Molecular design of polymer precursors for controlling microstructure of organic and carbon aerogels

Organic and carbon aerogels were prepared by sol–gel polymerization of phenol, melamine and formaldehyde, followed by supercritical drying and pyrolysis. The effect of the mole ratio of melamine/phenol (M/P) on microstructure of organic and carbon aerogels was investigated by N₂ adsorption, SEM and TEM. Coordination M/P could change the hydrophilicity and cross-linking density of polymer framework, thereby affecting polymer colloid nanoparticle nucleation and growth, and ultimately determine the 3-dimensional network of the gels. The bulk densities of organic and carbon aerogels have maxima at M/P of 0.1, which are inversely proportional to volume shrinkage of gels during drying and pyrolysis. The size of the nanoparticles could be adjusted by varying M/P in the range from 10 to 22 nm. The mesopore volumes of organic and carbon aerogels are tailored in the range of 1.4–2.9 and 0.8–2.5 cm³/g, respectively. The average mesopore diameter has experienced a decreasing first and increasing afterward tendency with the increase of M/P, and exhibit a minimum at M/P of 0.1.     

Ultralow density silica aerogels prepared with PEDS

This paper deals with the synthesis of ultralow density silica aerogels using polyethoxydisiloxanes (PEDS) as the precursor via sol-gel process followed by supercritical drying using ethanol solvent extraction. Ultralow density silica aerogels with 5 mg/cc of density were made for the molar ratio by this method. A remarkable reduction in the gelation time was observed by the effect of the catalyst NH₄OH at room temperature. The microstructure and morphology of the ultralow density silica aerogels were characterized by the specific surface area, S_BET, SEM, TEM and the pore size distribution techniques. The results show that the diameter of the silica particles is about 13 nm and the pore size of the silica aerogels is about several nm. The specific surface area of the silica aerogel is 339 m²/g and the specific surface area, pore volume and average pore diameter decrease with increasing density of the silica aerogel.     

Cost-effective synthesis of silica aerogels from fly ash via ambient pressure drying

Silica aerogels were synthesized from the industrial fly ash by ambient pressure drying method. The process consists of two stages, preparation of sodium silicate solution from fly ash by hydrothermal reaction with sodium hydroxide, and synthesis of porous silica aerogels from the obtained sodium silicate solution. Silica wet gels were formed by vitriol-catalysis or resin-exchange-alkali-catalysis of the obtained sodium silicate solution. The trimethylchlorosilane(TMCS)/ethanol(EtOH)/hexane mixed solution was used for solvent exchange/surface modification of the wet gel so as to obtain porous silica aerogels via ambient pressure drying. The results indicated that the synthesized silica aerogels were lightweight and hydrophobic. The BET specific surface area, pore volume and average pore diameter were 362.2-907.9 m² g^− 1, 0.738-4.875 cm³ g^− 1, and 7.69-24.09 nm respectively. Particularly, the synthesized silica aerogels by resin-exchange-alkali-catalysis method showed uniform mesoporous structure, and had much higher specific surface area (907.9 m² g^− 1) and pore volume (4.875 cm³ g^− 1) than that of by vitriol-catalysis process.     

HNTs/SiO2复合气凝胶制备及其性能研究

采用正硅酸乙酯(TEOS)为硅原,以硅烷改性的埃洛石纳米管(HNTs)为增强相,利用CO2超临界干燥技术制备具有优良力学和隔热性能的HNTs/SiO2复合气凝胶.利用傅立叶红外光谱、扫描电镜、比表面积与孔径分析仪、万能试验机和导热率测量仪等手段对HNTs改性后的表面状态、HNTs/SiO2复合气凝胶的微观形貌、孔结构、力学和导热性能进行了测试分析.结果表明:改性后的HNTs均匀分散到二氧化硅气凝胶基体中,并与SiO2纳米颗粒实现良好的结合,HNTs/SiO2复合气凝胶呈三维网络结构,当HNTs含量为15wt;时,平均孔径为10.47 nm;随着HNTs含量的增加,复合气凝胶的力学性能不断增强,同时其导热系数也不断增大,当HNTs含量为15wt;时,HNTs/SiO2复合气凝胶的抗压强度为0.85 MPa,导热系数为0.024 W/mK.     

