Silica Aerogel Synthesis and Applications A.

Introduction An aerogel is an open-celled, mesoporous, solid foam that is composed of a network of interconnected nanostructures and that exhibits a porosity (non-solid volume) of no less than 50% (aerogel.org). The discrete liquid in a hydrogel is replaced by air in aerogel. Silica aerogel comprises of rigid three dimensional network of contiguous particles of colloidal silica (1100 nm in diameter) (Iler 1978). The colloidal particles are connected via siloxane (Si-O-Si) bridge which constitutes the framework and decides the properties of silica aerogel. Silicon (Si) atom being tetravalent, is capable of forming four covalent bonds, and this leads to variation in arrangement of silica particle with a general formula of (SiO2). In general, silica can be broadly characterized as crystalline and amorphous; density of crystalline quartz, which is hardest form of silica, is 2.66 g/cm3 whereas density of amorphous clay is 2.2 g/cm3. Silica aerogel is categorized under amorphous silica due of absence of ordered arrangement. Silica aerogel on an average posses high surface area (500-1200m2/g), high porosity (80-99.8%), low density (~0.003g/cm3), low thermal conductivity (0.005W/mK), low dielectric constant (k=1.0-2.0) and low refractive index (~1.5) (Dorcheh and Abbasi, 2008). Silica aerogel in recent has received lot of attention due to its unusual properties. The properties of silica aerogel are largely determined by the protocol of its synthesis. Evaluating its chemical and structural properties is crucial where newer technologies are pouring in to accurately estimate its parameters and make measurement easier and quicker. Another area which interests the scientific community is application of aerogel. Newer niche are emerging in field of silica aerogel research. This seminar report presents a brief summary of important aspects of aerogel, viz. synthesis, properties and applications. B. Synthesis Silica aerogel was first prepared by Samuel Stephens Kistler in year 1931 as a result of obtaining liquid free gel. He started with silica hydrogel and used ethyl alcohol at critical point to replace water, without shrinkage in pore structure (Kistler, 1932). Silica aerogel is now largely produced using sol-gel process. Sol-gel process is a technique to get integrated network of particle or polymer (gel) from a finely dispersed colloidal solution (sol). Three reactions used to describe the sol-gel process are, (Brinker and Scherer, 1990) a. Hydrolysis of silica source to form silica monomer (silicic acid). b. Polymerization of silica monomer by water condensation reaction. c. Polymerization of silica source by alcohol condensation reaction (Figure 1)

Figure 1: Sol gel reactions Synthesis of silica aerogel can be divided into three main regimes: (gel formation, aging and drying) 1. Gel formation Alkoxysilane (Si-(OR)4), watergalss (Na2SiO3) and sand (SiO2) are the prominent precursors for silica gel formation and alkoxysilane are widely used because of their high purity and ease of operations. Among the alkoxysilane group, low molecular weight members such as tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), methyltrimethoxysilane (MTMS) are preferred choices (Figure 2).

Figure 2: Silica precursor (alkoxysilane) Preparation of sol involves forming homogeneous mixture of silica source in suitable medium. Alkoxysilane are immiscible in water and hence organic solvents such as alcohols, acetone, dioxane, tetrahydrofurane are used to solubilize water and alkoxysilane both, so that hydrolysis (reaction 1 in Figure 1) reaction can be initiated. Water to alkoxysilane (H2O/Si(OR)4) ratio should be at least 4:1 for complete hydrolysis. Hydrolysis of alkoxysilane is a facilitated by acid and base catalyst. Hydrochloric acid (HCl), sulphuric acid (H2SO4), formic acid (CH2O2), acetic acid (C2H4O2), oxalic acid (H2C2O4) etc., are widely used as acid catalysts. For hydrolysis under basic condition, ammonia (NH3) in dilute concentration is preferred over sodium hydroxide (NaOH) and ammonium fluoride (NH4F). Both, hydrolysis and condensation reactions (reaction 2 in Figure 1) occur simultaneously. Rate of hydrolysis and condensation varies non-monotonously with pH (as shown in Figure 3). Hydrolysis is favored in acidic pH where as condensation is favored in basic pH, hence, mixed (combination of acid and base) 2

catalyst is used to increase the overall reaction rate (Iler, 1978). Synthesis of sol using basic catalyst creates uniform particle size distribution whereas acid catalyst gives randomly linked silica particles.

Figure 3: Effect of pH on relative rate of hydrolysis and condensation (Reprinted from Dorcheh and Abbasi, 2008).

