Porosity and Optical Properties of Clay Coatings

B. ALINCE AND P. L E P O U T R E
Pulp and Paper Research Institute o f Canada, Pointe Claire, P, Q., Canada

Received September 26, 1979; accepted November 21, 1979

The porosity of paper coatings based on a given clay has been varied by pH control, and the optical
properties have been measured. A linear relationship established between the porosity and the light-
scattering coefficient seems to demonstrate the importance of void structure on light-scattering.
The variation in pigment packing has also been shown to affect the surface smoothness and gloss.

The opacity of white pigmented coatings
derives from the scattering of light at the
pigment's surfaces. The scattering efficiency
is determined by several factors: (i) the re-
fractive indices of the pigment and the sur-
rounding medium-- the larger the difference
the more effective is the scattering; (ii) the
size of the pigment particles--for each pig-
ment there is an optimum size depending on
the wavelength of light; (iii) the extent of the
interface upon which scattering takes
p l a c e - - m o r e pigment particles of a given
size per unit weight of coating means higher
hiding power.
The last factor is subject to a limitation
that is noted in conventional paints com-
posed from pigments embedded in a binder.
When the paint film becomes crowded with
pigment particles, their mutual interference
results in a decreased light-scattering ef-
ficiency per unit weight of pigment. The
detrimental effect of crowding also explains
why, in paints, well-dispersed particles are
more effective than their aggregates.
However, in paper coatings, unlike paints,
the best dispersion may be counterproduc-
tive from the optical point of view. The
reason lies in the different structure char-
acterized by the presence of microvoids.
The paper coating is composed of packed
pigment particle held together by a binder,
but because common clay pigments and
binders have similar refractive indices, little
scattering takes place from their interface.
It is the interface between air and solid that
is important and therefore the coating can be
considered as a continuous solid phase con-
taining air voids that are the scattering ele-
ments. Since well-dispersed particles tend
to produce the most densely packed struc-
ture, the void volume and, consequently,
the light-scattering efficiency, will be at a
minimum.
The intention here is to demonstrate that
the light-scattering or hiding power of clay
coatings is determined by the air voids. The
approach was to change the void volume of
coatings formulated from a given pigment.
Binder-flee coatings of different porosity
were produced from plate-like delaminated
clay particles by affecting their mutual inter-
action and consequently the packing density
through pH control.
It is generally accepted that at low pH
clay plates may carry opposite charges,
negative on the faces and positive on the
edges (1). Because of the natural attraction
between the opposite charges the clay par-
ticles dispersed in water form a three-dimen-
sional "card-house" matrix of plates associ-
ated face to edge. This kind of structure is
responsible for the gelling of concentrated
clay suspensions at low pH, when the matrix
fills the entire available volume. In more

439
0021-9797/80/080439-06502.00/0
Copyright© 1980by AcademicPress, Inc.
Journal of Colloidand Interface Science, Vol.76, No. 2, August 1980 All rightsof reproductionin any formreserved.
440 ALINCE AND LEPOUTRE
lO~
and (ii) a mixture of clay and a nonfilming
50O BROOKFIELD VISCOMETER SB latex acting as a plastic pigment. De-
laminated clay, Alphaplate (Anglo-American
20O Clays Corp.), was dispersed in water at 60%
10o solids in the presence of 0.02% (on clay) of
P, each of TSPP and Tamol 850 (Rohm and
..._%0 50
Haas) in a Premier Mill Dispersator and
20
diluted to 50% solids content. The clay-
>-
latex mixture (weight ratio 100/30) was pre-
pared by admixing the latex having 50% solid
m
> 5 content with the clay dispersion using a
magnetic stirrer. The suspensions had an
CLAY
2- initial pH near 9 and were adjusted to the
12
I I I I I I required pH by gradual addition of HC1.
3 4 5 6 7 8 9
After each pH adjustment the viscosity was
pH
determined with a Brookfield viscometer at
FIG. |. Viscosityof clay and a clay-plasticpigment 100 rpm and a coating was applied on a
mixture (ratio 100/30) as a functionof pH. transparent polyester film (Mylar) with a
metering rod.
dilute suspensions such linked plate par- Upon drying the mass per unit area (g/cm~)
ticles have the character of voluminous was determined, and the porosity and opti-
flocs. It is expected that if the linkages are cal properties were measured. The porosity
strong enough the structure, upon drying, was evaluated from the amount of oil held in
will be highly porous. With increasing pH the coating after full impregnation followed
the positive charge at the edges becomes by a removal of the excess oil (2). The 75°
less pronounced and consequently the de- gloss was determined on a Hunter gloss-
creased mutual attraction results in a less meter. The light-scattering coefficient S and
rigid structure. At high pH, the positive the reflectivity R~ were calculated from
charge of the edges is eliminated and the reflectances over white and black back-
clay plates repel each other owing to the
remaining negative charge of the faces. Thus
62
the system becomes well dispersed and
upon drying the structure has the lowest
porosity.
The various modes of particle association 54

