The effect of simple ionic electrolytes on CNC stability (Fig. 2)
was explored, showing a gradual reduction in the zeta potential
with increasing salt concentration (both Na+ and Ca2+ ions). This
is because the Debye-Huckel screening strength is increased upon
increasing the salt concentration and therefore the Debye length
decreases. This encourages adsorption of ions and ion pairs to the
CNC surface and the increase in adsorption of ions is directly facilitated
by the compression ofthe double layer. As expected, Ca2+ ions
showed more screening strength than Na+ ions, as seen by a greater
reductioninCNCzeta potential.Asimilar study onthe effect of divalent
counterions on the electrophoretic mobility of sulfate latex
particles showed a reduction in absolute mobility with an increase
in concentration of divalent counterions [29]. However, the effect
of the divalent ion for CNCs was significantly less dramatic than
expected from, for example the Schulze-Hardy prediction [14].
To determine the interplay of pH and electrolyte effects, the
effect of Na+ ions at low (pH 2) and high pH (pH 10) was studied
(Fig. 2). There is considerably less change in zeta potential when
the pH of the CNC/NaCl solution is significantly acidic or basic. This
may be due to a constant potential condition arising with change
in surface charge density so as to maintain ion adsorption equilibrium
[30]. The contribution of the Na+ and Cl− used to control pH
(from NaOH and HCl) are expected to play a negligible role, except
in determining the ionic strength of the medium. In each case,
the increased overall ionic strength results in a significantly compressed
double-layer – as evidenced by the much shorter Debye
lengths, on the order of 3 nm or less for NaCl experiments at pH 2
– see Supplementary material.
To understand whether any specific ion effects exist for CNCs, in
addition to the simple electrolyte effects explored above, the effect
of hydrophobic anions and cations on the zeta potential of CNC suspensions
was studied (Fig. 3). We assume that the surface charge
of CNCs is dominated by the covalent sulphate ester groups on the
CNC surfaces, which have a very low pKa value and are therefore
dissociated down to extremely low pH values. This is corroborated
by the insensitivity of the measured zeta potential to pH when salts