Physicalchemisty

Topic: NanoarchiTecture of silica and polydimethysiloxane

Introduction Mold clay to form a bowl. It is the empty space which makes the bowl useful. Lao Tzu This old Chinese proverb expresses the essence in working with porous materials. We can shape them, make pores in varying sizes and structures and finally use all the surface and empty space in them for multiple applications. Materials with large surface area have applications such as matrixes for catalysts, chemical reactors and gas storage. To increase the surface area of a material, the

particle size of the material can be reduced or open pores can be introduced. In this thesis highly porous silica will be studied.

Mold clay to form a bowl Mesoporous materials have pores in the size range of 2 to 50 nm. It is common to use two different paths for syntheses of materials on the nanoscale: top-down or bottom-up. In the top-down approach one starts from the top, from a larger unit, and shape this unit into a nanostructure by for example cutting or milling. The top-down approach is used for manufacturing e.g. microchips and micropatterning. The bottom-up approach is based on properties of single molecules which can self-assemble and form structures. This approach is common when mesoporous materials are synthesized by self-assembly of surfactants to form micelles and condensation of metal species onto these micelles. Variations in the final material such as different pore sizes and morphologies can be gained by changing the properties of the original molecule.

It is the empty space that makes the bowl useful Materials with high open porosity have a large available surface area compared to materials with no or closed porosity. In mesoporous silica the specific surface area is commonly 500-1000 m2/g which is approximately the area of a handball court in the volume of a water glass. The high specific surface area of mesoporous silica makes it an excellent substrate for catalysts and mesoreactors where chemical reactions take place in the pores. Available surface in (a) solids and materials with (b) closed and (c) open porosity.

The narrow pore size distribution of mesoporous silica also makes it suitable as templates for other materials and as a constrainer when growing nanoparticles inside the pores The synthesis, characterization and application of mesoporous silica SBA-15 with unusually large pores ( 18 nm) is presented. The material consists of ~400 nm crystallites with cylindrical, hexagonally ordered pores running through them. The crystallites are either monodispersed or attached to each other, forming different morphologies such as fibers or sheets. If instead the crystallites are attached to a substrate, a porous film is formed in which the pores can be oriented parallel or perpendicular to the substrate. The monodispersed crystallites can be elongated and thereby the thickness of the mesoporous film is controlled.

MESOPOROUS MATERIALS
Mesoporous materials are materials with pores in the range of 250 nm according to the IUPAC classification in which micropores have a diameter < 2 nm, mesopores have a diameter between 2 and 50 nm and macropores have a diameter > 50 nm . The pores can have different shapes such as spherical or cylindrical and be arranged in varying structures. Some structures have pores that are

larger than 50 nm in one dimension,but there the width of the pore is in the mesorange and the material is still considered to be mesoporous. Mesoporous materials are materials with pores in the range of 250 nm.

Figure 1. Different pore structures of mesoporous materials. Mesoporous materials can have a wide range of compositions but mainly consists of oxides such as SiO2, TiO2, ZnO2, Fe2O3 or combinations of metal oxides, but also mesoporous carbon can be synthesized. Most commonly is to use amicellar solution and grow oxide walls around the micelles. Both organic metal precursors such as alkoxides as well as inorganic salts such as metal chloride salts can be used. Alternatively a mesoporous template can be used to grow another type of mesoporous material inside it. This is often used for synthesizing e.g. mesoporous carbon.

Mesoporous silica In 1992 a new family of ordered mesoporous materials was reported and this became the starting point of a new research field. These materials are named MCM-X (Mobil Crystalline of Materials) and were synthesized by Mobile Corporation laboratories. Mesoporous silica with different pore structures were synthesized e.g. MCM-41 with hexagonally ordered cylindrical pores and MCM48 with a cubic pore structure. These materials are synthesized with cationic surfactants under basic conditions. This was though not the first attempt of synthesizing mesoporous silica. There is a patent from 1971 regarding synthesis of low-density silica where cationic surfactants were used . In this patent there is no report concerning porosity, only the low bulk density was of importance. Later this material has been synthesized, characterized and compared to MCM-41. It is clear that this

