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Colloids and Surfaces

A: Physicochemical and Engineering Aspects 159 (1999) 89 – 101


www.elsevier.nl/locate/colsurfa

Complexation between lignosulfonates and cationic


surfactants and its influence on emulsion and foam stability
Kjell Magne Askvik a, Stig Are Gundersen a, Johan Sjöblom a,*, Juha Merta b,
Per Stenius b
a
Department of Chemistry, Uni6ersity of Bergen, Allégaten 41, N-5007 Bergen, Norway
b
Department of Forest Products Technology, Laboratory of Forest Products Technology, Helsinki Uni6ersity of Technology,
FIN-02015 HUT Helsinki, Finland

Abstract

The association between sodium lignosulfonates and cationic as well as nonionic surfactants (quaternary ammo-
nium bromides, cetylpyridinium chloride (CPC)) has been investigated by means of surface tension measurements,
with additional information from measurements of viscosities and electrophoretic mobilities. A strong interaction is
revealed between the lignosulfonate (LS) and micelles of the cationic surfactant, whereas no interaction is found in
the case of a polyethyleneoxide-based nonionic surfactant. This is in agreement with the general behavior of
polyelectrolyte-surfactant systems. LS as emulsifier in oil/water emulsions (o/w) gives rapid creaming into a highly
concentrated emulsion, which is stable towards coalescence. The addition of cationic surfactant enhances the stability
towards creaming. LS is a poor foaming agent, but the addition of cationic surfactant greatly improves the foam
stability. © 1999 Elsevier Science B.V. All rights reserved.

Keywords: Lignosulfonates; Foam stability; Micelles

1. Introduction (P) and another enriched in surfactant (S) with


approximately similar total concentration (P+S),
Systems containing polymer, surfactant and or associate into one concentrated phase (P+S)
water have recently been extensively investigated. in equilibrium with a very dilute solution [2–5].
For a review of their properties, see [1]. Depend- For the two different types of equilibria, the terms
ing on the nature of the polymer and the surfac- segregative and associative phase separation have
tant, different association patterns may arise. been introduced [6]. Associative phase separation
Studies of phase equilibria show that, in general, occurs in systems containing oppositely charged
two main classes of phase equilibria occur. The polymers and surfactants [7]. For these systems, it
is typical that the concentrated complex phase
polymer/surfactant/water mixture may segregate
separates when roughly charge equivalent
into two different phases, one enriched in polymer
amounts of polymer and surfactant are present.
* Corresponding author. Tel.: +47-55-583358; fax: + 47-5-
The complex phase is in equilibrium with very
589495. dilute surfactant solutions. The phase usually re-
E-mail address: johan.sjoblom@kj.uib.no (J. Sjöblom) dissolves when excess surfactant is added. Associ-

0927-7757/99/$ - see front matter © 1999 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 7 - 7 7 5 7 ( 9 9 ) 0 0 1 6 5 - X
90 K. M. Ask6ik et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 159 (1999) 89–101

