Journal of Sol-Gel Science and Technology 18, 105113, 2000 c 2000 Kluwer Academic Publishers. Manufactured in The Netherlands.

Effect of TiO2 on the Pore Structure of SiO2 -PDMS Ormosils

F. RUBIO, J. RUBIO AND J.L. OTEO Instituto de Cer mica y Vidrio (C.S.I.C.), 28500 Arganda del Rey, Madrid, Spain a
frubio@icv.csic.es

Received June 16, 1999; Accepted February 28, 2000

Abstract. In this work, pore structure evolution of Ormosils containing TBT (Tetrabutyl titanate) has been characterized by means of mercury porosimetry, nitrogen adsorption and helium pycnometry. These ormosils have been prepared by the sol-gel method by the reaction of TEOS (tetraethoxysilane), PDMS (polydimethylsiloxane, silanol terminated) and TBT under acid-catalyzed conditions. The addition of TiO2 increases the volume and specic surface of secondary micropores and at the same time decreases the corresponding volumes of mesopores and macropores. The presence of TiO2 gives also a continuous decreasing in the pore connectivity being 9.7 for the ormosil without TiO2 and 4.4 for that of the higher concentration of TiO2 . However, the pore length shows a signicant decrease with the rst addition of TiO2 changing from 9.1 to 2.2 at the higher TiO2 concentration. Pore volumes show a decrease as the TiO2 concentration is increased in the ormosil. On the other hand, density increases and porosity decreases with the TiO2 concentration. These results are in accordance with the presence of TiO2 nanoparticles in the ormosil and the size of such nanoparticles increases with the TiO2 concentration. Fractal constant has a low value, close to 2, for all different samples meaning that these ormosils can be considered as low surface roughness materials. Keywords: mercury porosimetry, titanium ormosils, pore structure, interconnection

1.

Introduction

Hybrid organic-inorganic materials have been widely studied during the last decade. This has been due to their relatively easy synthesis utilizing the sol-gel process. These hybrid materials are a mixture of organic and inorganic groups at a molecular level, their properties being dependent on both organic and inorganic parts. ORganically MOdied SILicates (ORMOSILS) are new hybrid materials with interesting properties. Ormosil materials prepared by the reaction of tetraethoxysilane (TEOS) and polydimethylsiloxane (PDMS) have been extensively studied by Mackenzie and co-workers [1]. These ormosils may be considered as ceramic rubbers depending on the TEOS/PDMS molar ratio. When the PDMS concentration is increased, the ormosil material presents rubbery
To

properties. However, for high TEOS concentrations very hard ormosils can also be obtained. These rubbery properties are also dependent on different reaction parameters, such as temperature, acid concentration, reaction time, etc. [2]. Mackenzie et al. [3] have shown that different pore structures can be obtained in the ormosil materials. SiO2 -TiO2 -PDMS ormosils may be used as passive waveguides [4] and their homogeneity level caused by the inorganic content may inuence the optical properties. Most of the time, preparation of ormosils by the sol-gel method leads to phase-separated materials in which SiO2 and TiO2 particles are dispersed in an organic polymer matrix [5]. It is the aim of this work to study the inuence of the incorporation of TiO2 in the pore structure of TEOS-PDMS ormosils.

whom correspondence should be addressed.

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2. 2.1.

Experimental Material Preparation

2.2.

