I INTRODUCTION TO COLLOID SCIENCE

HANS LYKLEMA

I. I Becoming acquainted with colloids

Volumes IV and V of FICS will deal with colloids and, by way of introduction, we shall
a d o p t the s a m e p r o c e d u r e as in sec. 1.1 of Volume I, viz., mentioning ten p h e n o m e n a
that all have colloidal roots. Three of these are repetitions from that section.
1. Rivers discharging in seas tend to form shorter deltas than do those flowing out
into a lake.
2. In the Royal Institution in London visitors can see a liquid which looks like
claret, but which is really a colloidal solution of gold, p r e p a r e d halfway through the
nineteenth century by Michael Faraday.
3. Children and adults are attracted and intrigued by the beautiful changing colour
p a t t e r n s of soap bubbles.
4. Many paints are interesting fluids: if applied by a b r u s h or by spraying, they
behave like liquids, but after application they no longer do so (or, at least, they should
not!).
5. Very long ago the Egyptians were able to p r e p a r e ink of finely divided soot in
water, although c a r b o n itself is insoluble in water.
6. Several dyes that are insoluble in water dissolve very well after the addition of
surfactants.
7. Under s o m e conditions turbid emulsions, stabilized by a surfactant, b e c o m e
t r a n s p a r e n t following the addition of a second surfactant.
8. As early as 1 2 0 0 - 1300 BC people living in what is now Israel and Palestine
were able to m a k e glasses with a silvery appearance.
9. Even m o d e r a t e cooks manage to p r e p a r e quasi-solid edible p r o d u c t s by adding
only a few percent of gelatin to w a r m mixtures, followed by cooling.
10. Many p o r o u s soils have the propensity of salt-sieving, m e a n i n g that if seawater
is percolated through them, the salt is withheld so that potable water emerges.

These ten illustrations may serve as an introduction to the scope and

phenomenological wealth of colloid science and its applications. Let us briefly review
the respective b a c k g r o u n d s , thereby profiting from the general knowledge already
obtained from Volume I and the interfacial science of Volumes II and III.

Fundamentals of Interface and Colloid Science, Volume IV 9 2005 Elsevier Ltd.

J. Lyklema (Editor) All rights reserved
1.2 INTRODUCTION

I. B e s i d e s d i s s o l v e d m a t t e r , rivers also c a r r y along s m a l l particles, covering the size

r a n g e f r o m a few n a n o m e t e r s (nanoparticles) a c r o s s the colloidal range (from several-
to t h o u s a n d s of n a n o m e t e r s , or m i c r o n s ) to those of m a c r o s c o p i c size. T h e a m o u n t of
p a r t i c u l a t e m a t t e r rivers can carry, as well as the size d i s t r i b u t i o n a n d the n a t u r e of
the particles, d e p e n d s on the source, the geology, rainfall, i n d u s t r i a l waste, a n d o t h e r
f a c t o r s along their c o u r s e . Generally, the lower the particle c o n c e n t r a t i o n a n d the
s m a l l e r the sizes, the m o r e t r a n s p a r e n t is the river. Most particles have a density
exceeding t h a t of water, leading to sedimentation u n l e s s the c u r r e n t w h i r l s t h e m up.
Bigger particles settle before the s m a l l e r ones. Delta f o r m a t i o n is an a u t o m a t i c
c o n s e q u e n c e of the r e d u c e d flow n e a r the estuary. However, on top of this c o m e s the
phenomenon of colloid stability, that is the resilience against aggregation of the
particles. Colloid stability can have a variety of origins a n d in rivers electrostatic a n d
steric r e p u l s i o n s b e t w e e n the particles p r o b a b l y b o t h play a role. It is typical for
electrostatically stabilized (so-called electrocratic colloids, a term coined by
F r e u n d l i c h ) t h a t they are sensitive to indifferent electrolytes, w h o s e a d d i t i o n leads to
coagulation. This is the principle b e h i n d o b s e r v a t i o n (I).
T h e D u t c h can give a telling illustration. In the N e t h e r l a n d s there is a b r a n c h of the
River Rhine, called the I J s s e l . Until the 1 9 3 0 s it d e b o u c h e d into a sea, the Z u i d e r z e e
( " S o u t h e r n Sea") w h i c h w a s salty b e c a u s e it h a d an o p e n c o n n e c t i o n to the N o r t h Sea.
However, the D u t c h have the n a t i o n a l habit of r e c l a i m i n g land f r o m the sea, a n d as
p a r t of their activities the c o n n e c t i o n b e t w e e n the Z u i d e r z e e a n d the N o r t h s e a w a s
s e v e r e d by a long dike. As a result, the salinity d r o p p e d a n d the I J s s e l delta b e c a m e
m o r e extended. Since t h e n the Z u i d e r z e e h a s b e e n r e n a m e d the "IJsselmeer" ( I J s s e l
lake).
2. Colloidal s o l u t i o n s (sols) of g o l d m a n d for t h a t m a t t e r , all other w a t e r - i n s o l u b l e
m a t e r i a l s m c a n n o t be m a d e directly s i m p l y by mixing large c h u n k s of the solid with
water. To o b t a i n particles of the right size, one basically has two options: to apply
dispersion (comminution), or condensation. According to the f o r m e r , large particles
are milled to create particles in the colloidal range. The latter a p p r o a c h s t a r t s f r o m
real solutions, r e n d e r i n g the dissolved m a t t e r insoluble by a physical or chemical
p r o c e s s , letting the c o n d e n s a t e g r o w until it is in the d e s i r e d range. The t r e n d is t h a t
the f o r m e r a p p r o a c h is m o s t l y followed in industry, w h e r e a s the latter prevails in basic
r e s e a r c h , b e c a u s e it allows b e t t e r control. F a r a d a y p r e p a r e d his sols by a c o n d e n s a t i o n
m e t h o d : he r e d u c e d a n a q u e o u s solution of gold chloride with p h o s p h o r o u s acid? T h e
technical i s s u e s are i m m e d i a t e l y appreciated: the particle g r o w t h h a s to be s t o p p e d
once the d e s i r e d size is attained, a n d the s y n t h e s i z e d particles s h o u l d be stable against
aggregation. Apparently, F a r a d a y w a s successful in b o t h r e s p e c t s .
T h e ruby, wine-like colour is a c o n s e q u e n c e of light a b s o r p t i o n at a specific wave-
length range of the s p e c t r u m . Larger particles tend to be m o r e b l u i s h (and less stable,
as s t u d e n t s of colloid science k n o w by experience). An additional p r o p e r t y of sols is
their s t r o n g lateral s c a t t e r i n g of light. This p h e n o m e n o n is n o w a d a y s k n o w n as the
INTRODUCTION 1.3

Tyndall effect, (see sec. 1.7.6), a l t h o u g h it w a s d i s c o v e r e d earlier by F a r a d a y .

