Understanding Dynamic Surface Tension in Coating Formulations

Study and Compilation by: Chetan Sharma and Anuj Agrawal

Date: 8th June 2022

Introduction

Solvent borne formulations, with their naturally lower surface

tensions, wet readily and transfer well onto most substrates. The
increasing shift to waterborne formulations, due to
environmental concerns, has inherent problems of surface
wetting, foaming, and flow & leveling, common to all waterborne
systems. Waterborne systems require alcohols and surfactants to
lower their surface tensions to acceptable levels for transfer,
spreading and adhesion.

What is Dynamic Surface Tension?

Dynamic surface tension is a non-linear function of surface age and concentration. This must be
considered when comparing surfactants. A coating application is a dynamic process, and active surfactants
cause surface tensions to change as speeds and formulations change. The surface tension of coatings must
be lower than the wetting tension of substrates to attain good laydown.

Classical belief is that many surface tension related properties such as detergency, foaming, and wetting,
either maximize or minimize at the surfactant critical micelle concentration (CMC). These relationships,
however, are based on classical measurements limited to static surface tension conditions, when
equilibrium has been established between the surface layer and the bulk solution. Dynamic surface
tension measurements of active surfactants
reveal levels at which surfactant effectiveness
is at its highest, which is not necessarily related
to equilibrium CMCs. Dynamic measurements
more accurately reflect actual, in-process,
surfactant, and coating performance. In effect,
if you limit surfactant migration time (by using
a faster coating process) you require more
surfactant to perform the same job as in the
slower process.

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Surface Tension and Surfactants

Surface tension dictates whether a coating will wet and spread over or retract from a solid substrate.
Coatings exhibit both an adhesive force that is a measurement of the degree of association of the
coating for the substrate, and a cohesive force that is a measure of the degree of self-adhesion of the
coating.

Spreading coefficient is the difference between work of adhesion and work of cohesion.

If work of adhesion > work of cohesion: Spontaneous spreading occurs.

If work of cohesion > work of adhesion: Retraction, a surface defect occurs.

Surfactants are used because of their ability to reduce surface tension. They are classified by the ionic
charge of the surface acting part of the molecule. Anionic surfactants have a negative molecular charge,
cationic positive, and nonionic no charge. Amphoteric have both positive and negative charges.

In general, surfactants with a smaller (lighter) molecule mass (short hydrophobic tail) diffuse more rapidly
to the interface, and are vertically adsorbed at the interface, causing a compressive force to act on the
surface thereby reducing surface energy or surface tension. Nonionic surfactants with ethylene oxide
groups usually diffuse very rapidly to the surface while fluorinated surfactants are slower and more
effective at equilibrium. Most surfactants at higher concentrations exert strong molecular attractions
between adjacent molecules causing strong surface films, the strength of which determines the surface
properties of the surfactant solutions.

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Surfactant Performance

Surfactants that diffuse slowly may not lower surface tensions sufficiently, to acceptable levels and may
be partially responsible for defects such as: Bénard cells, craters or pin holes, crawling or retraction,
floating, orange peel, and picture framing (edge buildup).

Surfactants that diffuse rapidly can mitigate surface defects by eliminating surface tension gradients. This
occurs through rapid surfactant migration from high concentrations (low surface tension) to low
concentrations (high surface tension). This type of surfactant can reduce surface tension with the extra
benefit of reducing or preventing foam. Formulators will sometimes mistakenly increase surfactant
concentration to reduce gradients, rather than use a better surfactant.

Formulators should try to use a suitable surfactant that ideally has both low equilibrium and low
dynamic surface tension values — low enough so that the coating is applied to the substrate at
process speeds with a desirable viscosity.

Surface Energy

Transfer and spreading of coating on a substrate depend on the surface energy of the material delivering
the coating, the surface tension of the coating, and the surface energy of the substrate receiving the
coating. The substrate must have a surface energy higher than the coating, with forces of attraction great
enough to promote good transfer and spreading, which in turn facilitates good adhesion.

Measuring the wetting tension, or surface energy, of

substrates is commonly and inexpensively done with
the use of “dyne liquid” solutions. These are
purchased as a series of premixed solutions, each of a
given wetting tension in dynes/cm. This allows a series
of wetting solutions to be formulated in a range from
30 to 56 dynes/cm, based on the proportions, as
shown in the table. The dyne liquid solution (DLS) is
used for measuring the wetting tension, or surface
energy, of substrates. The dyne liquid solution (DLS)
must readily wet the surface for the substrate material
to be at a wetting tension equal to the surface tension
of the DLS used.

Reference:

1. Paints & Coatings Industry. Dynamic Surface Tension and Surface Energy in Ink Formulation & Substrates. 2001.