are reflected in the viscosity. The edge-to-

face association results in an increased 5O

viscosity because of the increased effective

46
volume of the particles in the flocs in which
water is occluded. The dispersed system of
like-charged plate particles has a lower vis-
342
cosity because of the mutual repulsion. The 38
particles slide easily over each other and DRY
align themselves in the flow direction. 34^ I I ~i
2 4 6 8 2 4 6 8

pH pH
EXPERIMENTAL
FIG. 2. Porosity of coatings formulatedfrom clay
Two binder-free coating formulations and a clay-plastic pigment mixture (ratio 100/30) as
were examined: (i) pure delaminated clay a functionof pH.
Journal of Colloid and Interface Science, Vol. 76, No. 2, August 1980
 P R O P E R T I E S OF C L A Y C O A T I N G S
grounds using the Kubelka-Munk theory
with a correction for the supporting poly-
ester film (3). Spectrophotometer Bausch &
Lomb Spectronic 505 with a sphere attach-
ment was used to determine the reflectances
in the gloss excluded mode at 2-nm intervals
throughout the visible range. The sphere
attachment has approximately normal/
diffuse geometry. To establish the baseline
at the same wavelength intervals as the
specimen reflectances a tablet pressed from
BaSO4 (calibrated throughout the visible
range at NRC) was used.
A sample of the pH adjusted suspension
was centrifuged in order to determine its
sediment volume and thus the volume of
water in the sediment. The water volume
represents the void volume of the compacted
but fully hydrated suspension.
RESULTS
Figure 1 records the viscosities deter-
mined for suspensions adjusted to a given
pH. Apparently the clay remains well dis-
persed down to pH 6. Upon further lowering
of pH the attraction between clay particles
increases and the formation of face-edge
association becomes more pronounced as
indicated by the increased viscosity. The
24
E CLAY CLAY & LATEX
~ 22
14
q
10
4 6
pH pH
F]o. 3. Specific light-scattering coefficient (cm 2 g-l)
of coatings formulated from a clay and clay-plastic
pigment mixture (ratio 100/30) as a function of pH.
441
~
24
CLAY
22
~"x 20
~ 18'
~d
CLAY& LATEX I
~o
U
16
32 36 40 44 48 52 56 60
POROSITY, °,~ (v°id v°lu~e 1
/v \Total volume]
FIG. 4. Specificlight-scatteringcoefficient(cm2g-l)
versus porosity of coatings formulatedfrom clay and
a clay-plastic pigmentmixture (ratio 100/30).
viscosity development of clay-latex mix-
tures is similar although somewhat less pro-
nounced than in the pure clay. The mutual
interaction of clay particles likely becomes
more complicated in the presence of the
spherical plastic pigments which themselves
may aggregate at low pH.
In Fig. 2 both the dry and wet porosities,
shown" as functions of pH, are expressed as
void volume per total volume (voids plus
solids) of the coating. A comparison of the
two values provides an indication of the
shrinkage that takes place during drying.
The porosity changes with pH as expected.
The well-dispersed system produces the
most compact structure while the increasing
tendency to form face-edge association leads
to an increase in the porosity.
Figure 3 shows the specific light-scatter-
ing coefficient determined at 458 nm, as a
function of pH. It is expressed in terms of
reciprocal mass per unit area of coating ac-
cording to the common practice in paper-
making. A plot of the specific light-scatter-
8 ing coefficient versus porosity in Fig. 4 shows
a direct relationship and thus confirms the
assumption that voids are determinative for
the light-scattering. It would seem that the
blend of clay and plastic pigment is more
Journal of Colloid and Interface Science, Vol. 76, No. 2, August 1980
442 ALINCE AND LEPOUTRE