Material Characterization

Ormosils were prepared by using TEOS (Merck for analysis) as source of SiO2 , PDMS OH terminated (Gelest, Germany) with an average molecular weight of 1750 was used as an organic component, and tetrabutyl titanate, TBT, (Aldrich for analysis) as a source of TiO2 . Isopropyl alcohol (iPrOH) was the solvent and hydrochloric acid (HCl) the catalyst. Firstly three solutions were prepared, A, B and C. The A solution contains the total volume of TEOS, PDMS and 1/3 of the total volume of iPrOH. The B solution contains 1/3 of iPrOH and the total volume of HCl and H2 O and the C solution contains the remaining iPrOH and the total volume of TBT. All solutions are stirred for 5 minutes at room temperature for homogenization. The A and B solutions are mixed in a ask container and introduced into a thermostatic bath at 80 C under reuxing and stirring. The C solution (TBT solution) was added, using a pipette, each 5 minutes in order to avoid precipitation of Ti(OH)4 . The reaction time was 25 minutes for all studied samples. After that time, the solution was cast in a plastic container and sealed until gelation. In order to know the inuence of TBT in the ormosils, samples with different TBT content were prepared. In our experiments, we kept constant the mass ratio Inorganic/Organic to 70/30 (where Inorganic is the sum of TEOS and TBT and Organic is the PDMS) and the molar ratios of H2 O/Inorganic = 3, HCl/Inorganic = 0.3 and iPrOH/Inorganic = 4.5. The ratios TEOS/TBT were 70/0, 69/1, 67/3, 65/5 and 60/10 (T00, T01, T03, T05 and T10 samples respectively). The total volume of solutions was always 75 ml in order to avoid volume inuence in the nal material properties. Gelation time of all these samples was about 3 hours. Samples are kept in closed containers for 1 week pouring out, each day, the syneresis liquid. After that time, containers are opened to evaporate solvents at room temperature for 5 days followed by a drying in an oven at 50 C until no weight loss was observed. All of the obtained ormosils were transparent showing that no apparent phase separation was produced during the reaction. In accordance with the high acid concentration, it is assumed that TEOS and TBT are fully hydrolysed and condensed to yield SiO2 and TiO2 respectively, and therefore they can react with PDMS to form SiO2 TiO2 -PDMS ormosils.

Material pore structures were characterized by Hg porosimetry, nitrogen adsorption and He pycnometry. For Hg porosimetry we have used an Autopore II 9215 (Micromeritics Corp.) in the range of pressures between 0 and 4.081 MPa. All samples were outgassed below 6.67 Pa at room temperature before measurements. Nitrogen adsorption-desorption isotherms were obtained with an Accusorb 2100 E (Micromeritics Corp.) in the whole partial pressure range. The temperature of measurement was 77 K. All samples were also degassed for 18 hours at 120 C. Density results have been obtained by He pycnometry and Hg porosimetry. We have assigned as real density to that measured with He assuming that such gas can penetrate into the smallest pores. Bulk density is assigned to that measured with Hg when no pressure is given and therefore any pores are lled with it. Finally, apparent density is dened as that measured with Hg when pores with sizes higher than 50 nm are lled with Hg. Real density values were performed in a micropycnometer (Multipycnometer, Quantachrome, USA).

3.

Results and Discussion

Mackenzie et al. [3, 6] and Babonneau et al. [7, 8] have mainly studied by 29 Si MAS-NMR and SEM the molecular structures and microscopic structures of different ormosils obtained by using TEOS and PDMS. Different structures have been proposed which explain the inuence of the addition of a titanium alkoxide to the TEOS-PDMS ormosil reaction. The TEOS plays a role of a cross-linking agent. On the other hand, titanium acts as both cross-linking agent between PDMS molecules and also catalyses the condensation reactions to form long PDMS chains [7, 8]. The nal ormosil may be described as a nanocomposite made of PDMS chains and oxide-based particles. Therefore, the ormosil pore structure must be formed by different type of pores corresponding to the above mentioned nanocomposite material. We have studied the changes produced in the pore structure when TiO2 is added to SiO2 -PDMS ormosils by means of nitrogen adsorption, mercury porosimetry and helium pycnometry. Nitrogen adsorption-desorption isotherms for the studied materials are presented in Fig. 1. In this gure, isotherms were vertically shifted in order to avoid

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Figure 1.

Nitrogen adsorption-desorption isotherms at 77 K for ormosil samples with different TiO2 content.

overlapping. These isotherms show well-dened hysteresis loops corresponding to a porous materials. Such hysteresis loops are of type H2 according to the IUPAC classication [9], and they were in the past attributed to a difference in mechanism between condensation and evaporation processes occurring in pores with narrow necks and wide bodies (ink-bottle pores). However, as it will be discussed below, it is now recognized that such hysteresis loops correspond to interconnected pore structures in which the pore size distribution can be determined from the nitrogen adsorption isotherm, and the desorption isotherm is determined by the distribution of neck sizes [10]. Mercury intrusion-extrusion curves obtained for the studied ormosils are shown in Fig. 2. These curves correspond to the Class I according to Day et al. [11] which are characterized by one-step intrusion curve and a similar extrusion curve. These curves correspond to unimodal pore distributions. All of these curves are very close to each other showing close pore volumes for all samples.

