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Characterization of Cationic Polyelectrolytes Adsorption to an Anionic Emulsion via Zeta-Potential and Microcalorimetry

  • Original Article
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Journal of Surfactants and Detergents

Abstract

The adsorption of cationic polyelectrolytes (PEs) onto anionic silicone emulsion droplets, suspended in a sodium chloride solution is studied via electrophoretic mobility measurements and isothermal titration calorimetry. These model systems are studied to better understand the interactions governing PE adsorption-induced emulsion flocculation, which is relevant to many industrial applications. Electrophoretic mobility measurements provide critical information for rationalizing the effect of the PE charge density on the loss of stability of silicone emulsions. The interaction strength is calculated from a Langmuir adsorption isotherm determined by a ζ-potential titration measurement. Microcalorimetry measurements independently validate the adsorption free energy. Emulsion flocculation and coacervation are observed in the visual phase behavior as well as the ζ-potential titration measurements. The effect of PE charge density shows that PE-surfactant coacervation is the driving force in these PE-emulsion systems.

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Abbreviations

a :

Radius of the emulsion droplet

e :

Elementary charge

k 1 :

Group parameter \(\equiv zeN_{1} k_{2} \;\)

k 2 :

Group parameter \(\equiv \exp ( - \Updelta \overline{G}_{\text{ads}} /N_{\text{A}} k_{\text{B}} T)/55.6 \times 1,000\;({\text{m}}^{3} /{\text{mol}})\)

k B :

Boltzmann constant (\(k_{\text{B}} = 1.381 \times 10^{ - 23} {\text{J/K}}\))

q(t):

ITC differential power input

x :

Mole fraction of PE in equivalence of the cationic charge

z :

Charge valence

C :

Molar concentration of PE in equivalence of the cationic charge

C inj :

Molar concentration of PE in equivalence of the cationic charge in ITC syringe

C j :

Molar concentration of PE in equivalence of the cationic charge at the jth injection

\(\Updelta \overline{H}_{\text{ads}}\) :

Molar adsorption enthalpy

\(\Updelta \overline{G}_{\text{ads}}\) :

Molar adsorption free energy

K :

Group constant \(\equiv \varepsilon (1 + \kappa a)/4\pi a\;({\text{C/V}} \cdot {\text{m}})\)

K ads :

Langmuir adsorption constant

N 1 :

Available charge sites for adsorption per m2

N A :

Avogadro’s constant (\(N_{\text{A}} = 6.023 \times 10^{23} / {\text{mol}}\))

Q j :

jth molar enthalpy per injection

Q cum,j :

jth cumulative molar enthalpy

\(\Updelta \overline{S}_{\text{ads}}\) :

Molar adsorption entropy

T :

Absolute temperature in Kelvin (K)

ΔV :

Volume of PE solution per injection

V j :

Volume of solution in ITC cell at the jth injection

σ :

Surface charge density of a spherical colloid

ζ :

ζ-potential

\(\varepsilon\) :

Dielectric constant of the medium (\(\varepsilon = \varepsilon_{\text{r}} \varepsilon_{0} = 78.54 \times 8.85 \times 10^{ - 12} \;{\text{F/m}}\))

κ −1 :

Debye length

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Acknowledgments

This work was supported by a grant from the Procter and Gamble Corporation. The cryo-TEM experiments carried out by Yingchao Chen (Department of Material Science and Engineering, University of Delaware) are gratefully acknowledged.

Author information

Authors and Affiliations

  1. Center for Molecular and Engineering Thermodynamics, Department of Chemical and Biomolecular Engineering, University of Delaware, Newark, DE, 19716, USA

    Dongcui Li & Norman J. Wagner

  2. The Procter and Gamble Company, 6210 Center Hill Avenue, Cincinnati, OH, 45224, USA

    Beth Schubert

Authors
  1. Dongcui Li
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  2. Beth Schubert
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  3. Norman J. Wagner
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Corresponding author

Correspondence to Norman J. Wagner.

Electronic supplementary material

Supporting Information Available: Supplementary information contains the derivation of the linearized Langmuir expression of the ζ-potential measurement and results from the auto-titration experiment. This material is available free of charge via the Internet. Below is the link to the electronic supplementary material.

Supplementary material 1 (DOCX 447 kb)

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Li, D., Schubert, B. & Wagner, N.J. Characterization of Cationic Polyelectrolytes Adsorption to an Anionic Emulsion via Zeta-Potential and Microcalorimetry. J Surfact Deterg 17, 655–667 (2014). https://doi.org/10.1007/s11743-013-1522-9

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