J Sol-Gel Sci Technol (2009) 52:328334 DOI 10.

1007/s10971-009-2042-y

ORIGINAL PAPER

Silicatitania aerogel monoliths with large pore volume and surface area by ambient pressure drying
P. R. Aravind P. Shajesh P. Mukundan K. G. K. Warrier

Received: 26 January 2009 / Accepted: 6 July 2009 / Published online: 23 July 2009 Springer Science+Business Media, LLC 2009

Abstract Ambient pressure drying has been carried out for the synthesis of silicatitania aerogel monoliths. The prepared aerogels show densities in the range 0.340.38 g/cm3. The surface area and pore volume of these mixed oxide aerogels are comparable to those of the supercritically dried ones. The surface area for 5wt% titania aerogel has been found to be as high as 685 m2/g with a pore volume of 2.34 cm3/g and the 10wt% titania aerogel has a surface area of 620 m2/g with a pore volume of 2.36 cm3/g. Some gels were also made hydrophobic by a surface treatment with methyltrimethoxysilane and trimethylchlorosilane. The surface modied aerogels possess high surface areas in the range of 540640 m2/g, and are thermally stable in terms of retaining hydrophobicity up to a temperature of 520 C. The pore size distribution of the aerogels clearly indicates the preservation of the aerogel structure. High Resolution Transmission Electron microscopy has been employed to characterise the aerogels and Fourier Transform infrared spectroscopy to study the effect of titania addition to silica and the surface modication. X-ray diffraction patterns were recorded to verify the molecular homogeneity of the aerogel. Keywords Silicatitania mixed oxide Aerogel BET surface area Porous materials Amorphous materials Ambient pressure drying Catalyst Hydrophobicity

1 Introduction SilicaTitania mixed oxide systems attract considerable academic and industrial attention owing to their application as catalyst for a number of reactions such as phenol amination [1], ethene hydration [1], olen epoxidation [2], butene isomerisation [3, 4], cumene dealkylation [5], 2-propanol dehydration [2] and 1,2-dichloroethane decomposition [6]. Further, highly porous forms of the catalyst facilitate their use in the removal of toxic volatile organic compounds (VOCs) where the sorption capacity of the catalyst plays an important role [7]. The efciency of silicatitania mixed oxide catalysts are heavily dependent on the molecular scale dispersion of titanium atoms, high surface area and pore diameters in the mesoporous range i.e. large enough for the easy accessibility of reactants. While molecular scale dispersion is ensured by a solgel synthesis, the need for high surface area and porosity brings in the importance of drying conditions. High surface area xerogels and aerogels are among the most investigated forms of these types of catalysts [2]. The xerogel contains a majority of micropores and as a consequence they are less active due to the limited accessibility to active sites. The hydrophobicity/hydrophilicity of the mixed oxides also play a major role in their performance as a catalyst. It is reported that no leaching of the active titanium species to the aqueous phase occurs when the catalyst is hydrophobic [8]. Moreover the hydroxyl groups of silica present a strongly hydrophilic environment limiting the access of organic substrates to the surface [9]. Supercritical drying of gels affords aerogels with a considerable fraction of mesopores and is accepted as a commercial process. But the high temperature induces considerable segregation and agglomeration of titania and silica results, which destroys to a large extent, the

P. R. Aravind P. Shajesh P. Mukundan K. G. K. Warrier (&) Materials and Minerals Division, National Institute for Interdisciplinary Science and Technology (NIIST) [Formerly Regional Research Laboratory (RRL)], Council of Scientic and Industrial Research (CSIR), Trivandrum 695019, India e-mail: wwarrierkgk@yahoo.co.in