Using both the nitrogen adsorption-desorption method and the mercury porosimetry technique, a complete picture of the whole pore size distribution can be obtained. It is well-known that nitrogen adsorption is used for studying pores of diameter between 0 and 25 nm. On the other hand, mercury porosimetry permits to study pores of diameter between 2 nm and 0.15 mm depending on the intrusion pressure. However, because high intrusion pressures can compress the sample, the measurements are nished at about 25 nm, i.e. at the end of the nitrogen method. Pore size distributions have been determined by the BJH method [12] in the range of mesopores (pores of radius between 1 and 25 nm). We have used the adsorption branch of the nitrogen isotherm for such analysis because, as has been mentioned before, now it is recognized that the step of the desorption branch corresponds to interconnected pore structures where larger pores are connected to small pores. Such small pores avoid nitrogen desorption until the equilibrium pressure reaches a value that corresponds to the evaporation of these small pores.

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Figure 2.

Hg intrusion-extrusion curves for ormosil samples with different TiO2 content.

Cylindrical geometry is assumed for all pores for both nitrogen isotherms and mercury porosimetry. Pore size distributions of the studied ormosil samples are shown in Fig. 3. These curves are very close except in the low pore radius region where an increase of the volume of pores is observed as the concentration of TiO2 in the ormosil is increased. The observed increase near the pore radius limit of 1 nm, indicates the presence of micropores (pores of radius below 1 nm). The continuous increase in the pore volume as the pore radius decreases is in accordance with a homogeneous distribution of pores in the samples. Here, in the SiO2 -TiO2 -PDMS ormosils, the pore size distribution is homogeneous, and the presence of TiO2 does not seem to change the form of the distribution. However, these pore size distributions do not take into account the respective microporosity. The analysis of microporosity can be carried out by the v- or v-t methods [13]. The v- or v-t methods can be used for assessment of microporosity in any kind of porous materials. Both methods consist on representing the experimental adsorbed volume versus a reference isotherm obtained for

a non-porous material. If the obtained representation is a straight line then the studied sample is also nonporous. However, if an upward or downward deviation is obtained, then the studied sample will have mesopores or micropores respectively. Figure 4 shows the v- plot for the studied ormosils. It can be observed that a more gradual downward deviation appears as the TiO2 concentration is increased in the ormosil. Therefore, the addition of TiO2 to TEOS-PDMS ormosils increases the amount of micropores. All curves of Fig. 4 show also a linear region that can be tted to a straight line passing through the origin axes. This result shows that all samples only have secondary micropores, i.e. micropores of size dimensions between 0.6 and 2 nm [14]. In the downward deviation of the v- plot a t to a straight line can also be made, and the corresponding intercept on the adsorption axis gives the micropore contribution, i.e., adsorbed volume of nitrogen in the micropores. Then, if this micropore volume is added to the mesopore one obtained by the BJH method and also to the macropore volume obtained by mercury

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Figure 3. Pore size distributions of ormosil samples containing TiO2 . The measurements above 102 m are carried out by Hg porosimetry and below 101 m by the nitrogen adsorption-desorption method.

porosimetry, the total pore volume of the studied ormosil samples can be calculated. These values are given in Table 1. In accordance with the results of Table 1, it is observed that the addition of TiO2 to the ormosil samples increases the volume of micropores and decreases the volumes of meso and macropores. The nal porosity of the ormosil also decreases with the TiO2 content. The ormosil sample T00, sample without TiO2 , has a lower micropore volume than those of meso or macropores, being that micropores about half of macropores. However, the ormosil sample with
Table 1. Pore volumes for the studied ormosil samples. T00 0.153 0.007 0.247 0.009 0.282 0.009 0.400 0.682 T01 0.171 0.007 0.228 0.008 0.281 0.009 0.399 0.680

higher concentration of TiO2 (T10 sample) the micropore volume is very close to that of macropores. These results are in accordance with the above description of these ormosils as nanocomposite materials. The increase in the TiO2 concentration in the ormosil forms nanometric particles in size where micropores are present. This result is in accordance with the structural model proposed by Babonneau [15]. In accordance with results of Table 1, it can be observed that as the TiO2 concentration is increased in the ormosil samples, a continuous increasing in the

Pore volume (cm3 /g) Micropores (A) Mesopores (B) Macropores (C) Sum (A + B) Sum (A + B + C)

T03 0.202 0.008 0.204 0.008 0.271 0.009 0.406 0.679

T05 0.209 0.008 0.178 0.007 0.270 0.009 0.387 0.657

T10 0.222 0.009 0.169 0.007 0.244 0.008 0.391 0.635

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Figure 4.