W h e n gold sols are electrocratic they can be coagulated by salt addition; w h e n they
are sterically stabilized they are ( m u c h better) salt-resilient.
3. C o l o u r s in s o a p films r e s u l t f r o m light diffraction a n d f r o m the fact t h a t the
refractive index d e p e n d s on the wavelength of the light. Light reflected f r o m one side
i n t e r f e r e s with t h a t f r o m the other. C h a n g i n g c o l o u r s imply c h a n g e s of t h i c k n e s s . On
b u b b l e s one can see t h a t large p a t c h e s of film of given t h i c k n e s s are m o v i n g with
r e s p e c t to t h o s e of o t h e r t h i c k n e s s e s . F r o m the o r d e r of the c o l o u r s one can even
e s t i m a t e the t h i c k n e s s as a function of time, a n d in this way follow the thinning or
drainage p r o c e s s . By c a r r y i n g out this analysis one will usually find the t h i c k n e s s to
be above the colloidal range. However, for the colloid scientist, things b e c o m e really
i n t e r e s t i n g for o t h e r t h a n aesthetic r e a s o n s if the t h i n n i n g of the film h a s p r o c e e d e d
until b e l o w a b o u t 10 -6 m. In sec. III.5.3 we have s e e n t h a t the colloidal interaction
forces a c r o s s it t h e n b e c o m e relevant; in principle one can m e a s u r e t h e m in this way,
o b t a i n i n g so-called disjoining pressure isotherms. T h i n s o a p films are therefore
excellent m o d e l s y s t e m s . Moreover, the o p t i o n s do not end here, b e c a u s e the way in
w h i c h the film continues, or ceases, to thin further, d e t e r m i n e s the stability against
r u p t u r e . U n d e r the right c o n d i t i o n s stable Newton f i l m s can be f o r m e d , i.e., p a t c h e s
t h a t are so thin t h a t they reflect h a r d l y any light. To the n a k e d eye they b e h a v e like
b l a c k holes a n d it is historically i n t e r e s t i n g that, long ago H o o k e I) o b s e r v e d t h e m ,
i n t e r p r e t i n g t h e m as such. However, real holes in a film are m e c h a n i c a l l y unstable;
they g r o w very rapidly, leading to r u p t u r e . It is c o n c l u d e d that the f o r m a t i o n of stable
black f i l m s is conducive for stability.
4. T h e p a i n t e x a m p l e t a k e s us to the r e a l m of rheology. Anticipating o u r s y s t e m a t i c
t r e a t m e n t , one can say t h a t the d e s i r e d b e h a v i o u r r e q u i r e s the paint to be thixotropic
(a t e r m briefly defined in sec. III.3b). T h i x o t r o p y can be realized if the disjoining
p r e s s u r e i s o t h e r m h a s a shallow m i n i m u m : w e a k attractive b o n d s k e e p the particles
together, giving rise to a t h r e e - d i m e n s i o n a l s t r u c t u r e at rest, b u t the application of a
s h e a r - f o r c e can d i s r u p t t h e s e b o n d s a n d fluidize the system. After c e s s a t i o n of the
a p p l i e d force the s y s t e m re-solidifies.
5. As early as 4 0 0 0 - 3 0 0 B.C. Egyptians w e r e able to write on p a p y r u s with r e d a n d
b l a c k ink, of w h i c h the latter a p p e a r s less p e r i s h a b l e over the centuries. Figure 1.1
gives an e x a m p l e . T h e r e d p i g m e n t s w e r e Pb304 ('red lead') a n d HgS ('cinnabar' or
'vermilion'), the b l a c k one w a s soot. None of these is soluble in water. Nevertheless, the
Egyptians managed to m a k e ink by stabilizing fine d i s p e r s i o n s of t h e m using a
vegetable b i o p o l y m e r f r o m the (gum arabic) b a r k of the Acacia Senegal or the a n i m a l
b i o p o l y m e r s c a s e i n a n d a l b u m i n as the stabilizer; these also function as adhesives.
S o m e of the stone-age cave paintings ( 1 5 , 0 0 0 - 12,000 B.C.) w e r e m a d e w i t h o u t

l) R. Hooke, On Holes in Soap Bubbles, Commun. Roy. Soc. March 2 8 th ( 1 6 7 2 ) .

1.4 INTRODUCTION

Figure I . I . Papyrus from the beginning

of our era with Greek handwriting des-
cribing a quarrel between Agamemnon
and Odysseus (Ilias IV, 340-346). The
ink has aged at least as well as the
papyrus (Courtesy Allard Pearson
museum, Amsterdam, NL.)

binder, b u t others were stabilized and m a d e to adhere by blood, honey or fats i)

Unwittingly these ancient artists anticipated the m o d e r n concepts of steric stabilization
by m a c r o m o l e c u l e s . In FICS, polymer a d s o r p t i o n has been d i s c u s s e d at s o m e length in
c h a p t e r II.5. Basically, the interaction between two polymer-covered particles is
repulsive if the polymers are, (I), sufficiently strongly b o u n d to r e m a i n on the surface
u p o n interaction and, (2), if the extending tails and loops repel each other across the
water into which they are e m b e d d e d - in t h e r m o d y n a m i c language, if water is a good
solvent for them.
There are various ways in which polymers can affect the stability of colloids. The
above-mentioned case of stabilization is called protection. This t e r m is used in
particular w h e n sols are m a d e m o r e resilient against coagulation by salts. Another
example is that of gold sols, which can be protected by low concentrations of gelatin
(below the gelation concentration). In all these cases, the stabilizing polymers are
a d s o r b i n g hydrophilic colloids, which by their very nature are soluble in the solvent, or
have soluble moieties extending into the solution. Gelatin-protected gold sols behave as
gelatin sols, though with a h e a r t of gold. However, u n d e r other conditions (mostly
achieved by adding small concentrations of a d s o r b i n g high molecular weight polymers)

1) K. Beneke, Zur Geschichte der Grenzfldchenerscheinungen, Mitteilungen der Kolloid-

Gesellschaft, Reinhard Knof (Kiel, Germany) (I 994).
INTRODUCTION 1.5

(a)

Figure 1.2. Three modes of

polymer-colloid interaction.
(a) Two polymer-covered
particles. The situation leads
to protection if the solvent is
good for the polymer; (b)
(b)
Adsorption flocculation by
long polymer molecules,
simultaneously adsorbing on
more particles; (c) Depletion
flocculation caused by the
solvent in the gap being
sucked out into the solution.