material is a predecessor to the mesoporous silica that is synthesized today, even though the importance of this type of material was not recognized then. The first mesoporous silicas synthesized with non-ionic triblock polymers were reported in 1998 by Zhao et al. [8,14]. These materials are named SBA-X (Santa Barbara Amorphous) where X is a number corresponding to a specific pore structure and surfactant, e.g. SBA-15 has hexagonally ordered cylindrical pores synthesized with P123 as surfactant while SBA-16 has spherical pores arranged in a body centred cubic structure and is synthesized with F127. SBA-15 is the most extensively studied mesoporous silica and also the subject of attention in this thesis.
Other families of mesoporous silicas are e.g. MSU [15], KIT [16], FDU [17] and AMS [18] where the materials are synthesized with variations in e.g. synthesis conditions and surfactants. SBA-15 SBA-15 is a mesoporous silica (SiO2) which has cylindrical pores arranged in a hexagonal order synthesized with the Pluronic triblock-copolymer P123. The structure of SBA-15 is illustrated in Figure 3. For this material, the pore size refers to the width of the cylindrical pores which can be tuned between 4-26 nm even though pore sizes above 12 nm are rare. The length of the pores varies from ~200 nm to several microns. Around each mesopore is a microporous network called the corona . This network interconnects the mesopores with each other and is responsible for the high surface area of SBA-15. The microporous network was first shown by platinum replicas where the nanorods from filled mesopores were interconnected by the network which makes the nanorods remain in the

hexagonal structure even after removal of the silica( Figure 2). The corona is mainly supposed to originate from trapped hydrophilic chains of the surfactants. An additional explanation for the corona is stressinduced defects where the micropore fraction increases with the effective pore wall thickness to average pore diameter ratio . It is stable up to 1173 K, but above this temperature the network disappears and the material has similar structure to MCM-41.

Figure 2. The structure of mesoporous silica SBA-15 (to the left) and its replica in form of rods (top right) and straws (down right). The corona plays a crucial role when using SBA-15 as a template for other materials.. Replicas can be synthesized in two variants, one rod-like and one straw-like see Figure 2. Due to that the micropores also will be filled with the replica material the mesopore replicas will be fixed in the hexagonal structure and the particle morphology will be retained. If instead MCM-41 is used as template, the end result is more similar to spillikin. COLLOID AND SOL-GEL CHEMISTRY The synthesis of SBA-15 is called sol-gel synthesis. The solution (sol) is the colloidal system where micelles are formed by surfactants and are dispersed in aqueous solution. When the silica precursor is added to the sol it hydrolyses and a silica network is formed in which the liquid is enclosed, a gel. The transition

between sol and gel is gradual and the sol becomes a gel when it can support a stress elastically. Finally the gel is heated (calcinated) whereby the surfactants decompose and evaporates. Left is now the porous silica network. Surfactants Surfactants (surface active agents) are amphiphilic molecules, i.e. they are composed of a hydrophilic (water-loving), and a hydrophobic (water-hating), par. Surfactants are classified by their head group: anionic, cationic, zwitterionic and non-ionic.

Micelle formation and structures When the concentration of surfactants is low in an aqueous solution, the surfactants are located as separate molecules in the air/water interface. This reduces the surface tension since it is larger for water than for the hydrocarbons. Increasing the surfactant concentration in the solution further reduces thesurface energy until a critical value. At this point, the critical micelle concentration (CMC) is reached and aggregates of surfactants (micelles) are formed. The CMC is determined by two competing factors; bringing the nonpolar chains out of the water phase into the oil phase (hydrophobic effect) and repulsion between the polar head groups which opposes the formation of micelles . The CMC and shape of the micelles are determined by the nature of the surfactant and conditions in the solution such as temperature or salt additions. The aggregate structure of the amphiphilic molecules is determined by the critical packing parameter (CPP)

3.2 Non-ionic triblock copolymers, Pluronics When mesoporous silica is synthesised, several types of surfactant can be used e.g. cationic CTAB [2,7], non-ionic PEO surfactants [15] or Pluronics [8]. In this work Pluronic P123, a non-ionic amphiphilic triblock copolymer, Figure 6, has been used as surfactant. CPP=v/l-a where v is the volume of the hydrophobic chain [nm3], a is the area of the hydrophilic part [nm2] and l [nm] the length of the hydrophobic chain. The volume v and length l can be expressed by v=0.027(nc+nme) l=0.15+0.27nc where nCis the number of carbon atoms and nMethe number of methyl groups. The relation between CPP and aggregate structure is illustrated in Figure 5. The cylindrical hexagonal micelles needed to form SBA-15 has 1/3 < CPP < 1/2. 3.2 Non-ionic triblock copolymers, Pluronics When mesoporous silica is synthesised, several types of surfactant can be used e.g. cationic CTAB , non-ionic PEO surfactants or Pluronics . In this work Pluronic P123, a non-ionic amphiphilic triblock copolymer, Figure 6, has been used as surfactant.

