Article No : a07_341
Colloids
GERHARD LAGALY, Institut f€ur Anorganische Chemie der Universit€at Kiel, Kiel,
Germany
1. Definitions . . . . . . . . . . . . . . . . . . . . .
2. Colloidal Systems in Industrial Uses .
3. Preparation of Colloidal Particles . . .
4. Properties of Colloidal Systems . . . . .
5. Colloid Stability . . . . . . . . . . . . . . . . .
1. Definitions
Colloid chemistry involves a number of disci-
plines, including chemistry, physics, material
sciences, and biology.
The particle dimension is the primary param-
eter that governs the properties of colloidal sys-
tems. In a practical sense, any particle that has a
linear dimension in the range 10
3 to 1 mm can be
defined as a colloidal particle. Very small colloi-
dal particles (nanoparticles) have received in-
creasing attention [1–8].
Colloidal particles can consist of finely sub-
divided bulk matter or of more or less flexible
macromolecules. Particulate colloids are broadly
classed as lyophobic (hydrophobic when dis-
persed in water) or lyophilic (hydrophilic). Mi-
cellar solutions can be considered as associative
colloids because the micelles formed by associ-
ation of surface active agents often have colloidal
dimensions [9]. This type of colloidal system is
not considered here (see ! Surfactants, !
Laundry Detergents [10]).
Lyophobic and lyophilic colloids differ pri-
marily in the relationship that exists between the
colloidal particle and the medium in which it is
dispersed. Lyophobic colloidal particles form a
two- (or multi-) phase system with the medium,
and a phase boundary exists between the particles
(dispersed phase) and the medium (continuous
phase) (Table 1). The interactions between the
particles and between the particles and the

2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
DOI: 10.1002/14356007.a07_341.pub2
Article with Color Figures
.... .. 519 6. Factors Controlling Colloid Stability . . . . . . . 540
.... .. 520 7. Heterocoagulation . . . . . . . . . . . . . . . . . . . . . 549
.... .. 522 References . . . . . . . . . . . . . . . . . . . . . . . . . . . 550
.... .. 523
.... .. 531
medium are governed by the structure of the
particle surface, in particular the surface charge
density and the extent to which it responds to
changes in system parameters such as salt con-
centration, organic materials, and pH.
Dispersions of lyophilic particles are true
solutions in a thermodynamic sense and are thus
one-phase systems. The dispersed and continu-
ous phases are considered as solute and solvent.
The colloidal particles are formed by coils of
macromolecules. The macromolecules may be a
long thread, more or less stretched, rolled up, or
folded. In any case, the coil is open to the
dispersion medium, and large parts of the macro-
molecules are in contact with it. Thus, the shape
and size of the coils can change considerably
with changes in solvent properties. The system
is governed by the laws of macromolecular
solutions [15].
Lyophobic and lyophilic colloids are also
called electrocratic and solvatocratic colloids,
reflecting the important role of electric interac-
tions in the former and of solvent–particle inter-
actions in the latter.
Dispersions of lyophilic particles form spon-
taneously when solute and solvent are brought
together, as is characteristic of true solutions. In
the case of lyophobic colloids, dispersions may
or may not be produced spontaneously when
finely subdivided matter is added to the disper-
sion medium. For these reasons, the terms ‘‘re-
versible’’ for lyophilic and ‘‘irreversible’’ for
520 Colloids Vol. 9

Table 1. Classification of colloidal systems that determine stability and instability of

Continuous
colloidal systems.
Dispersed phase phase Descriptive names Areas in which particles of colloidal size are
regularly encountered either in stable dispersions
liquid gas aerosol, fog, mist
solid gas smoke, aerosol or in coagulated or flocculated states are the
gas liquid foam following [9, 10, 15–18]:
liquid liquid emulsion, microemulsion
solid liquid dispersion, suspension, Chemical Products Paints, pigments, paper coat-
sola
gas solid solid foam
ing [5], adhesives, thickening agents, lubri-
liquid solid solid emulsion, solid foam cants [19], catalysts, decolorizing and absor-
solid solid solid sol, solid–solid bent materials, and light-sensitive coatings
dispersion, alloy (photography).
a
The term colloidal solution should be avoided. Suspension is Paper Industry and Printing Fillers, coating
often incorrectly used instead of dispersion. A dispersion is colors, printing inks and pastes, carbonless
called suspension when the particles settle rapidly.
copying papers, deinking.