(c)

p o l y m e r s can also act as flocculants, i.e., they lead to aggregation (in this case called
flocculation. P r o b a b l y the m e c h a n i s m is bridging, i.e., the f o r m a t i o n of interparticle
p o l y m e r links. A t h i r d m e c h a n i s m is depletion flocculation, which o c c u r s with non-
a d s o r b i n g p o l y m e r s . Now the m e c h a n i s m h a s an o s m o t i c or e n t r o p i c origin. As
p o l y m e r s have a certain coil size in dilute solution 1), the n a r r o w g a p s b e t w e e n
a p p r o a c h i n g particles have to b e c o m e d e p l e t e d of p o l y m e r s ; the negatively a d s o r b e d
p o l y m e r h a s to find its way in the p a r t of the s o l u t i o n far away f r o m the interacting
pair. T h e e n s u i n g entropically driven t e n d e n c y of the solution to move f r o m the gap to
the b u l k drives the particles together. T h r e e possibilities of polymer-colloid interaction
are s k e t c h e d in fig. 1.2. All of this will be d i s c u s s e d in m o r e detail in c h a p t e r V. 1.
6. Although h y d r o p h o b i c dyes are insoluble in water, they do dissolve in the
h y d r o c a r b o n core of micelles. This p r o c e s s is called solubilization and, as it r e q u i r e s
the presence of micelles, it can only be observed above the critical miceUe
concentration, c.m.c. In fact, solubilization h a s b e e n invoked as a m e t h o d for
e s t a b l i s h i n g the c.m.c. Micelles b e l o n g to the category of association colloids.
7. T h e d i s a p p e a r a n c e of turbidity suggests that a t r u e s o l u t i o n is f o r m e d (or an

1) See the discussion in sec. II.5.2.

1.6 INTRODUCTION

e m u l s i o n with d r o p l e t s having exactly the s a m e refractive index as the c o n t i n u o u s

m e d i u m , a r a t h e r hypothetical situation), b u t further study h a s indicated that the sys-
t e m s do contain very tiny droplets. S u c h s y s t e m s are called micro-emulsions. Between
c o m m o n (or macro-) a n d m i c r o - e m u l s i o n s there is a difference of principle. Unlike the
f o r m e r, m i c r o - e m u l s i o n s are t h e r m o d y n a m i c a l l y stable. When the ingredients are
m i x e d in the right p r o p o r t i o n s a n d at the right t e m p e r a t u r e , the micro- e m u l s i o n f o r m s
s p o n t a n e o u s l y l Another difference is that, unlike m a c r o - e m u l s i o n s , m i c r o - e m u l s i o n s
t e n d to be a l m o s t h o m o d t s p e r s e (all d r o p l e t s having the s a m e size). M i c r o - e m u l s i o n s
c o n s t i t u t e a n o t h e r category of s y s t e m s with typical colloidal properties.
8. The silvery a p p e a r a n c e of glass b e a d s was achieved u n d e r the cross-fertilization
of S y r i a n a n d Egyptian culture. The Syrians h a d a s t r o n g glass i n d u s t r y w h e r e a s the
Egyptians were e x p e r i e n c e d in m a k i n g faience. The silvery a p p e a r a n c e was p r o b a b l y
c a u s e d by colloidal silver 1). It is not k n o w n how our p r e d e c e s s o r s s y n t h e s i z e d s u c h
solid-in-solid colloids, b u t it is interesting to note that n o w a d a y s m a n y cerami c
m a t e r i a l s are m a d e from ( h o m o d i s p e r s e ) colloids.
9. Solidified gelatin s o l u t i o n s in water are e x a m p l e s of thermo-rerversible gels; at
high t e m p e r a t u r e they are fluid, b u t u p o n cooling they solidify a n d can be cut with a
knife. They constitute a s y s t e m with striking m e c h a n i c a l properties; m a c r o s c o p i c a l l y
speaking, they behave as a solid, b u t if the self-diffusion coefficient of the water is
m e a s u r e d it is h a r d l y lower t h a n that in p u r e water. Apparently the gelatin m o l e c u l e s
f o r m c r o s s - l i n k s in s u c h a way that a t h r e e - d i m e n s i o n a l n e t w o r k is formed, into the
m a z e of which the water is p h e n o m e n o l o g i c a l l y immobilized.
10. Salt sieving is a p r o c e s s o c c u r r i n g in d e n s e p o r o u s plugs of charged particles.
The p h e n o m e n o n can be explained on the b a s i s of the negative a d s o r p t i o n of
electrolytes by c h a r g e d colloids (the D o n n a n effect). Theory can be found in secs.
II.3.5f a n d 7e. Briefly, n e a r c h a r g e d surfaces there is a zone which is depleted of co-
ions, which is p h e n o m e n o l o g i c a l l y equivalent to a salt-depleted volume. When two s u c h
surfaces b e c o m e so close t h a t the depleted zones overlap, the gap bet ween t h e m
b e c o m e s d e p l e t e d as a whole, a n d therefore electrolytes c a n n o t be t r a n s p o r t e d along
these pores.

The ten e x a m p l e s given above i n t r o d u c e us not only to the fascinating r i c h n e s s a n d

m u l t i f a r i o u s a p p e a r a n c e of colloids, b u t also call for systematic t r e a t m e n t . We see that
c o m m o n features r e c u r (for example, the effect of particle interaction in s e d i m e n t a t i o n ,
sol stability, a n d rheology) b u t s o m e t i m e s manifest t h e m s e l v e s in different ways
(disjoining p r e s s u r e s a c r o s s free- or wetting films are of the s a m e n a t u r e as those
b e t w e e n particles). To u n d e r s t a n d this, it helps to recognize c o m m o n roots b e t w e e n
different p h e n o m e n a . However, one m u s t be continually aware of the complexity of
a p p l i e d colloid science - c o m p a r e the p r o b l e m s faced by our pre-historic artists a n d

1) P.S. Zurer, Chem. Eng. News, Feb. 21 (1983) 26.

