Propagation of ultrasonic waves
suspensions and emulsions
2. Relation between ultrasonic
properties and certain characteristics
of the medium
A. PIOTROWSKA
The results obtained in the measurement of ultrasound
ficient in pigment suspensions merit an attempt to interpret the functional
of these ultrasonic propsrties on suspension concentration
Sound propagation in physically nonhomogeneous media
like aerosols, emulsions and suspensions is a complex prob-
lem, which has not been adequately described either theo-
retically or experimentally. Such propagation has been
investigated in an atmosphere contaminated with smoke
and fog,1,2,3 in river and sea water 4 (which is usually a
suspension of organic and inorganic particles). The latter
investigativn is in connection with ultrasonic sea soundage,
work which has been done at the Naval Research Labora-
tory. Of.the two quantities characterising sound propaga-
tion, absorption coefficient is the more sensitive to changes
occurring in a medium, especially in suspensions and dis:
cussion will centre on this quantity rather than sound
velocity.
Sound velocity
Herzfeld’s theoretical work concerning sound velocity in
physically nonhomogeneous medium 5,6 was not confirmed
by experiment. In 1947, Urick 7 published some results
of sound velocity measurements in emulsions and suspen-
sions. He assumed that, in the case where the acoustic
wavelength is much greater than the particle size of the
dispersed phase, the emulsion or suspension will behave as
if it were a homogeneous medium; density and compres-
sibility of both components of the system (dispersive fluid
and pigment) may be regarded as additive if we take into
account the volume concentration. The author has intro-
duced the same assumption for interpreting the results of
present work. Urick has checked this assumption for
kaolin/water suspension, and for xylemwater and water/
xylen emulsions. The points corresponding to these two
types of emulsion lie on the same curve, which in fact
confirms the assumption of homogeneity in the system.
Confirmation was also obtained by Allison for benzene/
water emulsions8
However, if the difference between acoustic impedance
values of the emulsion components is high, the system
Anna Piotrowska is with the Division of Technical Physics, Institute
of General Chemistry, Warsaw, Poland
ULTRASONICS. OCTOBER 1971
in
velocity and absorption coef-
dependence
and dispersion degree.
cannot be regarded as homogeneous. For such a system,
Urick and Ament 9 were able to take into account the
scattering of acoustic waves on emulsion spheres, which
gave agreement with the experimental data for bromoform-
in-water and mercury-in-water emulsions.
Busby and Richardson lo mvestigated the relationship
between sound velocity and the concentration of an
aqueous suspension of spherical glass particles (the dia-
meter of these spheres was 95 pm). They found that the
velocity increased linearly with concentration up to 15%,
the increments involved being small.
Kudriawcew and Samgina l1 investigated emulsions of
liquids of the same densities. It appeared that their
volumes (and hence their densities) were additive, but the
compressibility was not,4 its value was higher than would
be expected in the case of additivity. The authors attribu-
ted the increase of compressibility to the spheres’
vibration.
It appears from the literature that sound velocity in emul-
sions and suspensions was investigated only in relation to
concentration, in contrast to sound absorption, which has
been investigated much more extensively, both theoreti-
cally and experimentally, than sound velocity.
Sound absorption
It is assumed that sound absorption in emulsions and
suspensions is composed of (1) absorption of the dispersive
phase, (2) absorption of the dispersive fluid, and (3)
absorption resulting from phenomena taking place at the
interface of the two media. The third contribution is, in
general, much greater than the first two, which in most
cases can be neglected. Phenomena at the interface are
(a) scattering of acoustic waves by the particles of a sus-
pension or an emulsion, and (b) the viscosity phenomena,
where a suspended particle takes part in vibration whose
amplitude is less than that of vibration of the continuous
fluid, causing a velocity difference between fluid and
particles. The friction resulting causes ultrasonic energy
losses. Sewell 3 derived a theoretical expression for the
235
 size is of different character, being dependent on the par-
ticle size range, the type of dispersive fluid, and the fre-
quency of the sound wave. To summarize: when particle
size increases, the value of the absorption coefficient
increases rapidly at first, then decreases to minimum, and
subsequently increases as in Fig.1. This can be explained
by the interference of scattering and viscosity affecting
the absorption coefficient value.4*13