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advantageous structure developed during solgel process and reduces dominance of titanium located in hardly active anatase particles [10]. Low temperature supercritical drying (using CO2 as solvent) has been reported which gives aerogels with lower microporosity, higher surface areas (up to 700 m2/g) and amorphous mixed oxide aerogels [10]. Attempts to nd a suitable alternative to supercritical drying is an essential part of growing aerogel technology [11, 12]. More over it is reported that crystallisation occurs in mutli component gels under high temperature supercritical conditions by which the aerogel property can be lost [13]. Mainly two strategies are used for preparation of aerogels by non-supercritical/subcritical drying. One is increasing the stiffness of the gel network by aging in a silane precursor [1416] and the other is capping the surface silanol groups by alkyl groups so that the gel springs back to shape after shrinkage due to repulsion between the alkyl groups [17, 18]. Davis et al. [14] inltrated the gel network by sodium silicate or Tetraethoxysilane (TEOS) prior to drying. In another work, the authors aged the gels in a series of alcohol and water bath and the physical and chemical structure of the gels were measured [15]. The authors noticed that the alcohol aging leads to small pore size distributions. The alcohol aged gels had a surface area of 1,5002,000 m2/g in the wet gel state, which decreased to 1,000 m2/g after drying. Einarsrud et al. [16] aged Tetramethoxysilane (TMOS) based alcogels in solutions of TEOS/MeOH which increased the strength and stiffness of the alcogels which reduced the shrinkage during drying Deshpande, Smith and Brinker put forward a new process (DSB process), in which the wet gels are washed with an aprotic solvent, reacted with Trimethylchlorosilane (TMCS) and then dried at ambient pressure [17, 18]. Recently we reported a subcritical drying technique for the preparation of silica aerogels through ambient pressure drying and its successful extention to mixed oxide systems [1922]. Here we present the successful implementation of this technique for the synthesis of silicatitania mixed oxide aerogel monoliths. Hydrophobic modication of the aerogels is also presented with possible applications as catalysts in mind.

2 Experimental section Tetraethoxysilane (TEOS) (Fluka, Switzerland), Titaniumisopropoxide [Ti (OiPr)4] (Aldrich), acetic acid (S.D. Fine chemicals, India), HCl (S. D. Fine Chemicals) and isopropanol (S.D. Fine Chemicals, India) were used as received. A stable titania sol was prepared by the method reported else where [23]. To prepare silica sol, the molar ratio of TEOS: isopropanol: acidied water (maintained at pH = 1.54 using HCl) was maintained at 1:4:16. In a

typical experiment for the preparation of 10wt% titania in silica, 0.53 g titanium isopropoxide in 1.12 ml acetic acid was hydrolysed with 11.83 ml water. Simultaneously silica sol was prepared by hydrolysing 4.66 g TEOS in 5.37 g isopropanol with 6.44 g water (acidied water). The hydrolysis pH was maintained at 1.54 due to the difference in reactivity of silicon and titanium isopropoxide. The two sols were stirred for 3 h each separately where upon the titania sol was added drop wise to the silica sol. The mixed sol was then stirred for 1 h and the gelation pH adjusted to 5 using 5 vol% ammonia solution. The visually homogeneous sol was then transferred to vials (2 cm diameter) and kept at 50 C for gelation. The gelation occurred within 15 min for all compositions. The gels were aged for 24 h at 50 C, and then were transferred into water and aged again for 24 h at 50 C. The gels were then solvent exchanged with isopropanol at 50 C. This was followed by aging the gels in an 80% TEOS in isopropanol for 48 h at 50 C and nally solvent exchanged with isopropanol at 50 C. The drying of the gels was done at 70 C, by covering the containers with aluminium foil. The foil was then sealed well with cellophane tape to make the drying as slow as possible. After 2 weeks a pin hole is made on the cover to let the vapour escape. The gels are then dried till their weights remain constant. Samples with titania content ranging from 2 to 20wt% were prepared. To induce hydrophobicity, the 10wt% titaniasilica alcogels were immersed for 24 h at 50 C in 20, 30 and 40 vol% Trimethylchlorosilane (TMCS) or Methyltrimethoxysilane (MTMS) in isopropanol. The gels were washed with isopropanol prior to drying and were dried using the same procedure explained above. The bulk density of the dried gels (cylindrical samples) was calculated from their mass and volume. The Fourier Transform Infrared Spectra of the heated gels were recorded in a Nicolet Magna-560-IR Spectrometer (KBr pellets). The BET surface area of calcined aerogels were determined by N2 adsorption at 77 K (Micromeritics, Gemini Model 2360, USA). The calcined samples were preheated in a ow of nitrogen for 3 h at 200 C to remove all the volatiles and chemically adsorbed water from the surface. The specic surface area was determined using the BET equation with an accuracy of 10 m2/g. The total pore volume was calculated as, Pore volume, V Va D where Va = volume adsorbed at P/P0 0.99, D = density conversion factor (0.0015468 for nitrogen as the adsorbate gas). The pore size distribution was obtained using the BarretteJoynereHalenda (BJH) method [24]. Assuming that the pores are cylindrical and open at both ends, the average pore size of a given sample is calculated using the equation,

