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Electrostatic Stabilization of Charged Colloidal Particles with Adsorbed

Polyelectrolytes of Opposite Charge
Jose Hierrezuelo, Amin Sadeghpour, Istvan Szilagyi, Andrea Vaccaro, and Michal Borkovec*
Department of Inorganic, Analytical, and Applied Chemistry, University of Geneva,
30 Quai Ernest-Ansermet, 1205 Geneva, Switzerland

Received July 22, 2010. Revised Manuscript Received September 1, 2010

Repulsive electrostatic double-layer forces are responsible for the stabilization of charged colloidal particles in the
presence of adsorbed polyelectrolytes of opposite and high line charge densities. This mechanism is revealed by studies of
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electrophoretic mobility and colloidal stability performed with dynamic light scattering as a function of the poly-
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electrolyte dose and the ionic strength for two different types of latex particles and four different types of polyelectro-
lytes. The dependence of these quantities is very similar for bare charged latex particles and the same particles in the
presence of the different oppositely charged polyelectrolytes. Positively charged particles in the presence of anionic
polyelectrolytes behave analogously to negatively charged particles in the presence of cationic polyelectrolytes.

Adsorption of polyelectrolytes to oppositely charged water- Derjaguin, Landau, Verwey, and Overbeek (DLVO),15-20 attrac-
solid interfaces is relevant to control properties of colloidal tive van der Waals forces acting between the neutral particles lead
suspensions (e.g., stability, rheology)1-4 or to create nanostruc- to rapid aggregation and floc formation. Increasing the polyelec-
tured surface coatings (e.g., multilayers, patterning).5-8 Suspen- trolyte dose leads to particle restabilization, but the correspond-
sion properties can be widely tuned by adding an oppositely ing mechanism is poorly understood. One knows that polyelectro-
charged polyelectrolyte to the suspension in question, which leads lyte adsorption continues beyond neutralization point and that
to the formation of an adsorbed polyelectrolyte layer. Surface the particles reverse their charge when the polyelectrolyte is in
coatings can be similarly obtained by exposing the surface to an excess.2,10-13 However, no consensus on the nature of the forces
appropriate polyelectrolyte solution, but in this case the stability responsible for the particle stabilization exists. Some authors have
of these layers and their desorption characteristics in polyelec- suggested that repulsive steric forces between the adsorbed poly-
trolyte-free solutions become crucial as well. electrolyte layers are responsible for suspension restabilization.11,21
This Letter discusses the former situation of suspension proper- Others have remarked the importance of electrostatic interactions
ties, and focuses on the control of colloidal stability of aqueous and proposed the concept of electrosteric forces.22,23
suspensions of charged colloidal particles at higher doses of Here we show that repulsive electrostatic double-layer forces as
oppositely charged polyelectrolytes. At low polyelectrolyte dose, expected from classical DLVO theory are mainly responsible for
the situation is relatively well understood.1,2,4,9-14 Added poly- the stabilization of a colloidal suspension with an excess of
electrolytes strongly adsorb on the particle surface and thereby polyelectrolyte of opposite charge and high line charge density
neutralize the surface charge. According to the classical theory of (Figure 1). This finding follows from the dependence of aggrega-
tion rates in suspensions of latex particles on the polyelectrolyte
*To whom correspondence should be addressed. Telephone: þ 41 22 379 dose and the ionic strength. The generic nature of the phenom-
6053. E-mail: [email protected]. enon can be established from the similarity between positively and
(1) Gregory, J. J. Colloid Interface Sci. 1973, 42, 448–456.
(2) Bouyer, F.; Robben, A.; Yu, W. L.; Borkovec, M. Langmuir 2001, 17, 5225– negatively charged latex particles in the presence of four different
5231. types of oppositely charged polyelectrolytes.
(3) Leong, Y. K.; Scales, P. J.; Healy, T. W.; Boger, D. V. Colloids Surf., A 1995, The charge reversal phenomenon is easily illustrated by elec-
95, 43–52.
(4) Howe, A. M.; Wesley, R. D.; Bertrand, M.; Cote, M.; Leroy, J. Langmuir trophoresis. Figure 2a (top) shows the electrophoretic mobility of
2006, 22, 4518–4525. positively charged amidine latex particles of 200 nm in diameter
(5) Decher, G. Science 1997, 277, 1232–1237.
(6) Pericet-Camara, R.; Cahill, B. P.; Papastavrou, G.; Borkovec, M. Chem.
upon addition of negatively charged poly(styrene sulfonate) (PSS)
Commun. 2007, 266–268. in a KCl electrolyte at pH 4. The mobility is initially positive, then
(7) Kolasinska, M.; Krastev, R.; Gutberlet, T.; Warszynski, P. Langmuir 2009, passes through the isoelectric point (IEP), and finally becomes
25, 1224–1232.
(8) Block, S.; Helm, C. A. Macromolecules 2009, 42, 6733–6740. negative, indicating that the adsorbed polyelectrolyte has reversed
(9) Borkovec, M.; Papastavrou, G. Curr. Opin. Colloid Interface Sci. 2008, 13,
429–437.
(10) Walker, H. W.; Grant, S. B. Colloids Surf., A 1996, 119, 229–239. (17) Behrens, S. H.; Christl, D. I.; Emmerzael, R.; Schurtenberger, P.; Borkovec,
(11) Bauer, D.; Buchhammer, H.; Fuchs, A.; Jaeger, W.; Killmann, E.; Lunkwitz, M. Langmuir 2000, 16, 2566–2575.
K.; Rehmet, R.; Schwarz, S. Colloids Surf., A 1999, 156, 291–305. (18) Lin, W.; Kobayashi, M.; Skarba, M.; Mu, C.; Galletto, P.; Borkovec, M.
(12) Ashmore, M.; Hearn, J. Langmuir 2000, 16, 4906–4911. Langmuir 2006, 22, 1038–1047.
(13) Kleimann, J.; Gehin-Delval, C.; Auweter, H.; Borkovec, M. Langmuir (19) Chen, K. L.; Elimelech, M. Environ. Sci. Technol. 2009, 43, 7270–7276.
2005, 21, 3688–3698. (20) Ehrl, L.; Jia, Z.; Wu, H.; Lattuada, M.; Soos, M.; Morbidelli, M. Langmuir
(14) Schwarz, S.; Jaeger, W.; Paulke, B. R.; Bratskaya, S.; Smolka, N.; Bohrisch, 2009, 25, 2696–2702.
J. J. Phys. Chem. B 2007, 111, 8649–8654. (21) Farrokhpay, S. Adv. Colloid Interface Sci. 2009, 151, 24–32.
(15) Russel, W. B.; Saville, D. A.; Schowalter, W. R. Colloidal Dispersions; (22) Bremmell, K. E.; Jameson, G. J.; Biggs, S. Colloids Surf., A 1998, 139,
Cambridge University Press: Cambridge, 1989. 199–211.
(16) Kihira, H.; Ryde, N.; Matijevic, E. J. Chem. Soc., Faraday Trans. 1992, 88, (23) Romero-Cano, M. S.; Martin-Rodriguez, A.; de las Nieves, F. J. Langmuir
2379–2386. 2001, 17, 3505–3511.

