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Emulsion Stability Determination From Turbidity
Emulsion Stability Determination From Turbidity
A novel technique for studying the stability of emulsions has been developed. Owing to the
fact that emulsion turbidity is a function of particle concentration and size, the stability of emul-
sions can be determined by measuring the change in turbidity with time. The relationship between
turbidity and particle size and concentration is derived for a polydispersed emulsion. The
stability of acoustically prepared emulsions determined by measuring the initial mean particle size
and changes in emulsion turbidity is compared with the stability determined from scanning
electron microscope measurements of the particle growth rate. The agreement between the two
methods is excellent.
INTRODUCTION and Void (1) and Bagchi and Void (3) used
this approximate method for comparing the
A novel method for studying emulsion
stabilities of nonaqueous suspensions. The
stability to flocculation has been developed.
turbidity of suspensions containing very
Emulsion stability is determined by measur-
coarse particles varies inversely with par-
ing the turbidity as a function of time.
ticle size. Hiemenz and Void (4) and Bagchi
This method can be applied to many oil-in-
and Vold (5) used the turbidity method
water emulsions by measuring the changes
for determining the size of very coarse
in emulsion turbidity, which is very easy and
particles. The turbidity of an emulsion
inexpensive. The turbidity of an emulsion is
containing very fine and polydispersed
a function of particle size and concentra-
particles is a complex function of particle
tion. Therefore, the change in turbidity indi-
size and concentration. In this study, a
cates the change in particle size and concen-
turbidity method is developed for deter-
tration. In an unstable emulsion, particle
mining the stability of emulsions containing
concentration and size change with time due
polydispersed small particles. Results ob-
to coagulation and coalescence of particles.
tained from the turbidity method are com-
The turbidity method has not been pre-
pared with direct particle size measure-
viously used for determining the stability
ments made by using a scanning electron
factor, W, of an electrostatically stabilized
microscope.
emulsion. The turbidity technique has been
used (1, 2) to determine approximately the
THEORY
stability of suspensions by assuming that
turbidity is directly proportional to particle The optical density or turbidity, z, of an
concentration. This assumption can lead to emulsion containing monodispersed par-
erroneous stability factors or aggregation ticles is given by the relationship (6, 7)
rate constants as will be shown later. Dunn
ln(Io/I)
i Presently at General Motors Research Labora-
,r - - - - K 1 r a Z N , [1]
l
tories, Fuels and Lubricants Department, Warren,
Mich. 48090. where I0 and I = the intensity of the in-
101
0021-9797/81/010101-04502.00/0
Copyright© 1981by AcademicPress, Inc.
Journal of Colloidand Interface Science, Vol.79, No. 1, January 1981 All rightsof reproductionin any formreserved.
102 REDDY AND FOGLER
cident and transmitted light, respectively; Solving the equation for the ratio of initial
a = the particle radius; l = scattering path turbidity, z0, to the turbidity at any time, ~-,
length; N = the concentration of particles; assuming no creaming (i.e. 49 = 490)
and K = the total scattering coefficient de-
•o _ (ao/X)" ° (a3~2) [9]
fined as
(a/x)" (a~/Oo
K = Ko(a/h) m, [2]
Assuming a/fi0 = (a312)/((a312)o) and sub-
w h e r e K0 = the size-independent c o m - stituting into Eq. [9],
p o n e n t of the scattering coefficient, and
"to (ao)-,o-lX-, .....
m = the e x p o n e n t of the wavelength, )% - [10]
T (a) m-i
d e p e n d e n t on particle size and refractive
index. In emulsion stability studies, it is desir-
By measuring the turbidity at different able to determine the ratio of initial particle
w a v e l e n g t h s , the value of m can be deter- concentration to the particle concentration
mined f r o m the slope of a l o g - l o g plot of at any time, No~N, as a function of time.
~- vs h according to the equation In the absence of any creaming the ratio
~- = constant ()k) m. [3] N o / N can be related to Zo/Z using the rela-
tionship
F o r a polydispersed system, the turbidity
No 63
is given b y - [11]
N ~
"r = 7r ~ K~a2Ni, [4]
i Solving Eq. [10] for ~ and substituting
in Eq. [11],
w h e r e Ki = Ko(ai/h) "~.
The equation can be further simplified NON _ ~L1[ Xm-rtl°(ao)m°-lTo/___~ ]3/.,-~. [12]
to a useful f o r m b y evaluating K~ at an
a v e r a g e particle radius, 6:
F o r a special case w h e n the particles are
K~ = Ko(~t/h)". [5] very large, mo = m = 0, Eq. [12] reduces to
Then
"f = 7rKo(~l/h) m ~ a~Ni. [6] No
i
T h e v o l u m e fraction, 49, of the dispersed H o w e v e r , Dunn and Vold (1) used the re-
p h a s e is given by lationship
4 No To
49 = ~ 7r ~ a~Ni. [7] -- - [14]
N ~-
for kinetics of particle flocculation. Equa- o From Particle Size Ar~lysis o///
tion [12] can be used to determine the ~C- zx From TurbidityAnalysis
stability of an emulsion by measuring the
8 N \TJ
initial average particle size, do, and turbidity f
No % ~ "
as a function of time. The values of m are -~-6 o
determined by measuring ~-of the same sam-
ple at different k and plotting In ~- vs In h. 4
From the kinetics of flocculation
- d N / d t = k N 2, [ 16]
where k = 4kT/3tz W. O~ I 1 I I ]
10 20 30 40 50
Integrating and using the initial condition TIME (rain)
N=Noatt = 0,
FIG. 1. E m u l s i o n s t a b i l i t y d e t e r m i n e d from the
No/N = 1 + Nokt. [17] turbidity measurements.