Sol → gel → glass: I. Gelation and gel structure

The mechanisms of gel formation in silicate systems derived from metal alkoxides were reviewed. There is compelling experimental evidence proving, that under many conditions employed in silica gel preparation, the resulting polysilicate species formed prior to gelation is not a dense colloidal particle of anhydrous silica but instead a solvated polymeric chain or cluster. The skeletal gel phase which results during desiccation is, therefore, expected to be less highly crosslinked than the corresponding melted glass, and perhaps to contain additional excess free volume. It is proposed that, during gel densification, the desiccated gel will change to become more highly crosslinked while reducing its surface area and free volume. Thus, it is necessary to consider both the macroscopic physical structure and the local chemical structure of gels in order to explain the gel to glass conversion.     

Colloidal sol/gel processing of ultra-low expansion TiO2/SiO2 glasses

A series of titania-silica glasses with 0–9% TiO₂ were fabricated using a sol/gel process. The sol was prepared by dispersing colloidal silica fume in an aqueous solution of titania which was synthesized through the acid-catalyzed hydrolysis of titanium isopropoxide. The sols gelled in 2–4 days, and then were dried for 6–8 days. The dry gels were sintered at 1450–1500°C to produce clear, dense, microstructure-free glasses. The gels underwent a total shrinkage of 50% to yield glass rods about 50 mm long and 5 mm in diameter, or glass discs about 4 cm in diameter and 5 mm thick. The drying step was most critical in the production of crack-free specimens.

In the gel, the transmission electron microscope (TEM) revealed the presence of 1–5 nm rutile microcrystallites uniformly distributed within a network of colloidal silica particles. After sintering to 1450–1500°C, though, a dense, transparent, microstructure-free glass was created. Fourier transform infrared spectroscopy (FTIR) verified the formation of an amorphous solid-solution of titania and silica after sintering.

The thermal expansion of the glasses was measured using a differential dilatometer. The average linear coefficients of thermal expansion (CTE @ 25–675°C) varied between +5 × 10⁻⁷ and −0.2 × 10⁻⁷°C⁻¹ in the range 0 to 9% TiO₂. The glass with 7.2% TiO₂ exhibited a zero thermal expansion coefficient at 150–210°C. The hysteresis in CTE on heating and cooling was of the order of 0.01–0.02 ppm.     

Aging and drying of gels

This review describes the chemical and physical processes occurring during the aging and drying of an inorganic gel. The chemical reactions that lead to gelation are shown to continue long after the solution gels, causing changes in the composition, structure, and properties of the gel. The formation of new crosslinks produces shrinkage (syneresis) and increases the modulus and viscosity of the gel, so that aging reduces the subsequent shrinkage during drying. If the solubility of the solid phase is drying, the small pores of the gel develop high capillary pressures that results in shrinkage. If the exterior surface shrinks much faster than the interior, the differential strain can cause warping and cracking; very slow drying is generally required to prevent such catastrophes. Fracture is most likely at the moment that shrinkage stops and the liquid/vapor meniscus moves into the gel; after that point, the meniscus may remain smooth or may become unstable and ragged. The theory of drying is reviewed and shown to account for the observed behavior. Several strategies are described that minimize the tendency of the gel to crack.     

Gel to glass conversion: Densification kinetics and controlling mechanisms

The densification kinetics and controlling mechanisms during the gel to glass conversion are revised. The goal has been to analyse the controlling factors that lead to species joining and porosity elimination. This review includes several sections. First of all, the current understanding of gel structures, the driving forces for densification and the mechanisms involved are examined. Further, an analysis is carried out on the shrinkage due to dehydration of gels. Finally, the general approaches that have been used to formulate the kinetics of viscous sintering analytically and the experimental results for viscous sintering of gels under conventional and applied load sintering are described.     

Densification kinetics of porous colloidal P2O5-doped silica gels using constant heating rate measurements

Commercially available fumed colloidal silica was gelled in an aqueous solution containing PO₄H₃. Instantaneous gelation was obtained by adding several drops of HF (48 wt%). The objective of this paper was to study the gel-to-glass conversion of these colloidal gels using constant heating rate (CHR) experiments.

Gel densification was measured at temperatures ranging from 50 to 1550°C at different heating rates (1 to 10°C/min) using a dilatometer.

Shrinkage and shrinkage rate as a function of temperature were measured and CHR equations were used to derive information on the densification mechanisms.