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J Sol-Gel Sci Technol (2009) 52:328334 Table 1 Density and BET surface area results of silicatitania aerogels Sample Density (g/cm3) 0.34 0.36 0.38 Surface area Total pore Pore ) diameter (A (m2/g) volume (cm3/g) 895 726 685 620 2.07 2.5 2.34 2.36 1.74 1.76 92 137 136 152 165 176

Average pore size 4Vtotal =SBET For Transmission electron microscopy (HRTEM) studies, the gel powder was dispersed in acetone. A few drops were placed on carbon coated copper grids. After ensuring the evaporation of the solvent, the copper grid was mounted in a FEI high resolution transmission electron microscope (HRTEM) Technai 30 G2 S-TWIN. The X-ray powder diffraction patterns of the calcined sample were recorded on a Philips diffractometer (PW 1710), using Ni ltered CuKa radiation. The samples were scanned from 0 to 60 (2h values) with a step speed of 2.4/min. The contact angle measurements were measured with a DCAT 11 tensiometer using Washburn equation. The DTA of the gel was carried out in Shimadzu 50H (Japan) thermal analyzer in owing nitrogen atmosphere.

Silica 2% Titania 5% Titania

10% Titania 0.35

15% Titania Cracked gel 412 20% Titania Cracked gel 399

3 Results and discussion 3.1 Silicatitania aerogels A high water/alkoxide ratio of 16:1 was chosen for the hydrolysis of silica precursor since our earlier studies revealed that gels prepared under these conditions result in porous gels with a high surface area [25]. Initial aging of the gel was done in water to allow the completion of the hydrolysis condensation reactions. The water aged gel was solvent exchanged with isopropanol prior to silane aging since silicon alkoxide is immiscible with water. Aging in a silane solution results in the dissolution and reprecipitation of silica particles on the gel network, coarsening the smooth necks between the particles thereby strengthening the gel network [19]. An aging time of 48 h and an aging solution having 80% silane in isopropanol were used. These gels were then solvent exchanged with isopropanol as the drying solvent, since liquids of low surface tension and high molecular volume favour the production of gels having high surface area [25].
Fig. 1 Photographs of Silica titania aerogels (From left 5wt% and Four 10wt%. In front 2wt% samples)

Crack free monoliths prepared by employing the ambient pressure drying technique described is shown in the photograph provided as Fig. 1. The bulk density of aerogels is provided in Table 1. Usually aerogels possess densities in the range of 0.0030.8 g/cm3, with high surface area extending up to 1,500 m2/g [2628]. Silica aerogels dried under ambient conditions had a density of 0.34 g/cm3 and the 2, 5 and 10wt% titania aerogel possess densities of 0.36, 0.38 and 0.35 g/cm3, respectively. Transmission Electron Microscopy (TEM) studies (Fig. 2) of 10wt% titaniasilica aerogel conrmed that the prepared aerogel is nanoporous with a network structure. The Selected area electron diffraction pattern (in-set of Fig. 2) indicates that the aerogel is amorphous which is a direct evidence to the structural homogeneity. The TEM micrographs of 600 C calcined silica-10% titania aerogel is provided in Fig. 3a. The micrograph indicates that the network structure has been preserved and the selected area diffraction pattern provided in the in-set conrms that the aerogel is still amorphous. More over, the EDS (Energy dispersive spectroscopy) spectrum provided in Fig. 3b reveals the presence of titania in the matrix. The XRD patterns of the 20% titaniasilica aerogel provided in Fig. 4, did not show any peaks corresponding to crystalline titania even after calcination at 600 C which supports that there is no segregation or agglomeration of silica and

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Fig. 2 TEM micrograph of 10wt% Titaniasilica aerogel. The selected area diffraction pattern is provided in the inset