Langmuir 2010, 26(19), 15109–15111 Published on Web 09/07/2010 DOI: 10.1021/la102912u 15109
Letter Hierrezuelo et al.

Figure 1. Schematic representation of the electrostatic stabiliza-

tion mechanism whereby the overlap of the diffuse layers generates
strong repulsive forces at low ionic strengths. (a) Positively charged
particle with a diffuse layer, which mainly consists of anions.
(b) Positively charged particle with adsorbed saturated layer of a
highly charged anionic polyelectrolyte, which makes the particle
negatively charged. In this case, the diffuse layer mainly consists of
cations. An analogous scenario applies to negatively charged
particles and a highly charged cationic polyelectrolyte.

Figure 3. Electrophoretic and stability data for bare latex particles

as a function of the ionic strength in KCl electrolyte with a
saturated layer of adsorbed polyelectrolyte and without. (a) Elec-
trophoretic mobility is shown in the left column, while (b) the
stability ratio is in the right one. (top) Bare amidine and sulfate
latex particles. (bottom) Amidine particles in the presence of
poly(styrene sulfonate) (PSS) and poly(acrylic acid) (PAA) and
sulfate latex particles in the presence of linear poly(ethylene imine)
(LPEI) and poly(diallyldimethyl ammonium chloride) (PDADMAC).
The latter data were obtained at a polyelectrolyte dose of 30 mg/g.
The data shown were measured at pH 4.0, except the PAA data at
pH 5.8. The solid lines serve to guide the eye.

