Surface Activity of Foam Fractions

of a Calcium Lignosulphonate
K . F . KEIRSTEAD, L. CAVERHILL"

Royal Military College of Canada, Kingston, Ontario K7L 2W3

and

D . DE KEE

Department of Chemical Engineering, University of Windsor, Windsor, Ontario N9B 3P4

Successive foam fractionation has been used to divide a proccsscd calcium lignosulphonate into fractions differing
appreciably in surface activity. Static surface tension has been measured by the de Nouy tensiometer and surface tension
aging hy the sessilc bubble (photographic)method. The effect of concentration on surface tension has been determined.
Thc cffcct of pH at 1% concentration on dynamic surface tension has been determined o n freshly prepared solutions.

On a cmploye Ic fractionnemcnt successif par moussagc pour skparcr un lignosutfonate de calcium traitk. en tractions
qui different d'une manikre appreciable en tension supcrficielle. On a mesure la tension superficicllc statiquc au nioycn
tlu tenxiornetrc dc Nouy et I'Cvotution dam le temps dc la tension supcrficielle par la mkthode (photographique)de la
gouttc sessile. On a etahli I'elfct dc la concentration sur la tension superficielle. On a dCtcrminC, sur des solutions
fraichement prkparees, I'cffct du pH a une concentration dc 1 % sur la tension dc surface dynamique.

S oluble lignins derived from the pulping of wood are

widely used as surface active agents either in the crude
state or after some degree of purification. Lignosulphonates
(LS) are derived from the acid sulphite pulping of soft
woods. Further chemical or physical treatment gives rise
to a variety of products of widely different surface active
properties.
The composition of crude LS is essentially as follows:
lignosulphonates (LS), 55%; hexose sugars, 14%; pentose
sugar, 6%; sugar acids and residues, 12%;resins and extrac-
tives, 3%; the balance being ash (Wenzl, 1965). Ligno-
sulphonates differ from many surfactants in their wide range
of niolecular sizes and surface active properties (Re-
zanowich et al., 1961). Soluble lignins display the chardc-
teristics of polyelectrolytes which Rezanowich and Goring
( 1960) have called microgels.
When unmodified LS are used as concrete additives
(water-reducing and set-retarding agents), the presence of
unmodified sugars tend to retard unduely the setting of
mortar (Hansen, 1970). To eliminate this problem, chemical
processing at high temperature and pressure is used to con-
vert reducing sugars into non-reducing sugar derivatives,
the resulting products being designated as Lignosol SF
(sugar free).
In concrete mixes, LS are strongly adsorbed at liquid-
solid interfaces giving rise to a reduction in viscosity thus
making possible a reduction in the water content. As a result
of the reduction in pore size there is a considerable increase
in the compressive strength of the hardened concrete. Rama-
chandran (1978) has studied the effect of the sugar-free
lignosulphonates used in the present work on cement hy-
dration.
Reduction in surface tension brought about by the LS at
the air-liquid interface during mechanical mixing facilitates
*Pre\ent address: Syncrude Canada Ltd. Fort McMurray. Alberta
the entrainment of air bubbles. The presence of microscopic
air bubbles, mainly less than 50 micrometers in diameter
(Verbeck, 1947) has proved effective in controlling surface
scaling during freezing and thawing (Bruerc, 1960). Bruere
found that with a series of surface active agents the surface
areas of entrained bubbles were markedly different. It was
concluded that the surface activity of concrete additives
might be a factor in optimizing the spacing factor of en-
trained bubbles, hence improving the frost resistance.
Foam fractionation as a unit operation for the separation
of surfactants has been studied by Lemlich ( 1 968, 1972) and
Addison ( 1945). The differential concentration of surfac-
tants at the interface is the basis of foam fractionation. This
technique has been used to remove a low concentration of
kraft liquor from kraft mill effluent (Brasch, 1974). More
recently, foam fractionation has been used to remove toxic
components from kraft and sulphite mill effluent (Ng et al.,
1974 and Zajic et al., 1979).
Typically the surface tension of a surfactant decreases
with time. The rate of change depends on the substance, the
concentration and the pH and is usually high during the first
few minutes. At the end of 60 minutes or so, the rate of
decrease becomes very slow and tends towards an equili-
brium value. During the period of change the process is
generally termed dynamic surface tension. When equili-
brium is finally reached, the value is more properly termed
static surface tedsion. The de Nouy tensiometer is quite
imensitive to aging times. The maximum bubble-pressure
method is appropriate for aging times up to 80 seconds. The
sessile bubble method is less convenient to use, but provides
a precise value for longer aging times (Keirstead, 1976).
The present investigation examines the surface active
properties of lignosulphonate foam fractions (Keirstead.
1978) prepared by repeated foam fractionation. Particillor
attention has been paid to the effect of pH on surface tension
lowering. In a future study, some of the fractions will be