The experimental results show that small additions of PO₄H₃ into pure silica dispersions give rise to gels which densify to high silica glass at much lower temperatures than pure colloidal silica gels. The bloating effects produced by pure colloidal silica gels at temperatures above 1280°C were also eliminated. For these P₂O₅-doped silica gels maximum shrinkage rates were found at temperatures between 1050 and 1150°C according to the heating rate used.

The CHR analysis showed that several different mechanisms seem to operate in a complex interdependence in the whole range of temperature studied. This CHR analysis was compared with those results obtained from isothermal shrinkage experiments in the range where viscous sintering is the predominant shrinkage-controlling mechanism (between 1000 and 1100°C).     

Glass formation through hydrolysis of Si(OC2H5)4 with NH4OH and HCl solution

Monolithic silica glass was obtained by heating the gels prepared by hydrolyzing Si(OC₂H₅)₄ with NH₄OH and HCl solution. The effect of the condition of hydrolysis of Si(OC₂H₅)₄ on glass formation was examined by measuring the bulk density, the infrared spectra and the thermal shrinkage of the gel on heating. The gel prepared by hydrolysis with NH₄OH solution consisted of numerous spherical particles, the bulk density being about 0.8. This gel abruptly shrank at about 1050°C, being converted to the pore free material similar to fused silica. The conversion of the gel to glass followed the sintering model in which the viscous flow controlled the sintering process. The viscosity and the activation energy for viscous flow were calculated on the basis of the Frenkel equation. On the other hand, the spherical particles were not observed in the gel prepared by hydrolysis with HCl solution. The bulk density of the gel was about 1.8. This gel was converted to glass at about 700°C, which was lower than the temperature of glass formation for the gel obtained by hydrolysis with NH₄OH solution.     

r-GRIN glass rods prepared by a sol-gel method

Preparation of radial gradient refractive index (r-GRIN) glass rods has been undertaken by a sol-gel process using metal alkoxides. Two binary systems, Si(OCH₃)₄---Ge(OC₂H₅)₄ and Si(OCH₃)₄−Ti(O−n-C₄H₉)₄ have been investigated. It has been shown that immersion of rod-shaped wet gels in neutral or acidic water gives rise to leaching of the dopants (germanium and titanium components). Since this leaching is controlled predominantly by diffusion, the dopants remaining in the gels are expected to form concentration gradients. Optical measurements of the glass rods obtained after drying and sintering of the leached gels have shown that the concentration gradients are retained in the glass rods and they give r-GRIN profiles.     

Sintering of silica gel derived from the alkoxysilane solution containing N,N-dimethylformamide

The sintering of three kinds of dried gels with different microstructures prepared from the tetramethoxysilane (TMOS) solutions containing N,N-dimethylformamide (DMF) with varying [H₂O]/[TMOS] mole ratios and different catalysts was investigated by measuring the pore size distribution, the Vickers hardness, the linear shrinkage and the apparent density of the gels heated to various temperatures. The marked shrinkage of the pores started at temperatures above 900 °C. The temperature required for the conversion of a gel to a pore-free silica glass depended on the average size of the pores contained in the dried gels; the average pore sizes of about 50 Å, 75 Å and 100 Å corresponded to 1040 °C, 1060°C and 1080°C, respectively. The Vickers hardness, the linear shrinkage and the density of the gel showed a corresponding change with a change in heating temperature.     

Physical and chemical evolutions occurring in glass formation from alkoxides of silicon,aluminum and sodium

A multicomponent glass was obtained on using the new method of glass preparation from gel. The reactions occurring in the ethanolic solution of the parent alkoxides give condensation of the monomers so that hydrolysis of the remaining alkoxides groups followed by polycondensation appears to proceed on preformed oligomers. DTA, TGA, density and chemical durability measurements indicate that the transition from gel to the final glass is a continuous process. During the gel to glass conversion, scanning electron microscopy results show considerable compacting of the material.     