2. Aging Aging is characterized by cross-linking of polymer matrix. Aging of silica gel progresses through a) Ostwald ripening and b) Neck growth. Ostwald ripening is characterized by further growth of larger particle at the expense of smaller particle. The phenomena is described by Kelvin equation which relates the solubility of a particle with its size as, ( ) , (1)

where, S and S0 are solubility of curved and flat surfaces respectively, sl is interfacial tension between silica precipitate and aging solution, Vm is molar volume of silica precipitate, R is gas constant, T is temperature and r is the radius of curvature (Brinker and Scherer, 1990). Based on the equation smaller particles have high solubility and hence dissolves into the solution, whereas larger particles grow due low solubility. When two large sol particles (colloidal particles) cross linked, they create a neck region at the intersection. As the curvature of neck region is concave, the solubility of this region is lesser compared to bulk (illustrated by the Kelvin equation). Due to this driving factor the small oligomers precipitates onto the neck region. The implication of theses growth mechanisms, occurring simultaneously, is that, it leads to stronger and rigid gel network by addition of small oligomers. However, when washing is performed using water or alcohol, it makes solid gel more permeable to liquids. It has been observed that when aging is performed in basic medium it leads to unimodal pore size distribution with increase in pore volume and mean pore diameters. When gelation time extends for days, the evaporation of solvent leads 3

to a shrinkage of framework, which could be avoided by using low vapor pressure solvents. Usage of ionic solvents, that have low vapor pressure, has also been reported in literature for silica aerogel synthesis (Dorcheh and Abbasi, 2008).

3. Drying The major challenge in drying is the capillary pressure exerted on the silica structure due to presence of liquid-vapour interface. Capillary pressure depends on, liquid-vapour interfacial tension (lv), contact angle () and size of pore (rp), which is illustrated by Young-Laplace equation (Brinker and Scherer, 1990),
( )

(2)

where, Pc is differential capillary pressure. For pores ranging from 2-50 nm, the differential pressure ranges from 100 to 200 MPa. This large capillary force is sufficient to destroy nano structure of silica framework, leading to a dense solid, known as xerogel. Such destructive forces need to be avoided to preserve the porous structure of wet gel. Since the major parameter responsible for capillary forces are contact angle and interfacial tension, one can mitigate the capillary forces by changing these two parameters, and device appropriate drying protocol based on them. a. By changing the surface characteristic of the silica aerogel, it can be changed from hydrophilic to hydrophobic, which will either reduce or reverse the direction of capillary forces (Figure 4).

Figure 4: Capillary forces in hydrophilic and hydrophobic silica aerogel In this method surface of silica network is modified using suitable silylating agents which replaces polar hydroxyl group (-OH) with non polar group as shown in Figure 5. Due to inverted liquid-vapour interface

the capillary pressure helps in expanding the pore, rather than collapsing and interns strengthen the silica aerogel.

Figure 5: Silylating of silica gel

Figure 6: Silylation agents Silylating agents such as trimethylchlorosiliane (TMCS), hexymethyldisilazane (HMDS) etc whose chemical structures are shown in Figure 6 are often used. Silylating agent should have at least one free site to react with terminal (-OH) in silica gel replace it with its non polar group. This modified silica gel can be dried at ambient pressure at 50 -100 C (Mahadik et al., 2011). Silylation of silica aerogel could be carried out either by adding surface modifying agents at the gel fromation step or by keeping wet gel in bath of silylating agents after it has been obtained by convential method. Gels obtained by this method is relatively less denser than conventional method and has larger pore volume. b. The other parameter to control capillary pressure is liquid vapour interfacial tension (lv), which vanishesh when interfacial boundary is dissolved. By operating at supercritical conditions of solvent, the liquid-vapor interfacial boundary can be dissolved, and hence avoid damages the due to capillary forces. Such successful attempts was first demonstrated by Kistler (Kistler, 1932), where he used low boiling solvents (ethanol) to prepare wet gel, and subsequently brought to critical conditions by slowly

increasing the temperature and pressure. Such modes of drying (where organic solvents are frequently used) is known as high temperature supercritical drying (HTSCD), since it has to be operate at very high temperature (>500 K). Since organic solvents are flammable, they are prone to accidents, and fire risk increases exponentially with increase in temperature. Low temperature supercritical drying (LTSCD) uses carbon dioxide (CO2) gas, whose critical point is close to ambient condition, hence can be operated at low temperature and pressure (around 310 K and 80 bar). It requires an additional step of replacing pore solvent by carbon dioxide (CO2) by flushing it at high pressure of 100 bar.