Pharmaceutical Industry Emulsions, microe-
lyophobic colloids have to be avoided, because mulsions, cremes, ointments, ad- and absorb-
they do not describe correctly the behavior of ing materials.
colloidal dispersions. Materials Science (Nano) composite materials,
The dispersed and continuous phases of col- powder metallurgy, pelletization, flotation,
loidal dispersions can be solid, liquid, or gaseous. ore enrichment, alloys, dispersion hardening,
‘‘Aerosol’’ is used for both liquid/gas and solid/ superalloys, superplasticity, ceramics [20,
gas dispersions. ‘‘Gel’’ designates solid/liquid 21], cement, fibers, plastics, additives for re-
dispersions which show a certain stability against inforcing plastics, tar, bitumen, and native and
mechanical forces [9, 15]. For instance, a test artificial asphalts.
tube containing such a dispersion can be turned Oil Recovery Drilling fluids, enhanced oil recov-
over without the dispersion flowing out. Coacer- ery, emulsification and de-emulsification.
vation is the separation of a colloidal dispersion Engineering Civil engineering, geotechniques,
(solid/liquid or liquid/liquid) into a phase with a soil engineering, soil stabilization.
high content of the dispersed material (coacer- Environmental Science Fog and smog, aerosols,
vate) and a phase with low content. It is an foams, cloud seeding, water purification,
important step in microencapsulation (! Micro- sludges, and pesticide formulations.
encapsulation, Section 4.1.). Consumer Products Dairy products, milk, mar-
garine, beer, waterproofing, cosmetics,
cleansing agents, encapsulated products, and
additives for foodstuffs.
2. Colloidal Systems in Industrial
Uses This list is supplemented by describing some
specific systems of practical importance:
Although colloidal dispersions are used in nu-
merous areas of science and technology, very few Colloidal Silica. Aqueous colloidal disper-
colloidal systems are produced solely because of sions of silica are easy to prepare by adding
their colloidal nature. The scientists in industry sodium silicate (water glass) solutions to dilute
use the laws of colloid stability to improve the hydrochloric acids (silica sols; see ! Silica,
applicability of materials, to find new fields of Chap. 4.) [22, 23]. They are produced on a large
applications, or to develop new products. Meth- scale, and different types of products are avail-
ods for stabilizing or destabilizing colloidal sys- able. They are also obtained by dispersing fine-
tems are indispensable for practical applications. grained silicas such as Aerosil in water or in
For example, it may be necessary to produce a organic solvents. Silica dispersions are widely
dispersion that is stable for a long period of used in paints, in pharmaceutical products, and as
storage but that destabilizes during application. thickening agents for aqueous and non-aqueous
Thus, it is important to understand the principles dispersions. Silica particles of colloidal size are
Vol. 9
used as filler material, e.g., for plastics and
rubber.
Oxides and Hydroxides. Titania (TiO2 as
rutil or anatase) is the best white pigment for
paints. Aluminum oxides (corund a-Al2O3),
oxyhydroxides (diaspore a-AlO(OH), boehmite
g-AlO(OH)) and hydroxides (bayerite a-Al
(OH)3, gibbsite g-Al(OH)3) are used in many
products such as abrasives, toothpaste, papers,
plastic materials and rubber (as fillers), and in
paints (as pigments, sometimes replacing titania
in lower-quality products).
Iron oxide and oxyhydroxide pigments (he-
matite a-Fe2O3, maghemite g-Fe2O3, goethite
a-FeO(OH), lepidocrocite g-FeO(OH)) are
used on a large scale (! Pigments, Inorganic,
1. General). A well-known application is the use
of maghemite as magnetic pigment in magnetic
tapes, which requires colloidal particles of dis-
tinct shape and sizes (! Information Storage
Materials). They are also used for preparing
ferrites (! Magnetic Materials).
Sulfides and Sulfur. Sulfides of various
metals can be obtained as colloidal dispersions.