Discussion of velocity measurements

In the first part of this work,15 it was shown that the
sound velocity in a suspension of certain inorganic pig-
Portlcle dlometer -
ments was less than that in dispersive fluid, and, at low
concentrations, decreased with increasing suspension con-
Fig.1 The relationship between sound absorption coef centration. In the case of organic pigments, sound velocity
ficient and grain dimensions, in a suspension was higher than that in dispersive fluid and increased with
suspension concentration. This is for low concentrations
only (up to 10%). The densities of all the pigments investi-
gated were higher than those of dispersive fluids. The
absorption coefficient which involves both phenomena. densities of inorganic pigments were about three times
He assumed that the particles of the dispersive phase are greater than those of organic ones.
rigid and immobile spheres with a diameter less than the The interpretation of these results is based on Urick’s
applied acoustic wavelengths, that the dispersive fluid is a assumption. Thus, a fine grain suspension is regarded as
viscous medium, and that the concentration of the a homogeneous mixture of two component substances
suspension is low. His theoretical consideration is of whose density and compressibility are additive.
suspensions in the atmosphere (eg fogs and clouds).
Sewell’s resultant expression for the absorption coefficient, Let k be the concentration by volume of solid particles
a, is in the suspension (0 < k < l), and p be density, then

7 ij4 ijlPrjl12 on
t-- 1 dv
2a=3C _ -a3+3J2 ~~ fl=-- _
4 { 9 c4 ca ca2 >
* 0 dps
where C = concentration by volume where /3 = adiabatic compressibility, c = sound velocity,
c = sound velocity and indexes s = 0, I,2 correspond to suspension, fluid and
d = angular frequency pigment respectively. Using this expression, Urick obtained
a = radius of particle
that
n = kinematic viscosity coefficient of the fluid
The first term of this expression represents absorption con-
nected with scattering, and the remaining two the absorp-
tion connected with viscous energy losses. The expression
has been expanded, and derived in another way, by Urick
and Ament.9 According to Sewell’s expression, there is a and also that sound velocities in fluid and suspension are
direct proportionality between the absorption coefficient respectively
and the volume concentration of the suspension. It also
implies that scattering absorption is much more important I
2_
than viscosity effects when the particles of the emulsion are c1
large (ie radius is of the same order as the wavelength). PIP1

In emulsions of liquids whose densities do not differ

1 I
greatly, one more factor involving absorption may appear 2 = _~ = ___~_~_ _____
This is deformation, leading to pulsing of emulsion cO
POPO [p2k+plCl k)l[P2k+P1(1 m-k)]
particles.12
The absorption in dispersed systems was investigated mainly From these equations it can be shown that
in aqueous suspensions, of kaolinP glass spherical parti-
cies,10,13 sand,4 lykopodium,4,14 in aqueous emulsions
of benzene,12 bromoform and mercury, and in emulsions
in water with different emulsifiers. The relationships
investigated were those between the absorption coefficient
and (1) concentration,4,‘0 (2) particle size 4,10,12 and (3) which gives
the viscosity of the dispersive phase.4 The linear relation-
ship between absorption coefficient and concentration c1 2
occurs in general when the concentrations are low. The
relationship between absorption coefficient and particle 0 L'O
=(I +ka)(l +kb)=f(k)

236 ULTRASONICS OCTOBER 1971

Urick analysed the function f(k), and found the expression where
for concentration of a suspension which corresponded to
the extreme value of this function to be f”(k) = 2ab < 0 7