680

45-
I
1 10
C (kg/rn3)
Figure I - Surface tension by the de Nouy ring method versus
concentration for fraction II-I(R).
a, pH 12: W, pH 5.5
used to examine the effect of surface activity on bubble size
distribution and freeze-thaw resistance in concrete.
Experimental
For routine analysis the surface tension was measured
using a Fisher Autotensiomat Surface Tension Analyzer (de
Nouy ring method) (Keirstead, 1976). The temperature was
maintained at 298 2 0.2 K. The pH was adjusted by using
either concentrated NaOH or H,SO,. The usual precautions
in cleaning the glassware and the de Nouy ring were ob-
served.
The dynamic surface tension was evaluated by the sessile
bubble method described previously (Keirstead, 1976 and
1978). Surface tension at different time intervals was deter-
mined by a photographic method from the measurement o f
bubble profiles on 3.5 cm negatives. The initial diameter of
the bubble on the rod was about 7 mm.
The surface tension y is given by:
y = pgb2/P . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ( 1 )
where the dimensionless group p is a measure of the shape
of a drop. It has been treated by Bashforth and Adams
(1883) as a variable over the range 0 - 100. b represents the
(spherical) radius at the pole. Using a vernier microscope,
the following parameters were measured to determine y: the
meridonial distance, the length of a chord near the base
(solid-gas interface) and the distance from the apex to that
chord. From tables a value of P is then found through which
the surface tension is determined. Calculation details are
outlined elsewhere (White, 1967). Accuracies of 0. I % have
been claimed.
A processed calcium lignosulphonate (Lignosol SF) sup-
plied by Reed Ltd., Chemical Products, was used as the
starting material for the foam fractionation.
The equipment for the foam fractionation has been de-
scribed previously (Keirstead, 1978). A batch system was
used for the preparation of all fractions. One litre of the
sample usually at a concentration of 20% was aerated con-
tinuously through a gas dispersion tube and the foam con-
tinuously removed at such a rate that the initial volume was
reduced to a given value, usually one half of its initial
volume, in one hour.
THE CANADIAN JOURNAL OF CHEMICAL. ENGINt1:KING. VOLUMF h(1 OC T O H I K 19x7
I
I11-l(K)
Ill-I(F) III-2(K) III-2(F)
-
[54.6] [50.8] [-I [41.7]
iJ \
IV-2(F)
[36.8]
100
ISF = original lignosulphonate
K = Retentate
F = Foamate
Results and discussion
The foam fractions obtained by a stepwise batch pro-
cedure are given in Table I . The surface tension values
shown are determined by the sessile bubble method at pH
5 . 5 , the unbuffered pH of the solutions. The concentration
was 10 kg/m' and the aging time was 60 minutes. The foam
fraction in each case was 50% of the sample except for the
refractionation of lI-I(R), where the foamate fraction,
111-I(F) was 20%. Each time the initial volue was I litre. A
significant change in surface tension was evident at each
fractionation stage. It is apparent that there is an upward
shift in surface tension as the lignin is purified by the re-
moval of surface active components; i.e. the foam fractions
have a lower surface tension than the retained fractions.
Corresponding values for the surface tensions at pH 12 are
given in Figures 2 and 3. The choice of pH 12 as a relevant
pH value was suggested by the use of foam fractions in
concrete mixes where the pH is about 12.
Figure 1 shows a semi-logarithmic representation of sur-
face tension versus concentration for the retentate 11- 1 (R) at
pH 5.5 and pH 12 as measured by the Autotensiomat at 298
K. The plot at pH 5.5 is similar to the one obtained for an
unmodified calcium lignosulphonate (Keirstead, 1976) at
the same pH.
However, the degree of organization of the molecules at
the air-liquid interface i s not necessarily the same at pH 5.5
and at pH 12. The increase in surface tension at high pH for
surfactants is well known (Keirstead, 1976). This effect is
less pronounced in the case of lignosulphonates. The LS
molecule is a random coil characterized by some covalent
crosslinking. The LS molecule undergoes less change in
shape than for example a linear sodium laurate molecule and
