Sol-gel processing of Silicates

Aqueous route
➢ Silica gels can be produced through a less expensive method involving an aqueous solution of sodium
silicate.
➢ Sodium silicate is an inexpensive white solid with a range of possible stoichiometries (which each have
different names)—Na2SiO3 or sodium metasilicate, sodium polysilicate or (Na2SiO3)n, sodium
orthosilicate Na4SiO4, and others.
➢ Sodium silicates are soluble in water, and when dissolved the resulting solution is referred to as
waterglass or liquid glass.
➢ Sodium silicates are slightly basic, and when neutralized with acid (such as hydrochloric or sulfuric
acid), hydrolysis will occur and silanol (Si-OH) groups will form.
➢ Once silanol groups form, the silicate molecules form siloxane bonds with other silicate molecules and
bridge together to form nanoparticles, resulting in a sol.
➢ This sol can then be used to make a gel.
Silica Gel formation via Waterglass Technique
Polymerisation
 Alkoxide route
➢ The most common technique used for producing silica gels today involves the reaction of a silicon alkoxide with water in a
solvent such as ethanol or acetone, usually in the presence of basic, acidic, and/or fluoride-containing catalyst.
➢ In this technique, a silicon alkoxide (usually either tetramethoxysilane or tetraethoxysilane) serves as the source for the silica,
water acts as a reactant to help join the alkoxide molecules together, and a catalyst (such as ammonium hydroxide or
ammonium fluoride) helps the underlying chemical reactions go fast enough to be practically useful.
➢ Because silicon alkoxides are usually non-polar liquids, however, they are not miscible with water. As a result, a solvent such as
ethanol or acetone, which is miscible with both silicon alkoxides and water, is added in order to get everything into the same
phase so the necessary chemical reactions can occur.
 Alkoxide reaction in acidic environments
Rapid protonation

➢ The oxygen atom in Si-OH or Si-OR is protonated leaving H-OH or H-OR groups.
➢ The electron density are shifted from the Si atom, making it more accessible for reaction with water (hydrolysis) or
silanol (condensation).
➢ It results mainly polymeric gels after condensation.

- +

- +
 Alkoxide reactions in basic environments

➢ Nucleophilic attack by OH- or Si-O- on the central Si atom. These species are formed by dissociation of water or Si-OH.
➢ The reactions are of SN2 type where OH- replaces OR- (hydrolysis) or silanolate replaces OH- or OR- (condensation).
➢ It results mainly particulate gel after condensation.
 Sol (far from gel point) Sol (near gel point) Gel point

Acid catalysed condition (Polymeric Gel)

Entangled primarily linear macro-molecules Additional crosslinks at junctions

Base catalysed condition (Particulate Gel)

Linked clusters
Growth and
additional branching
Branched clusters
Residual spaces in between the clusters
Comperisn between two preparation methods:
Water based system:
Na2SiO3 is dissolved in water
The reactive groups in water glass are
silanol. Gelation therefore starts with a
change in pH
Morphology control via pH, presence of
salts, concentration
Water free systems - alkoxides:
Alkoxide is dissolved in an organic
solvent, usually an alcohol
Hydrolysis reaction occur, converting
Si-OR to Si-OH. Sol-gel therefore starts
by adding water (+ catalyst)
Two reaction paths; acidic and basic
environments:
 Parameters that control condensation

The ratio between alkoxide and water RW (OR/H2O)

Si(OR)4 + 2H2O SiO2 + 4ROH

✓ The reaction states that a water ratio of RW = 2 (H2O/OR) is needed to convert everything to SiO2.
✓ A water ratio of RW = 1 leads to complete hydrolysis but no condensation.
✓ Increasing the water content (i.e. lower RW) will reduce condensation.
✓ Reducing the water content increases the condensation.
✓ The morphology of gel greatly depends on Rw

Rw Catalyst Sol gel structure

1 Rw  2 Acidic Fibrous structure
0.1  Rw  1 Acidic Linear/branched structure
Rw  2 Basic Cluster chains
7  Rw  25 Basic Mono dispersed spheres
 Parameters that control condensation

pH, Reaction rate is pH dependent:

➢ The minimal reaction rate for hydrolysis is at

pH 7, and increases exponentially at both lower
and higher pH.
➢ the rate of condensation, exhibits a minimum at
pH = 4.5 and a maximum around pH = 7.
➢ At pH 5 hydrolysis is favored, and
condensation is the rate-determining step. A
large number of monomers or small oligomers
with reactive Si-OH groups are simultaneously
formed.
➢ In contrast, hydrolysis is the rate-determining
step at pH > 5, and hydrolyzed species are
immediately consumed because of the faster
condensation.
 Parameters that control condensation
Precursor:
➢ Different from water glass as a precursor, the Si-OR groups of silicon alkoxides must first be hydrolyzed before
condensation reactions can take place.
➢ The hydrolysis rates of alkoxysilanes are influenced by steric factors. Any branching of the alkoxo group or increasing
of the chain length lowers the hydrolysis rate of the alkoxysilanes.
Reactivity: Si(OMe)4 > Si(OEt)4 > Si(OnPr)4 > Si(OiPr)4
Me = methoxy Et = ethoxy Pr = propoxy
➢ Electron density on Si (Si-R > Si-OR > Si-OH > Si-O-Si) also influence the reaction kinetics
✓ Acid catalyzed reaction demands high electron density , produce more straight chains
✓ Base catalyzed reaction demands low electron density, produce more branched network

Other parameters:

➢ Temperature
➢ Solvent,
➢ Electrolytes,
➢ Relative and absolute concentrations of the reactants.