and

a > 0, b < 0.
dco(k)
The case when a and b are such that 0 < k < 1 corresponds The function co(k) has an extreme value when p= 0,
dk
to the extreme value of the function f(k).
from Equation 3, when f’(k) = 0. Now f’(k) = 2abk + a +
Urick showed that experimental data for the suspension of -(a + b)
kaolin in water with an emulsifier was in agreement with b=Owhenk,=--- which is in agreement with
his assumption. The function co/c1 plotted against the 2ab ’
concentration showed a minimum at a concentration of Urick’s result. The sign of the second derivative at the
10%; the ratio co/c1 equals unity at k = 0% and at k = 40%. point km is positive, since in Equation 4, [f(k)] -3/2 > 0,
Urick has not presented any explanation of the character f’(k) = 0, f”(k) < 0 and hence
of the curve at higher concentrations, or considered the
possibility of different behaviour for other systems. d2c,W
In the present work, the nature of the function co(k) has
~ >o
dk2
been analysed in its dependence on density and compres-
sibility (the quantities characterising the two components So the function co(k) can only have a minimumvalue. The
of a suspension). The variables of the function were as -(a + b)
minimum value obtains when 0 < km < 1; then ~ >o
follows: a = p2 - p1 re t e re a rve 1 erence between 2ub
p1- ( h ’ t. d’ff
the densities of the two media), and b = ‘9 (ie the -(a + b)
(hence b > -a) and ~ < 1 (hence b < T--~)
2ab
relative difference between the compressibilities of the two
media). Thus the minimum of the function co(k) exists provided
that
This author has assumed that, for a pigment suspension,
u > 0 (because we know from experiment that p2 > ~1)
and b < 0 (because f12 <PI, the solid substances being less -a
-a<b<---
compressible than the fluids). In addition, it is known that 1+2a
c1 is a constant greater than zero (the same dispersive
fluid), and that sound velocity in a suspension, co(k) is also
The concentration axis meets the velocity axis in the point
greater than zero.
cr (sound velocity in the dispersive fluid) ie at k = 0, a
On transformation, Urick’s expression point through which the curve co(k) also passes. If the
minimum exists, the curve co(k) crosses the concentration
2 axis once more, so that co(k) takes the value ct for a
= f(k) second time. From Equation 2, f(k) = 1 gives

f(k) = abk2 + (a + b)k + 1 = 1

becomes
and hence
co(k) = cl [f(k)] p1/2 2

The first and second derivatives of co(k) are

I‘ = -(a + b)
P ab
dco(W
= .- ‘,’ [f(k)] -3/2f’(k) 3 Thus, kp = 2k,.
dk
On the assumption that sound velocity in a solid substance
d2co(k)
is higher than that in fluid (ie co( 1) > c,(O)), the curve
- ~- ; [f(k)] - ~ :2 (f(k)))‘(f’(k))2 + f”(k) 4 en(k) must cross the concentration axis at the point
dk2 I -(a + b)
kp< 1. Then--- < I and b < ga The curve
ab
Analysis of the function f(k) and its first and secohd deriva- representing the function co(k) is shown in Fig.2
tives gives Finally we found that sound velocity in a suspension
reaches a minimum value (so that at low concentration it
f(k)=(l +ka)(l +kb)=abk2 +(a+b)k+ 1 5 decreases with increasing concentration), provided that

which is greater than zero since f(k) = cl/co. Also -a

-a<b<- 8
f’(k) = 2ubk + a + b 6 1 +a

ULTRASONICS. OCTOBER 1971 237

 hence

c12pfll< Pl

01 P2 Pl
+I
Pl

hence

Fig.2 Predicted curves for the function co(k)

so that
So this condition must be satisfied for the group of inor-
ganic pigemnts and for kaolin (Urick).
Let us examine the change in velocity with increasing con- 10
centration over the whole range of concentration. The
maximum of the function does not exist, as pointed out
above. (The author has previously covered this case for 3-. For inorganic pigments:
organic pigment suspensions of low concentration.f5 Thus
de,(k)
the case when ~ d,- > 0, must be applicable: hence

f’(k) < 0 (see Equation 3). Therefore ?labk+ u + b<O;

2abk < 0.

Now f’(k) tends to zero if k tends to zero. hence p2 p2

-<? - 11

9 01 PI
a + b < 0, ie b < -a

On the basis of these restraints and the known density

The function c,,(k) is represented also in this case by the
values for pigments and fluids it is possible to draw some
curve of Fig.?. The curve is convex downwards because
conclusions concerning compressibility. The density of
d%,(k) the inorganic pigments is about 4 gcmP3, and that of
~- ~ >o.
dk’ organic pigments is about 1.5 gcmP3. The value of dis-
persive fluid density is about I gcmP3. Thus for the group
of inorganic pigments we obtain from Equation IO that
To evaluate the compressibility for both groups of pig-
ments. the conditions obtained on making the substitutions