hence, the change in surface tension with pH is less pro-
nounced. Also, the movement of the ring during the relative
displacement of the ring and the liquid surface affects the
organization of the surface molecules in a different way,
depending on the pH. From the sessible bubble method of
determining surface tension, it was found that the Auto-
tensiomat value at a concentration of 10 kg/mJ weight per
volume represents an undisturbed surface age of less than 2
minutes at pH 12, while the corresponding value at pH 5.5
yields a value obtained after 25 minutes, if a technique is
used for which the surface remains undisturbed during the
68 I
 IT -I(R)
I SF
35 I I I I I I I I
20 40 60
AGING TIME. MIN
Figure 2 - Surface tension ageing plots by the sessible bubble
method for the original sample (ISF) and two foam fractions II-
1(R) and III-2(F).
= pH 12; A = pH 5.5; Concentration, 10 kg/m3
measurement. No significant difference in surface tension
readings was found for elevator speeds of 0.015 and 0.076
m/s, or in surface ages from 5-60 minutes before beginning
the movement of the ring.
Lignin compositions show a pronounced lowering of sur-
face tension with the age of the air-liquid interface. The
sessible bubble (photographic) method suitably provides a
precise measure of the surface tension of an undisturbed
air-liquid surface. At appropriate intervals, electronic flash
photographs are taken of the bubble placed at the end of a
vertical stainless steel rod, placed in a thermostated solu-
tion. As the surface tension lowers, the bubble becomes
visibly less spherical. Appropriate measurements and calcu-
lations (White, 1967) provide a value for the surface tension
at each time interval.
Plots for the original unfractionated solution, a foamate
III-2(F) and a retentate sample It-I(R) at pH 5.5 and pH 12
are shown in Figure 2. The surface tension lowering with
time is due to a gradual orientation of the most asymmetric
molecules at the surface, following a diffusion to the surface
(Keirstead, 1976).
The effect of pH on the surface tension for a 1% concen-
tration as measured by the sessible bubble method (60 min.
value) is given in Figure 3 for the original unfractionated
solution, a foamate II-2(F) and the retentate sample II-l(R).
The surface tension from pH 7 to pH 12 is essentially con-
stant as shown in Figure 3 when fresh samples are used. For
682 THE CANADIAN JOIJRNAI. OF CHEMICAL ENGINEERING, VOLIJME 60. OC'IOHER 1982
40 t
35 i 4 6
PH
8 10
Figure 3 - Surface tension by the sessile bubble method for the
12
original sample (ISF) and two fractions 11-l(R), and II-Z(F)? versus
pH. Concetration, 10 kg/m3.
different conditions, Zajic et al. (1979) reported a drop in
surface tension from pH 4 to pH 8 for spent sulphite liquor.
An inflection at pH 6 has also been observed previously
(Keirstead, 1976). The peak at pH 6 is more pronounced at
higher concentration (Keirstead, 1980), probably due to a
significant change in the shape of the molecule at this level
of pH.
It is apparent that there is an upward shift in surface
tension (upper curve) as the lignin is purified by thc removal
of the surface active components. The present work has
suggested a study of highly purified lignins, which is now
under preparation.
It has also been observed that for a constant value of pH
12 the surface tension increases with time, whereas the
surface tension decreases with time when the pH is allowed
to drift to a lower value. Growth of fungi or bacteria in the
solution would affect the results.
For example, over a period of 1 1 days sample Ill-2(F)
( 1 % by weight) increased from a 60 minute surface age
surface tension of 40.2 X 10 ' N m - ' to a value of
46.5 X 10-' Nm-'. It may therefore be possible to follow
the rate of a hydrolysis reaction such as methoxy group
cleavage (Croon and Swan, 1964) by surface tension mea-
surements at constant temperature and pH. This also will be
the subject of further study.
Finally, we wish to propose a conceptual framework
which may explain the observations made. The surface ten-
sion behavior of surfactants is correlated with the adsorption
characteristics of these molecules at the air-liquid interface.
