SOL-GEL AND ITS APPLICATIONS

Submitted by - PRIYANKA SINGH (TT)

M. TECH. 1ST YEAR

Sol-Gel
A sol is a colloidal (the dispersed phase is so small that gravitational forces do not exist; only Van der
Waals forces and surface charges are present) or molecular suspension of solid particles of ions in a
solvent.

A gel is a semi-rigid mass that forms when the solvent from the sol begins to evaporate and the
particles or ions left behind begin to join together in a continuous network.

Sol-gel is a chemical solution process used to make ceramic and glass materials in the form of thin
films, fibers, or powders.

The sol evolves then towards the formation of an inorganic network containing a liquid phase
(gel).Formation of a metal oxide involves connecting the metal centres with oxo (M-O-M) or hydroxo
(M-OH-M) bridges, therefore generating metal- oxo or metal- hydroxo polymers in solution.

The drying process serves to remove the liquid phase from the gel thus forming a porous material,
then a thermal treatment (firing) may be performed in order to favor further polycondensation and
enhance mechanical properties.

Typical precursors are metal alkoxides and metal chlorides, which undergo hydrolysis (Hydrolysis is
a chemical reaction or process in which a chemical compound is broken down by reaction with water)
and polycondensation reactions (A chemical reaction in which two or more molecules combine upon
the separation of water or some other simple substance) to form a colloid, a system composed of solid
particles (size ranging from 1 nm to 1 μm) dispersed in a solvent.

The precursor sol can be either deposited on a substrate to form a film (e.g. by dip-coating or spin-
coating), cast into a suitable container with the desired shape (e.g. to obtain a monolithic ceramics,
glasses, fibers, membranes, aerogels), or used to synthesize powders (e.g. microspheres, nanospheres).

Sol-Gel Process
In essence, the sol-gel process usually consists of 4 steps:

(1) The desired colloidal particles once dispersed in a liquid to form a sol.

(2) The deposition of sol solution produces the coatings on the substrates by spraying, dipping or
spinning.

(3) The particles in sol are polymerized through the removal of the stabilizing components and
produce a gel in a state of a continuous network.

(4) The final heat treatments pyrolyze the remaining organic or inorganic components and form an
amorphous or crystalline coating.

• The Sol-Gel process allows to synthesize ceramic materials of high purity and homogeneity by a
process occurs in liquid solution of organometallic precursors (TMOS, TEOS, Zr (IV)- Propoxide,
Ti(IV)- Butoxide, etc.), which, by means of hydrolysis and condensation reactions, lead to the
formation of a new phase (SOL).
M-O-R + H2 O → M-OH + R-OH (hydrolysis)

M-OH + HO-M → M-O-M + H2O (water condensation)

M-O-R + HO-M → M-O-M + R-OH (alcohol condensation) (M = Si, Zr, Ti)

Factors affecting Reactivity

• pH,

• Water content,

• Concentration,

• Temperature,

• Drying conditions

The amount of water added is expressed in terms of hydrolysis ratio ‘h’ and defined as

When h<1, there is less possibility of forming infinite network because of the presence of few M-
OH groups for cross linking and gelation. If excess amount of water is present, that is h>m,
extensively cross linked gel can be formed. For a given amount of water another way to control the
process is to control the rate of addition of water.

The pH of the system affects the relative rate of hydrolysis and condensation. The rates of hydrolysis
and condensation of tetra ethyl ortho silicate (TEOS), very widely used precursors, as a function of
pH. Under acidic conditions, hydrolysis occurs at a faster rate than condensation and the resulting gel
is weakly branched. Under basic conditions, the reverse occurs and the resulting gel is highly
branched and contains colloidal aggregates. Subsequently, dried and heat treated samples have
different surface functions and pore structures.

The sol-gel approach is interesting in that it is a cheap and low-temperature technique that allows for
the fine control on the product's chemical composition, as even small quantities of dopants, such as
organic dyes and rare earth metals, can be introduced in the sol and end up in the final product finely
dispersed.