TMOS hydrolysis rapidly and gives narrow and uniform pores with high surface area than TEOS. MTMS gives high surface area with more flexible network than TEOS. Addition of MTMS to TMOS yields more hydrophobic aerogel, compare to TMOS alone. Addition of dimethyldiethoxysilane to TEOS shifts pore size to larger pore radii. Alkoxides are highly hazardous and causes blindness. It is also expensive and hence not commercialized, therefore now trend is to search for cleaner and less expensive silica source. Waterglass is cheaper and gives monolithic and large pore size aerogel. Important parameter while using waterglass is Na2O/SiO2 molar ratio which gives best results at 1:3.3 and Na2SiO3/H2O > 8:1000 (Dorcheh and Abbasi, 2008).

4. Additives Additive such as polyethylen glycol(PEG), polyvinyl alcohol (PVA), methyltriethoxysilane (MTEOS) have been used during synthesis to imporve properties of resulting aerogel. PEG reacts with silica structures to forms a spacing between them, thus, acting as a template for pore. In small concentration it strenthen the solid matrix however, in large concentration it weakens the solid matrix. Water soluble polymer such as PVA can be used for controlleing pore size of aerogel. PEG and PVA promotes lipase activity and therfore can be used as biocatalyst support. Surfactant in water- ethanol solution gives surfactant templated aerogel. C. Characterization With advent of sophisticated instruments it is now possible to accurately measure different properties of silica aerogel. This section explains important properties of silica aerogel and their characterization technique used. 1. Pore structure The porous silica aerogel is termed by IUPAC as mesoporous materials as its majority of pores lies in the range of 2 to 50 nm. Silica aerogel is also termed as open pore of interconnected network, because fluid can flow from one pore to another. The structural properties of interest relates pore size, crystallinity and porosity. BET characterization based on nitrogen adsorption/desorption technique is used to estimate pore size, size distribution and surface area of aerogel. This method is suitable for silica aerogel because of its smaller pore size where conventional technique such as Mercury intrusion technique is not suitable. Typically silica aerogel have average pore diameter in range of 20-40 nm and BET surface area of 6001000 m2/g and porosity of 99%. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) is used for studying micro structure of silica aerogel. Although it gives direct examination of aerogel there may be electrostatic loading of fine aerogel powder and may alter the 6

observation. In addition, predicting 3D structure from 2D images is difficult, however primary structures of (2-3 nm) which have micro pores and secondary structure are obtained as a network of primary structures thus giving low density can be observed from the images. Atomic force microscopy (AFM) can be used to study densification of aerogel. Nuclear magnetic resonance (NMR) is used to study stages of condensation reactions.

2. Thermal conductivity Silica aerogel has very low thermal conductivity, even lesser than air (Dorcheh and Abbasi, 2008). Its thermal conductivity is in order of 0.02 W/mK at ambient condition and 0.01 W/mK when air from the pores is evacuated. Transmission of energy in form of radiation is also less, because aerogel is significantly opaque in infrared (IR) region of spectrum. Being open pore structure, hot gases can pass through and still conduct energy. To calculate total thermal conductivity all the three modes are to be coupled which is carried out in vacuum insulation conductivity tester (VICTOR).

3. Optical Properties Silica microstructures are smaller than wave length of visible light, therefore it appears as transparent porous material. It has small amount of light scattering in blue region thus giving it a characteristic blue tint. Scattering characteristic is measured using Rayleigh scattering apparatus. Refractive index of aerogel is calculated using Clausis-Mosotti equation (Poelz and Riethmuller, 1982); , (3)

where, n is refractive index, is density of aerogel, ns = 1.46 is the refractive index of crystalline silica of density, s = 2.2 g/cm3, which depends only on density of aerogel. 4. Surface property Silica aerogel are highly hydrophilic in nature due to presence of polar (-OH) group at terminals of silica network. Surface (-OH) group of silica aerogel can be modified by a) adding silylating agent during sol-gel synthesis process or b) passing methanol gas through the dried aerogel (Lee and Kim, 1995). The silylated aerogel are hydrophobic because all (-OH) groups are replaced by non polar groups. Fourier transform infrared spectroscopy (FTIR) is used to confirm the presence/absence of nonpolar/polar group in modified silica aerogel. The wetting behavior of aerogel is estimated by evaluating contact angles and surface energies (sv). Surface energy can be calculated by using Neumanns equation, which incorporates general Youngs equation, (Mahadik, 2011)