Textural characterization of high temperature silica aerogels

Silica alcogels were synthetized by the sol–gel polymerization of tetraethylorthosilicate in acid media. Conventional and supercritical drying was performed in order to obtain xerogels and aerogels. Different process parameters of the supercritical drying were altered in order to control the texture of the resulting gel. The texture and the structural evolution of xero- and aerogels were studied by thermogravimetric-differential thermal analysis, Fourier-transform infrared spectroscopy, transmission electron microscopy and N₂ physisorption at 77 K. ²⁹Si magic angle spinning nuclear magnetic resonance experiments on silica samples were used to resolve various silicon local environments. Hydrophilic microporous xerogels and hydrophobic micro- or mesoporous silica aerogels were obtained, whose microscopic structure is very similar. However, the samples obtained by different drying procedures exhibit a different structural evolution with temperature.     

碳气凝胶修饰SnSb复合负极材料的制备及性能研究

采用超临界干燥法制备了碳气凝胶( Carbon Aerogels,CA),然后通过简单的化学还原法制备CA/SnSb复合负极材料。采用XRD和SEM等手段对材料的结构及形貌进行了表征,利用恒电流充放电测试了材料的循环性能。研究结果表明,碳气凝胶表现出纳米多孔三维网络结构,当对SnSb合金采用碳气凝胶修饰后,纳米SnSb颗粒包含在碳气凝胶的网络骨架中,呈现出碳气凝胶和纳米SnSb合金颗粒相互交错分布的结构,极大改善了复合材料的团聚性。 CA/SnSb复合负极材料首次放电容量高达1120.2 mAh·g-1,循环50次后放电容量仍达到557.3 mAh· g-1,远高于未经碳气凝胶修饰的SnSb合金。循环性能的改善主要归因于碳气凝胶的引入,不仅极大的改善了复合材料的团聚现象,而且可以缓冲SnSb合金在充放电过程中体积变化。     

Polyaniline nanofiber–silica composite aerogels

Strong, electrically conducting aerogels were prepared by introducing polyaniline nanofibers to a silica sol just prior to gelation and drying through supercritical carbon dioxide processing. The addition of a few milligrams of polyaniline per cm³ increased the flexural strength of the cylindrical monoliths by 200%. Using preformed polymeric nanofibers avoided filling of microporosity often observed with polymer reinforcement of aerogels and allowed preparation of polyaniline–silica composite aerogels with surface areas over 900 m²/g. Despite the small amount of polyaniline nanofibers (1.3–16.5 wt.%), the composite aerogels were electrically conducting (8.0 × 10^? 8–1.83 × 10^? 5 S/cm) and it was possible to prepare chemiresistor sensors for detection of acidic (HCl) and basic (ammonia) gaseous molecules with response times similar to thin film sensors containing orders of magnitude more polyaniline.     

Synthesis and structural characteristics of carbon aerogels with a high content of Fe,Co, Ni,Cu, and Pd

High content metal carbon aerogels have been prepared by sol–gel polymerization of formaldehyde with potassium salt of 2,4-dihydroxybenzoic acid, followed by K⁺-exchange with Fe(II), Fe(III), Co(II), Ni(II), Cu(II) and Pd(II) ions from an aqueous or acetoneous solution and subsequent supercritical drying with CO₂. Carbonization at 1050 °C, under an inert atmosphere, transforms the metal ion doped organic aerogels into metal and/or metal oxide nanoparticles-doped carbon aerogels. The resulting materials were characterized by means of elemental analysis, nitrogen adsorption, transmission electron microscopy and X-ray diffraction. The structural properties and metal concentration of the doped carbon aerogel depend on the type and valence of the precursor metal salt. The presence of some graphitic nano-ribbons was evidenced in the case of Fe-, Co-, and Ni-doped carbon aerogels.     

Formation and characterization of tin oxide aerogel derived from sol-gel process based on Tetra(n-butoxy)tin(IV)

Transparent and translucent SnO₂ aerogels with high specific surface area (>300 m²/g) have been prepared by sol-gel process using tetra(n-butoxy)tin(IV) as a starting compound, and supercritical drying technique for solvent extraction. Light scattering measurements reveal that the polymeric cluster size distribution in sol system is gradually broadened during sol-gel transition. SEM images show that the aerogels are made up of the cottonlike oxide agglomerates with a large number of pores. TEM images show that these aerogels seem to be self-similar at different magnifications. Their pore size distribution is pretty wide ranging from mesopore to macropore especially for that of translucent aerogel.     