plots for the studied ormosil samples corresponding to the isotherms presented in Fig. 1.

micropore volume and a continuous decreasing in the mesopore volume is obtained. From T00 sample to T10 sample the increase in the micropore volume is about 31% and this value is similar to the decreasing in the mesopore volume (31.6%). On the other hand, if we add the volume of micro and mesopores (A + B of Table 1), such volume is about 0.4 cm3 /g for all samples. It means that the incorporation of TiO2 creates new microporosity inside the mesopores. However, a different behaviour is observed for macropores. In this case, the volume of macropores does not change with additions of TiO2 lower than 3%, and slightly decreases with additions up to 10%. This result shows that TiO2 is well-incorporated in the ormosil network. The addition of titanium alkoxide in part catalyzes the siloxane network formation and, in parallel, titano-siloxane bonds are also developed. The particulate heterogeneities of titania and silica are the results of somewhat preferential formation of pure titanoxane and siloxane bonds. These particulate heterogeneities are then the responsible for the increase in the observed micropore volume.

In the characterization of a porous solid it is not at all sufcient to consider a pore size distribution, but the more delicate aspect it is to know the morphology or how these pores are topologically distributed throughout the system. Morphology plays an equal or even more an important role than the mere pore size distribution. Several works are related with the morphology of pore materials [16, 17]. One important aspect of pore morphology is the connectivity between pores. The nitrogen isotherms of Fig. 1 correspond to the interconnected pore structures. In other work, we have shown that pore interconnection can be used for characterizing the pore structure of silica xerogels [18]. Seaton [19] has presented an analysis method, based on the percolation theory, that allows a measure of the connectivity and the mean coordination number of the pore network. These data can be easily determined from nitrogen adsorption measurements. This method is applicable to hysteresis loops of the IUPAC types H1 and H2. In these types of pores, the adsorption of nitrogen occurs according to a multilayer-capillary condensation mechanism where the condensation pressure

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is a function of pore size, with nitrogen condensing in smaller pores at lower pressures. However, during the desorption process, nitrogen vaporises from a liquidlled pore when two conditions are satised: (i) the applied pressure is below the condensation pressure for a pore of that size, and (ii) the pore has access to the vapour phase. Figure 1 shows nitrogen isotherms which have type H2 hysteresis loops and then percolation theory can be applied. These hysteresis loops show a different mechanism of adsorption-desorption. The adsorption of nitrogen increases with pressure. However, the desorption at high pressures is practically prevented when decreases the pressure until reaching a given pressure from which desorption takes place very rapidly. In the high pressure region, the desorption occurs in some pores which are on the surface of the sample. However, most part of these pores located on the surface have a pore size which condensation pressure is lower than the experimental applied pressure and, therefore, these pores prevent the evaporation of nitrogen of other inner pores of higher pore size. When the experimentally applied pressure is lower than the condensation pressure, those surface pores release nitrogen and permits the evaporation of nitrogen condensed in the inner pores. This evaporation occurs through a percolation mechanism. At the end of the hysteresis loop all pores have access to the vapour phase and the desorption and adsorption isotherms coincide. Therefore, desorption isotherms show a sharp knee while adsorption isotherms show an increasing trend, as can be seen in Fig. 1. Seaton [19] has proposed a method from which the connectivity of the pore structure is dened by the mean coordination number, Z , and the mean linear dimension of pores, L. This linear dimension is dened as a hypothetical number of mean pore lengths. Both parameters can be determined from adsorption-desorption nitrogen isotherms. This method is based on the percolation theory of porous materials. In the application of the percolation theory to the nitrogen desorption process, the pore occupation probability, X , is dened as the ratio of the number of pores in which nitrogen is below its condensation pressure to the total number of pores in the network, and the accessibility, X A , is dened as the ratio of the number of pores from which nitrogen has vaporised to the total number of pores. Experimental values of X and X A determined from nitrogen isotherms are used in an universal function from which Z and L can be obtained [20]. Figure 5 shows the results for the accessibility as a function of pore occupation