Figure 3. Critical packing parameters of surfactant molecules and preferred aggregate structures for geometrical packing reasons There are several non-ionic triblock copolymers under the trademark Pluronics. These polymers were patented in 1973 and are also called Poloxamers . They all consist of hydrophilic polyethylene oxide chains (PEO) and hydrophobic polypropylene oxide chains (PPO). There are several different Pluronics with varying molecular weights and PEO/PPO ratios (EOxPOyEOx). The notation for a Pluronic triblock copolymer starts with a letter followed by two or three

numbers. The letter describes the appearance of the polymer: F (flake), P (paste) or L (liquid). The first one or two numbers multiplied with 300 indicates the molecular weight of the PPO block and the last number gives the PEO weight fraction . Hence, P123 is a paste with ~3 600 g/mol PPO and 30 wt% PEO while F127 is solid flakes with the same weight of PPO but 70 wt% PEO. These differences give rise to the variation of pore structures observed in the mesoporous materials, e.g. F127 is used for synthesizing spherical pores in a body centred cubic structure while P123 is used for hexagonally ordered cylindrical pores .

Micelle formation with Pluronics As mentioned earlier, the concentration of surfactants and temperature of the solvent is crucial for the formation of micelles. These two parameters vary for the PEO-PPO-PEO surfactants with respect to the structure and weight of the polymers. For example, Pluronics with PEO segments of the same size have both the CMC and critical micelle temperature (CMT) decreasing with increasing PPO size. The size effect of the PEO chain is less pronounced than the effect of the PPO size. It is clear that for Pluronics the micelle formation is driven by the PPO chain . The micelles consist of a hydrophobic PPO core surrounded by hydrophilic PEO chains which form a corona around the core. Temperature dependence The properties of the PEO and PPO blocks are highly temperature dependant since the hydration of methyl groups in both blocks depends on the temperature During the micelle formation process there are three temperature regions of importance: the unimer region (where the surfactants are not aggregated), the

transition region and the micelle region . At low temperatures, the unimer region, the methyl groups of the PPO blocks becomes hydrated and can form hydrogen bonds with the water. When the temperature is increased the methyl groups rotate and the hydrogen bonds are broken . At CMT and during the transition region there is a mixture between micelles and unimers. In this region the interaction between PPO and water is reduced and the PPO chains instead interact with each other. Thereby the micelles with nonpolar, hydrophobic cores are formed. This is happening gradually for a small temperature interval of ~10 C . Finally the micelle region is reached and all surfactants are aggregated to form micelles. The CMT depends on the concentration of micelles in the solution. This is of great importance when synthesising mesoporous materials. The CMT can be changed for a given surfactant concentration by adding salts. This will be discussed further in section 3.3.3. Above CMT, spherical micelles increase in size with increasing temperature until the micellar core reaches the radius of a completely stretched PPO chain. At this point the structure of the micelles changes from spheres to cylinders . A phase diagram is useful for finding CMC, CMT and micellar shapes. Water becomes a worse solvent for the PPO and PEO chains when the temperature is increased due to the increasing number of polar states. Above a critical temperature, the cloud point (CP), the surfactants can no longer be dissolved to form micelles and instead they precipitate from the solution . Sphere-to-rod transition To form the cylindrical pores in SBA-15 the micelles must undergo a transition from spherical to cylindrical shape. During the synthesis, the temperature and

surfactant concentrations are kept constant. Hence, other parameters during the synthesis are responsible for this change in CPP leading to the sphere-to-rod transition. During the synthesis, this transition occurs upon addition of the silica precursor, TEOS. Ethanol is a decay product of TEOS, and in a given temperature range PPO is soluble in ethanol. When the ethanol goes into the hydrophobic core of the micelles, the core volume expands and the CPP increases according to Eq. (1) . The transition can also occur upon additions of salt , or increasing the temperature [60] since these decrease the hydrophilic area of the surfactants due to dehydration of the PEO chains. Salt additions The addition of salt to the synthesis of SBA-15 makes it possible to decrease the synthesis temperature from 35 55 C to as low as 10 C , Smaller pore sizes are achieved when a combination of salt additions and a low temperature (and no swelling agents) are used. The properties of non-ionic triblock copolymers, such as P123, are also strongly affected by salt additions. By salt additions CMT, the sphere-to-rod transition and CP can be shifted. The shifts are proportional to the concentration of salt. For example, F, Cl, Br, Na+, K+ and Li+ decreases the CMT, sphere-to-rod transition and CP while SCN increases the solubility of P123 that gives higher temperatures for the transitions. Anions have a larger effect on the CMC and CP than cations . It has been shown that CMTno salt CMTsalt = CPno salt CPsalt when salt are added to a solution except for I which instead increases CP and decreases CMT.