from the IEP, the suspension is stabilized by repulsive electrostatic

double-layer forces. At low doses, the stability ratio reaches a
plateau corresponding to the aggregation rate of the bare parti-
cles. At higher doses, surprisingly, one observes a similar plateau.
The latter plateau corresponds to the aggregation rate of the
particles with a saturated adsorbed polyelectrolyte layer. As the
Figure 2. Electrophoretic and stability data for charged latex ionic strength is increased, the stability ratio decreases substan-
particles as a function of the dose of an oppositely charged tially. This strong decrease indicates the importance of repulsive
polyelectrolyte for two different ionic strengths of 0.01 and 0.1 M electrostatic interactions, which are progressively being screened
in KCl electrolyte at pH 4.0. (a) Electrophoretic mobility is shown as ionic strength is increased.
in the left column, while (b) the stability ratio is in the right one.
(top) Amidine latex and poly(styrene sulfonate) (PSS). (bottom)
Negatively charged sulfate latex particles of 135 nm in radius in
Sulfate latex and linear poly(ethylene imine) (LPEI). The solid lines the presence of the cationic polyelectrolyte linear poly(ethylene
serve to guide the eye. imine) (LPEI) behave analogously. Figure 2a (bottom) shows
that, with increasing LPEI dose, the mobility of the particles
the particle charge. The adsorption process stops when the plateau passes the IEP and saturates at a positive value of the mobility.
in the mobility is reached. Beyond this plateau, the adsorbed This positive value indicates that a charge reversal did take place
amount remains constant and the excess polyelectrolyte is dis- too. Figure 2b (bottom) shows that, near the IEP, the suspension
solved in the solution. Prior to the onset of the plateau, the is unstable, and the stability increases away from the IEP. At low
adsorption of the polyelectrolyte is quantitative and there is and high doses, the stability ratio reaches a plateau. With
basically no free polyelectrolyte in solution.13 increasing ionic strength, the suspension becomes less stable,
Stability ratios are determined by time-resolved dynamic light indicating the importance of electrostatic interactions. The fact
scattering in the early stages of the aggregation.2,13,17 This that negatively charged particles in the presence of a cationic
quantity represents the ratio between the aggregation rate of polyelectrolyte behave analogously to positively charged particles
the bare particles in excess salt and the actual aggregation rate. in the presence of an anionic polyelectrolyte strongly suggests that
This ratio is close to unity for an unstable suspension and electrostatic forces govern the interactions in these systems.
increases with increasing suspension stability. Figure 2b (top) The electrostatic origin of the stabilization mechanism becomes
shows the stability ratio for amidine particles as a function of fully obvious when mobility and stability are studied as a function
the PSS dose. Around the IEP, particles are neutral and they of the ionic strength. Recall the classical case of electrostatic
aggregate rapidly due to attractive van der Waals forces. Away stabilization described by DLVO theory15-20 illustrated here with