Colloidal arsenic sulfide (As2S3) has been known
for a long time. The stability of colloidal nickel
and cobalt sulfides is familiar to students of
analytical chemistry because these sulfides form
readily colloidal dispersions instead of precipi-
tates when metal ions are reacted with hydrogen
sulfide ions. (Only hydrogen sulfide ions exist in
aqueous systems!) Colloidal sulfur with particle
sizes of 0.5–2 mm, produced by ball milling of
sulfur, is used for vulcanization and as fungicide
in viniculture and fruit farming.
Silver Halides. Well-known is the applica-
tion of silver halides in light-sensitive coatings
(! Photography). AgI crystals are used as nuclei
in cloud seeding.
Clays. Clay minerals, major components of
bentonites and kaolins, form platelike or some-
times lath-shaped colloidal particles (! Clays).
The annual world use of these natural colloidal
materials has grown to more than 13  106 t of
bentonite, 20  106 t of kaolins, and several
hundred million tons (exact values are unknown)
of common clays. The widespread industrial uses
of clays as colloidal dispersions, thixotropic gels
Colloids 521
or dry materials have been described extensively
[24–30, 18, 31, 32].
Zeolites. Zeolites of almost colloidal parti-
cle sizes (1–12 mm) are used as phosphate sub-
stitutes in detergents [33]. Cracking catalysts
consist of zeolites in colloidal size deposited on
cardhouse-type aggregates of kaolinite particles
[34]. The supporting network of kaolinite parti-
cles ensures the diffusion of the reactants and
products to and from the catalyst particles.
Colloidal metals are usually obtained by re-
duction of their salts in solution [15]. Colloidal
gold dispersions illustrate the effect of particle
size on color. Dispersions of 16-nm particles are
orange, those with 41-nm particles are red, and
those with 98-nm particles are violet with a
yellow Tyndall effect of the scattered light [23,
35]. Some unsupported metals in colloidal dis-
persion are used as catalysts.
Colloidal alkali and alkaline earth metals are
available in organic solvents (Na in benzene; Ca,
Sr, and Ba in propyl and isopropyl alcohol). Blue
rock salt (sodium chloride) contains sodium in
colloidal dispersion.
Semiconductor Colloids. Research in
semiconductor colloids is developing in two
directions: (1) preparation of particles with nar-
row size distribution and regular shape and
investigation of their properties, and (2) their
self-assembly into new materials and devices
[36, 37].
The quantum size effect is a characteristic
property of colloidal semiconductor particles (ca.
2–4 nm in diameter). A nanoparticle represents a
three-dimensional potential well for the charge
carriers that are generated by absorption of a
photon. The consequence is a blue shift of the
threshold of absorption and fluorescence band
with decreasing particle size. For semiconduc-
tors, this blue shift can be very pronounced [38].
The color of Cd3P2 particles changes from black
(coarse particles) to brown (3 nm diameter), red,
yellow, and white (1.5 nm)
Latices. Polymer particles of different
structure and surface morphology (Fig. 1) are
formed by emulsion, dispersion and suspension
polymerization [15, Chap. 6].
The particles usually carry negative surface
charges, although positively charged latices and
522 Colloids
Figure 1. Types of latex particles [15] A) Monomers;
B) ‘‘Classical’’ particles; C) Bristly latices (surface with
adsorbed emulsifier molecules); D) Hairy latices; E) Core –
shell particles; F) Polymer coils
amphoteric forms (with both positive and nega-
tive surface charges) are also available.
Latices are used in many applications, for
instance as binders in paints, for paper filling,
coating, impregnation, diving equipment, latex,
and latex foam. Many of these applications are
based on the film-forming properties of latex
particles [39].
Hydrophilic Colloids. Typical examples
are gelatin, pectins, alginates, alginic acids, and
proteins. Synthetic products are, for instance, poly
(acrylic acid) and its salts. Alginates, gelatin, and
pectins are used as thickening and thixotropic
agents, emulsifiers for pharmaceutical products,
cosmetics, and in the food-processing industry.
3. Preparation of Colloidal Particles
Colloidal particles are prepared by dispersion of
larger particles or by condensation of atoms,
ions, or molecules [9, 15, 40].
