4

Faults related to drying

and curing

4.1 Excessive drying periods - air drying

The majority of liquid paints (a notable exception being the solvent-free epoxies)
contain volatile solvent which acts solely as an aid to application. When a paint
fIlm has been applied to a surface the following sequence of changes takes place.

Loss of volatile solvent

If the material is a non-convertible type such as chlorinated rubber or cellulose
lacquer, loss of solvent leaves the mm in its final form and no further change takes
place. The mm remains soluble in the solvents used in the liquid paint. The rate at
which the solvent leaves the mm depends on a number of factors: the vapour
pressure or volatility of the solvent (e.g. xylol evaporates much more rapidly than
white spirit); the relative humidity of the air (low humidity favours evaporation);
temperature (low temperatures delay evaporation); the movement of air to remove
the solvent vapour and the solvent-releasing properties of the mm [1]. The majority
of non-convertible coatings contain very volatile solvents and the problem of slow
drying is not often encountered.
Vinyl [2] and acrylic [3] emulsion paints also qualify for the description 'non-
convertible' coatings. Loss of water from the wet mm leaves a matrix of polymer
particles or globules together with pigment and additives. Provided the temperature
of the mm is above the Glass Transition Temperature (Tg) the polymer particles
will coalesce and incorporate the pigment into a mm. Film formation is purely a
physical process, no chemical reactions being involved. If the temperature of the
fIlm is below the Tg of the polymer then a discontinuous mm is formed. With
copolymer types of emulsion the Tg of the polymer can be lowered by the use of
coalescing solvents. When emulsion paints are applied to a porous substrate
absorption takes place and this can appear to reduce the drying time. Such sub-
strates require a specially formulated sealer, otherwise the absorption will result in
an underbound mm.
64
H. R. Hamburg et al. (eds.), Hess’s Paint Film Defects
© M. Hess, H.R. Hamburg and W.M. Morgans 1979
 Faults related to drying and curing 65

Loss of volatile solvent followed by chemical reaction in the film

Materials of this class are known as 'convertible' coatings and can be divided into
two types: (l) coatings which dry or harden by absorption of atmospheric oxygen,
the process being catalysed by certain metallic compounds (notably those of cobalt,
manganese, lead and zirconium); and (2) coatings which cure by stoving or harden
by chemical reaction in which atmospheric oxygen is not involved. Among the
latter are the two-pack systems and include epoxies, polyurethanes, acid-cured
alkyd-amino and some polyester systems.
Type ( 1) includes oleoresinous media, alkyds (including the modified types),
epoxy esters and urethane oils. Drying commences as soon as most of the solvent
has left the surface and involves several stages:
(i) Film set.
(ii) The 'tacky' condition.
(iii) The 'surface dry' or 'touch dry' condition.
(iv) The 'through dry' or 'hard dry' condition.
(v) The state of fitness for overcoating.
The binders mentioned all contain esters of unsaturated fatty acids and the initial
reaction is absorption of oxygen at points adjacent to the unsaturated linkages, a
reaction catalysed principally by cobalt and to some extent by the other drier
metals [4]. This absorption of oxygen takes place through the fIlm surface and the
role of cobalt is described as 'surface drying'. Hydroperoxides are formed at the
unsaturated centres and decompose to give 'free radicals' which, in turn, induce
polymerization of the mass of the binder. This polymerization is catalysed by lead,
manganese and zirconium which are described as 'through' driers and the reaction
'through drying'. It is important to maintain a correct balance between the quantities
of 'surface' and 'through' driers used. If these are out of balance, drying of the
mm will not take place uniformly.
The drier metals are usually added as solutions of their salts with organic acids,
the commonest being naphthenate and ethyl hexoate. The drying process does not
appear to be influenced by the nature of the acid radical.
Since the drying process involves fatty acids it is influenced by the amount of
fatty acid present in the binder (often referred to as the 'oil length').
The 'oil length' of a varnish is the ratio of oil to resin by weight. Varnishes are
described as 'long oil', 'medium oil' or 'short oil' and these correspond roughly to
the ratios of 3/1 and upwards, 2/1-3/1 and 1/3-2/1 respectively. The properties
are controlled to a large extent by the oil length, the long oil types being slow
drying and durable while the short oil types are rapid drying and not suited to
exterior exposure. The term 'oil length' is also applied to alkyds and refers to the
percentage of fatty acid present. There are long oil, medium oil and short oil
alkyds whose properties also vary with the fatty acid content.
In the U.S.A. oil length is expressed as gallons (U.S.) of oil per 100 pounds of
resin. Thus a '3D-gallon oil length' varnish would contain oil and resin in the ratio
of 30 gallons to 100 lb.