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Physico-chemical properties of
81
Chapter - 5
Chapter - 5
Physico-chemical properties of ambiently dried sodium
silicate based aerogels catalyzed with various acids
5.1 Introduction
Generally silica aergels are produced by hydrolysis and condensation
of silicon alkoxides like TMOS or TEOS in the presence of an acidic or basic
catalyst followed by supercritical drying in an autoclave. Since, various
research groups have prepared monolithic and transparent silica aerogels
applying the same method [1-5]. However, this method of preparation of
aerogels in an autoclave is very risky and expensive. Because the drying
occurs at high temperature and pressure with evacuation of highly
flammable gases and the chemicals used are hazardous for health and
costly. Hence, for commercialization, it is necessary to produce silica
aerogels using low cost inorganic precursor and drying the gels at ambient
pressure. Therefore, for easy availability we prepared the silica aerogels
using sodium silicate precursor and dried the gels at ambient pressure. So,
in this chapter we studied the effect of various acid catalysts for the
preparation and characterization of silica aerogels.
5.2 Experimental
The schematic presentation of the silica aerogels catalyzed with
various acids is shown in fig. 5.1. Wet gels were prepared from commercial
sodium silicate precursor of specific gravity 1.05 diluted from specific gravity
of 1.39 (Na2SiO3, s-d fine chemicals, India, Na2SiO3 content 36 wt%,
Na2O:SiO2=1:3.33) using various strong and weak acids as catalysts
keeping molar ratio of Na2SiO3:H2O constant at 1:146.67. The sols were
prepared by adding acid dropwise in sodium silicate solution while stirring
and were kept for gelation at 50oC in a temperature controlled oven to form a
gel. The formed gels were aged for 3 h at 50oC to give strength to the gel
network. To study the effect of various acids, the monolithic gels were first
cut into very small pieces then exchanged with 50 ml water four times so that
the sodium salt trapped in the pores of gel will come out and once with
Physico-chemical properties of
82
Chapter - 5
Gelation at 50 C
Hydrogel
Aging for 3 h at 500C
Aged Gel
Washed with water for
0
4 times in 24 h at 50 C
Hydrogel
Exchanged with methanol
once in 24 h at 50 0C
Alcogel
Silylated with 1:1:1 volume
ratio of methanol, hexane
o
and TMCS for 24 h at 50 C
Silylated alcogel
Dried at room temperature
0
0
for 24 h and 50 C & 200 C
for 1 h each
Physico-chemical properties of
83
Chapter - 5
Physico-chemical properties of
KA =
84
[B][H+]
[A]
Chapter - 5
--- (5.1)
--- (5.2)
85
Physico-chemical properties of
Chapter - 5
NaO
H .OH
Si
O
O- Na
NaO
(-)
HO
Si
HO
O
H+
+
(-)
NaO-
NaO
H .OH
Si
Si
+ NaOH
O
Pentavalent inetrmediate
Sodium silicate
HO
NaO
HO
Si
OH
HO
Si
OH
O
+ NaOH
O
(-)
OH
HO
F-
Si
O
OH
(-)
F-
OH
HO
Si
H2O
Si
(-)
F-
Si
O
(-)
H2O
OH
OH
HO
Si
HO
OH
HO
OH
F
OH
OH
OH
+ HF
OH
HO
Si
OH
Si
OH
HO
HO
OH2
H2O
Si
Si
Si
OH
HO
F
F-
HO
F-
OH
HO
+ HF
OH
---(5.3)
86
Physico-chemical properties of
Chapter - 5
H2O
Acid
Sodium silicate
Si (OH)4
---(5.4)
Sodium salt
Silicic acid
Condensation
OH
Si OH
OH
n HO Si OH + HO Si OH
OH
Si
OH
+ 2n H2O ---(5.5)
O
OH
Silica gel
Since, the formed silica gels contain the hygroscopic OH groups on their
surface which are modified with TMCS as in the following reaction.
Surface chemical modification
Si OH
O
Si
Cl Si (CH3)3
+
OH
Si O Si (CH3)3
O
Cl Si (CH3)3
Si
+ 2HCl ---(5.6)
O Si (CH3)3
Physico-chemical properties of
87
Chapter - 5
Gelation
Volume
Poro
Pore
Thermal
Contact
tration of
time
shrin-
-sity
volume
conductivity
angle
acid (M)
(min.)
kage (%)
(%)
(cc/g)
(W/m.K)
(deg.)