Dispersion Methods. Dispersion of larger
particles into particles of colloidal size often
requires high mechanical forces and can only be
attained in high-energy mills such as colloid
mills. Cavitation processes in the solvent [41]
during milling promote particle size reduction
[15, Chap. 5]. However, agglomeration process-
es become effective at high inputs of mechanical
energy, so that the particle size reaches a lower
Vol. 9
limit. On the other hand, the forces in high-
energy mills are so strong that solid materials
can be alloyed like iron and silver which usually
do not form alloys. Mechanical alloying is an
important technical process, for instance for
hardening of metals by dispersed oxides (disper-
sion hardening; see, e.g., ! Gold, Gold Alloys,
and Gold Compounds, Chap. 8.; ! High-Tem-
perature Materials, Chap. 4.; ! Powder Metal-
lurgy and Sintered Materials, Chap. 9.).
During particle size reduction, new surfaces
are created which must be covered by sufficient
stabilizing agent to prevent reaggregation.
Therefore, more powerful equipment which
yields smaller particle sizes often requires higher
amounts of stabilizers.
In the early 1900s, BREDIG and SVEDBERG
studied the scattering of metals by arcs formed
between two metal electrodes within a solvent. A
modern version is ion beam sputtering, which has
become important for preparing nanocrystalline
materials.
Dispersion of a liquid phase into an other
liquid phase (emulsification) is much more easi-
er, as everyone knows from the preparation of
mayonnaise. Nevertheless, technical preparation
of emulsions often needs considerable amounts
of energy. In all cases a careful selection of
effective emulsifiers or emulsifier mixtures is
imperative.
Condensation Reactions. A well-known
condensation method for preparing colloidal dis-
persions is the reduction of nobel metal salts in
aqueous or non-aqueous solvents [15, 42, 43].
Another simple method is precipitation of low-
solubility compounds from solution. In many
cases, particles with broad size distributions and
irregular shape are obtained. Precipitation from
homogeneous systems is of great advantage. The
starting system is a homogeneous solution, and
precipitation is slowly initiated by hydrolytic
reactions or the slow decomposition of com-
plexes. Often, a precursor compound is dissolved
in organic solvents, then slowly hydrolyzed by
addition of water [15, Chap. 5]. A well-known
procedure is the preparation of monodisperse
silica particles by the St€ober process [44, 45].
A variety of monodisperse colloidal particles of
different sizes and shapes were prepared by
MATIJEVI
c et al. [15, Chap. 5], [40, 46–49]. The
morphological control of particle shape is pres-
Vol. 9
ently en vogue, especially for the preparation of
colloidal particles of nanometer size, may be by
templating processes with surfactants and poly-
mers [50] or in the context of biomineralization.
Hollow capsules of nanometer to micrometer
dimensions provide an important class of new
materials for diverse applications [51].
Polymer colloids (microgel particles) are pre-
pared by emulsion, dispersion, and suspension
polymerization. Latices are obtained by emul-
sion polymerization (with or without emulsifier)
of styrene, butadiene/styrene, acrylamide, N-iso-
propylacrylamide, etc. They are usually obtained
as spherical particles, but many other forms and
surface morphologies can also be produced [15,
Chap. 6], [39, 52, 53]. Hairy-like macromole-
cules on the surface of latex particles provide
particular properties such as enhanced colloidal
stability [15, 54–56] or temperature-sensitive
behavior [15, 57–60].
An example for gas phase reactions is the
flame hydrolysis of SiCl4 and TiCl4 forming
finely dispersed silica (! Silica, Chap. 6.) and
titania. Chemical vapor deposition can be used to
coat preformed particles.
A problem in the preparation of colloidal par-
ticles is the need to stop particle growth when the
desired size is attained [15, 61, 62] and to consider
subsequent changes of colloidal particles in con-
tact with the dispersion medium. VOGELSBERGER
et al. [63, 64] developed a thermodynamic and
kinetic model of all processes (nucleation,
growth, Ostwald ripening, and dissolution) that
may occur in a system of colloidal particles–
solution. Preparation in confined systems pro-
vides advantages. One method consists of nucle-
ation and growth of the particles within the dis-
persed water of microemulsions [15, Chap. 5],
[65–67] or within the water cores of reverse
micelles [68, 69]. Different types of nanosized
colloidal particles were prepared in block copol-
ymer micelles [70–72]. The use of polymer gels is
another way to produce porous materials, parti-
cles of unusual shape, and to stabilize less stable
modifications [73, 74]. D
eK
aNY et al. [75–79]
described the production of nanoparticles in the
confined spaces between clay mineral particles.