ation between oppositely charged surfactants and The present work is an investigation into the
polyelectrolyte occurs already in aqueous solution association between LS’s and cationic surfactants
at surfactant concentrations orders of magnitude and one nonionic surfactant in aqueous systems
below those leading to segregative phase separa- at neutral pH, through measurements of surface
tion. This association is usually cooperative, lead- tension, viscosities and electrophoretic mobility.
ing to the occurrence of a more or less sharply The effect of the addition of simple electrolytes on
defined critical association concentration (cac) of the association patterns is also investigated.
surfactant.
This paper reports on studies of the systems
based on anionic polyelectrolyte (different LS), 2. Experimental
cationic surfactant and water. LS’s are hy-
drophilic polyelectrolytes, containing a consider-
2.1. Materials
able number of anionic groups [8,9]. These
include sulfonic and carboxylic acid as well as (at
The LS used in this work was purified, fraction-
high pH) phenolic hydroxyl groups. LS’s are poly-
ated and analyzed by Borregaard Lignotech A/S.
disperse, with regard to both molecular weight
Three different molecular-weight fractions of
and structure. Furthermore, the structure may be
sodium LS were used. Fractionation was done by
polydisperse both in number and distribution of
ultrafiltration. The properties of the fractions are
ionic groups and in the composition of the carbon
summarized in Table 1.
backbone, which is highly cross-linked [10]. Sev-
Alkyltrimethylammonium bromides (CnTAB)
eral studies show that the LS molecules assume a
and cetylpyridinium chloride (CPC) were deliv-
roughly spherical shape in the aqueous phase. The
ered by Fluka. The nonylphenylpolyethoxylate
interior of the molecule contains some ionic was from Akzo Nobel AB. All surfactants were
groups, giving the molecule a capacity to swell used without further purification.
[11–14]. This means that the extension of the All solutions were made from distilled water
molecule in aqueous solution depends on ionic purified further by a Serapur PRO 90CN deioniz-
strength. The molecular charge is mainly due to ing and adsorption unit.
sulfonate groups. Hence, the charge and dimen-
sions of the crosslinked coil will also depend
strongly on pH. 2.2. Methods

Table 1 Surface tensions were measured with a KSV


Properties of the sodium lignosulfonate fractions Sigma 70 instrument fitted with a Wilhelmy plate
for the measurements of CPC, and with a du
Product A B C
Nuoy ring for CnTAB measurements. The diffu-
Mw 62 700 76 400 9300 sion of LS to the surface is slow, making it
Sodium, % 5.94 6.03 7.17 difficult to establish equilibrium conditions. The
Calcium, % 0.11 0.02 0.06 measurements were carried out until five consecu-
Organic sul- 6.1 6.0 6.8 tive readings gave a non-monotonic change within
phur, %
9 50 mN m − 1.
Inorganic sul- 0.01 0.07 0.28
phur, % Viscosities were determined with a computer
Total sulphur, 6.2 6.1 7.1 controlled Ubbelohde capillary viscometer system
% (Schott-Gerate AVS 350). The correction factors
Methoxyl, % 11.9 12.1 9.2 of Hagenbach were used to calculate the real
Carboxyl, % 4.5 5.4 5.9
efflux times.
Phenolic hy- 2.4 2.4 2.4
droxyl, % Turbidities were determined with a Perkin-
Sugars, % 0.6 0.4 4.3 Elmer Lambda 6 U/V-VIS spectrophotometer,
operating at 550 nm and fitted with 1 cm cuvettes.
K. M. Ask6ik et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 159 (1999) 89–101 91

Fig. 1. Surface tension of aqueous solutions of polyelectrolytes (PE) in 0.07 M sodium chloride. Concentrations are given in (a)
moles of PE l − 1; and (b) moles of ionic groups l − 1.
92 K. M. Ask6ik et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 159 (1999) 89–101

Fig. 2. Surface tension of aqueous solutions of 0.01% (w) lignosulfonate A as a function of sodium chloride concentration.