Preparation of cresol–formaldehyde carbon aerogels via drying aquagel at ambient pressure

Carbon aerogels were prepared from mixed cresol (Cm) and formaldehyde (F) via the sol–gel process followed by drying at ambient pressure and carbonization. The inexpensive feedstock of mixed cresol and the simple drying process could be as an alternative economical route to the classical resorcinol–formaldehyde synthesis process. In our process, organic precursor gels were synthesized via polycondensation of cresol with formaldehyde in an aqueous alkaline (NaOH) solution. After gelation the solvent was removed via drying at ambient pressure to obtain organic aerogels that exhibit a drying shrinkage below 5% (linear). Upon carbonization of the organic aerogels at 1173 K, monolithic carbon aerogels (denoted as CmF carbon aerogels) can be produced. Nitrogen adsorption results showed that the CmF carbon aerogels have abundant mesopores and micropores with a dominant pore diameter of 25–40 nm. An increase of the BET surface area and a modification of the pore size distribution of CmF can be realized by a CO₂ activation. The images of scanning electron microscopy (SEM) indicated that the microstructure of carbon aerogels can be effectively controlled and tailored by varying the synthetic conditions during the initial sol–gel process.     

A 3-D numerical heat transfer model for silica aerogels based on the porous secondary nanoparticle aggregate structure

A 3-D finite volume numerical model based on the porous secondary nanoparticle random aggregate structure was developed to predict the total thermal conductivity of silica aerogels. An improved 3-D diffusion-limited cluster–cluster aggregation (DLCA) method was used to generate an approximately real silica aerogel structure. The model includes the effects of the random and irregular nanoparticle aggregate structure for silica aerogels, solid–gas coupling, combined conduction and radiation, nanoparticle and pore sizes, secondary nanoparticle porosity and contact length between adjacent nanoparticles. The results show that the contact length and porosity of the secondary aerogel nanoparticle significantly affect the aerogel microstructure for a give density and, thus, greatly affect the total thermal conductivity of silica aerogels. The present model is fully validated by experimental results and is much better than the model based on a periodic cubic array of full density primary nanoparticles, especially for higher densities. The minimum total thermal conductivity for various silica aerogel microstructures can be well predicted by the present model for various temperatures, pressures and densities.     

Microstructural and physical properties of the ambient pressure dried hydrophobic silica aerogels with various solvent mixtures

The experimental results on the microstructural and physical properties of the ambient pressure dried hydrophobic silica aerogels with various solvent mixtures have been reported. The aerogels were prepared with sodium silicate precursor, ammonium hydroxide catalyst, trimethylchlorosilane (TMCS) silylating agent, solvent mixture of methanol-isopropanol (MeOH/IPA) and various aprotic solvent mixtures namely, hexane and benzene (HB), hexane and toluene (HT), hexane and xylene (HX), heptane and benzene (HpB), heptane and toluene (HpT), heptane and xylene (HpX). The physical properties of the aerogels such as % of volume shrinkage, density, % of optical transmission, surface area, % of porosity, pore volume, thermal conductivity and heat capacities of the aerogels were studied. The hydrophobicity of the aerogels was studied by contact angle measurements. The HX and HpX aerogels have been found to be more hydrophobic (contact angle, θ > 155°) than the other aerogels. It has been observed that the % of weight increase is highest (1%) for the HT aerogels and lowest (0.25%) for HpX aerogels by keeping them at 70% humidity for 350 h. Further, the aerogels have been characterized by pore size distribution (PSD), Fourier transform infra red spectroscopy (FTIR) and thermogravimetric and differential thermal (TG-DGA) analysis and transmission electron microscopy (TEM) techniques. The results have been discussed by taking into account the surface tension, vapor pressure, molecular weight and chain length of the solvents. Low density (0.051 g/cc), hydrophobic (165°), transparent (85%), low thermal conductive (0.059 W/m K), low heat capacity (180 kJ/m³ K) and highly porous (97.38%) silica aerogels were obtained with HpX solvent mixture.     