titania and the advantageous structure developed during solgel process is preserved. FTIR of the aerogels calcined at 200 C, (Fig. 5a) show the presence of molecular vibrational modes at around 940 cm-1. The band developed at ca. 940 cm-1 is indicative of the presence of SiOTi species [10]. This indicates good mixing of Ti and Si at the atomic level has resulted, which is a crucial factor in catalytic applications. Details of the BET surface area analysis are given in Table 1. Dutoit et al. [10] has reported exhaustive structural characterization of xerogels and supercritically dried high temperature and low temperature silicatitania aerogels. The authors found that although the surface areas of the gels dried under different conditions are comparable, the aerogels had very large pore volumes in comparison with their xerogel counterpart. The ambient pressure dried aerogels prepared by us have surface areas and pore volumes comparable with the ones reported by Dutoit et al. [10]. Moreover, the prepared aerogels have high pore volume, advantageous for catalytic applications. The surface area of silicatitania aerogels decreases as the percentage of titania is increased as evident from Table 1. Based on earlier reports, the reduction in surface area with aluminium incorporation was attributed to reduction in pore accessibility and not pore collapse [29, 30] and Sinko et al. [31] found that Al incorporation did not decrease the porosity in the series of gels prepared with varying amounts of Al. In a silversilica aerogel system, the decrease in surface area with increasing silver content was reported to be due to crystallisation of silver particles in the pores of the aerogel matrix [32]. In our

Fig. 3 a TEM micrograph of 10wt % Titaniasilica aerogel calcined at 600 C. The selected area diffraction pattern is provided in the inset. b EDS spectrum of 10wt% titaniasilica aerogel calcined at 600 C

system, the decrease in surface area may be due to the occupation of titania in the pores of the aerogel. The AdsorptionDesorption isotherms of silicatitania aerogels are provided in Fig. 6a. The presence of a hysterisis loop indicates Type IV behaviour, characteristic for the mesoporous nature. The 5wt% sample has the maximum area under the hysterisis loop indicating that it has the maximum pore size distribution in the mesopore region. The adsorption isotherms of the 15 and 20 wt% samples lie below indicating the lower pore volume, but has a similar pattern as that observed for the 2 and 10wt% samples. Microporosity, which is manifested as the non linear rise in adsorption at very low pressures (\0.1 P/P0) is comparable for the samples with titania weight percentages \15wt%

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Volume Adsorbed [(cm3)STP/g]

1600 1400 1200 1000 800 600 400 200 0

2 5 10 15 20

(a)

Intensity

20

30

40

50

60

0.0

0.2

0.4

0.6

0.8

1.0

Angle [2]
Fig. 4 XRD spectrum of 20% titania calcined at 600 C
1800 20 MTMS

Relative Pressure (P/P0)

Volume absorbed [(cm3)STP/g]

1600 1400 1200 1000 800 600 400 200 0 0.0 0.2 0.4 0.6

(A)

20 TMCS 30 TMCS 20 MTMS 30 MTMS 40 MTMS

(b)

0.8

1.0

Relative pressure (P/Po)

Fig. 6 a Adsorption isotherms of silicatitania aerogels. Isotherm of 5wt% titania aerogel is given in the inset for clarity. b Adsorption Desorption isotherms of surface modied aerogels. The isotherm of 20% MTMS is provided in inset for better clarity

(B)

Transmittance (arb.)

a
2928 2978 850

4000

Wave numbers (cm-1)

400

primary particles in the mixed oxide system and reduces the micropore volume with increasing titania content. The pore size distribution curves obtained for silicatitania aerogels is provided in Fig. 7a. The pore size distribution , which conrms that the mesoextends from 20 to 300 A porous gel network is preserved after ambient drying. 3.2 Surface modied silicatitania aerogels There are two common methods to fabricate hydrophobic aerogels, (1) By co-precursor method [33] and (2) By derivatisation of the inner surfaces [34]. In this work, gels were made hydrophobic by derivatisation method where in the silane aged alcogels were immersed in 20, 30 and 40 vol % of TMCS and MTMS.

Fig. 5 A FT-IR spectra of (a) 2wt% Titania (b) 5wt% Titania (c) 10 wt% Titania (d) 15wt% Titania (e) 20wt% silicatitania aerogels. B FT-IR of surface modied aerogels (a) TMCS modied (b) MTMS modied

and similar for 15 and 20wt% samples. Microporosity is considered to reside mainly with the primary particles in aerogels. The added titania particles become part of the

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100

333

Contact Angle []

2 5 10 15 20

(a)
95

%(TMCS Treated) %(MTMS Treated)

d (V)/ d log D

90

85

80

75

1
70

0 0 50 100 150 200 250 300

15

20

25

30

35

40

45

Percentage of Surface Treatment

Fig. 8 Contact angle measurements of TMCS modied and MTMS modied aerogels

Pore Diameter ()
3.0 20 MTMS 30 MTMS 40 MTMS 20 TMCS 30 TMCS 40 TMCS

(b)
A- 40 % MTMS B- 40 % TMCS

2.5

2.0

d (V)/ dlogD

1.5

Endo Exo

1.0

0.5

0.0 0 50 100 150 200 250 300

Pore Diameter ()
Fig. 7 a Pore size distribution of silicatitania aerogels. b Pore size distribution of surface modied silicatitania aerogels