Electrophoretic mobilities were measured using formed by bubbling air through a sinter into a
a Zetasizer 4 microelectrophoresis instrument column containing an aqueous solution of LS and
from Malvern Instruments. The mobilities are CPC until a given height of foam is reached. The
obtained from the measured Doppler shift in the air flow is cut off and the half-life of the foam is
scattered laser light due the movement of the recorded, The results are given in Table 3.
macromolecules or particles in an electric field.
The solutions were buffered with acetic acid and
adjusted to pH 5.00 using sodium hydroxide. 3. Results
Emulsion stability. All oil-in-water emulsions
were 40% in dispersed phase, and were prepared
3.1. Lignosulfonates
by adding Exxol D80 (aliphatic hydrocarbons) to
an aqueous phase containing the LS and CPC in Fig. 1(a) shows the surface tension of aqueous
different ratios. The samples were mixed for 2 min solutions of high and low molecular weight LS as
at 8000 rpm using an Ultra Turrax T25 homoge- well as some synthetic linear polyelectrolytes. All
nizer. In Fig. 9, the percentages refer to the fractions show some degree of surface activity.
dispersed (oil) phase. Since the coalescence pro- The high molecular weight fraction reduces the
cess is very slow but creaming is rapid, we charac- surface tension to  40 mN m − 1 at concentra-
terize stability by recording the separation of an tions of 10 − 4 M. The low molecular weight frac-
aqueous phase. Hence, the remaining emulsion is tion shows a similar trend, although the data are
a highly concentrated and viscous o/w emulsion. parallel shifted towards higher concentrations.
Foam stability. In the foam tests, a typical The different fractions have a varying degree of
Bikerman procedure was adopted. Foam is substitution of SO− 3 groups. When normalizing
K. M. Ask6ik et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 159 (1999) 89–101 93

with respect to the amount of SO− 3 , as shown in corresponding changes occur for pure surfactant
Fig. 1(b), all data for the LS fall roughly on the solutions), indicating that adsorption of surfac-
same curve. In all cases, LS is much more surface tant at the air/water interface is enhanced by the
active than the synthetic polyelectrolytes. This is oppositely charged polymer. In these systems the
clearly due to the amphiphilic nature of LS, which cac of the surfactants which usually is seen as a
consists of a water-insoluble polymer network sharp break in the surface tension curve, is
rendered soluble by substitution of SO− 3 groups. difficult to determine exactly. Partially this may
The addition of NaCl further decreases the be due to the sensitivity of interactions to ionic
surface tension of the LS solutions. This is shown strength, and to the difficulties in establishing
in Fig. 2 for fraction A. The surface tension equilibrium at the surface. The separation of a
decreases linearly with log Ctot,NaCl, where concentrated phase is indicated in the figures and
Ctot,NaCl = CNa(LS) +CNaCl results in an increase in the surface tension of the
aqueous solutions due to the enrichment of sur-
3.2. Lignosulfonates and surfactants factant into the complex phase. Since the total
number of sulfonate groups is the same for the
The surface tension of dilute LS solutions upon high and low molecular weight fractions, separa-
addition of surfactants is shown in Fig. 3 tion occurs at the same concentration of the sur-
(CnTAB) and Fig. 4 (CPC). As is typical of many factant, i.e. the location depends solely on the
polymer/surfactant systems, the surface tension neutralization of the anionic headgroups with the
decreases markedly already at very low surfactant cationic surfactant. Further evidence of this is
concentrations (much lower than those at which found in Fig. 5, which shows the electrophoretic

Fig. 3. Surface tension of aqueous solutions of 0.01% (w) lignosulfonates and C16TAB as a function of surfactant concentration in
10 − 3 M sodium chloride. The cmc of pure C16TAB is marked by a vertical arrow. The horizontal arrows indicate the presence of
a particulate complex phase.
94 K. M. Ask6ik et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 159 (1999) 89–101

Fig. 4. Surface tension of aqueous solutions of 0.01% (w) lignosulfonates and CPC as a function of surfactant concentration in 10 − 3
M sodium chloride. The cmc of pure CPC is marked by a vertical arrow. The horizontal arrows indicate the presence of a particulate
complex phase.