( )+

( )+

(4)

where, = 0.000125 (mJ/m2), is contact angle, sv and lv are surface energies of solid-vapour and liquid-vapour respectively. Contact angle of hydrophobic silica aerogel is observed to be in range of 130150 C. Hydrophobicity can be retained for higher temperature up to 673 K, after which alkyl group (CH3) decomposes giving back hydrophilic aerogel. Table 1: Properties of Silica aerogel Property Apparent density (g/cm3) Internal surface area(m2/g) Primary particle diameter(nm) Refractive index Coefficient of thermal expansion (micro strain /C) Thermal conductivity(W/mK) Dielectric constant Speed of sound(m/s) 0.016-0.03 1.008-2.27 70-130 VICTOR Values 0.0011-0.65 500-1000 2-5 1.002-1.08 2-4 10-6 Ultra sonic method BET Surface area Electron microscopy Instruments

D. Applications Due to its versatile properties, silica aerogel have potential applications in various areas. However it not commercial utilized because preparation of silica aerogel is expensive so as to use in day to day application. This section will explore some of the applications of silica aerogel in representative areas. 1. Catalysis and reaction engineering Silica aerogel poses high porosity (>85%) and very large surface area (1000m2/g), which is desirable property for catalytic application, and already being used for synthesis of nitrile from hydrocarbon and nitric oxide (Rousset J. L., et al., 1990). Because of its three dimensioned network, it can be used as catalyst support as demonstrated in the study of aerogel supported copper zirconia catalyst for synthesis of methanol from carbon monoxide (Gurav, et al., 2010). Its porous nature can also be used in adsorption based applications such as filters, adsorbing media and encapsulation medium etc.

2. Biotechnology Silica aerogel being non toxic and chemically inert, can be used in biotechnology as a carrier for drug delivery. After coating its surface with Eudragit L, it can be used for targeted drug delivery (Alnaief et al., 2012). Because of its large internal network it can be used as biosensor to recognize specific bioactive molecule, recently shown in case of recognizing human gene ATP50 by oligonucleotide immobilized in aerogel (Gurav, et al. 2010).

3. Architectural application By incorporating hydrophobicity in silica aerogel, it has potential application as transparent window insulating material, due to its low thermal conductivity (< 3W/m K). It is used as a template for dye sensitized solar cell (DSSC), when it is deposited with atomic layer of titanium dioxide (TiO2) because of its large surface area to efficiently load TiO2. Brittleness of silica aerogel can be avoided by obtaining composites with suitable polymer like polyester, leading to flexible insulating blankets. Such blankets have potentials to replace conventional insulators.

4. Physical science Because of very low dielectric constant of silica aerogel, it is used in the form of thin film for inter layer dielectric spacer in integrated circuits. Being optically transparent, Cherenkov radiation, occurring due to particle passing through medium, could be detected. Aerogel doped with radioactive substance like tritium and phosphor can be used as efficient radio luminescent light source. Hydrophilic silica aerogel shows increase in electric conductivity with increase in relative humidity, and has potential to be used as humidity sensor (Gurav, et al. 2010).

5. Space science research The insulating property of silica aerogel is manifested in providing thermal shield to space craft, space suits and Martian Rovers. Being highly porous with large network, high velocity cosmic particle can be trapped inside silica aerogel matrix. Thus it is been used as hypervelocity particle collector in Sprit and Opportunity space programs. It was successfully employed in Stardust project to capture particles from comet Wild2 (aerogel.org).

E. Summary and Conclusion We have discussed various aspects of silica aerogel synthesis such as raw material, different stages of synthesis and effect of additive on properties of silica aerogel. Crucial properties of silica aerogel which gives detail insight of specific properties, its measurement and instrumentation required. We also highlighted some of its potential and trapped applications of silica aerogel. Silica aerogel is still in a developing stage. There are several issues pertaining during synthesis process and reproducibility, property optimization and overall cost of production. For commercializing the silica aerogel such challenges are need to be addressed.

F. Scope for future work

The challenge in the field of aerogel commercialization is its cost of production. This issue can be address by exploring inexpensive raw materials and economical technology. Silica aerogel is also unsuitable in ambient condition because of its hydrophilic surface which adsorbs water onto it. Surface modification by silylating agent is to used to overcome this problem. But in application of drug we need to alter its surface property as per local condition in this case we need to explore special coatings which alter its properties as required. There can be several modifications possible in conventional synthesis of aerogel to alter its properties as recently demonstrated by addition of aluminum ions which alters the mean particle size distribution of primary structure (Shyong and Chang, 2004). By incorporating various other parameters, tailor made silica aerogel could be prepared as shown in recent study, where silica aerogel composites of metal organic framework was prepared, (Ulker and Erucar, 2013). Such tailor made aerogel can be utilized for trapping CO2 and catalytically converting in valuable fuel.

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