200

400

600

800

Temperature (C)
Fig. 9 DTA of (A) MTMS modied and (B) TMCS modied aerogels

Figure 5b shows the FT-IR spectra of surface treated aerogels. The peaks at 2,978 and 2,928 cm-1 corresponds to terminalCH3 groups. The peak at 850 cm-1 corresponds to SiC bonds. The presence of this band conrms the successful hydrophobisization of the material. Contact angle of the surface modied mixed oxide aerogels are provided in Fig. 8. The trimethylchlorosilane-treated aerogels possess a contact angle of 90, while the methyltrimethoxysilane-modied aerogels have contact angles between 75 and 80. The contact angle obtained for unmodied silicatitania aerogel was 39. The trimethylchlorosilane-treated gels have a higher contact angle in comparison with the methyltrimethoxysilane-modied gels. This is well in agreement with the expected results if we consider the R/Si ratio for the two hydrophobic reagents. The TMCS is having an R/Si ratio of 3 and the MTMS, is having a ratio of 1. The larger the R/Si ratio, the

better is the hydrophobic covering resulting in higher contact angle. Generally it has been observed that the aerogels are known to retain their hydrophobic behaviour up to 320C, and above this temperature they become hydrophilic [35]. This may be attributed to the oxidation of surfaceCH3 groups, leaving behind the hydrophilic silicatitania backbone. The Differential thermal analysis (DTA) of the surface treated gels is provided in Fig. 9. The thermal stability of chlorosilane-modied aerogel is much higher (520 C) than the methyl trimethoxysilane-modied aerogel. The specic surface area and porosity features of aerogels are provided in Table 2. The nitrogen AdsorptionDesorption isotherms are provided in Fig. 6b. The gure suggests a Type IV isotherm which is characteristic feature of mesoporous

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334 Table 2 BET surface area results of surface modied aerogels Surface modied aerogel 20% TMCS 30% TMCS 40% TMCS 20% MTMS 30% MTMS 40% MTMS Surface area (m2/g) 540 640 610 617 582 554 Total pore volume (Cm3/g) 1.52 1.66 0.61 1.97 2.02 1.90 Pore ) diameter (A 112 104 40 128 138 137

J Sol-Gel Sci Technol (2009) 52:328334 Acknowledgments P. R. Aravind and P. Shajesh acknowledge the Council of Scientic and Industrial Research (CSIR) for nancial support.

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materials. The desorption cycle of the isotherms showed a hysteresis loop which is attributed to the capillary condensation occurring in the mesopores. The pore size distribution of the hydrophobic aerogels is provided in Fig. 7b. All the aerogels showed a pronounced peak in the ). This conrms that the mesoporous region (20300 A aerogel structure is preserved by drying at ambient temperature.

8. 9. 10. 11. 12. 13.

14.

4 Conclusion In conclusion we have demonstrated an ambient pressure drying technique for the synthesis of silicatitania mixed oxide aerogels. The aerogels are homogeneous and possess large surface areas and mesopore volumes ideal for catalytic applications. The mixed oxide aerogels thus prepared had densities in the range of 0.340.38 g/cm3. TEM studies indicated that the aerogels were nanoporous with a networked structure and the selected area diffraction patterns suggested that the aerogels were amorphous. The selected area diffraction pattern of a 600 C conrmed that the aerogel is amorphous. Moreover the EDS spectrum revealed the presence of titania in the matrix. The absence of anatase peak in the XRD pattern even after calcining at 600 C conrmed molecular scale dispersion of titania in silica. The surface area of a 5wt% titania aerogel was as high as 685 m2/g with a pore volume of 2.34 cm3/g. The FTIR studies indicated the presence of SiOTi bonds in the mixed oxide system. The hydrophobic mixed oxide aerogels possess high surface areas and the values range between 540 and 640 m2/g. The thermal stability of chlorosilane-modied aerogels was very high compared to the reported value for chlorosilane-modied aerogels. The pore size distributions of the aerogels were between 20 and which conrms that the aerogel structure is pre300 A served even after modifying the surface.

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34. 35.

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