INTRODUCTION 1.7

p r o d u c e r s of i n k for m o d e r n ink-jet printers.

T h e s e c o n s i d e r a t i o n s m o r e or less define the t a s k s set for V o l u m e s IV a n d V; to give
a s y s t e m a t i c t r e a t m e n t of the f u n d a m e n t a l s of colloid science, with an eye o p e n for
applications.

1.2 Some definitions

For v a r i o u s r e a s o n s , it is not e a s y - a n d p e r h a p s not n e c e s s a r y - to give a simple a n d

c o m p r e h e n s i v e definition of a colloid. The t e r m itself is a m i s n o m e r . It s t e m s from the
G r e e k Ko)~)~ct, m e a n i n g glue, a n d was coined by G r a h a m I) b e c a u s e s o m e of his colloidal
s y s t e m s were glue-like. Nowadays we k n o w that m o s t colloids are not glue-ish, b u t the
name has stuck. Over the y e a r s the notion h a s been subject to changes; s o m e
investigators give it a wider, o t h e r s a m o r e r e s t r i c t e d meaning. In FICS we shall not
a d h e r e strictly to a defined size range b u t r a t h e r c o n s i d e r colloids as a p a r t i c u l a r state
of matter, b e t w e e n true s o l u t i o n s a n d s u s p e n s i o n s . For p a r t i c u l a t e m a t t e r this state is
c h a r a c t e r i z e d by the relatively large fractions of m o l e c u l e s in the s y s t e m t h a t are in an
interface. One of the fascinating o p t i o n s is that, c o m p a r e d to m o l e c u l e s in true
solutions, the i n t e r a c t i o n b e t w e e n the particles can be t u n e d , for e x a m p l e by changing
the electrolyte c o n c e n t r a t i o n . Although definition-wise the size-range of colloids is
p e r h a p s not of p a r a m o u n t relevance, in physical p r o c e s s e s sizes play i m p o r t a n t roles,
so we have to say s o m e t h i n g a b o u t them. The classic definition is on the b a s i s of size,
a n d the IUPAC definition r e a d s as follows 2).
"The term 'colloidal' refers to a s t a t e of subdivision, implying that the
m o l e c u l e s or p o l y m o l e c u l a r p a r t i c l e s , d i s p e r s e d in a m e d i u m , have at least
in o n e d i r e c t i o n a d i m e n s i o n roughly between 1 n m a n d 1 It or t h a t in a
system discontinuities are found at distances of that order. It is not
n e c e s s a r y f o r all t h r e e d i m e n s i o n s to b e in t h e c o l l o i d a l r a n g e : f i b e r s , in
which only two dimensions a r e in this r a n g e , a n d t h i n f i l m s , in w h i c h o n e
d i m e n s i o n is in t h i s r a n g e , m a y a l s o b e c l a s s i f i e d a s c o l l o i d a l . "
A c c o r d i n g to this definition, p o l y m e r coils in s o l u t i o n are c o u n t e d as colloids; a
claim t h a t m o s t p o l y m e r c h e m i s t s feel as t r e s p a s s i n g . We shall not c o n s i d e r p o l y m e r s
as colloids b u t do t r e a t t h e m in volume V, mainly b e c a u s e of their relevance for steric
stabilization. To the lower particle size, in recent y e a r s the t e r m s n a n o s c i e n c e and
nanotechnology have b e c o m e f a s h i o n a b l e for d e s c r i b i n g s m a l l particles c o m p o s e d of a
limited n u m b e r of a t o m s . However, n a n o t e c h n o l o g i s t s s o m e t i m e s also claim as
n a n o p a r t i c l e s particles t h a t are tens-, or even h u n d r e d s - , of n m large. We shall not do
that, a n d as a rule only c o n s i d e r particles that are so large t h a t they have their
m a c r o s c o p i c b u l k p r o p e r t i e s . S o m e t i m e s we have to c o n s i d e r the n a n o s i z e range, for

I) T. Graham, Phil. Trans. 151 (1861) 183.

2) See the IUPAC manual mentioned in sec. 1.5.
1.8 INTRODUCTION

e x a m p l e in d e s c r i b i n g the s y n t h e s i s of colloids (chapter IV.2). To the u p p e r particle-

size side one finds the suspensions (for solids), or the s o m e t i m e s large d r o p s in a n
emulsion (for liquids). We shall c o n s i d e r these as far as they exhibit colloidal
properties.
R e g a r d i n g n o m e n c l a t u r e , one s h o u l d be aware of the fact that, in recent literature,
colloidal p h e n o m e n a are s o m e t i m e s d e s c r i b e d u n d e r t e r m s s u c h as mesoscopic
physics, or mesoparticle science. The origin of these t e r m s s t e m s m o s t l y from the side
of p h y s i c i s t s who b e c a m e increasingly c o n s c i o u s of the potentialities of colloids as
s y s t e m s having a scale i n t e r m e d i a t e b e t w e e n 'molecular' a n d 'macro'. Recall t h a t in sec.
II. 1.6a we have a l r e a d y m e t the classification of pore sizes in a d s o r b e n t s as m i c r o p o r e s
(< 2 nm), m e s o p o r e s (= 2-50 nm) a n d m a c r o p o r e s (> 50 nm). A c c o r d i n g to this
s c h e m e , m e s o p o r e s are of the (lower) size range of colloids. So, the prefix 'meso' is
b a s i c a l l y c o r r e c t b u t d o e s not a d d a n y t h i n g new u n l e s s it is further specified. We shall
t h e r e f o r e refrain from u s i n g s u c h t e r m s . However, the caveat m u s t be m a d e that,
because of the differing n o m e n c l a t u r e and hence the differences in key w o r d s ,
important papers in the physical literature m a y escape the a t t e n t i o n of colloid
s c i e n t i s t s a n d vice versa. The s a m e applies to the fashionable t e r m soft condensed
matter.

