38 E. I.

Akpan

1.4 Lignin Colloid and Surface Chemistry

The surface and colloid chemistry of lignin are additional properties that are of
interest if lignin is intended for bulk processing into valuable products. Producing
fibres from lignin will require that lignin either dissolves or becomes molten to be
drawn. Moreover, lignin is often blended with other polymers to improve its pro-
cessability. How polymers dissolve in solvents and their free energy of dissolution
is an important fundamental principle in polymer science. Surface energy and wet-
tability are also important aspects of surface chemistry. For lignin, surface energy
and wettability are important for certain industrial applications. Applications such
as papers, cardboards and engineered wood products in some cases are made from
wood fibres containing lignin at the interface [167, 168]. The surface energy of this
lignin rich surface has a direct effect on the capillary forces during the drying and
consolidation phases which in turn affect the strength of the material. For medium
density fibreboards, it is important to carefully consider the interfacial energy so as
to develop a strong adhesion between the fibre and the resin used. In ceramics, lig-
nin has been used as dispersants which means they are localised at the interfacial
region. It is evident, that a full understanding of lignin interfacial properties is a
necessary requirement [6, 169, 170].

1.4.1 Lignin Colloidal Chemistry

The chemical structure of lignin is not clearly defined because of the difference in
the structure arising from the difference in sources and at large on the difference in
the chemistry of the extraction methods used. The extraction methods usually leave
lignin with structural changes, depolymerisation and introduction of external func-
tional groups during bond cleavage. With such a large difference in chemical struc-
ture, it is expected that the solubility and interfacial properties of lignin will be
severely changed. Lignin molecule in solution can be viewed as consisting of a
strongly immobilised network core surrounded by a loose surface region with
possible local chain mobility [171]. They behave as either lyophobic or lyophilic
colloids depending on the interaction with the solute species. Due to the occurrence
of irregular particle structure, intermolecular and intramolecular association, charge
distribution and ion exchangeability, quantitative interpretation of lignin colloidal
behaviour is challenging. Generally, it is accepted that lignin behaves as a spherical,
amorphous macromolecule having polydisperse molecular weight distribution [172,
173]. Lignosulphonate molecules have been viewed as a polyelectrolytic microgel.
The polyelectrolytic behaviour was also reported for alkali lignin. They possess
ability to aggregate, coagulate and swell in various solutions. The aggregation
behaviour of Kraft lignin in aqueous solution is linked to the undissociated
carboxylic groups and long range van der Waal’s forces [174]. The coagulation
behaviour of Kraft lignin has also been linked to the long range van der Waal’s
forces [171]. Lindström and Westman [175] also reported that Kraft lignin gels
swell (macrosyneresis and hysteresis swelling) typical as a polyelectrolytic network