mobility for the LS + CPC complexes. At the the head group seems to be of minor importance.
phase separation point the electrophoretic mobil- Thus,
ity is close to or equal to zero. (cac)C12TAB\ (cac)C14TAB\ (cac)C16TAB
The phase separation was also investigated by
means of viscosity measurements as shown in Fig. : (cac)C16PC
6. The reduced viscosity, as expected, is higher for The concentration at which the cac occurs follows
the higher Mw fraction. It does not depend on the pattern of the cmc of the pure surfactants.
surfactant concentration at very low concentra- There is no indication of association of the non-
tions, but decreases sharply when the cac is ionic surfactant with the LS either in terms of cac
reached. Thus, it can be concluded that associa- or in the form of a phase separation.
tion of the surfactant with the polymer results in
a strong reduction of the molecular extension in 3.3. Lignosulfonates. surfactants and simple salt
solution. Similar behavior has been observed for
many other systems. The viscosities increase when The effect of added NaCl on the surface tension
particles of concentrated polymer/surfactant of LS solutions to which CPC and CTAB have
phase are formed. Redissolution of the phase been added is shown in Figs. 8 and 9. In both
results in a reduction of the viscosity. cases, the cac is shifted towards lower concentra-
Fig. 7 compares the effect of adding cationic tions. The surface tension at high surfactant con-
and nonionic surfactants to dilute solutions of centrations is 36 mN m − 1 in 0.1 M NaCl. The
high molecular weight LS. The cac is a function of concentration range of CTAB in which associative
carbon chain length (Table 2), while the nature of phase separation occurs contracts upon the addi-
K. M. Ask6ik et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 159 (1999) 89–101 95

tion of simple salts. Using CPC however, this factant/surfactant interactions, i.e. formation of
concentration range will expand upon the addi- micelles. The polymer will act as a large counte-
tion of simple salts. rion, making the micellization more favorable
The effects are similar when applying CaCl2 as than in pure surfactant solution. Accordingly, the
a simple electrolyte. cac is lower than the cmc of the pure surfactant.
Thirdly, when surfactant has been added to
roughly neutralize the polymer, associative phase
separation occurs. In analogy with the formation
4. Discussion
of complexes between cationic and anionic
polyelectrolytes, the driving force for formation of
The association between oppositely charged
the concentrated phase is the gain in entropy on
polymers and surfactants is characterized by some
release of small counterions into the aqueous so-
general trends. The first sign of an interaction is lution [1]. Hydrophobic interactions may possibly
the enhanced adsorption at the air/liquid inter- also play a role. In the presence of excess surfac-
face, which leads to a strong lowering of the tant cationic complexes form, leading to redisso-
surface tension at concentrations orders of a mag- lution of the concentrated phase. This mechanism
nitude below those at which pure surfactants or has been well established in previous studies in-
pure polymer lower the surface tension. LS be- cluding linear polyelectrolytes such as polyacrylic
haves analogously to many other polymers in this acid (PAA) [15,16] and poly(dimethyldiallylam-
respect. The second general phenomenon is the monium chloride) (PDMDAAC) [17], copolymers
occurrence of the cac [7]. At this point, the surfac- such as acrylate-amide copolymer [18] and
tant/polymer interaction leads to cooperative sur- modified cellulose [19,20].

Fig. 5. Electrophoretic mobilities of complexes of 0.01% (w) lignosulfonate and CPC in aqueous solution as a function of surfactant
concentration. The concentration of sodium chloride is 0.1 moles and the pH is 5.00. The horizontal arrow indicates the presence
of a particulate complex phase.
96 K. M. Ask6ik et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 159 (1999) 89–101

Fig. 6. Reduced viscosities of 0.01% (w) lignosulfonates and C16TAB in aqueous solution as a function of surfactant concentration.
The vertical arrows indicate the cmc of the pure surfactant.