O, o
oOyo0 o (a)

OOO0
oOO O OO O
Figure 1.3. Sols with
spherical particles. (a)
Homodisperse (very nar-
row size distribution);
o O 0 o (b) Polydisperse (wide
size distribution).

o rO o (b)
INTRODUCTION 1.9

S p e a k i n g of sizes implies s p e a k i n g of size distributions. Sols in w h i c h the particles

all have exactly the s a m e size a n d the s a m e s h a p e we shall call homodisperse. Figure
1.3a is a n illustration. T h e t e r m is identical to isodisperse and monodisperse. Lin-
guistically t h e r e is no r e a s o n to prefer one n a m e over the o t h e r since all t h r e e have a
G r e e k prefix a n d a Latin stem. However, we shall avoid the t e r m h o m o d i s p e r s e d
b e c a u s e the perfect participle suggests t h a t the sol w a s m a d e h o m o d i s p e r s e by
fractionation. W h e n the particles have different sizes a n d / o r s h a p e s they will be called
heterodisperse, or, w h e n we w a n t to e m p h a s i z e t h a t the size d i s t r i b u t i o n is wide,
polydisperse (see fig. 1.3b). In m o d e r n t i m e s the t e c h n i q u e s for p r e p a r i n g well-defined
sols have m a d e m u c h p r o g r e s s , b u t 100% h o m o d i s p e r s i t y is rare. P e r h a p s biocolloids
s u c h as i m m u n o g l o b u l i n s are the sole illustrations. Very n a r r o w size d i s t r i b u t i o n s are
o b s e r v e d for h y d r o p h i l i c colloids s u c h as m i c r o - e m u l s i o n s , b u t h y d r o p h o b i c colloids
can n o w a d a y s also be m a d e synthetically with s u c h a n a r r o w d i s t r i b u t i o n t h a t u p o n
s e d i m e n t a t i o n or c o m p r e s s i o n they can crystallize into crystallographically perfectly
o r d e r e d a r r a y s ( s u c h as hexagonal packing). See fig. 1.4 for an illustration. Recall that
in sec. II.1.2 we p r e s e n t e d s o m e electron m i c r o g r a p h s of synthetic m o d e l colloids.
Figure 1.5 gives an illustration of the o t h e r extreme. It is the l a s t - m e n t i o n e d s y s t e m s
t h a t p a i n t t e c h n i c i a n s have to deal with, w h e r e a s the s y s t e m s belonging to the category
of fig. 1.3a are r a t h e r the p l a y g r o u n d for scientists. We shall have m o r e to say a b o u t
this in c h a p t e r 2 a n d the following c h a p t e r s .
A colloidal dispersion is a s y s t e m in which colloidal particles are d i s p e r s e d in a
continuous p h a s e of a different c o m p o s i t i o n , or state. In F a r a d a y ' s gold sols, a n d in
foams, w a t e r is the c o n t i n u o u s phase. S o m e t i m e s we shall use the t e r m 'colloid' as
s y n o n y m o u s with 'colloidal system'. A fluid colloidal s y s t e m m a y also be called a sol.
B e s i d e s F a r a d a y ' s gold sols, river w a t e r with finely d i s p e r s e d particles in it, s u r f a c t a n t
s o l u t i o n s above the c.m.c., a n d m i c r o - e m u l s i o n s are all sols.
E m u l s i o n s a r e sols c o n s i s t i n g of liquid d r o p l e t s , d i s p e r s e d in a n o t h e r liquid with
w h i c h they do not mix. T h e latter is the c o n t i n u o u s phase. Usually, one of the p h a s e s
(w), is an a q u e o u s solution, a n d the o t h e r an organic liquid w h i c h d o e s not mix with
w a t e r (o, for 'oil'). So, e m u l s i o n s can be of the oil-in-water (o/w) or water-in-oil type
(w/o). C h a n g i n g the type of an e m u l s i o n (from w/o ----> o/w or the o t h e r way a r o u n d ) is
called inversion. More c o m p l i c a t e d emulsions also exist, for e x a m p l e o/w/o (oil
d r o p l e t s in w a t e r in oil). T h e s e are called multiple emulsions. Although e m u l s i o n
d r o p l e t s m o s t l y exceed the u s u a l u p p e r size of colloids we shall include t h e m in o u r
d i s c u s s i o n ( c h a p t e r V.8) b e c a u s e of their i n t e r e s t i n g stability f e a t u r e s (in a d d i t i o n to
aggregation, d r o p l e t s c a n also m e r g e to f o r m a larger one or coalesce), a n d i m m e n s e
practical interest. Paradoxically, in the j a r g o n of p h o t o g r a p h y , p h o t o g r a p h i c 'emulsions'
are not e m u l s i o n s b u t particulate sols, w h e r e a s s u c h sols are called 'emulsions'.
A latex is an e m u l s i o n or sol of polymeric particles. The p l u r a l is latices (or
latexes). Latices are also k n o w n as polymeric colloids. As they can be m a d e with
n a r r o w size d i s t r i b u t i o n s a n d with specific bulk- a n d s u r f a c e p r o p e r t i e s they are
1.10 INTRODUCTION

Figure 1.4. Electron micrograph of a crystallized homodisperse silica. Marker equals 1 kt. (Re-
drawn from J. M a t e r . Sci. L e t t . 8 (1989) 1371; courtesy of A.P. Philipse, Utrecht, The
Netherlands. )

Figure 1.5. Electron micrograph of a copper phthalocyanine pigment for automotive paints,
made by ball milling. (Courtesy, J. Schr6der, BASF, Ludwigshafen, Germany.)
INTRODUCTION 1.1 1

favoured m o d e l s y s t e m s , b o t h in science a n d technology.

