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The stability of hydrocarbon oil droplets at the surfactant/oil interface

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  • Colloid Science
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Summary

The effect of the nature of the oil on the coalescence of single oil droplets at the plane aqueous surfactant solution/oil interface has been investigated. The drop rest-times for the first stage coalescence of a range of hydrocarbon oils have been measured with constant drop volume. The apparatus was based on a design byNielsen et al. (13). Variables that affected drop lifetimes such as drop size, apparatus dimensions, saturation of the two phases with the other component, and surfactant concentration and chain length were investigated and a standard technique was developed. For saturated hydrocarbons the droplet stability falls progressively with increase in chain length. Unsaturation or aromatic character brings about a decrease in droplet stability. The results are discussed in terms of the balance between the cohesive forces between oil molecules and the adhesive forces, between the alkyl chain of the surfactant and oil molecules.

The addition of small quantities of long chain alcohol brings about a marked increase in stability through the formation of a complex condensed film at the oil/water interface. Attempts to correlate droplet stability data and the stabilities of bulk emulsion systems and spreading coefficient were not successful.

Zusammenfassung

Die Koaleszenz von Öltropfen auf planen Oberflächen von Tensiden wurde untersucht, wozu eine Standardtechnik entwickelt wurde. Bei gesättigten Kohlenwasserstoffn nimmt die Stabilität der Tröpfchen mit zunehmender Kettenlänge ab. Auch ungesättigte Bindungen und aromatische Gruppen erniedrigen die Stabilität.

Die Resultate werden diskutiert unter Berücksichtigung der kohäsiven Kräfte zwischen den Molekülen des Kohlenwasserstoffes und den adhäsiven Kräften zwischen den Alkylketten der Tenside und den Kohlenwasserstoffmolekülen.

Die Stabilität wird stark erhöht, wenn geringe Mengen langkettigen Alkohols zugesetzt werden, infolge der Bildung eines komplexen kondensierten Films an der Öl/Wasser-Grenzfläche. Versuche, die gewonnenen Stabilitätsdaten mit der Stabilität der „Bulkemulsionen” und des Spreitungskoeffizienten in Beziehung zu setzen, waren nicht erfolgreich.

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Abbreviations

A :

area per molecule of surfactant at the interface (nm2)

a :

activity

C :

concentration (mol dm−3)

d :

drop diameter (cm or mm)

d 0 :

mean droplet diameter on volume basis at initial storage

d t :

mean droplet diameter on volume basis aftert days storage

h :

film thickness

K :

Boltzmann's constant

K 1 :

coalescence constant

k :

first order rate constant for coalescence (s-1)

k 1 :

coalescence constant

k 2 :

empirical constant

L :

distance from needle to interface (cm)

M :

geometric mean rest-time (s)

N :

number of droplets not coalesced

n :

exponent

R :

gas constant

S :

spreading coefficient (Nm-1)

T :

absolute temperature

T1/2 :

first order half-life for coalescence (s)

t :

time (s)

t d :

drainage time (s)

t1/2 :

time required for half of droplets to coalesce (s)

tmean:

mean rest-time (s)

V :

molar volume

v :

velocity of hole formation

ΔHv :

latent heat of vaporization

δ :

solubility parameter

γ:

interfacial tension (Nm-1)

γ0 :

interfacial tension between pure oil and water

η e :

viscosity of continuous phase

ϱ:

density

Δϱ:

density difference

σ :

surface tension

ag:

geometric standard deviation

T :

surface excess

T 0 :

saturation adsorption

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  1. Department of Pharmacy, The University of Nottingham, University Park, NG7 2RD, Nottingham, England

    S. S. Davis & A. Smith

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Davis, S.S., Smith, A. The stability of hydrocarbon oil droplets at the surfactant/oil interface. Colloid & Polymer Sci 254, 82–98 (1976). https://doi.org/10.1007/BF01526744

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