An overview of the sol-gel process is presented in a simple graphic work below;

Flow chart of basic steps in sol gel processing is given below;

Fig.2. Basic steps in sol gel processing

Advantages of Sol-Gel Technique:
1. Can produce thin bond-coating to provide excellent adhesion between the metallic substrate and the
top coat.

2. Can produce thick coating to provide corrosion protection performance.

3. Can easily shape materials into complex geometries in a gel state.

4. Can produce high purity products because the organo -metallic precursor of the desired ceramic
oxides can be mixed, dissolved in a specified solvent and hydrolyzed into a sol, and subsequently a
gel, the composition can be highly controllable.

5. Can have low temperature sintering capability, usually 200-600°C.

6. Can provide a simple, economic and effective method to produce high quality coatings.

Applications
• It can be used in ceramics manufacturing processes, as an investment casting material, or as a
means of producing very thin films of metal oxides for various purposes.
• Sol-gel derived materials have diverse applications in optics, electronics, energy, space, (bio)
sensors, medicine (e.g. controlled drug release) and separation (e.g. chromatography)
technology. One of the more important applications of sol-gel processing is to carry out
zeolites synthesis.
• Other elements (metals, metal oxides) can be easily incorporated into the final product and the
silicalite sol formed by this method is very stable.
• Other products fabricated with this process include various ceramic membranes for
microfiltration, ultrafiltration, nanofiltration , preevaporation and reverse osmosis.
• The coating of textiles with chemically or physically modified silica sols with particle diameters
smaller than 50 nm (“nanosols”) enables the manifold alteration of their physico-mechanical,
optical, electrical and biological properties. Thus the protection of textiles against destruction and
the creation of new advantageous functions can be realised. Prospective new products to be
developed include textiles with water, oil and soil repellency and with antimicrobial properties.
 sol‐gel technology makes enabling multifunctional properties in one step which is not
possible by conventional textile finishing methods because of incompatibility of chemical
materials. In conventional textile finishing methods, the treatments haveseparately been
applied in several steps to obtain functional properties and these multistep processes increase
the costs of the textile mills. Therefore, enabling multifunctional properties in one step is a
challenging process to overcome in terms of decreasing water and energy consumption and
costs. On the other hand, besides the various advantages,sol‐gel technology has a
disadvantage of high costs of precursor materials used in sol‐gel technology. In sol‐gel
technology, metal alkoxides and metallic salts have been used as precursors and by the
catalytic effect of an acid or alkali, hydrolysis and condensation reactions occur [1, 2]. The
reactions of precursor materials with textile surfaces are given in Figure 1. Nanosols can be
applied to fabric by pad‐dry‐cure process. Application steps of nanosols to textiles are
illustrated in Figure 2.

Figure 1. The reactions of precursor materials with some textile surfaces.

 By sol‐gel technology, various functional properties can be given to textile materials or some
properties that already exist can be developed in one or more steps. The use of sol‐gel
technology in textile industry for flame retardancy, antimosquito , water or oil repellency ,
antibacterial activity , antiwrinkle, anticrease, durable press or easy‐care effect, ultraviolet
(UV) protection, self‐cleaning or soil repellency, photocatalytic activity, development
infastness behavior, abrasion resistance, tensile and thermal properties, and in
microencapsulation process have been studied in detail. In Figure 3, the application areas of
sol‐gel technology in textile finishing processes have been demonstrated. The aim of this
review is to introduce the usage possibilities of sol‐gel technology in textile applications.
Figure 2. Application steps of nanosols to textiles.

Figure3. Application areas of sol‐gel technology in textile finishing process.

References:
1. K.P. de Jong. , Synthesis of solid catalysts , Wiley –VCH, 2009
2. J.T. Richardson, Principle of catalysts development, Plenum Press, 1989
3. G. Ertl, H. Knozinger & J. Weitkamp, Handbook of Heterogeneous Catalysis Vol 1, Wiley –
VCH, 1997
4. R. J. Farrauto & C. H. Bartholomew, Fundamentals of Industrial Catalytic Processes, Blackie
Academic & Professional, 1997
5. brinker,c.Jeffrey ,” sol –gel scince :the physics and chemistry of sol-gel processing “ , boston ,
academic press ,1990.