Gold clusters and colloidal gold particles were
formed in alumina nanotubes [80].
Core-Shell Particles. Core-shell particles
are required in many applications [81]. Silica
Colloids 523
hydrogels or alumosilicates are deposited on
TiO2-particles (see Chapter 7) to reduce the
photocatalytic activity of these pigments in
paints [82]. Iron oxides used as magnetic pig-
ments or conducting polymer particles may be
stabilized by silica shells [83–86] (see ! Poly-
mers, Electrically Conducting). Envelops around
particles are not only needed for optical index
matching of colloidal particles but also for opti-
cal trapping [87]. Inorganic particles can also be
covered by conducting polymers [88]. Core-shell
latices including hairy particles are industrially
important types of microgel particles.
Peptization. In several cases the particles
are of colloidal size but are aggregated. Colloidal
dispersions are then prepared by peptization. The
methods required for successful peptization de-
pend on the chemical nature of the aggregated
particles [15, 50]. Ultrasound can promote the
dispersion process of coagulated colloidal parti-
cles [41, 89]. CHENG et al. [90] described the
dispersion of organic pigments in supercritical
carbon dioxide.
Concentrated Dispersions. [21, 91] Dis-
persions of high solid content (slurries, slips) are
needed, for instance, in the production of cera-
mics by slip casting, colloid filtration, gel coat-
ing, electrodeposition, sol-gel techniques [20],
thin film preparation [21], coating processes and
paper production (coating colors). Kaolin slips,
for instance, contain  70 % (by mass, or  47%
by volume) kaolin [25]. Liquefying of concen-
trated dispersions requires the choice of the
appropriate particle shapes and size distribution
(rather polydisperse than monodisperse) [15,
Chap. 12], [93–97] and addition of liquefying
agents like multivalent anions (see Chapter 6)
and especially sterically stabilizing polymers to
impede coagulation and ensure low viscosity [7,
15, 17, 21, 28, 98, 29, 30, 18]. Preparation of
concentrated dispersions with optimal rheologi-
cal properties (viscosity, flow behavior, yield
value, thixotropy) is a challenge for every colloid
scientist.
4. Properties of Colloidal Systems
Shape and Size of Colloidal Particles.
Many colloidal compounds form spherical par-
524 Colloids
ticles (e.g. silica, alumina, titania, metals, and
latices), but particles with other shapes are abun-
dant, e.g., rod- and needle-shaped boehmite,
platelike gibbsite, or needle-shaped goethite par-
ticles. Particle anisometry affects the colloid
stability, particularly, when both positive and
negative surface charges are present, as in clay
minerals.
The shape of the particles can be determined
by transmission or raster electron microscopy.
Difficulty arises with smectitic clay minerals
which often form broad undulating mosaic
sheets, making individual particles barely dis-
cernible. Modern transmission electron micros-
copy, however, allows the observation of very
thin particles [99]. The jet-freezing technique
allows the imaging of particles dispersed in the
solvent phase [100] or of the structure of micro-
emulsions [101]. More recently, colloidal parti-
cles and aggregation processes in aqueous media
were made visible in situ by X-ray microscopy
[102–105].
Colloidally dispersed particles can be mono-
disperse or polydisperse. The size distribution
can be narrow or wide, uniform or bimodal, or
even more complex [23]. Modern preparative
techniques produce particles with very narrow
size distribution (monodisperse systems).
In the case of particle size distributions or
anisometric particles [106, 107], the different
experimental methods yield different types of
average diameters. The light-scattering mean
value is larger than the volume-average mean
diameter which in turn is larger than the number
average diameter [15, Chap. 8].