This is very useful, since sometimes only one of these two parameters can be studied. Most, but not all, salts decrease the solubility of organic polymers (salting out phenomena). Some salts act as structure makers for the water and increases the self-hydration of water through hydrogen-bonding. Other salts act as structure breakers and decrease the number of hydrogen-bonded OH groups . Anions give a stronger effect on solubility of polymers and their salting out strength at a given molar concentration follows the Hofmeister series: SO4
2 HPO4

2 > F > Cl > Br > I > SCN. Ions preceding Cl in the series are polar water-structure makers and those after Cl water-structure breakers. Cl has little effect on water structure . It is commonly said that salts increase the solvophobicity of PEO and PPO chains and therefore induce micelle formations and it is known that PEO chains form aggregates in water solutions with salt additions. It has been suggested that this aggregation is driven by the structuring of water. The PEO chains are surrounded by a zone where water has increased structure . When an ion approaches a PEO segment the amount of water between these two decreases. PEO is far less polarisable than water and the removal of the polarized water will induce a repulsive force between the ion and PEO chains. On the other hand, the removal of water leads to an attractive force between the PEO chains. The total force from these two contributions depends on the ion. The larger the ion, the more attractive the force will become. This is due to that for larger ions, a larger amount of structured water will be expelled .

The effect of cations on the other hand, does not follow the Hofmeister series, but instead the effect depends on the counter ion . This can be due to that there is not as large size difference between cations as for anions . For Cl as anion the effectiveness of cations follow Cs+ K+ > Li+ [59]. Silica precursor Several types of silica precursors can be used for mesoporous silica. The most common are alkoxides, especially tetramethyl orthosilicate (TMOS) or tetraethyl orthosilicate (TEOS), see Figure 9, but other alkoxides with longer alkyl chains can be used . An alternative, cheaper, silica precursor that can be used is sodium silicate or combinations of this and alkoxides . In this work, only TEOS has been used as the silica source In aqueous solutions the alkoxides hydrolyses (i) and polymerises to form a silica network (ii) and (iii). Both steps can be controlled by varying pH and adding salts to the aqueous solutions as described in literature reviews [75,76] and references therein. (i) Hydrolysis Si OR + H2O Si OH + ROH (ii) Alcohol condensation Si OR + HO Si Si O Si + ROH (iii) Water condensation Si OH + HO Si Si O Si + H2O The hydrolysis of TEOS needs an acid or basic catalyst to occur, and the hydrolysis rate is directly proportional to the concentration of acid or base. In general, short alkyl chains hydrolyse faster than long chains. Hydrolysis and gelatation occurs simultaneously. H3O+ increases the rate of hydrolysis while OH increases the gelatation rate, so at pH suitable for synthesis of SBA-15 (pH 2) the hydrolysis is fast but the polymerization is slow. In the presence of alcohols, the hydrolysis rate of TEOS is reduced . This can

be used for controlling the morphologies of SBA-15. The hydrolysis of TEOS needs an acid or basic catalyst to occur, and the hydrolysis rate is directly proportional to the concentration of acid or base. In general, short alkyl chains hydrolyse faster than long chains. Hydrolysis and gelatation occurs simultaneously. H3O+ increases the rate of hydrolysis while OH increases the gelatation rate, so at pH suitable for synthesis of SBA-15 (pH 2) the hydrolysis is fast but the polymerization is slow. In the presence of alcohols, the hydrolysis rate of TEOS is reduced . This can be used for controlling the morphologies of SBA-15.

SBA-15 SYNTHESIS
The synthesis of SBA-15 is straight forward and uncomplicated. First the surfactant, P123, is dissolved in hydrochloric acid and then the silica precursor, e.g. TEOS, is added. This solution is stirred for a given time (2-20 h) at 40 C and then heated to 80-130 C for 24-72 h (hydrothermal treatment). Finally the product is collected by filtration and calcinated at 550 C to remove the template. There are several ways to control the pore size, microporosity and particle morphology to obtain the optimal product, e.g. addition of salt, swelling agents and/or temperature variations which will be discussed here. 4.1 Formation The formation mechanism of SBA-15 is assumed to be similar to the formation of MCM-41 which was suggested by Beck et al. to be a liquid crystal mechanism. This can be seen in Figure 10 and shows how the micelles starts as spherical and when the silica precursor is added, the micelles becomes elongated and

arranges themselves in a hexagonal pattern while the silica walls are built. After calcination, the surfactants are removed and only the mesoporous silica remains.