P2 _Pl
a= ~~~-- ; b = p?_P1

Pl 01
The left inequality is always satisfied, so
must be considered.
pz < 0.25 p1

1. For inorganic pigments: In the case of organic pigments, from Equation 1 1,

a 87 1.5
~a<b< _- < 3__ ~_ 12
a+l 01 1

therefore
P2 PI < 02 -p1

Pl 01 !32 < 0.5 01 13

238 ULTRASONICS. OCTOBER 1971

Thus, in the case of inorganic pigments the upper limit of
compressibility is lower than that in the case of organic
pigments. The higher compressibility of the organic pig-
ments may be caused, among other things, by air absor-
bed on the surface of the particles. The air adsorption
may also be regarded as the reason for the lower density
of these pigments.
Discussion of absorption coefficient
measurements
The linear relationship l5 between sound absorption coef-
ficient and suspension concentration is in agreement with
Sewell’s expression. It is also intuitively understandable.
It should be emphasized that in the present work the con-
centration by weight was used instead of the volume con-
centration which occurs in Sewell’s expression. In the case
of low concentrations, this does not change the basic
character of the relationship.
The decrease of absorption coefficient as a result of increas-
ing degree of dispersion (ie of decreasing particle diameter)
cannot be explained on the basis of Sewell’s expression.
Sewell assumed the immobility of the suspension particles
during acoustic wave propagation - it is dispersive fluid
only which vibrates and his shift against the particles is
the reason of viscosity absorption. However, if the sus-
pended particle is sufficiently small its inertia decreases
so that it begins to vibrate together with the dispersive
fluid. The difference between the amplitude of the
particle vibration and that of dispersive fluid vibration
is less the smaller is the particle size. This phenomenon is
considered to be the r:ason of the decrease in absorption
coefficient with the increase of the degree of pigment dis-
persion. The term representing scattering contribution
the absorption coefficient is, in the considered case, not
very important as the particle size is very small (less than
100 pm) compared with the applied acoustic wavelength
(0. I- 1 mm). This hypothesis does not apply to the sus-
pension of phtalocyanic blue produced by means of the
acoustic cogged generator at different frequencies. It may
be supposed that in this case the effect of increased sur-
face area is more evident than that of smaller mass of the
particle.
Conclusion
The assumption of additivity of density and compres-
sibility of both dispersive fluid and pigment led to an
interpretation of the results of sound velocity measure-
ments in pigment suspensions. Some restrictions were
established for compressibility values from considerations
of sound velocity in pigment suspension and of pigment
density measurements.
A decrease in absorption coefficient as a result of increas-
ing degree of dispersion was attributed to the compara-
bility of vibration amplitudes of the smallest pigment
particles and the dispersive phase.
References
Knudsen, V.O., J Acoust Sot Am, Vol 18, (1946) p 90.
Leidler, T. S.. Richardson, E. G., ibid, Voi 9 (1938) p 217.
Sewell C. J. T., Proc Roy Sot, Vol A83 (1910) p 547.
Urick, R. J., J Acoust Sot Am, Vol 20 (1948) p 283
Herzfeld, K. F., Phil Mag, Vol9 (1930) p 741.
Herzfeld, K. F., Phil Mag, Vol 9 (1930) p 752.
Urick, R. J., Appl Phys, Vol 18 (1947) p 983.
Allison, P. A., J Colloid Sci, Vol 13 (1958) p 513.
Urick, R. J., Aemnt, W. S., J Acoust Sot Am, Vol 21
(1949) p 115.
10 Busby, J., Richardson, E. G. Proc Phys Sot, Vol 59 (1953)
p 193.
11 Kudriawcew, B. B., Samgina, G. A., Zurn 1% Chim, Vol 36
(1962) p 393.
to 12 Allison, P. A., Richardson, E. G.. Proc Phys Sot, Vol 72
(1958) p 833.
13 Barron, K., Lawley, L. E.. Proc Phys Sot, Vol 72 (1958)
p 933.
14 Hartmann, G. K., Focke, A. W., Phys Rev, V0156 (1939)
p 217; ibid, Vol 57 (1940) p 212.
15 Piotrowska, A., ULTRASONICS, Vol 9, No 1 (1971)
ppl4-20.

ULTRASONICS. OCTOBER 1971 239