Rapid synthesis of amine cross-linked epoxy and methyl co-modified silica aerogels by ambient pressure drying

The silica aerogels were synthesized by sol–gel method via ambient pressure drying. Tetraethyl orthosilicate (TEOS) was used as a main silica source, methyltriethoxysilane (MTES) as a co-precursor silica source and (3-Glycidoxypropyl)trimethoxysilane (GPTMS) as a silane coupling agent. The silica aerogels obtained were further undergoing cross-linking epoxy from GPTMS with amine from diethylenetriamine (DETA) which played a dual role of base catalyst and reagent. The cumulative volumes for open pores of the cross-linked aerogels were evaluated to be 1.4 cm³/g. The Young's modulus and maximum compression strength were 25.4 MPa and 6.17 MPa, respectively. The addition of MTES accelerated the solvent exchange of alcohol within the pores with n-hexane and reduced the shrinkage of aerogels network during the ambient pressure drying. The formation of organic network enhanced the strength of the cross-linked aerogels to prevent the crack generation and the subsequent failure of the monolith during the ambient drying, therefore, protected the nanoporous structure of aerogels.     

The preparation of carbon aerogels based upon the gelation of resorcinol-furfural in isopropanol with organic base catalyst

Carbon aerogels with high BET surface area were developed by sol-gel polycondensation of resorcinol and furfural in isopropanol using hexamethylenetetramine (HMTA) as a catalyst, and then directly drying the organic gels under isopropanol supercritical conditions, followed by carbonization under a nitrogen atmosphere. The preparation conditions of carbon aerogels were explored by changing the mole ratio of resorcinol to basic catalyst HMTA (R/C), the ratio of resorcinol to isopropanol (R/I), and the mole ratio of resorcinol to furfural (R/F). The effect of these preparation conditions on the porous structure of the carbon aerogels obtained was studied by nitrogen adsorption isotherms. According to the characterizations of TEM, SEM and nitrogen adsorption, the carbon aerogels obtained have a three-dimensional network that consists of carbon nano-particles with size from 20 to 30 nm, which define numerous micropores, mesopores and macropores. HMTA reacts not only as a catalyst but also as a reagent in the gelation polymerization. XRD characterization indicates that carbon aerogels have disordered nanocrystalline structures similar to activated carbon.     

Structure and electrochemical properties of carbon aerogels synthesized at ambient temperatures as supercapacitors

In this paper, the carbon aerogels derived from organic sol-gel process were prepared by means of ambient drying technique. Morphology and physical properties of the carbon aerogels were characterized by scanning electron microscopy (SEM) and N₂ sorption isotherm. It was found that the carbon aerogels were porous materials with pearly network structure, the particle size of carbon aerogels increased with the increase of R/C ratio (molar ratio of resorcinol to catalyst). The BET surface areas of obtained carbon aerogels were in the range 600-1000 m²/g. Electrochemical performances of the carbon aerogels electrodes were studied by cyclic voltammetry, galvanostatic charge/discharge measurements and electrochemical impedance measurement. The results indicated that carbon aerogels electrodes had good electrochemical performance, high reversibility and high specific capacitance. Moreover, the utilization efficiency of carbon aerogels was promoted due to excellent electronic conductivity and extensive mesoporous network of carbon aerogels. The specific capacitance of the electrode is 183.6 F/g with R/C ratio 1500. In addition, the carbon aerogel electrode for the application of supercapacitor had low resistance, small leakage current and good electrical conductivity.     

Transparent SiO2 aerogels prepared by ambient pressure drying with ternary azeotropes as components of pore fluid

Transparent SiO₂ aerogels were prepared by two-step sol–gel processing followed by ambient pressure drying at temperatures from 70 to 250 °C. The wet gels were synthesized via acid–base catalysis using tetraethyl orthosilicate as a silica precursor and isopropanol as a solvent. Isopropanol was exchanged with n-butanol, and the gel surface was modified using a trimethylchlorosilane solution in n-butanol. Next, the solvent was exchanged in several steps with saturated hydrocarbon in order to obtain pore fluids containing azeotropic mixtures of water, n-butanol and a corresponding hydrocarbon (hexane, heptane, octane, nonane). Ambient pressure drying was performed in two steps, at the boiling points of the ternary azeotropes and hydrocarbons, respectively. In this way, transparent, crack-free aerogels of different shapes, with a specific surface area of 1000 m²/g, average pore diameter of ～40–55 Å and density in the range 0.4–0.57 g/cm³ were obtained.     