Experimental studies of the formation of SBA-15 with e.g. SAXS, NMR and TEM have shown that when the silica source is hydrolyzed it is adsorbed on the PEO chains of the micelles. The polymerization of the silica introduces an attractive interaction between the micelles which leads to the formation of flocs of micelles. These domains grow larger and the final structure is reached. The

time for elongation of the micelles has been thoroughly discussed, if it occurs prior to or during the formation of flocs. SAXS and cryo-TEM have though shown the presence of separate threadlike (cylindrical) micelles prior to the floc formation . The mechanism of the elongation of the micelles has been studied with various techniques. Prior to the addition of silica precursors the micelles are spherical but TEOS and TMOS are hydrophobic, so when they are added to the synthesis they enter the hydrophobic core of the micelles. The hydrolyzed precursors then diffuse into the corona region and adsorb onto the P123 and the polymerization process begins in the core/corona interface and continues then only in the corona. The polymerization in the core/corona region is simultaneous to the elongation of the micelles while the polymerization in the pure corona is associated with the precipitation of flocs. When the silica precursor is polymerized on the PEO chains, the water content in this area is decreased. This changes the polarity resulting in a reduced curvature of the micelle and hence, the micelles become elongated. Theoretical modelling of the formation of mesoporous materials has shown that the silica preferably adsorbs onto low curvature sections of the micelles. During the elongation of the micelles the surface energy of the spherical caps on the ends increases and therefore no silica will attach there, leaving the pore ends open in the calcinated material .

Hydrothermal treatment When the formation of SBA-15 is finished, the temperature is increased and the hydrothermal treatment begins. As mentioned in section 3.3.1 the properties of

P123 is temperature dependent and therefore this is a good way of tuning the properties in term of pore size, micropore volume and surface area of the final product. Several studies of the effect of the hydrothermal treatment have been performed on standard syntheses , with varying silica precursors ,and syntheses with swelling agents . The effect of the hydrothermal treatment is twofold. First, after the formation of the hexagonal structure, the PEO chains are trapped into the silica network and they are the source for the micropores in the final product. When the temperature is elevated, the hydrophilicity of the PEO chains change and becomes more hydrophobic. The chains then retract from the silica wall and go into the more hydrophobic core of the micelles. The result of this is an increased pore size and reduced microporosity and surface area. Secondly, the hydrothermal treatment decreases the shrinkage of the silica walls upon calcination. The effect of hydrothermal treatment is illustrated in Figure 11.

Figure :.The effect of the hydrothermal treatment.

By increasing the hydrothermal treatment temperature from 35 to 130 C it is possible increase the mesopore size with several nanometers, with significant changes noticed above 60 C . Above this temperature, the microporosity and surface area are decreased and when the treatment is performed at 130 C no

micropores remains and all surface originates from the mesopores. The unit cell parameter is though nearly constant for calcinated samples with hydrothermal treatment temperature exceeding 60 C, so during the increase of mesopore size the wall thickness decreases and the wall becomes denser and the microporosity is lost . Similar effect, but not as pronounced, is obtained by increasing the hydrothermal treatment time Removal of surfactants The final step of the synthesis is the removal of the surfactants. This is most often done by calcination, but there are alternatives such as chemical removal of the template or decomposition by microwaves. Regardless of which method used, the aim is always to completely remove the surfactants in a way that is as cheap and time effective as possible. Calcination Calcination is the most common way to remove the surfactants from SBA-15. During the calcination, which is performed in air, the material is heated to 550 C and this temperature is held for 5 h before the material is cooled down to room temperature. Most of the surfactants decompose between 150-250 C and at this stage the hexagonal structure retains its size. Above 300 C water is released and the rest of the polymers are combusted and the hexagonal framework is decreased probably due to condensation in the framework and closing of micropores . During the shrinkage of the hexagonal structure, the mesopore volume is decreased but the micropore volume is almost constant . This indicates that the micropores are still being emptied from surfactant residues simultaneously to the framework shrinkage.