Surface potential and surface moments suggest that lignin
monomers are standing on their phenolic and benzylic acid
groups (Luner and Kempf, 1970). Linear surfactant mole-
cules tend to concentrate at the interface with the lyophobic
end in the air. Typically, such solutions show surface ten-
sion lowering with time, as more surface molecules displace
less surface active molecules at the interface. All surfactants
exhibit an increase in surface tension with an increase in pH
(Keirstead, 1976). The lignosulphonate molecule is a poly-
disperse polyelectrolyte existing in solution as a semi-
flexible, slightly crosslinked random coil of which the
lyophilic groups are mainly on the surface. To account for
surface tension effects, one must postulate that semilinear
(ellipsoid) molecules, differing in polar asymmetry, are
present at the interface. Diffusion or preferential bonding
with adjacent molecules leads to a selective orientation of
the more asymmetric molecules, resulting in a time de-
pendent lowering of the surface tension; the coil unwinds at
the interface. A decrease in surface tension lowering at high
pH may indicate a change in shape by which the molecules
become more symmetric. The inflection at pH 6-7 has been
observed before (Keirstead, 1976). Covalent bonding be-
tween adjacent acidic phenolic and carboxylic groups may
be more likely at high pH.
The tentative nature of these concepts suggests further
study o f this area in order to be conclusive.
References
Addison, C., “Time Factor in Surface Tension Measurements”,
Nature 156, 600-1 (1945).
Bashforth, F. and J . Adams. “An Attempt to Test Theories of
Capillary Action”, University Press, Cambridge ( I 883).
Brash. D.. “Foam Fractionation of Kraft Lignin”, Appita 28,
29-32 (1974).
Bruere. G., “Effect of Type of Surface Active Agent on Spacing
Factors and Surface Areas of Entrained Bubbles in Cement
Paste”, Aust. J . Appl. Sci. 11, 289-94 (1960).
Croon, I . and B . Swan. “The Reactions of Some Simple Lignin
Models with Sulfite Solutions”, Svensk Papperstidn 67.
177-81 (1964).
Hansen. W., “Interactions of Organic Compounds in Portland
Cement Pastes”, Materials, JMLSA 5, 842-55 (1970).
Keirstcad, K., “Surface Tension and Gas Permeability Data for
THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, VOLUME 60, OCTOBER 1982
Soluble Lignins at an Air-Liquid Interface”, Colloid and Inter-
face Sci., Academic Press, Vol. 111, 431-42 (1976).
Keirstead, K., “Foam Fractionation and Surface Tension Method
of Characterizing Soluble Lignins”, Pulp Paper Mag. Can. 4,
T-6-9 (1978).
Keirstead, K., Unpublished Data (1980).
Lemlich, R., “Adsorptive Bubble Separation Methods”, Ind.
Eng. Chem. 60 (lo), 16-29 (1968).
Lemlich, R., “Some Physical Aspects of Foam”, J. Soc. Cosmet.
Chem. 23, 299-31 1 (1972).
Lemlich, R., “Adsorptive Bubble Separation Techniques -
Bubble Fractionation”, Academic Press, 133- 143 (1972).
Luner, P. and U. Kempf. “Properties of Lignin Monolayers at the
Air-Water Interface”, Tappi 53, 2069-76 (1970).
Ng, K . , J. Meubler, and C. Walden, “Process Parameters of Foam
Fractionation of Kraft Effluent”, Pulp Paper Mag. Can. 75(7),
T-263, 101-6 (1974).
Ramachandran, V., “Effect of Sugar-Free Lignosulphonates on
Cement Hydration”, Zement-Kalk-Gips 31 (4). 206- 10
(1978).
Rezanowich, A. and D. Goring, “Polyelectrolyte Expansion of a
Lignin Sulphonate Microgel”, J. Colloid Sci. 15, 452-71
( 1960).
Rezanowich, A,, J . Jaworzyn, and D. Goring, “The Dispersion of
Aqueous Suspensions of Titanium Dioxide by Water Soluble
Lignin Derivatives”, Pulp Paper Mag. Can. 62: T-172, T-181
(1962).
Verbeck, G., “The Camera Lucide Method of Measuring Air
Voids in Hardened Concrete”, J . Am. Concr. Inst. 18,
1025-39 (1947).
Wenzl, H . , in Sarkanen and Ludwig, “Lignins”, Wiley (1971).
White, D., “Supplement to the Tables of Bashforth and Adams”,
Mines Branch, Physical Metallurgy Division, Internal Report
PM-1-67-4, 1-128, Ottawa (1967).
Zajic, J . , D. Berk, and L. Behie, “Foam Fractionation of Spent
Sulphite Liquor; Part 1, Separation of Surfactants”, Can. J.
Chem. Eng. 57, 321 -26 (1979).
Manuscript received December 2 , 1980; revised manuscript re-
ceived July 12, 1982; accepted for publication July 19, 1982.
683