15110 DOI: 10.1021/la102912u Langmuir 2010, 26(19), 15109–15111

Hierrezuelo et al. Letter

bare latex particles. Figure 3a (top) shows the electrophoretic However, there is one difference between the stability of the
mobility of both latices as a function of the ionic strength. With bare particles and those with an adsorbed polyelectrolyte layer.
decreasing ionic strength, the magnitude of the mobility initially When comparing the top and bottom panels of Figure 3b, the
increases due to the increase in the magnitude of the electrostatic slopes of the stability plot in the slow aggregation regime are
surface potential. While the magnitude of surface potential smaller for the polyelectrolyte coated particles than for the bare
continues to increase, the maximum or minimum in the mobility ones. We suspect that this difference originates from the lateral
originates from the polarization effect and can be quantified with heterogeneity of the adsorbed polyelectrolyte layer. When this
the standard electrokinetic model.18 Figure 3b (top) shows the layer is heterogeneous, an additional attractive electrostatic force
corresponding stability data. At high ionic strength, the suspen- will be operational.27,28 When a patch with an adsorbed poly-
sion becomes unstable with a stability ratio close to unity. The electrolyte will be interacting with a patch of the bare surface, the
rapid aggregation is induced by van der Waals forces, since resulting attractive electrostatic force will lead to a decrease in the
electrostatic interactions are fully screened. With decreasing ionic suspension stability. Similar patch-charge effects are suspected to
strength, the suspension stability increases. The slowdown of the decrease the stability of bare colloidal particles and to weaken the
aggregation is induced by the onset of repulsive electrostatic dependence of the stability ratio on pH or salt concentra-
forces, whose strength increases with decreasing ionic strength. tion.16,25,26 Patch-charge effects are likely to play an important
The sharp transition between fast and slow aggregation regimes is role for adsorbed polyelectrolyte layers due to their lateral hetero-
indicated by the cusp in the stability plot and is referred to as geneity.8,28 They are also suspected to be responsible for the
critical coagulation concentration (CCC).15,24 For monovalent decrease of the stability of colloidal particles with increasing
electrolytes, DLVO theory predicts the CCC between 0.1 and 1.0 molecular mass of added oppositely charged polyelectrolytes.29,30
M, in agreement with experiment. The electrostatic stabilization Nevertheless, the electrostatic double-layer repulsion remains the
mechanism is well established for latex and oxide particles.15-20,25,26 principal stabilization mechanism in these systems. The impor-
For weakly charged particles, DLVO theory even describes tance of electrostatic forces was also suggested by atomic force
the aggregation rates quantitatively.17,20 For highly charged par- microscopy (AFM) for amidine latex particles in the presence of
ticles, as the ones used here, the agreement with DLVO theory PSS. Direct force measurements with AFM confirmed the im-
is only semiquantitative.16,18,25,26 The existing discrepancies are portance of electrostatic repulsion at high polyelectrolyte dose,
probably due to lateral charge heterogeneities or discrete charge while imaging with AFM revealed the lateral heterogeneity of the
effects. adsorbed polyelectrolyte layers.8,28
The main result of this Letter is that the colloidal stability of We conclude that repulsive electrostatic double-layer forces are
latex particles with and without an adsorbed polyelectrolyte layer principally responsible for the stabilization of charged colloidal
behaves entirely analogously. Figure 3a (bottom) shows the particles with excess of adsorbed polyelectrolytes of opposite charge
electrophoretic mobilities of polyelectrolyte-coated particles as a and high line charge densities. This classical DLVO stabilization
function of ionic strength. While the corresponding signs are mechanism is evidenced through the analogous ionic strength
reversed due to polyelectrolyte adsorption, the overall behavior dependence of the stability of bare charged latex particles and of
remains the same. The mobilities increase in magnitude with the same particles with adsorbed oppositely charged polyelectro-
decreasing ionic strength and then pass through the correspond- lytes at saturation. In the presence of highly charged polyelectro-
ing maximum or minimum as observed for the bare particles. lytes, the stability ratio remains close to unity at high ionic strength.
Figure 3b (bottom) shows the stability as a function of the ionic Moreover, positively charged particles behave analogously in the
strength. At high ionic strength, the aggregation is rapid with a presence of anionic polyelectrolytes to negatively charged particles
stability ratio close to unity. With decreasing ionic strength, it in the presence of cationic polyelectrolytes. This conclusion is based
shows an analogous slowdown to the one of bare particles. The on the congruence of experimental data for two different types of
CCC lies again between 0.1 and 1.0 M. latex particles and four different highly charged polyelectrolytes.
To illustrate the generic nature of the phenomenon, we have For the polyelectrolytes investigated, repulsive steric forces between
further investigated similar amidine latex particles in the presence the adsorbed polyelectrolyte layers remain unimportant in stabiliz-
of poly(acrylic acid) (PAA) at pH 5.8 and sulfate latex particles ing these systems. However, such forces could become relevant in
in the presence of poly(diallyldimethyl ammonium chloride) the case of weakly charged polyelectrolytes.
(PDADMAC) at pH 4.0. As illustrated in Figure 3, one observes
analogous dependence of the mobility and stability on the ionic Acknowledgment. This research was supported by the Swiss
strength. Again, the stability ratio is close to unity at high ionic National Science Foundation and the University of Geneva.
strength and shows the characteristic transition between fast and Excellent technical support of Olivier Vassalli is acknowledged.
slow aggregation with a CCC located between 0.1 and 1.0 M. The
latter feature indicates that the repulsive forces are mainly of Supporting Information Available: Details on the materials
electrostatic nature, as they can be fully screened by addition and experimental protocols. This material is available free of
of salt. charge via the Internet at http://pubs.acs.org.

(24) Elimelech, M.; Gregory, J.; Jia, X.; Williams, R. A. Particle Deposition and (27) Miklavic, S. J.; Chan, D. Y. C.; White, L. R.; Healy, T. W. J. Phys. Chem.
Aggregation: Measurement, Modeling, and Simulation; Butterworth-Heinemann 1994, 98, 9022–9032.
Ltd.: Oxford, 1995. (28) Popa, I.; Gillies, G.; Papastavrou, G.; Borkovec, M. J. Phys. Chem. B 2010,
(25) Schudel, M.; Behrens, S. H.; Holthoff, H.; Kretzschmar, R.; Borkovec, M. 114, 3170–3177.
J. Colloid Interface Sci. 1997, 196, 241–253. (29) Gillies, G.; Lin, W.; Borkovec, M. J. Phys. Chem. B 2007, 111, 8626–8633.
(26) Hiemstra, T.; van Riemsdijk, W. H. Langmuir 1999, 15, 8045–8051. (30) Lin, W.; Galletto, P.; Borkovec, M. Langmuir 2004, 20, 7465–7473.

Langmuir 2010, 26(19), 15109–15111 DOI: 10.1021/la102912u 15111