19,920
95
95
10.0
0.100
<90
1,470
91
85
2.9
0.150
<90
10
86
84
2.8
0.151
135
77
87
3.6
0.137
138
73
89
4.4
0.118
145
30,420
86
95
9.7
0.101
140
2,940
89
86
3.3
0.145
<90
90
86
88
3.8
0.146
137
81
86
3.1
0.147
134
77
88
3.9
0.125
147
33,480
95
92
6.1
0.112
140
2,700
80
91
5.7
0.114
140
1,800
84
85
3.1
0.147
100
86
78
1.8
0.170
100
84
79
2.0
0.165
110
88
Physico-chemical properties of
Chapter - 5
Density (g/cc)
0.434
0.372
0.310
0.248
0.186
H2SO4
0.270
0.225
0.180
0.135
0.090
HNO3
0.288
0.240
0.192
0.144
0.096
HCl
Physico-chemical properties of
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Chapter - 5
(a)
50 nm
(b)
50 nm
Fig. 5.3 TEM micrographs of the aerogels prepared using strong acid
(a) H2SO4 - 2M (b) H2SO4 - 5M
FTIR spectra of the silica aerogels prepared using strong acids (2M)
catalyst are shown in fig. 5.4. It is evident from fig. 5.4 that the intensity of
the peaks around 3400 and 1630 cm-1 correspond to O-H absorption band
Physico-chemical properties of
90
Chapter - 5
[11] decreased in the manner HCl> HNO3> H2SO4. And the intensity of
absorption peaks at 2923 and 1450 cm-1 correspond to terminal CH3 and
peak at 845 cm-1 correspond to Si-C groups [12], increased in the manner
HCl< HNO3< H2SO4. The presence of absorption peak at 1096 cm-1
correspond to Si-O-Si is expected for the silica materials [13].
c
b
a
-OH
Si-C
C-H
C-H
-OH
Si-O-Si
4000
3000
2000
1500
Wavenumber (cm-1)
1000
500
Fig. 5.4 FTIR spectra of aerogels prepared using strong acids (2M)
a) HCl, b) HNO3, c) H2SO4
5.4.2 Effect of weak acids
The effect of weak acids and their concentration on the physicochemical properties of silica aerogels have been studied as given in the table
5.2. From table 5.2 it is observed that for the acids HF, CH3COOH, HCOOH
and H3PO4, the gelation time decreased with increase in concentration
(<4M) and then remained constant. And for the acids C3H6O2, C4H6O6,
C6H8O7.H2O the gelation time first decreased with an increase in
concentration and then increased. The increase in gelation time at higher
concentration may be because of the presence of large amount of protons
and less amount of OH- groups. The lower gelation times for the weak acids
are due to the fact that the anions of weak acids are basic [5].
Physico-chemical properties of
91
Chapter - 5
Gelation
Volume
Poro
Pore
Thermal
Contact
tration of
time
shrinka-
-sity
volume
conductivity
angle
acid (M)
(min.)
ge (%)
(%)
(cc/g)
(W/m.K)
(deg.)
1
2
3
4
5
1
2
3
4
5
1
2
3
4
5
1
2
3
4
5
1
2
3
4
5
1
2
3
4
1
2
3
4
130
133
100
100
140
146
148
144
147
140
147
143
144
145
146
145
135
147
147
148
145
137
145
147
145
147
144
136
147
145
143
148
148
92
Physico-chemical properties of
Chapter - 5
Figs. 5.5 and 5.6 show the effect of weak acid concentration on the
density of the silica aerogels. From fig. 5.5 it clears that for the silica
aerogels prepared using the acids HF, CH3COOH, HCOOH and C3H6O2, the
variation in the density is same as that of strong acids. But for the aerogels
prepared using the acids H3PO4, C4H6O6 and C6H8O7.H2O, the density
increased with increase in concentration, then decreased, and further
increased with concentration of acid as seen from the fig. 5.6.
Density (g/cc)
0.210
0.175
0.140
0.105
0.070
C3H6O2
0.280
0.245
0.210
0.175
0.140
HCOOH
0.312
0.260
0.208
0.156
0.104
0.350
0.315
0.280
0.245
0.210
CH3COOH
HF
Physico-chemical properties of
93
Chapter - 5
low density (0.086 g/cc). These aerogels were obtained for the molar ratio of
Na2SiO3:H2O:Citric acid:TMCS at 1:146.67:0.72:9.46.
Density (g/cc)
0.252
0.210
0.168
0.126
0.084
C6H8O7.H2O
0.245
0.210
0.175
0.140
0.105
C4H6O6
0.238
0.204
0.170
0.136
0.102
H3PO4
Physico-chemical properties of
94
Chapter - 5
(a)
50 nm
(b)
50 nm
Fig. 5.7 TEM micrographs of the silica aerogels prepared using weak acid
(a) Citric-2M (b) Citric-3M
Fig. 5.8 shows the FTIR spectra of silica aerogels catalyzed with
weak acid (3M). It is observed that there is not much noticeable difference in
the intensity of the peaks around 3400 and 1630 cm-1 which correspond to
O-H absorption band [11]. But the intensity of absorption peaks at 2923 and
1450 cm-1 correspond to terminal CH3 and peak at 845 cm-1 correspond to
Si-C groups [13], increased in the manner CH3COOH<HCOOH< C3H6O2<
H3PO4<C4H6O6<C6H8O7.H2O. This indicates that the silica aerogels
catalyzed with citric acid (3M) are hydrophobic in character.