Study of the influence of some DCCAs on the structure of sol–gel silica membranes

We obtained silica gel membranes by sol–gel processing. In order to study the effect of some drying control chemical additives, we used an alkoxide/additive molar ratio of 1/1. The performance of the drying additives in obtaining crack-free gels was evaluated through monolithicity measurements. The structural evolution occurring in the interconnected network of the membranes during thermal treatment was monitored by Fourier transform infrared spectroscopy, structural density measurements and nitrogen gas sorption. The degree of cross-linking of the silica network was inferred from the frequency of the Si–O(Si) vibration in the range. We noted that in the presence of formamide and N,N-dimethylformamide, the Si–O–Si bonds are stronger and belong to a more cross-linked structure. Changes in the chemical properties of the membranes, evaluated by quantities of molecular water and silanol groups on their surface, were monitored by absorption bands in the range of 3800–3000 cm⁻¹. Membranes obtained with additives have surfaces covered by a large content of isolated silanol groups even when annealed at 800 °C. The membrane obtained in the presence of amide has larger pore volume and its pore structure is in the range of mesoporosity. The membranes without additive and with propylene carbonate are microporous. Formamide and N,N-dimethylformamide allowed the preparation of crack-free membranes stabilized at high temperatures.     

The phase transformation behaviors of Sn2+-doped Titania gels

The transformation behaviors of Sn²⁺-doped titania gels, such as transformation temperature, conversion rate and the crystal granularity, were studied by using thermo-gravimetric/differential thermal analysis and X-ray diffraction methods. Experimental results show that, anatase, rutile and SnO₂ phases can exist in the sintering products by varying Sn²⁺ content and sintering temperature. Sn²⁺-doping greatly depresses the growth of anatase and rutile crystals and so obtaining nanosized crystals The transformation temperatures of gel to anatase and anatase to rutile first decrease and then increase with an increase of Sn²⁺ content, while both of the transformation rates are associated with Sn²⁺ content, change in its valence and the sintering temperature. It is suggested that by adjusting Ti⁴⁺/Sn⁴⁺ ratio and sintering temperature, the crystal granularity and the ratio of anatase to rutile can be tailored to optimize properties of TiO₂–SnO₂ humidity sensing ceramics.     

Gradient-index glass rods of PbO---K2O---B2O3---SiO2 system prepared by the sol-gel process

A glass rod of the PbO---K₂O---B₂O₃---SiO₂ system having a radial gradient of refractive index has been prepared by the sol-gel process using aqueous solutions of lead acetate and potassium nitrate as the sources for index-modifying cations. A gel prepared by gelatinizing a sol from the mixture of tetramethoxysilane, tetraethoxysilane, and the aqueous solutions of boric acid and lead acetate was placed in an aqueous solution of potassium nitrate to form the concentration gradient of modifier cations by diffusion through the micropores of the gel. The glass rod of about 7 mm in diameter obtained by drying and sintering the gel had a refractive index of parabolic profile changing from the center toward the perimeter with a maximum difference of about 0.04.     

Some characteristics of glass in the Al2O3---B2O3---SiO2 system from the gel

The colorless and transparent glasses in the Al₂O₃---B₂O₃---SiO₃ system with high B₂O₃ and SiO₂ content were prepared from gels at low temperature. Their IR spectra not only revealed the evolution of the gel to glass conversion, but also showed that the formation of mixed bonds in the glasses obtained did not show any effect due to the B₂O₃ content. The accuracy of the glass composition is dependent upon the SiO₂/B₂O₃ molar ratio. The higher the ratio, the less the deviation of the analyzed compositions of the resulting glasses from their original calculated values. It is obvious that the higher the ratio, the lower the thermal expansion coefficient and the higher the transformation temperature of the glass, and the temperature at which the thermal contraction reaches an equilibrium is higher.     

Gel synthesis of glass powders in the BaO---Al2O3---SiO2 system

Homogeneous glass powders were prepared from multicomponent silicate gels in the BaO---Al₂O₃---SiO₂ system. Gels synthesized from TEOS, Al-sec-butoxide, and Ba-acetate were characterized by TGA, DSC, and single-point BET analysis. Amorphous oxide powders of controlled composition were obtained through an appropriate drying and heat treatment schedule. Inclusion-free clear oxynitride glasses were also prepared by co-melting gel synthesized oxide powders with silicon nitride powders.     

Shrinkage behavior of silica gels during drying

The shrinkage behavior during drying has been studied for silica gels prepared from a mixture of TEOS, water and ethanol. Significant differences in the shrinkage were noted between base- and acid-catalyzed gels after that the volumes shrank to about 40% of the initial value. The volume shrinkage was also affected by the alcohol/water ratio of the pore liquid. The gel had a tendency to shrink still more with increasing water concentration in the liquid. On the other hand, the higher the alcohol content of the pore liquid, the lower the bulk density of the dried gel. SEM pictures illustrate that both base- and acid-catalyzed gels have granular structures consisting of particles of similar size initially and, when dried, the packing state of the gel particles are different, depending on catalysis for the hydrolysis-polymerization and alcohol/water ratio of the pore liquid.     