24 80
E
7~< 22

6G
x
o~
g 18 5O

4O
o
3O

12 20
CLAY & LATEX

I I I
10,20 0,25 0.30 0,35 0.40 0.45 4 6 8 2 4 6 8
VOID VOLUME,cm~/g coating pH pH
FIG. 5. Specificlight-scattering coefficient ( c m 2 g - l ) FIG. 7. Gloss 75° of coatings formulated from clay
versus void volume (cm3 g-l) of coatings formulated and a clay-plastic pigment mixture (ratio 100/30)
from a clay and clay-plastic pigment mixture (ratio as a function of pH.
100/30).

effective since, at the same porosity, the
specific light-scattering coefficient is higher
than that o f the pure clay. H o w e v e r , it has
to be realized that the same porosity (void
volume per total volume) means a larger
void volume per unit mass for the blended
coating because o f the lower density of the
plastic pigment. Therefore a more realistic
comparison is based on the void 9olume
per unit mass of coating as shown in Fig. 5.
The void volume V is calculated from the
porosity P taking into account the density p
of the solids (V = P / ( 1 - P ) p ) .
.86
,84
1~.82
zr~ 6 a
pH pH
FIG. 6. ReflectivityR® at 458 nm of coatings formu-
lated from clay and a clay-plastic pigment mixture
(ratio 100/30)as a function of pH.
Journal of Colloid and Interface Science, Vol. 76, No. 2, August 1980
It is of interest to note that if the light-
scattering coefficient is expressed per unit
volume of voids rather than of mass per unit
area (simply done by dividing S in cm~-/g by
the void volume in cm3/g of coating) the S
(cm -a) values for the clay coatings will be all
close to 5000 and those for the clay-latex
mixture around 4000. It has been shown
theoretically (4, 5) as well as experimentally
(6, 7) that the light-scattering power is a
function of void size. The almost constant
values o f S (cm -1) then may lead to a specu-
lation that the void size distribution of either
type of coating does not change significantly
with pH. Consequently the increased light-
scattering efficiency could be caused by the
increased number of voids rather than by the
change in their dimension. However, insuffi-
cient knowledge of the changes in the actual
void structure prevents any final conclusion.
Another important optical characteris-
t i c - t h e reflectivity R ~ - - i s also affected by
the change in void structure as shown in
Fig. 6. Figure 7 shows the gloss as a function
6 8
of pH. With the increased tendency to form
edge-face association at lower pH, the coat-
ing surface becomes naturally more dis-
turbed. As a consequence the gloss, which
is thought to reflect the surface smoothness,
 PROPERTIES OF CLAY COATINGS 443

FIG. 8. Scanning electron micrographs (x6000) of a clay coating's surface: (A) pH 8; (B) pH 3.

decreases with pH. The scanning electron CONCLUSION

micrographs in Fig. 8 demonstrate that the
coating surface at pH 8 is considerably The structure of clay coatings can be con-
smoother than at pH 3. trolled by affecting the mutual interaction
Journal of Colloid and Interface Science, Vol. 76, No. 2, August1980
444
of the clay particles. As a result of the dif-
ferent association o f pigment particles, t h e
porosity as well as the optical properties of
the coating are altered. The relation between
porosity and light-scattering verifies tha~t the
void structure of a coating affects its light-
scattering efficiency even though the size of
the pigment particle remains unchanged.
Therefore, from the optical point o f view,
the voids can be considered to be the scat-
tering sites.
Although it is apparently not practical to
improve the light-scattering efficiency by
destabilizing the clay suspension other pro-
Journal of Colloid and Interface Science, Vol. 76, No. 2, August 1980
ALINCE AND LEPOUTRE
cedures that result in increased porosity will
likely be beneficial.
REFERENCES
1. van Olphen, H., Prog. Colloid Polym. Sci. 61,
46 (1976).
2. Lepoutre, P., and Rezanowich, A., Tappi 60, 86
(1977).
3. Borch, J., and Lepoutre, P., Tappi 61, 45 (1978).
4. Ross, W. D., J. Paint Technol. 43, 50 (1971).
5. Kerker, M., Cooke, D. D., and Ross, W. D., J.
Paint Technol. 47, 33 (1975).
6. E1-Aasser,M. S., Igbal, S., and Vanderhoff, 1. W.,
in "Colloid and Interface Science" (M. Kerker,
Ed.), Vol. V, p. 381. Academic Press, New
York, 1976.