A f o a m is a d i s p e r s i o n in which a large fraction of the v o l u m e is a gas, d i s p e r s e d in
a liquid, a solid, or a gel. Young f o a m s often c o n s i s t of spheri cal b u b b l e s in the
continuous phase; bubble f o a m s or spherical f o a m s (the latter n a m e is r a t h e r
unfortunate). Older f o a m s tend to c o n s i s t of fiat lamellae, c o n n e c t e d to each o t h e r by
Plateau borders. They form the familiar polyhedric s t r u c t u r e s , in which the fiat
lamellae are of colloidal t h i c k n e s s , w h e r e a s the gas c o m p a r t m e n t s are m u c h larger. We
shall use the terms f o a m and f r o t h as equivalent. In s o m e b r a n c h e s of technology one
of the t e r m s is m o r e fashionable t h a n the other (e.g., 'froth flotation'). Scientifically
speaking, m u c h m o r e h a s to be said a b o u t f o a m s t h a n that they are s e e n as a set of
c o n n e c t e d thin films. Therefore, we shall treat thin films a n d f o a m s in two successive
c h a p t e r s , viz. V.6 a n d 7, respectively.
With r e s p e c t to their stability in the t h e r m o d y n a m i c s e n s e colloids can be sub-
divided into two groups.
(i) lyophobic (hydrophobic if water is the c o n t i n u o u s phase) or irreversible colloids,
which are t h e r m o d y n a m i c a l l y unstable.
(ii) lyophilic (hydrophilic) or reversible colloids, which are t h e r m o d y n a m i c a l l y
stable.
Sols belonging to the f o r m e r category c a n n o t be m a d e by simply mixing the m a t e r i a l
to be d i s p e r s e d a n d the liquid. A d e t o u r is n e e d e d a n d we shall devote an entire
c h a p t e r to it (chapter IV.2). S u c h sols are only kinetically stable, in the s e n s e that the
particles are k e p t from contacting each o t h e r by special m e a n s . Electrical charging is
one of the i m p o r t a n t m e c h a n i s m s . It leads to d o u b l e layer f o r m a t i o n a n d two d o u b l e
layers of the s a m e sign repel each other. We have al ready n o t e d that s u c h electrocratic
sols are sensitive to indifferent electrolytes (electrolytes t h a t do not contain charge-
d e t e r m i n i n g ions)" w h e n their c o n c e n t r a t i o n s exceed a certain critical coagulation
concentration (c.c.c.) stability is lost a n d coagulation ensues. Although there is no
s h a r p d e m a r c a t i o n b e t w e e n slow a n d fast coagulation, c.c.c, values can be e s t a b l i s h e d
fairly r e p r o d u c i b l y . It w a s already k n o w n by the year 1900 that the c.c.c, is drastically
lowered (more t h a n proportionally) if the valency:of the c o u n t e r i o n is increased. This
qualitative rule, k n o w n as the Schulze-Hardy rulel) was one of the challenges to be
m e t in the d e v e l o p m e n t of stability theory (chapters IV.3 a n d 4).
Sols belonging to category (ii) can be m a d e s i m p l y by mixing the ingredients. The
G i b b s energy of this p r o c e s s is negative.
E x a m p l e s of h y d r o p h o b i c colloids are:- all inorganic sols, thin films, a n d (macro-)
emulsions; e x a m p l e s of hydrophilic sols include several biocolloids, association
colloids, a n d m i c r o - e m u l s i o n s .
It s h o u l d be n o t e d t h a t the t e r m s 'hydrophobic' a n d 'hydrophilic' have m e a n i n g s

I) After H. Schulze, J. Prakt. Chem. (2) 25 (1882) 431" 27 (1883) 320 and W.B. Hardy, Proc.
Roy. Soc. 66 (1900) 110; Z. Physik. Chem. 33 (1900) 3051
1.12 INTRODUCTION

which differ from those used to indicate the relative affinity of water for a surface, as
quantified in t e r m s of the water contact angle (sec. III.5.1 la) or the heat of i m m e r s i o n
(table II. 1.3 in sec. II. 1.3f). Even if an ultra-clean gold surface has a zero contact angle
for water (table III.A4.1 ) the Gibbs energy of a collection of gold microcrystals in water
is always higher t h a n that of one large gold crystal having the s a m e mass.
This list of definitions is not complete. We shall, of course, use all the definitions
already given in previous volumes and introduce new ones where needed in specific
chapters.

1.3 D e m a r c a t i o n s a n d o u t l i n e o f V o l u m e s IV a n d V

There are several ways of condensing into two Volumes the rich variety that colloid
science has to offer; each of these involves choices about what to include and what to
exclude. The style of FICS requires a deductive approach, rather than a t r e a t m e n t by
kind of system. In a deductive t r e a t m e n t one would choose an initial discussion of
principles (such as particle interaction) and typical m e t h o d s (such as light scattering
a n d rheology), and applying all of this to specific systems in later chapters. On the
other hand, a system-oriented a p p r o a c h would call for a discussion of each kind of
colloid (hydrophobic sols, association colloids, etc.) and, in passing, considering all
applied techniques and their typical properties. Both p r o c e d u r e s have their merits and
d r a w b a c k s . We shall take a kind of hybrid route, in which a n u m b e r of principles of
wide relevance will be treated as such whereas s o m e systems with special charac-
teristics will be allocated to separate chapters. More specifically, in the p r e s e n t Volume
we shall e m p h a s i z e 'particulate' colloids (lyophobic colloids in which particles can be
distinguished), treating relevant properties such as preparation, characterization (size
distribution, surface properties), interaction between pairs of particles (electrostatic,
and other contributions to the disjoining pressure), with consequences for the kinetics
and dynamics (e.g., how fast does a sol coagulate and what are the mechanistic steps
in this process?), and concentrated systems (phase separation, fractal aggregates). As
the rheological properties of particulate sols primarily d e p e n d on the n u m b e r ,
properties, and interactions between the particles, a special chapter will be devoted to
that. Volume V will contain one methodical chapter (on steric interactions), but
otherwise it will deal with 'non-particulate' colloids (polyelectrolytes, biopolymers,
association colloids, micro-emulsions, thin films, foams and emulsions), which for
easy reference are collectively called 'soft colloids'.
In designing these Volumes, a certain restraint m u s t be applied to the degree of
complexity to be covered. Among items to be omitted one could think of the fine-tuning
of particle interaction models, mixtures of colloids, mixtures of surfactants in
association colloids, and polymer-surfactant interactions. These, and other multi-
c o m p o n e n t interactions lead to a plethora of, s o m e t i m e s exhilaratingly complex,
p h e n o m e n a , that are a b u n d a n t in colloid science. We shall also de-emphasize liquid
INTRODUCTION 1.13

crystals and m o r e descriptive features such as ternary p h a s e diagrams, notwith-

s t a n d i n g their practical interest. It is simply beyond the scope of FICS to cover all of
that, but we shall try and indicate where such extensions and applications come into
the picture. We shall mostly consider systems in which a liquid is the continuous
phase, m e a n i n g that a e r o s o l s (colloids in the gas phase) will at m o s t be included
cursorily. Overall, these two Volumes will cover the f u n d a m e n t a l s of colloid science.