Phase separation in the solution of water glass and poly(vinyl alcohol)

Silica gel samples with macropores were prepared from solutions of silicate and poly(vinyl alcohol) (PVA), where macropores were formed by fixing a transitional structure of phase separation. Among the silica sources tested, tetraethoxysilane (TEOS), colloidal silica and water glass, only the system with water glass shows phase separation and forms macroporous silica gel. In the system with TEOS, ethanol formed during hydrolysis of TEOS becomes good solution and stabilizes the system not to induce phase separation. In the system with colloidal silica, dense structure of silica is probably not suitable for controlling phase separation and gelation. In the system with water glass, driving force of phase separation is considered to be a repulsive interaction between solvent molecules and PVA interacting with silica surface and the solution separates into a phase rich in solvent and that rich in silica and PVA. One of the features in the water glass-PVA system is insensitivity of macropore size against compositional change in the solution, i.e. macroporous morphology in the resultant silica gel hardly changes by changing the composition ratio in the solution. This would be an advantage in the preparation of well-defined macroporous silica from water glass, whose composition varies among the product lot number, because reproducibility in macroporous morphology is ensured regardless of the lot number of the water glass.     

Polymeric Precursors for Inorganic Materials

Standard ceramic processing centers around the growth, compaction, and sintering of compact colloidal particles. Recently, however, it has become clear that numerous glass and ceramic processing techniques cannot be understood in terms of standard colloid physics. The purpose of this talk is to demonstrate several areas where polymer concepts are not only necessary for the understanding of ceramic processing, but also provide the insights necessary to tailor the properties of ceramic materials to achieve specific goals. The talk will center on the polymerization of silicates in solution. By control of the growth conditions such as catalysis, pH, and reaction sequence, it is possible to create a variety of structures from dense colloidal particles to randomly branched polymers. By mapping the polymerization process onto simple fractal models, it is possible to identify the essential factors that control the structure.     

Synthesis of window glazing coated with silica aerogel films via ambient drying

An ambient drying process (1 atm, 270 °C) has been developed in order to synthesize window glazing coated with silica aerogel films. The aerogel film could be manufactured by this process of wet gel films obtained via a dip-/spin-coating of the silica sol on a glass slide. Before drying, the isoproponol solvent in wet gels was exchanged with n-heptane to minimize the drying shrinkage. The thickness, refractive index, and porosity of silica films were 0.16–10 μm, 1.08–1.09, and 80–84%, respectively. The transmittance of window glazing was over 90% and we could predict that the optimal thermal conductivity (0.2 W/(m K)) of the window glazing would be obtained at the aerogel thickness of 100 μm (0.016 W/(m K)).     

Assembling ultra-thick and crack-free colloidal crystals via an isothermal heating evaporation induced self-assembly method

Ultra-thick and crack-free colloidal crystals have many advantages in a number of existing and emerging applications. In this work, such systems are fabricated by a simple and reproducible method based on assembly of monodisperse silica particles by a crystalline layer assembly technique (CLAT). We find that high quality of colloidal crystals is obtained by using two simple processes: sintering of silica particles and thermal treatment of colloidal crystals. The crack-free colloidal crystal with a thickness of 100 μm is fabricated. The morphologies and microstructures of colloidal crystals are identified by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The reflection spectra are measured by UV-VIS spectrum measurement. The reflection spectra of the colloidal crystal with different thicknesses are calculated by using multiple scattering methods. When the thickness of the colloidal crystal is smaller than 60 μm, the reflection spectra of experimental measurements agree very well with that of theoretical calculations.     

Different morphologies of the dry physical gels as a function of the sample preparation method

Xerogels obtained by drying the gels formed by glucofuranose derivatives with organic solvents were studied. The xerogels were characterized using the SEM, XRD, DSC and OPM techniques. The morphology of a xerogel observed by SEM may change from ‘amorphous, fibrillar’ to ‘crystal-like’, which may be caused by time or temperature. The results suggest that a similar transition may take place when the xerogel is being prepared. Thus SEM pictures of xerogels should be treated with great caution as they may not reflect the gelator network morphology in the bulk gel.