Catalytic Effect of Trace Excess Water on the Rate of Gel Shrinkage

Allen Blankenship Chem.: 491 Section: 001 Grace Columbia, Davison Catalysis Research Jan.3 Jan. 23, 2002 Submitted: Jan. 23, 2002 Resubmitted : April 2, 2002

Silica gel is a solid, amorphous, porous form of polysilicic acid made by a process in which a silica sol is aggregated to form a solid gel structure. Silica gel often is heated commercially to remove both physically adsorbed water and some of the silanols (chemically adsorbed water). Such thermal treatment was carried out in predried air (below 2ppm water) and in wet air (equal to or less than 300 ppm water) at 871C, 927C, and 982C in order to determine the effects of trace amounts of water on the shrinkage in gel structure. Reduction in both surface area and pore volume was observed. This study suggests a possible catalytic effect of small traces of water on silica gel shrinkage.

An introduction to the structure of silica gel is helpful for an understanding of the theories derived to explain the chemistry of thermal activation. Silica Gel Silica gel is a coherent, rigid three-dimensional network of contiguous particles of colloidal silica. A silicate solution is combined with an acid to be converted into silicic acid. In the silicic acid system, the formation of gel has usually been ascribed to the condensation of Si(OH)4 into siloxane chains, then branching and crosslinking to form a three- dimensional network. The very early stages of the polymerization of Si(OH)4 involves the formation of very small discrete particles of SiO2 bearing surface SiOH (silanol) groups (See Figure 1). These discrete units are called micelles. When the micelles collide, SiOH groups on the surface condense to form Si-O-Si, thus growing together because of differences in solubility of silica (See Figure 2). The necks joining the micelles increase in diameter until the difference in solubility becomes too small to cause measurable changes. (See Figure 3). (1) Thus a simplified view of silica gel is a random three-dimensional network of linked micelles. Figure 1

Micelle Bridging Model

Si O Si Si O Si Si O H HO Si Si O H Si OH HO Si OH Si H2 O

Figure 2

The radius of the neck, rn, is negative because the center of curvature is outside the solid phase; the radius of the micelle, rp, is positive. Material tends to dissolve from surfaces with positive curvature and deposit in regions with negative curvature.

Figure 3

Gel Structure Commercially, gel structures can be well characterized through controlled process parameters to yield gels for specific applications. A complete description of an aggregate structure includes the size, shape, spatial distribution of the particles, as well as a characterization of the strength of the bond between the particles. For the purpose of this paper, we will define "gel shrinkage" as reductions in specific surface area (m2/g) and in specific pore volume (cm3/g). A significant change in gel structure is a reduction of at least 20 m2/g in specific surface area (SA) and a reduction of at least 0.15 cm3/g in specific pore volume (PV). Changes of this magnitude in S.A. and P.V. will change the silica gel properties significantly.

Figure 4 Micelle Surface Area

Specific surface area measured by adsorption of N2 is a dependable and accurate measurement. The BET ( Brunauuer, Emmett, Teller) method of calculating specific surface | ~2.5 nm | area from an adsorption isotherm is widely 1/ d 3 V= 6 used. The surface area of the linked micelles, 2 the solid phase of the three-dimensional A= d 6 3 network, determine the surface area of the gel. 2.1 x 10 gm/m The pores, void space in the gel network (See SA = A/( x V) 1140 m2/gm figure 5), determine the pore volume. Pore volume can be derived from gas desorption isotherms. (3) In this work, all samples were sent to an analytical lab at Davison Catalysis in Columbiato be evaluated under a Quantachrome Autosorb-1 for both specific surface area (S.A.) and specific pore volume (P.V.). For the Autosorb-1 machine used, accuracy of measurements is within 0.2% of the measurement according to the manufacturers literature. Samples that have been resubmitted to this lab for analysis on this machine have historically come within these guidelines.