Silica aerogels prepared via rapid supercritical extraction: Effect of process variables on aerogel properties

We have examined experimentally the effects of rapid supercritical extraction (RSCE) process variables and their resulting pressure and temperature characteristics on aerogel properties. We employ an RSCE process that uses a hydraulic hot press to seal and heat a contained mold until the aerogel precursors reach a supercritical state. After a short stabilization period the hot press restraining force is lowered and the supercritical fluid is allowed to escape, leaving behind an aerogel monolith. The entire process can be accomplished in fewer than 3 h. To control the process, we set the restraining force, the maximum temperature, the heating and cooling rates, the pressure release rate and the mold volume fill ratio (related to the amount of initial precursor material). To investigate the effects of these variables we made silica aerogels from a TMOS-based recipe. We varied the volume of precursor material from 10 to 15 mL (60-97% fill volume), the restraining force from 43 to 111 kN, the temperature heat rate from 0.7 to 4.2 °C/min, the maximum temperature from 288 to 371 °C and the pressure release rate from 0.23 to 0.66 MPa/min. The RSCE process is robust. We were able to make transparent, monolithic aerogels under almost all conditions with little effect on the resulting aerogel properties. Typical density measurements yielded values of approximately 0.065 g/mL (bulk) and 1.9 g/mL (skeletal). The samples were translucent and transmitted 70% of the light at 800 nm (for 5-mm thick samples). The BET surface areas ranged from 517 to 590 m²/g. Maximum temperature was the only variable found to have a significant effect on the aerogels’ properties. As the maximum temperature increased from 288 to 371 °C the surface area decreased from 560 to 395 m²/g and average pore diameter (BJH desorption) increased from 21 to 32 nm.     

Nitridation of SiO2–B2O3 aerogels

SiO₂–B₂O₃ aerogels have been prepared by drying wet gels at a supercritical condition for ethanol in an autoclave. Aerogels have been nitrided for 6 h in flowing ammonia at the temperature of 1200 °C. It has been found that the amount of nitrogen incorporated in these aerogels always exceeds 20 wt%. This is a much higher value compared with the amount of nitrogen incorporated in a pure silica aerogel nitrided at the same conditions. The specific surface area of SiO₂–B₂O₃ aerogels has been between 312 and 359 m²/g. After nitridation some shrinkage of aerogels has been observed and the surface area decreases about 20%. In FTIR spectra of SiO₂–B₂O₃ aerogels a typical bands for SiO₂ are observed. After nitridation a shift and broadening of 1100 cm^?1 band to lower wavenumbers indicates that Si–N and B–N bonds are formed in nitrided aerogels.     

An analytical model for combined radiative and conductive heat transfer in fiber-loaded silica aerogels

An improved analytical model for the total thermal conductivity of fiber-loaded silica aerogels was developed based on the complex refractive index, size, orientation, volume fraction and morphology of the fibers and silica aerogel. A cubic array of spherical porous secondary nanoparticles and a modified parallel-series model were proposed to model the combined solid and gaseous thermal conductivities. An anomalous diffraction theory (ADT) was used to predict the fiber extinction coefficient. Five common fiber types in the composites were studied including amorphous SiO₂ glass, silicon glass, common float glass, soda lime silica glass and borosilicate glass. The results show that the total extinction coefficient of the silica aerogel system is largest by loading with the common float glass fiber and lowest by loading with the soda lime silica glass among the five fiber types. The model provides theoretic guidelines for material designs with optimum parameters, such as the type, inclination angle, volume fraction and diameter of the fibers as well as the aerogel nanoparticle and pore sizes. The optimum fiber for improved thermal insulation should have a large spectral complex refractive index throughout the infrared region.     

Characterization of nickel–alumina aerogels with high thermal stability

The characterization of NiO–Al₂O₃ aerogels prepared from nickel nitrate and aluminum iso-propoxide through a sol–gel processing and subsequent supercritical drying was performed. The UV–visible, XPS and FT–IR investigations revealed that nickel ions were incorporated into alumina spinel structure as nickel aluminate form, not as nickel oxide, after calcination. TEM observations after the subsequent reduction exhibited uniform and fine nickel particles less than 6 nm diameter throughout the alumina aerogel support with high dispersion, by which not only high thermal stability of the metal at elevated temperatures but also high reforming activity and stability should be brought about. The large surface area and pore volume also provided the catalyst stability through the improvement of the thermal stability of alumina support.