guarded hot plate and hot-wire transient methods. This study offers a new facile route for the synthesis of silica aerogel from recycled solid waste coal gangue and suggests a method, which may lead to a cost reduction in terms of industrial production.

Adsorption of cationic dyes from aqueous solution using hydrophilic silica aerogel via ambient pressure drying

In order to remove the organic dyes of textile waste water,the silica aerogel was successfully prepared by using E-40 as a novel precursor and then dried in ambient pressure.The synthesized sample was verified by Scanning Electron Microscopy(SEM)and Fourier Transform Infrared Spectroscopy(FTIR).After calcining,the hydrophilic silica aerogel(HSA)was used as adsorbent to remove Methylene Blue(MB),Malachite Green(MG),and Gentian Violet(GV)from aqueous solution.The effects of initial concentration of dyes and adsorbent dosage on the adsorption process were examined.It was found that HSA showed excellent adsorption capacities,the maximum percentage of removal dyes could reach 98%.Herein,the Langmuir,Freundlich and de Boer-Zwikker isotherm modes were employed to discuss the adsorption behavior.The results indicated that the de Boer–Zwikker model can effectively describe the adsorption behavior.Besides,the HSA could be utilized as the recyclable adsorbent in degradation experiment,after five cycles,no obvious loss of adsorption capacity was found.As an efficient,low-cost,environmental friendly and recyclable adsorbent,silica aerogel is expected to be used for dyes removal.

High-sensitivity intelligent packaging films harnessing rose anthocyanins and hydrophilic silica aerogel for visual food freshness monitoring

The enhancement of the sensitivity for anthocyanin-based indicator films in food freshness monitoring in real time is important for application.In this study,hydrophilic silica aerogel(SiO2 NA)was incorporated into corn starch(CS)/chitosan(CH)/rose anthocyanins(RACNs)-encapsulated potato amylopectin nanoparticles(APNPs)composite film to increase the sensitivity for shrimp freshness detection.The microstructure of films revealed that the gas absorption capacity was improved by amorphous SiO2 NA via hydrogen interactions.The pore size(1.74–5.60 times),pore volume(3.92–5.60 times),and specific surface area(2.21–2.34 times)of films increased with the addition of SiO2 NA.The sensing of NH3 and pH and the reversibility of films were also reinforced.Meanwhile,the pH-responsive films containing SiO2 NA changed visibly in color from purple–red to orange–gray and finally to gray,enabling effective monitoring of shrimp freshness during storage at 4°C.Thus,anthocyanin-based indicator films with improved sensitivity by adding SiO2 NA were successfully designed for monitoring shrimp freshness.

Improving Thermal-oxidative Aging Resistance of Styrene-butadiene Rubber by Antioxidant Loaded Silica Aerogel

The antioxidant N-isopropyl-N'-phenyl-p-phenylenediamine(4010NA)was dissolved in ethanol and impregnated into silica aerogel(SAG)via vacuum-pressure cycles,yielding composite particles(A-N)with enhanced sustained-release and reinforcing capabilities.The effect of A-N on the mechanical properties and thermal-oxidative aging resistance of styrene-butadiene rubber(SBR)vulcanizates was investigated.TGA and BET assessments indicated that the loading efficiency of 4010NA in SAG reached 14.26%within ethanol's solu bility limit.Incorporating A-N into SBR vulcanizates significantly elevated tensile strength by 17.5%and elongation at break by 41.9%over those with fumed silica and free4010NA.Furthermore,A-N notably enhanced the thermal-oxidative aging resistance of SBR.After aging for 96 h at 100℃,the tensile strength and elongation at break of SBR with A-N sustained 70.09%and 58.61%of their initial values,respectively,with the retention rate of elongation at break being 62.8%higher than that of SBR with fumed silica and free antioxidant.The study revealed that A-N composite particles significantly inhibited the crosslinking in SBR's molecular chains,reducing hardening and embrittlement during later thermal-oxidative aging stages.