Table 2. Interconnection (Z ) and mean pore length (L) values for the ormosil samples. Ormosil sample T00 Z L 9.7 0.1 9.1 0.1 T01 7.9 0.1 2.5 0.1 T03 6.7 0.1 2.3 0.1 T05 5.8 0.1 2.3 0.1 T10 4.4 0.1 2.2 0.1

probability for the studied ormosils, and Table 2 gives the obtained values of Z and L when such curves are tted to the universal function. This tting procedure was carried out using a non-linear least-squares algorithm. Values of Table 2 show that important changes are produced in the pore structure of the ormosils when TiO2 is incorporated. It must be taken into account that these results only refer to mesopores because the calculation procedure is applied to nitrogen isotherms. Similarly, such procedure could be applied to the mercury porosimetry curves. However, curves of Fig. 2 do not show any sharp knee characteristic of a percolation process as nitrogen isotherms do. Seaton has shown that the more highly connected the network the righter deviation of the knee is observed [19]. In the limit of innite mean coordination number, the adsorption and desorption isotherms should coincide over the whole pressure range. Intrusion and extrusion Hg curves of Fig. 2 coincide and we can assume that a high connectivity exists between macropores in the studied ormosils and such connectivity does not change with TiO2 addition. On the other hand, there is not any method for obtaining the connectivity between micropores. The ormosil without TiO2 shows the highest values of Z and L showing both a high connectivity between mesopores and high mean pore length. The addition of TiO2 continuously decreases the connectivity. This result is in accordance with the formation of particulate heterogeneities of titania due to the result of preferential formation of pure titanoxane bonds. These nanoparticles of TiO2 are located so as to disturb the connectivity of mesopores and, therefore, the pore interconnection decreases. These nanoparticles increase also the micropore volume of the ormosil, as it is presented in Table 1. However, the mean pore length shows a drastic change with the rst addition of TiO2 to the ormosil structure, remaining practically constant the mean pore length as the TiO2 concentration in the ormosil is increased. These results show that for the lowest addition of TiO2 (1%) a homogeneous

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Figure 5.

Accessibility (X A ) as a function of pore occupation probability (X ) for the studied ormosil samples.

distribution of TiO2 is achieved where nanoparticles of TiO2 are formed suppressing both the growth of the mesopore length and their interconnection. The size of these TiO2 nanoparticles increases with the TiO2 concentration in the ormosil and new nanoparticles of TiO2 are formed where mesopores are connected. That results in an increment of the micropore volume, remaining constant the mesopore mean length. Therefore the incorporation of TiO2 to TEOSPDMS ormosils forms nanocomposite materials in accordance with the description of Babonneau et al. [7, 8].
Table 3.

Finally, we have studied the evolution of the density and the surface fractal constant (Ds ) as a function of the TiO2 concentration in the TEOS- PDMS ormosils. Table 3 gives density values obtained for the studied samples. It can be observed that the addition of TiO2 increases the density of ormosils and decreases their porosity. Such increase is associated to both the higher density of TiO2 than SiO2 and the above mentioned elimination of mesopores and macropores (Table 1). The observed decrease in porosity is also consistent with the elimination of mesopores and macropores and also with the loss of pore connectivity.

Density, porosity and fractal constant for the studied ormosil samples. Ormosil sample T00 T01 1.30 0.02 1.29 0.02 0.91 0.02 30 2 2.00 0.09 T03 1.32 0.03 1.30 0.03 0.93 0.02 29 2 2.04 0.08 T05 1.33 0.03 1.31 0.03 0.96 0.02 27 2 2.07 0.07 T10 1.34 0.03 1.33 0.03 0.98 0.03 26 2 2.16 0.09

Real density (cm3 /g) Apparent density (cm3 /g) Bulk density (cm3 /g) % Porosity Ds

1.30 0.02 1.29 0.02 0.90 0.02 30 2 2.00 0.09

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Fractal characterization of the ormosil samples has been carried out by the method proposed by Ismail et al. [21] using the adsorption-desorption nitrogen isotherms. Such method is based on plotting the adsorption isotherm according to the Frenkel-Halsey-Hill equation [21] and tting to a straight line in the range of 1 to 2 monolayers. The exponent of this equation is related to the surface fractal dimension, Ds . Data of this analysis is also shown in Table 3. Fractal constant (Ds) is close to 2 (smooth surface) for all studied samples meaning that the incorporation of TiO2 does not increase the surface roughness. These results are in accordance with those obtained by Mostakef et al. [22] where SiO2 -TiO2 -PDMS ormosils can be considered as high volume homogeneity and low surface roughness materials. However it can be observed how Ds shows a gradual increase as the titania concentration in the ormosil is increased. It indicates that there is an average increase of the roughness of pore surfaces, suggesting that the effect of the added titanium alkoxide on the overall structure of the silicaPDMS ormosil network is not limited only to both the local particle formation and the change in the pore structure. The increase of TiO2 in the ormosil network produces also an increase in the surface roughness of such materials. 4. Conclusions

Acknowledgments We are grateful to the Comisi n Interministerial de o Ciencia y Tecnologia (CICYT) of Spain for support of this work under project MAT96-0564.

