Chemistry Reference
In-Depth Information
lysozyme and CTAB, the width of the distribution increased after mixing with
saliva. The increased polydispersity of the above mentioned emulsion + saliva
mixtures also affects the d
32
values. This, together with the previously men-
tioned considerations, might explain why the measured d
32
values (e.g.,45mm
for the CTAB-stabilized emulsion + saliva mixture) are far from the sizes
observed by microscopy (4 200 mm).
Flocculation affects the viscosity of emulsions, typically leading to shear-
thinning behaviour.
19,20
Viscosity measurements can therefore provide useful
information about the state of flocculation and hence about the flocculation
mechanism. Higher viscosities, even at high shear-rates, are obtained in samples
where droplets are strongly and irreversibly bound to each other. Conversely,
aggregates in emulsions flocculated by depletion fall apart at high shear-rates,
resulting in similar viscosities to non-flocculated emulsions. A convenient way
to evaluate different flocculating emulsion + saliva mixtures is to calculate the
ratio
Z
mix
/
Z
emul
in which the viscosity of the mixture (
Z
mix
) is normalized by the
viscosity of the corresponding emulsion (
Z
emul
). In this way, the viscosity
increase due to flocculation caused by saliva is independent of the original
emulsion viscosity. As expected, emulsion + saliva mixtures exhibited shear-
thinning behaviour (Figure 3). Higher positive
z
-potential values of the emul-
sions resulted in a stronger increase in the viscosity after saliva addition, as
indicated by the greater values of
Z
mix
/
Z
emul
. The results indicate that the flocs
of positively charged emulsions in the presence of saliva are not completely
disrupted by shear over the applied shear-rate range, which is in line with the
irreversibility of the flocculation towards dilution (Figures 1 and 2).
14
12
12
10
8
6.3
6.2
6
3.6
4
3.1
2.9
2.8
2.2
1.9
1.7
1.6
2
1.2
0
-44
21
30
74
ζ
(mV)
Figure 3 Viscosity of the emulsion + saliva mixtures normalized by the viscosity of the
emulsions calculated at 10 s
1
(white columns), 100 s
1
(black columns) and
900 s
1
(shaded columns) for different
z
-potentials:
44 mV for
b
-lg (pH
¼
6.7); +21 mV for
b
-lg (pH
¼
4.3) (as in the mixture of saliva); +30 mV for
lysozyme; and +74 mV for CTAB
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