Figure 5

Gel Particle
LOW MAGNIFICATION

PORE STRUCTURE MAGNIFIED

SILICA MICELLES

Silica Gel Surface In 1934, Hoffman postulated the existence of silanol groups (=Si-OH) on the silica surface. (4) It is now generally accepted that surface silicon atoms tend to have a complete tetrahedral configuration and that in an aqueous medium their free valence becomes saturated with hydroxyl groups, forming silanol groups. Silanol groups in turn, may condense to form siloxane bridges (=Si-O-Si=). (5) Therefore, the surface composition of silica gel is made up of physically adsorbed water, chemically bound water, and silicon dioxide (See Figure 6).

Figure 6

Silica Gel Surface

Chemically Adsorbed Water O H H O Si O O Si O H O Si O H O Si O H H O Si O H H O Si O Physically Adsorbed Water

O H H O Si H

Chemically adsorbed water - 4 to 6 OH / nm 2 Physically adsorbed water - 0.1 to 0.7 fractional

monolayer

Thermal Activation of Silica Gel Experimental Details Activation began with placing approximately 30 cc of silica gel on a porous frit in a quartz tube. A constant flow of air with a flow rate of 42 L/hr at 10psig was blown through the bottom of the tube causing the silica gel to be fluidized. Activations were completed initially under dry air (H2O < 2ppm) but then repeated with air having trace amounts of H2O (10ppm, 30ppm, 100ppm, and 300ppm). The tube was loaded into a tube furnace and the temperature raised at a rate of 400 C per hour until it reached the set point. Once at the set point, temperatures were kept constant for five hours. Temperatures used in this experiment were 871, 927,and 982 C. Three silica gel samples lot A, lot B, and lot C were used for the study. When pure silica gel is heated to moderate temperatures (up to 1000C) under dry conditions, one always observes a decrease in SA and PV. This type of sintering results from amorphous silica being converted to crystalline silica in very small-localized atomic regions. However, because the starting material is pure, the final product still has high and well-defined internal porosity. Impurities are known to affect the kinetics of sintering, and even under milder gel shrinkage conditions, small amounts of Na2O (e.g. 0.5%) are known to enhance the loss of porosity. In this study, all impurities known to accelerate sintering were kept at a minimum; the only exception being water, which is an integral part of the freshly prepared silica gels. The water levels were kept much below the levels needed to effect "steaming", because we purposely wanted to avoid collapse of gel structure. Results
Table 1 summarizes all results. Table 1
Lot Wet Air - hrs

A
0 5 Difference between 0 5

B
Difference between 0 5

C
Difference between

dry & wet air Dry Air - hrs AS IS % Na2O S.A. (m2/g) N2 P.V. (cm3/g) 871C - 10ppm H2O S.A. (m2/g) N2 P.V. (cm3/g) 982C - 30ppm H2O S.A. (m2/g) N2 P.V. (cm3/g) 871C - 100ppm H2O S.A. (m2/g) N2 P.V. (cm3/g) 927C - 100ppm H2O S.A (m2/g) N2 P.V. (cm3/g) 982C - 100ppm H2O S.A. (m2/g) N2 P.V. (cm3/g) 927C - 300ppm H2O S.A. (m2/g) N2 P.V. (cm3/g) 982C - 300ppm H2O S.A. (m2/g) N2 P.V. (cm3/g) 5 0.06 6 317 1.62 0 5 0.06 7 298 1.67 0 -

dry & wet air 5 0.05 6 307 1.59 0 -

dry & wet air

270 1.48

265 273 1.46 1.51

+8 +0.05

209 198 0.98 0.90

-11 -0.08

196 176 1.02 0.86

-20 -0.16

211 202 1.01 0.92

-9 -0.09

270 1.48

265 259 1.45 1.43

-6 -0.02

245 254 1.31 1.35

+9 +0.04

240 231 1.43 1.33

-9 -0.10

245 241 1.32 1.27

-4 -0.05

209 187 0.98 0.79

-22 -0.19

196 189 1.02 0.94

-7 -0.08

211 201 1.01 0.93

-10 -0.08

245 245 1.31 1.26

0 -0.05

240 228 1.43 1.28

-12 -0.15

245 241 1.32 1.26

-4 -0.06

209 172 0.98 0.70

-37 -0.28

196 185 1.02 0.92

-11 -0.10

211 211 1.01 1.01

0 0

The dry air activations and the wet air activations showed relatively the same gel shrinkage except for the activations completed at 982 C. Below is a table summarizing only those activations.
Table 2 A
0 5 Difference 0 5