The particle size can be obtained from elec-
tron micrographs, by light scattering (turbidity
measurement, static and dynamic light scatter-
ing), sedimentation methods, cuvette and disk
centrifuge photo-sedimentation, and streaming
methods (Coulter counter, capillary fraction-
ation, field flow fractionation) [15, Chap. 8],
[108, 111, 113]. Electroacoustic studies (still
in development!) allow the determination
of particle sizes in concentrated dispersions
[109, 110].
Shape, particle size, and size distribution are
very important for highly concentrated disper-
sions like paper coatings and ceramic masses.
The desired fluidity of such dispersions not only
requires the appropriate chemical treatment but
also careful selection of particle sizes and size
Vol. 9
distribution. Bimodal size distributions distinctly
reduce the viscosity of a dispersion. A broader
size distribution is therefore advantageous for
obtaining a lower viscosity [15, Chap. 12],
[93–97].
Light scattering [9, 23, 111, 112, 114] is
theoretically complicated, but rigorous solutions
of scattering patterns are available. The use of
dynamic light scattering (photon correlation
spectroscopy) for particle size determination is
very common. However, the data are often un-
critically accepted. Polydispersity cannot be rec-
ognized in every case. As the scattered light
intensity is proportional to d6, the presence of
even small amounts of larger particles strongly
influences the average particle diameter [15,
Chap. 8], [108, 111, 113, 115].
The Tyndall effect is a well-known light
scattering phenomenon. When the dispersion is
viewed against the light, it appears to be perfectly
transparent, but when viewed from the side, the
dispersion seems to be turbid. This effect is
demonstrated by colloidal sulfur. Addition of
dilute hydrochloric acid to sodium thiosulfate
solution precipitates colloidal particles of sulfur,
which grow in size with time [15, 23]. When the
dispersion is viewed directly in white light, the
initial white color becomes yellow, then orange,
then red, and finally dark brown. However, if the
illuminated dispersion is viewed from the side, it
looks turbid, milky, and the optical density in-
creases with time.
Stability. Dispersions of lyophobic colloids
may be stable for weeks, months, or years, de-
spite their inherent thermodynamic instability.
Such dispersions are called sols or are said to be
peptized. These dispersions are destabilized by
the addition of salts. When specific threshold
concentrations are exceeded, the dispersion coa-
gulates. The critical coagulation concentration,
cK, is essentially dependent on the valency of the
ion that is charged oppositely to the particle
surface (counterion, gegenion). This fact has
been established in the early days of colloid
science by the Schulze (1882, 1883) – Hardy
(1900) rule. The chemical nature of the counter-
ion is far less important, as are the valency and
nature of the ion with the same sign of charge as
the particle (co-ion), if there is no chemical
interaction. Variations of cK with the nature of
the counterions are observable, but are small
Vol. 9
compared with the changes due to different
valencies.
According to the Hardy–Schulze rule, the
ratio of cK values is
cK ð1Þ : cK ð2Þ : cK ð3Þ ¼ 1 : x : x2
where x varies from 1/40 to 1/30. cK(i) is the
critical coagulation concentration of counterions
with valency i. One can also write
cK ð1Þ ¼ ð30
40Þ : cK ð2Þ ¼ ð900
1600ÞcK ð3Þ
The experimental cK values of monovalent ca-
tions range from 25 to 500 mmol/L. For di- and
trivalent counterions, cK values of 0.1–10 mmol/
L and 0.01–1 mmol/L, respectively, are typical
[15, Chap. 3]. Hence, di- or trivalent counterions
are preferred for coagulation of peptized
dispersions.
Within the series of alkali cations as counter-
ions, the cK decreases in the order (Hofmeister
series)
Liþ > Naþ > Kþ > NHþ þ
4 > Cs > Rb
þ
and for anions as monovalent counterions
SCN
> I
> NO



3 > Br > Cl > F


Hence, a negative AgI dispersion is coagulated
by 165 mmol/L of LiNO3 and 126 mmol/L of
RbNO3, a positive Al2O3 dispersion by
60 mmol/L of KNO3 and 46 mmol/L of KCl.
Dispersions of lyophobic particles are also
affected by addition of polymers.