Experiments and numerical study on heat transfer of moist silica aerogel composites at high temperatures

Silica aerogel composites have promising applications in high-temperature heat storage insulation.However,the impact of high temperatures and moisture on their insulation performance remains unclear.To reveal the influences of high temperature and moisture absorption property on the heat transfer of silica aerogel composites,an experimental and numerical study was conducted to explore the micromorphology,thermophysical parameters,moisture absorption characteristics,and temperature response.The service temperature limit of the silica aerogel composite has been clarified.Measurements have conducted for the thermal conductivity,specific heat capacity,thermal diffusivity,specific surface area,density,porosity,and pore size distribution of the heated silica aerogel composite(at temperatures of 600,800,1,000,1,100 and 1,200℃).The moisture absorption characteristic curve at 20℃ has been obtained.Thermal testing of silica aerogel composites under varying heating temperatures and moisture content has been completed.Additionally,a numerical method has been developed to calculate the temperature curve of moist silica aerogel composites.The insulation performance of silica aerogel composite with varying moisture contents depends on the game between thermal conductivity and latent heat.Compared with the negative effect of the moisture content on insulation performance,the positive influence of moisture evaporation and heat absorption is dominant in situations involving temperatures higher than the phase transition temperature.

Preparation and Adsorption Property of Phenyltriethoxysilane Modified SiO_2 Aerogel

The hydrophobic silica aerogel （SiO2 aerogel） was prepared by/n situ polymerization sol-gel method and ethanol supercritical drying, with tetraethoxysilane （TEOS） as silica source, phenyltriethoxysilane （PTES） as modifier, ethanol as solvent and ammonia as catalyst. The effects of n（PTES）/n（TOES） were investigated on gel time, structure, and hydrophobicity. The SiO2 aerogel was measured by Fourier transform infrared spectroscopy （FT-IR） and scanning electron microscopy （SEM）. The effects of n（PTES）/n（TOES） were also studied on adsorption property of pentane, hexane, heptane, octane, benzene, toluene, o-xylenc, nitromethane, nitroethane, and nitrobenzene. The adsorption intensity of SiO2 aerogel was compared with that of activated carbon. The results show, with the increasing ofn（PTES）/n（TOES）, the surface area, pore volume, and pore size of SiO2 aerogel decreased, gel time and hydrophobicity increased, and the contact angle could be 154° with n（PTES）/n（TOES）=0.7. The adsorption intensity of SiO2 aerogel with n（PTES）/n（TOES）=0.5 was bigger than that of activated carbon with an average 5.84 times of 10 organic liquid. The adsorption intensity of aerogel with n（PTES）/n（TOES） =0.1 was the best one in all samples with the average 8.33 times compared with that of activated carbon.

A review on heat transfer in nanoporous silica aerogel insulation materials and its modeling

Silica aerogels are widely used in many fields for thermal insulation,such as building insulation,electric power energy,energy storage systems,and high-temperature thermal protection due to their excellent insulation per-formance.Therefore,the heat transfer in silica aerogels and its modeling in recent years have attracted much attention and many valuable achievements have been acquired.The heat transfer in nano-porous silica aerogels and its modeling methods are reviewed in this work.This review starts with a brief introduction of heat transfer characteristics in silica aerogels,including the multi-component and multi-mode coupling effect,size effect,and multiscale effect.Then the heat transfer mechanism of each mode,including heat transfer via gas phase,solid phase,and thermal radiation,is reviewed,and the models for predicting the gaseous thermal conductivity in nanoscale pores,gas-contributed thermal conductivity,the apparent thermal conductivity of solid skeleton,and finally the effective thermal conductivity are collected and discussed in details.Besides,modeling of transient heat transfer in silica aerogels is also briefly introduced.Finally,the conclusions and some problems which need to be further investigated in the future are provided.