ANALYSIS TECHNIQUES There is not one universal analysis technique that provides all information necessary to characterize a porous material. The surface area, pore size, pore volume, and, to some extent, pore shape of the materials are measured using physisorption with N2 gas but this technique does not reveal the pore order. This information is instead given by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The particle morphology is imaged using scanning electron microscopy (SEM) and in some cases even the mesopores can be resolved and seen here. The functional groups attached to the material walls have been studied with Fourier transformed infrared spectroscopy (FT-IR). There is not one universal analysis technique that provides all information necessary to characterize a porous material. The surface area, pore size, pore volume, and, to some extent, pore shape of the materials are measured using physisorption with N2 gas but this technique does not reveal the pore order. This information is instead given by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The particle morphology is imaged using scanning electron microscopy (SEM) and in some cases even the mesopores can be resolved and seen here. The functional groups attached to the material walls have been studied with Fourier transformed infrared spectroscopy (FT-IR). Physisorption isotherms The physisorption data is presented in sorption isotherms with the amount of gas adsorbed on the solid plotted versus the relative pressure. The isotherms can be grouped into six types . Type I isotherms: This type is characteristic for microporous materials. In micropores there is an increased adsorbent-adsorbate interaction. The nearly horizontal plateau is reached at low relative pressures which indicate a small external surface area. Type II isotherms: These isotherms are typical for non-porous, microporous and macroporous materials. Here there is a monolayer-multilayer adsorption on an open and stable surface. The knee-point at B indicates where the monolayer adsorption is complete and multilayer adsorption begins. B indicates the materials monolayer capacity as it is measured how much adsorbate is required to cover the unit mass of solid surface with a monolayer of adsorbate .Type III isotherms: These isotherms are very uncommon and are characteristic for materials with very weak adsorbate-adsorbent interactions.

Type IV isotherms: This type of isotherm is typical for porous materials. At the beginning the isotherm is similar to the type II isotherms. The knee-point at B indicates here, as well as for type II isotherms, the monolayer capacity of the material. At higher pressures, there is a hysteresis loop, for different types of hysteresis loops , which is characteristic for type IV isotherms. Type V isotherms: The type V isotherms are characteristic for porous materials with weak adsorbate-adsorbent interactions. Initially they are similar to the type III isotherms but at higher pressures there is a hysteresis loop. Type VI isotherms: These isotherms are due to layer-by-layer adsorption on a highly uniform surface. The steps are formed by separate layers adsorbing onto each other.

X-Ray Diffraction X-ray diffraction (XRD) is a technique used to study periodically ordered structures at atomic scales. The wavelengths of X-rays are in the same order of magnitude as the distance between lattice planes in crystalline materials. When the X-rays enter the material they will be scattered by the electron clouds around the atoms. The periodicity of the lattice planes gives rise to constructive interference of the X-rays, see Figure 21, and the intensity of the scattered X-rays is plotted against the angle 2. From the plotted peaks the lattice distance can be calculated using Braggs law n=2dhklsin where n is the order of diffraction, the wavelength, dhkl the distance between lattice planes and the angle of the incoming light.

Figure : Schematic illustration of diffraction according to Braggs law.

SBA-15 has a hexagonally ordered pore structure. As illustrated in Figure 22, the unit cell size, a, can be calculated from the first Bragg peak position. For crystalline materials the lattice planes are often in the order of a couple of A which gives a scattering angle of ~20 if CuK radiation ( = 1.54 A) is used and scans between 20-80 are common for characterization of the atomic structure of the material. For amorphous materials, such as mesoporous silica, there are no periodic atomic planes but the technique is still useful for characterization of the ordered pore structure.

Mesoporous materials with periodically ordered pores give reflections for low angles, 2 < 3. These low angles makes detection by reflection difficult since some of the X-ray beam can go straight into the detector and cause high background radiation which makes it difficult to see and identify the peaks. Therefore a transmission detector is preferable when measuring on mesoporous materials. Scanning Electron Microscopy Scanning electron microscope (SEM) is used to study the topography of materials, and has a resolution of ~2 nm. An electron probe is scanning over the surface of the material and these electrons interact with the material. Secondary electrons are emitted from the surface of the specimen and recorded. The height differences in the sample give contrast in the image. In this work, SEM has been used to study morphology of the particles and the pore direction in the mesoporous films.

Figure : Micrographs and Fourier transform of SBA-15 sheets imaged using (a) SEM and (b) TEM.

Self assembly of polydimethylsiloxane

Fig: Closed packed array formed by the self assembly of hexagons of polydimethlysiloxane coated with hydrophobic layers on all six sides.

Fig:The wide range of self- assembly of objects

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