1.4 Some historical notes

Colloid science has a relatively long history. Although prehistoric m a n applied colloidal
know-how m a n y t h o u s a n d s of years ago, the cradle of colloid science dates to halfway
t h r o u g h the nineteenth century, which is still long before the existence of molecules was
irrefutably established. In retrospect, people such as Selmil) and G r a h a m 2) are usually
called the founding fathers of colloid science because they were the first to start
systematic w o r k on the preparation, characterization and stability of colloids. Selmi
had already established the strong detrimental influence that electrolytes have on the
stability of sulphur, and other sols. To these w o r k e r s the n a m e of Faraday 3), who did
his f a m o u s e x p e r i m e n t s with gold sols a r o u n d 1857, may be added. He also noted the
salt effect, and considered light-scattering and the protection by gelatin. He went so far
as to realize that changes in the properties of the gold-solution interface play an
i m p o r t a n t role. Had he subjected his sols to an electrical field, he would have
discovered that stability and electrophoretic mobility are related. Electrokinetic
p h e n o m e n a have been known since 1809 (see chapter II.4) but the relationship to
stability was only established a r o u n d 1900 by Hardy 4). Perrin, Burton, Kruyt, and
m a n y other investigators p u r s u e d this line further. One of the m a i n findings was the
d r a m a t i c difference between (what are now called) hydrophobic and hydrophilic
colloids. The latter category is m u c h m o r e resilient towards electrolytes which, in these
systems, essentially act as modifiers of the solvent quality (sec. 1.5.4).
The discovery of the colloidal state p r o m p t e d the development of a n u m b e r of
physical techniques. Besides electrokinetics we may mention the discovery of the ultra-
microscope by Siedentopf and Z s i g m u n d y 5) in 1903, which allowed the direct
observation of (particulate) colloids on the basis of their laterally scattered light (the
Tyndall effect) which won Zsigmundi a Nobel prize. In this connection, the Nobel prize
a w a r d e d to Svedberg in 1926 for inventing the u l t r a c e n t r i f u g e may also be mentioned.

11 F. Selmi, Nuovi Ann. di S c i e n z e Naturale di Bologna, Ser. II, IV (1845).

2) T. Graham, loc. cit.
3) M. Faraday, Phil. Trans. Roy. Soc. 147 (1857) 145.
4) W.B. Hardy, loc. cit.
5) See R. Zsigmundy, Zur E r k e n n t n i s s der Kolloide: fiber Irreversible Hydrosole und
Ultramlkroskopie. Gustav Fischer (1905); R. Zsigmundi, Colloids a n d the Ultramicroscope: A
M a n u a l of Colloid C h e m i s t r y a n d Ultramicroscopy (transl. by J. Alexander) John Wiley (1909).
1.14 INTRODUCTION

Essentially this w a s an i n s t r u m e n t with which hydrophilic colloids, having a s m a l l

den s i t y difference from water, could be fractionated.
The q u e s t for a c o m p r e h e n s i v e theory to a c c o u n t for the stability of h y d r o p h o b i c
colloids d o m i n a t e d the n i n e t e e n twenties to -forties a n d c u l m i n a t e d in the d e v e l o p m e n t
of the n o w well-known DLVO theory, n a m e d after Deryagin a n d L a n d a u , a n d Verwey
a n d Overbeek, who d e v e l o p e d it i n d e p e n d e n t l y d u r i n g the s e c o n d world war 1"2). The
a c r o n y m w a s coined by S a m Levine. (In passing, a n d tongue-in-cheek, the A m e r i c a n
colloid scientists Marjorie a n d R o b e r t Vold referred to it as the Verwey-Overbeek-
Landau-Deryagin (VOLD) theory.) This theory d e s c r i b e s particle-pair interaction
insofar as it is d e t e r m i n e d by electrostatic r e p u l s i o n a n d Van der Waals attraction. One
of the basic i s s u e s t h a t h a d to be solved was the accounting for the r e - d i s t r i b u t i o n of
the c o u n t e r c h a r g e u p o n interaction as a whole, electric d o u b l e layers are electro-
neutral, so why w o u l d two identical d o u b l e layers always repel each other at any
d i s t a n c e ? One of the m e r i t s of the DLVO theory was that it could a c c o u n t for the
S c h u l z e - H a r d y rule. We shall d i s c u s s a n d extend this theory in c h a p t e r s IV.3 a n d 4. Of
the m a n y o t h e r scientists who c o n t r i b u t e d significantly to this d e v e l o p m e n t , we men-
tion F r e u n d l i c h , who e m p h a s i z e d the r e l a t i o n s h i p between a d s o r p t i o n a n d stability 3).
As we shall show, the d e s o r p t i o n of m o l e c u l e s or ions d u r i n g particle e n c o u n t e r is a
key e l e m e n t (although not fully a p p r e c i a t e d ) in u n d e r s t a n d i n g stability p h e n o m e n a .
The other two c o n t r i b u t i o n s to pair interaction, steric- a n d solvent-structure
i n t e r a c t i o n s e n t e r e d quantification in the later half of the twentieth century. Theory for
the effect of p o l y m e r s on colloid stability was initiated by S c h e u t j e n s a n d Fleer 4) a n d
de G e n n e s 5), using a lattice theory a n d a scaling a p p r o a c h , respectively: see c h a p t e r
V.I. Solvent s t r u c t u r e - m e d i a t e d forces were quantified by several Schools, particularly
in the Soviet Union. In FICS they have already b e e n d i s c u s s e d in sec. III.5.3.
M o d e r n colloid science h a s profited greatly from the d e v e l o p m e n t of well-defined
m o d e l colloids a n d new physical techniques. Special m e n t i o n m u s t be m a d e of the
surface force a p p a r a t u s , which allows direct m e a s u r e m e n t of the forces b e t w e e n two
surfaces. It w a s p a r t i c u l a r l y Israelachvili a n d his co-workers 6) who, after m u c h basic
w o r k by others, m a d e this a p p a r a t u s so user-friendly that it can now be found in m a n y
colloid c h e m i c a l l a b o r a t o r i e s . The m o d e r n variant of this is atomic force microscopy
or AFM.