95
Physico-chemical properties of
Chapter - 5
g
f
e
d
c
C-H
Si-C
-OH
C-H
a
-OH
Si-O-Si
4000
3000
2000
1500
1000
500
-1
Wavenumber (cm )
Fig. 5.8 FTIR spectra of the aerogels prepared using weak acids (3M)
a) HF, b) CH3COOH, c)HCOOH, d)C3H6O2, e)H3PO4, f)C4H6O6, g)C6H8O7.H2O
Further, the hydrophobicity is confirmed by measuring the contact
angle of water on the surface of aerogel. Fig. 5.9 illustrates the drop of water
on a hydrophobic aerogel surface catalyzed with citric acid (3M) showing
148o contact angle.
Fig. 5.9 Water drop on the aerogel surface catalyzed with citric acid (3M); =148o
96
Physico-chemical properties of
Chapter - 5
100
Weight (%)
420oC
98
0.4
96
0.2
94
92
- 0.2
90
0
200
400
600
800
TGA
DTA
- 0.4
1000
Temperature (oC)
Fig. 5.10 TG-DT analyses of the aerogel prepared using citric acid (3M)
5.4.3 N2 adsorption-desorption of silica aerogels
Fig. 5.11 shows the N2 adsorption-desorption isotherms of the
aerogels prepared using H2SO4-2M (fig. a), 5M (fig. b) and citric acid-2M (fig.
c), 3M (fig. d). From the shape of the isotherms it can be observed that the
materials exhibited the type IV isotherms for all the four samples, which is
Physico-chemical properties of
97
Chapter - 5
(c)
Pressure (mmHg)
(b)
(a)
(d)
Pressure (mmHg)
Physico-chemical properties of
98
Chapter - 5
The results of fig. 5.11 are illustrated in table 5.3. It is observed that
for the silica aerogels prepared using H2SO4, the increase in the
concentration shifts the BET surface area towards maximum (458 m2/g) due
to decrease in the particle size. Further, for the aerogels prepared using
citric acid, the BET surface area increased from 448 to 719 m2/g when the
concentration of citric acid increased from 2 to 3M. The increase in the BET
surface area with decrease in the particle size can be explained on the
model proposed by Zarzycki et al. [15]. According to this model, the specific
surface area of a dry gel is related to particle and pore sizes. Assuming that
the particles are spheres having uniform size, the specific surface area has
been related to the inverse of the particle radius. Among all the strong and
weak acids, the weak acid, citric acid-3M produced low density (0.086 g/cc)
silica aerogels with large specific surface area (719 m2/g).
Table 5.3 BET surface area, pore volume and average pore diameter of
the aerogels catalyzed using H2SO4 and citric acids.
Physical Properties
BET surface area (m2/g)
H2SO4
H2SO4
2M
5M
H2O 2M
3M
458
283
448
719
C6H8O7. C6H8O7.H2O
5.5 Conclusions
Silica aerogels were obtained by catalyzing the hydrolysis and
condensation of sodium silicate with different acid catalysts varying their
concentration
followed
by
simultaneous
solvent
exchange,
surface
ratio
of
Na2SiO3:H2O:Citric
acid:TMCS
at
1:146.67:0.72:9.46
repectively. They have low thermal conductivity (0.09 W/m.K) with good
hydrophobicity (148o). TEM spectra expressed the well connected network of
silica particles with high porosity. These aerogels exhibited large specific
surface area (719 m2/g) with mesopores in their network. And these aerogels
are thermally stable up to a temperature of around 420oC.
Physico-chemical properties of
99
Chapter - 5
References
[1] S. Henning and L. Svensson, Phys. Scr., 23 (1981) 697
[2] G. Poelz and R. Riethmuller, Nucl. Instrum. Methods, 195 (1982) 491
[3] M. Prassas, J. Phalippou, and J. Zarzycki, J. Mater. Sci., 19 (1984) 1665
[4] G. M. Pajonk, A. Venkateswara Rao, P. B. Wagh, and D. Haranath,
J. Mater. Synt. and Processing, 5 (1997) 6
[5] A. Venkateswara Rao, G. M. Pajonk, N. N. Parvathy, J. Mater. Sci.,
29 (1994) 1807
[6] A. Parvathy Rao, G. M. Pajonk, A. Venkateswara Rao, J. Mater. Sci., 40
(2005) 3481
[7] R. P. Bell F. R. S., Acids and Base: Their Quantitative Behavior, Ch. 2,
p. 17
[8] R. Aelion, A. Loebel, and F. Eirich, J. Am. Chem. Soc., 72 (1950) 5705
[9] R. Aelion, A. Loebel, F. Eirich, Recueil Travaux Chimiques, 69 (1950) 61
[10] Z. Z. Vysotskii and D. N. Strazhesko, Wiley, New York, (1973)
[11] C. J. Lee, G. S. Kim, and S. H. Hyun, J. Mater. Sci., 37 [11] (2002) 2237
[12] S. S. Prakash, C. J. Brinker, and A. J. Hurd, J. Non-Cryst. Solids, 190[3]
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(in Chinese)
[14] K. S. W. Sing, D. H. Everett, R. A. W. Haw, L. Moscow, R. A. Pierotti,
J. Rouquerol, T. Siemieniewska, Pure Appl. Chem., 57(4) (1985) 603
[15] J. Zarzycki, M. Prassas and J. Phalippou, J. Mater. Sci. 17 (1982) 3371
Physico-chemical properties of
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Chapter - 5