While this association behavior of linear poly- amphiphilic so as to form aggregates with a hy-
mers is relatively well understood, it is no trivial- drophobic core and a hydrophilic shell.
ity that LS’s and surfactants follow a similar Monomeric surfactant may then be solubilized in
association pattern. In this case, we are dealing the polymer; this is termed polymer centered asso-
with a highly cross-linked polyelectrolyte that has ciation. A cac is not observed in this case, al-
a more or less spherical configuration with some though the cmc of the pure surfactant may be
rigidity of the internal carbon structure. shifted.
Generally, the association between polyelec- From what is known about the structure of LS
trolytes and surfactants may be classified into in aqueous solution, it can be inferred that the LS
three groups, depending on the nature of the molecules should be more or less amphiphilic, as
polymer [1]. If the polymer is predominantly hy- is also indicated by their relatively strong surface
drophilic, it acts as a large counterion and the activity. The considerable cross-linking of the hy-
interaction is considered to occur between the drophobic polymer backbone implies that it is
polyion and micelles of the pure surfactant. If the more compact and less mobile than the backbone
polymer is mainly hydrophilic but possesses some of most synthetic polymers. In addition, the sam-
degree of hydrophobicity, the interactions are still ples studied here are polydisperse with respect to
considered to be between micelles and the poly- both molecular size and charge density. Hence,
mer. However, the hydrophobic parts of the poly- LS does not fit unambiguously into any of the
mer may serve as micellization sites for the three cases described above. The surface tensions
surfactant. These modes of association are termed and viscosities indicate that some cooperative sur-
surfactant centered and they always show a cac. factant interaction is induced by the presence of
The third mode is occurring if the polymer is LS, but the very sharp cac and the region of
K. M. Ask6ik et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 159 (1999) 89–101 97

Fig. 7. Surface tension of aqueous solutions of 0.01% (w) lignosulfonate A and ionic and non ionic surfactants as a function of
surfactant concentration in 10 − 3 M sodium chloride. The cmc of the pure surfactants is marked by a vertical arrow. The horizontal
arrows indicate the presence of a particulate complex phase.

constant surface tension typical of the interaction segregative phase separation, reminiscent of the
between linear hydrophilic polyions and oppo- case of two neutral macromolecules [1].
sitely charged surfactant, do not occur. Thus, The narrowing upon addition of salt to the
electrostatic interactions provide an important LS/C16TAB system of the concentration range of
driving force for LS/cationic surfactant associa-
tion, but interaction of the surfactant with the Table 2
hydrophobic moiety of LS may also play a role. Cmc of pure surfactants [21] and cac of surfactants in the
presence of product A
On the other hand, no interaction are observed
for the nonionic surfactant, indicating that the Surfactant NaCl content cmc (mM) cac (mM)
hydrophobic interactions must be relatively weak. (M)
The associative phase separation is certainly
driven by the electro-osmotic interactions de- C12TAB – 5.27 0.035
C14TAB – 3.32 0.028
scribed above, and could be looked upon as a
C16TAB 10−3 0.82 0.020
heterocoagulation between the swollen LS C16TAB 10−2 0.49 0.0025
molecules and surfactant aggregates. C16TAB 10−1 0.23 0.0015
When electrostatic interactions are predomi- CPC – 0.63 0.015
nant, the effect of increasing the ionic strength in CPC 10−2 0.16 0.013
oppositely charged P + S systems is to screen the CPC 10−1 0.038 –
C9Ph(EO)8,5 – 0.05–0.07 None
interactions that lead to association. Hence, the C9Ph(EO)9 – 0.075 None
associative phase separation changes through an C9Ph(EO)9,5 – 0.085 None
intermediate stage of complete miscibility into a
98 K. M. Ask6ik et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 159 (1999) 89–101

Fig. 8. Surface tension of aqueous solutions of 0.01% (w) lignosulfonate A and CPC as a function of surfactant concentration and
sodium chloride concentration. The cmc of pure CPC is marked by a vertical arrow. The horizontal arrows indicate the presence
of a particulate complex phase.