References
1. Y. Hu, Y.J. Chung, and J.D. Mackenzie, J. Mater. Sci. 28, 6549 (1993). 2. J.D. Mackenzie, Q. Huang, and T. Iwamoto, J. Non-Cryst. Solids 7, 151 (1996). 3. J.D. Mackenzie, Y.J. Chung, and Y. Hu, J. Non-Cryst. Solids 147/148, 271 (1992). 4. S. Motakef, T. Suratwala, R.L. Roncone, J.M. Boulton, G. Teowee, and D.R. Uhlmann, J. Non-Cryst. Solids 178, 37 (1994). 5. B. Lantelme, M. Dumon, C. Mai, and J.P. Pascault, J. Non-Cryst. Solids 194, 63 (1996). 6. T. Iwamoto, K. Morita, and J.D. Mackenzie, J. Non-Cryst. Solids 159, 65 (1993). 7. F. Babonneau, L. Bois, J. Livage, and S. Dire, Mat. Res. Soc. Symp. 286, 289 (1993). 8. S. Dire, F. Babonneau, C. Sanchez, and J. Livage, J. Mater. Chem. 2(2), 239 (1992). 9. K.S.W. Sing, D.H. Everett, R.A.W. Haul, L. Moscou, R.A. Pierotti, J. Rouquerol, and T. Siemieniewska, Pure and Appl. Chem. 57(4), 603 (1985). 10. G.C. Wall and R.J.C. Brown, J. Colloid Interface Sci. 82(1), 141 (1981). 11. M. Day, I.B. Parker, J. Bell, J. Fletcher, R. Dufe, K.S.W. Sing, and D. Nicholson, in Characterization of Porous Solids III, edited by J. Rouquerol, F. Rodrguez-Reinoso, K.S.W. Sing, and K.K. Unger (Elsevier Science, Amsterdam, 1994), p. 225. 12. E.P. Barret, L.G. Joyner, and P.H. Halenda, J. Am. Chem. Soc. 73, 373 (1951). 13. S.J. Gregg and K.S.W. Sing, Adsorption, Surface Area and Porosity (Academic Press, London, 1982), p. 94. 14. P.J.M. Carrot and K.S.W. Sing, in Characterization of Porous Solids, edited by K.K. Unger, J. Rouquerol, K.S.G. Sing, and H. Kral (Elsevier Science, Amsterdam, 1988), p. 77. 15. F. Babonneau, New J. Chem., 18, 1065 (1994). 16. V. Mayagoitia, M.J. Cruz, and F. Rojas, J. Chem. Soc. Faraday Trans. 85(1), 2071 (1989). 17. V. Mayagoitia, A. Domnguez, and F. Rojas, J. Non-Cryst. Solids, 147/148, 183 (1992). 18. F. Rubio, J. Rubio, and J.L. Oteo, J. Sol-Gel Sci. Tech. 8, 159 (1997). 19. N.A. Seaton, Chem. Eng. Sci. 46, 1895 (1991). 20. S. Kirkpatrick, Rev. Mod. Phys. 45, 574 (1973). 21. I.M.K. Ismail and P. Pfeifer, Langmuir, 10, 1532 (1994). 22. S. Motakef, T. Suratwala, R.L. Roncone, J.M. Boulton, G. Teowee, and D.R. Uhlmann, J. Non-Cryst. Solids 178, 37 (1994).

We have studied the inuence of TiO2 in the pore structure of TEOS-PDMS ormosils by means of nitrogen adsorption, mercury porosimetry and He pycnometry. The addition of TiO2 increases the volume of micropores and decreases the volume of mesopores and macropores. On the other hand, the connectivity between adjacent pores decreases continuously when TiO2 is added to a TEOS-PDMS ormosil, and at the same time the main pore length is drastically decreased. The density of such ormosils increases with the incorporation of TiO2 due to the removal of porosity. Due to the low value of the fractal constant this kind of ormosils can be considered as high volume homogeneity and low surface roughness. The observed increase of the fractal constant with the TiO2 concentration in the ormosil shows that the pore structure, density and surface roughness are affected by the addition of a titanium alkoxide to the TEOS-PDMS composition.