I) B.V. Derjaguin (= Deryagin), L.V. Landau, Acta Physicochim. URSS 14 (I 94 I) 633.

2) E.J.W. Verwey, J.Th.G. Overbeek, Theory of the Stability of Lyophobic Colloids, Elsevier
(1948).
3) H. Freundlich, see the reference in sec. 1.5b.
4) G.J. Fleer, M.A. Cohen Stuart, J.M.H.M. Scheutjens, T. Cosgrove and B. Vincent, Polymers
at Interfaces, Chapman and Hall (I 993).
5) P.G. de Gennes, Scaling Concepts in Polymer Physics, Cornell Univ. Press (1974).
6) J.N. Israelachvili, Intermolecular and Surface Forces, 2 "d ed. Academic Press (I 992).
INTRODUCTION 1.15

When one surveys the d e v e l o p m e n t of colloid science one m a y conclude that there
has been a continuing cross-fertilization with physical sciences in general, b o t h with
respect to the d e v e l o p m e n t of concepts and experimental techniques.
All of this a n d m u c h more, will be d i s c u s s e d in the coming Volumes.

1.5 G e n e r a l R e f e r e n c e s

1.5a IUPAC recommendation

The general r e c o m m e n d a t i o n s are: Definitions, Terminology and Symbols in
Colloid and Surface Chemistry, p r e p a r e d for publication by D.H. Everett, Part I, Pure
Applied Chem. 31 (1972) 579 and Quantities, Units and Symbols in Physical
Chemistry, p r e p a r e d for publication by I. Mills, T. Cvita~,, N. Kallay, K. H o m a n n and K.
Kuchitsu, Blackwell (i 988). We largely heed their r e c o m m e n d a t i o n s .

1.5b General texts on colloid science.

A.W. A d a m s o n , A.P. Gast, Physical Chemistry of Surfaces, 64 ed. Wiley (1997).
(This well-known textbook also contains s o m e sections on colloids; of necessity m o r e
concise t h a n FICS.)

A.E. Alexander, P. J o h n s o n , Colloid Science I and II. C a m b r i d g e University Press

(1949). (Has been, for a long time, one of the leading books, b u t is not so quantitative.)

A. von Buz~h, Kolloidik; eine EinfCthrung in die Probleme der Modernen

KoUoidwissenschafft. (Of historical interest, by a H u n g a r i a n author.) (English transl.
Colloid Systems, Technical Press, L o n d o n (1937).)

D.F. Evans, H. W e n n e r s t r 6 m , The Colloidal Domain; where Physics, Chemistry,

Biology and Technology Meet, VCH (1994). (About the s a m e level as FICS b u t m o r e
condensed; with an e m p h a s i s on association colloids; also contains s o m e interfacial
science. Generally well written, b u t u n d e r e x p o s e s non-electrostatic contributions to
electrical double layers.)

D.H. Everett, Basic Principles of Colloid Science, Royal Society of C h e m i s t r y

(I 988). (Concise introduction, also contains s o m e surface science; r a t h e r classical.)

H. Freundlich, Kapillarchemie, I st ed. (Leipzig, 1909) and m a n y updates, including

the English t r a n s l a t i o n Colloid and Capillary Chemistry, Methuen (1926). (Of m o r e
t h a n p a s s i n g historical interest because it contains a plethora of discriminating
e x p e r i m e n t s a n d perspective views.)

E. Hatschek, The Foundations of Colloid Chemistry. E. Benn (London) (1925).

(Contains r e p r i n t s and English t r a n s l a t i o n s of historical p a p e r s from the second half of
the n i n e t e e n t h century.)
1.16 INTRODUCTION

P.C. Hiemenz, R. Rajagopalan, Principles of Colloid and Surface Chemistry, 3 rd ed.

Marcel D e k k e r (1997). (The well-known introductory text by the first a u t h o r is now
revised a n d expanded. Generally well written and informative. About 400 out of m o r e
t h a n 600 pages are devoted to colloid science.)

Handbook of Applied Surface and Colloid Chemistry. K. Holmberg, Ed., J o h n

Wiley (2001). (Extensive review, g r o u p e d into five categories. Surface c h e m i s t r y in
i m p o r t a n t technologies, surfactants, colloidal s y s t e m s and layer s t r u c t u r e s at surfaces.
P h e n o m e n a in surface chemistry, analysis and characterization in surface chemistry);
m a y be c o n s i d e r e d the 'applied' c o u n t e r p a r t of FICS.)

R.J. Hunter, Foundations of Colloid Science. Oxford Science Publ. I (1987); II

(I 989). (With respect to their level and size, these books m a y be considered ' p r i m u s
inter pares' as the c o m p a r i s o n of other texts with FICS IV and V are concerned; they
are informative; 12 out of the 18 c h a p t e r s deal with colloids, the others with topics
already dealt with in FICS II a n d HI. The level of the various c h a p t e r s is variable and
generally the t r e a t m e n t is less systematic.) Later, Hunter wrote a second edition,
p u b l i s h e d in 2000, in which the material of Volumes I and H was c o n d e n s e d into one
volume.

Colloid Science, H.R. Kruyt, Ed., Elsevier. Irreversible S y s t e m s (1952). Reversible

S y s t e m s (1949). (Reversible and irreversible = lyophobic and lyophilic, respectively.
Very well p r e s e n t e d overview; FICS IV and V m a y be considered their successors.)

K.J. Mysels, Introduction to Colloid Chemistry. Interscience (1959). (Introduction

for a course; covers m o s t aspects of colloid science. Original, with enlightening
e x p l a n a t i o n s and capricious definitions in places.)

W.B. Russell, D.A. Saville a n d W.R. Showalter, Colloidal Dispersions, C a m b r i d g e

Univ. Press (1989). (Rather advanced, compactly written, requires vector and tensor
analysis; e m p h a s i s on rheology, diffusion and t r a n s p o r t p h e n o m e n a . )

D.J. Shaw, Introduction to Colloid and Surface Chemistry, e.g. 3 r~ ed. B u t t e r w o r t h

(1980). (Has for a long time b e e n a first introduction to the field.)

M.J. Vold, R.D. Vold, Colloid Chemistry, Addison-Wesley (1983). (Covers our
V o l u m e s I I - V and is, of necessity, m o r e condensed.)