Lot Wet Air - hrs

B
Difference 0 5

C
Difference

between dry & wet air Dry Air - hrs AS IS % Na2O S.A. (m2/g) N2 P.V. (cm3/g) 982C - 30ppm H2O S.A. (m2/g) N2 P.V. (cm3/g) 982C - 100ppm H2O S.A. (m2/g) N2 P.V. (cm3/g) 982C - 300ppm H2O S.A. (m2/g) N2 P.V. (cm3/g) 5 0.06 6 317 1.62 0 5 0.06 7 298 1.67 0 -

between dry & wet air 5 0.05 6 307 1.59 0 -

between dry & wet air

209 198 0.98 0.90

-11 -0.08

196 176 1.02 0.86

-20 -0.16

211 202 1.01 0.92

-9 -0.09

209 187 0.98 0.79

-22 -0.19

196 189 1.02 0.94

-7 -0.08

211 201 1.01 0.93

-10 -0.08

209 172 0.98 0.70

-37 -0.28

196 185 1.02 0.92

-11 -0.10

211 211 1.01 1.01

0 0

Discussion At 982 C, the first sample (lot A) showed a large amount of gel shrinkage with increasing ppm H2O. The second sample (lot B) showed a significant shrinkage with 30 ppm H2O at 982 C but did not maintain a significant additional shrinkage when the ppm H2O was increased. The third sample (lot C) showed a small amount of gel shrinkage at 30 ppm and 100ppm H2O and none at 300ppm H2O at 982 C. The changes on the third sample were not significant. The observed differences in S.A. and P.V. could have been the result of different production histories of the three gels. The results show the beginning of the catalytic effect of small traces of water on silica gel shrinkage. Another type of sintering known to occur in silica gel activation takes place in the presence of steam. This type of sintering is macroscopic. Although macroscopic sintering is not part of this study, the theories of this phenomenon may be useful in explaining the observed gel shrinkage. Gel shrinkage can be rationalized as the onset sintering. Sintering is driven by the energy gained by the reduction in surface area of the porous body. Material moves by viscous flow or diffusion in such a way

as to eliminate porosity and thereby reduce the solid-vapor interfacial area. In gels, this area is enormous, so the driving force is great enough to produce sintering at exceptionally low temperatures, where the transport processes are relatively slow. (6) Since we are only at the beginning stages of sintering, mass transport is at localized levels of atomic dimensions and occurring on the surface only. Mass transport obviously involves making and breaking of chemical bonds. The condensation of two silanols leads to formation of water and a siloxane bond. The reverse of this reaction involves the breaking of siloxane bond by water. And it is this reversal, although short lived and transient, that is believed to be the cause of the observed acceleration of gel shrinkage in the presence of excess water. It is suggested that for continued study, these experiments be repeated at 982 C and with 300 ppm H2O. Also, carrying out the experiment at 982 C and 700 ppm H2O. More than doubling the water content might show more of an effect on the gel shrinkage. Acknowledgments I thank Dr. Rimantas Glemza, Research Associate for Davison Catalysis, for his eleven years of teaching, advising, and guiding me in the ways of silica gel technology. I would like to thank Patricia McCrary for her work measuring surface area and pore volume of the samples on the Quantachrome Autosorb-1. I thank Dr. Nordulf Debye in his guidance and advice for this experiment.

References: 1. Iler, R. K. The Chemistry of Silica; Wiley: New York, 1979, p222-239 2. A.VonBuzagh, Colloid Systems, The Technicle Press, London, 1937, p.149 3. Bergna, Horatio The Colloid Chemistry of Silica, 1994 ACS Publications, p341-353. 4. Hoffman, P Angewan. Chem. 1934, p 539-558 5. Bergna, Horatio The Colloid Chemistry of Silica, 1994 ACS Publications, p21-30 6. Brinker, C.J., Scherer, George, Sol-Gel Science, 1990 Academic Press, p675-738