C16TAB at which precipitation occurs conforms monodisperse spheres. By adding CPC, the
to this general behavior. On the other hand, the creaming process is gradually retarded. However,
LS/CPC system shows a broadening of the range when the amounts of LS and CPC correspond to
in which precipitation occurs. This again suggests charge equivalence, an instantaneous separation
that the association patterns of LS may be more of oil and water is observed. The water contains
complex than those characteristic of polymers the highly viscous complex phase. Obviously, this
which interact predominantly electrostatically charge-neutralized phase does not provide protec-
with surfactant micelles. tion against creaming and coalescence. Hence, the
stability picture arising from Fig. 9 is the follow-
ing. In the presence of a high molecular LS frac-
4.1. Lignosulfonate-CPC complexes as o/w
tion, the system is easily flocculated, resulting in
emulsion and foam stabilizers
creaming. However, due to a combination of elec-
The influence of the complexation between LS’s trostatic and steric effects the coalescence process
and CPC on emulsion and foam stability is shown in the concentrated remaining emulsion is highly
in Fig. 10 and Table 3. o/w emulsions stabilized retarded. By adding the CPC at concentrations
by LS cream rapidly, so that 65% of the well above the critical micelle concentration
aqueous phase separates within 15 h. A highly (CMC), the creaming is substantially slowed
stable o/w emulsion remains in which the disperse down. Obviously, the flocculating effect of the LS
phase is  80% of the volume. This is slightly on the oil droplets under these conditions is much
above the maximum close packing of lower than in the absence of CPC. Under these
K. M. Ask6ik et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 159 (1999) 89–101 99

conditions, the LS will associate with an excess of 5. Conclusions


CPC into a positively charged complex. This com-
plex obviously enhances the electrostatic stabiliza- LS and cationic surfactants associate strongly.
tion as compared to the pure LS, giving a better The main driving force of the association is elec-
protection towards creaming. The strong interac- trostatic interactions, mainly between micelles and
tion between CPC and LS is consistent with the the LS. The cac depends on the carbon chain
surface tension curves (Fig. 8). length of the surfactant in the same way as the
The conclusions from the foam destabilizing cmc. However, the amphiphilic nature of the
experiments described in Table 3 are similar to
cross-linked LS molecule also affect the interac-
those from the emulsion stability experiments.
tions so that the cooperativity in the interaction
The foam drainage is much faster for pure LS and
seems to be less marked than between linear
high LS/CPC ratios. The charge neutralized LS-
CPC complex shows no ability to stabilize foams. polyelectrolytes and surfactants.
The film lamellae containing pure LS obviously Association results in charge neutralization
have a lower disjoining pressure and drain very and the precipitation of a concentrated com-
rapidly. The electrostatic component of the dis- plex phase. Further association leads to charge
joining pressure will increase when CPC is added reversal and the redissolution of the complex
in excess. Consequently, the collapse of the water- phase. LS and nonionic surfactant do not
based foam is considerably delayed. Thus, the associate, due to the small contribution of hydro-
results from the emulsion creaming and the foam phobic interaction to the driving forces of associa-
destabilization experiments run parallel. tion.

Fig. 9. Surface tension of aqueous solution of 0.01% (w) lignosulfonate A and C16TAB as a function of surfactant concentration
and sodium chloride concentration. The cmc of pure C16TAB is marked by a vertical arrow. The horizontal arrows indicate the
presence of a particulate complex phase.
100 K. M. Ask6ik et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 159 (1999) 89–101

Fig. 10. Creaming of o/w emulsions: water separated as a function of time. Emulsifier is lignosulfonate A, CPC and lignosulfonate
A +CPC.
Table 3 Acknowledgements
Half-time of water-based foams containing lignosulfonates and
CPC Kjell Magne Askvik and Stig Are Gundersen
acknowledge Ph.D. grants from Borregaard Lig-
Lignosul- CPC (%) Ratio A:CPC Half-time
fonate A (%) (min)
notech A/S and the Norwegian Research Council
(NFR). Johan Sjöblom acknowledges funding
0.66 0 – 1.5 from NorFa and Per Stenius a grant from Borre-
0.67 0.09 5:1 15 gaard Lignotech A/S.
0.67 0.45 1:1 No foam
0.65 2.23 1:5 120
0 0.10 35 References

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