Peptization and Repeptization. Colloidal
dispersions are formed spontaneously when cer-
tain finely subdivided materials are added to a
liquid under suitable conditions. For instance, fine
grained quartz, amorphous silica, or sodium-rich
clays peptize by simply shaking the powder with
water. Other materials require small quantities of
specific electrolytes for peptization [Agþ or I

ions for AgI, SH
ions for sulfides, Hþ or OH

ions for oxides and hydroxides (see Chapter 6)].
Dispersions that have been coagulated by salts
may or may not repeptize by removing the salt,
for instance by simply washing with the solvent
(usually water) or by dialysis. Generally, parti-
cles coagulated with di- or trivalent counterions
are more difficult to redisperse than those coag-
ulated with monovalent ions. An exchange of the
multivalent ions by sodium ions is often impera-
Colloids 525
tive for repeptization. This is particularly true for
clay minerals that do not peptize in the presence
of calcium ions and in the absence of sodium
ions. The Ca2þ/Naþ ratio is thus a very important
factor in practical uses of clays. On an industrial
scale clays and clay minerals are peptized by
addition of sodium ions (in amounts similar to the
cation exchange capacity), mostly in form of
soda (soda-activated or alkali-activated clays)
[15, 17, 18, 31, 116, 117].
In other cases, the pH must be changed (see
Chapter 3). Surfactants can also be used as dis-
persants. One of the most important methods is
the use of protective compounds. These are
macromolecules that are adsorbed on the parti-
cles and give them enhanced surface charge
density or stabilize them sterically. Steric stabi-
lization is often needed in ceramics [18, 31, 21,
118] and drilling fluids [17, 18, 31, 119, 120].
When sterically stabilized dispersions are
flocculated, the particles can easily be repeptized
by changing the solvency of the solvent or, in
some cases, by changing the temperature.
In many cases, repeptization is prevented by
secondary reactions between the coagulated par-
ticles (aging processes). The particles can grow
together or may undergo structural changes that
render repeptization difficult or impossible.
Aggregation. The theory of colloid stability
(see Chapter 5) pertains to the initial states of
aggregation. The subsequent steps and the way in
which the particles aggregate and settle to form a
sediment are very important in practical applica-
tions [15, Chap. 12]. For instance, the coagula-
tion process is important in the production and
storage of microgel particles to avoid powder
explosion [97].
Different types of aggregation are illustrated
in Figure 2. Sediments that are produced from
highly peptized dispersions are compact and
difficult to stir. Such sediments form when par-
ticles settle slowly from well-peptized disper-
sions at low salt concentrations (below cK), on
standing for longer periods, by slow evaporation
of the solvent, or by filtration. At higher salt
concentrations, if the dispersion coagulates more
rapidly, voluminous sediments are formed that
are easy to redisperse by stirring. Types of sedi-
ments intermediate between the examples shown
in Figure 2 can be obtained by selecting appro-
priate experimental conditions, for instance, by
526 Colloids Vol. 9

Figure 2. Sediments from peptized and coagulated or flocculated dispersions a) Spherical particles
A) Dense sediment with repulsive interaction between the particles; B) Voluminous sediment with attractive interaction
between the particles.
b) Platelike particles
C) Dense sediment with repulsive interactions between the particles; D) Band-type structure with attractive face/face
interactions between the particles; E) House-of-cards structure with attractive edge/face interactions between the particles

carefully adjusting the salt (or polymer) concen-
tration or by changing pH or the type of counter-
ion. Coagulation with divalent counterions often
favors formation of voluminous sediments.
Compact sediments form if the interaction
between the particles is repulsive. Such particles
are able to move, sliding and rolling past each
other as they settle to form a closely packed
sediment, but without coming into actual contact
because of their mutual repulsion.
With sufficiently monodisperse spherical par-
ticles of latices [121, 122] and various other
materials, for instance, silica [22, 123], the par-
ticles can settle in regular arrays which give
Bragg reflections with light, similar to those from
crystals of closely packed spheres with X-rays
[124–127]. Due to the presence of ordered do-
mains, the dispersion shows a pronounced play of
color when viewed in white light at different
angles (iridescence) [123, 128]. The name col-
loidal crystals is used for these highly ordered
aggregates [129].
If conditions in solution are such that the
particle–particle interaction becomes attractive,
the particles aggregate to some extent in the
dispersion. The haphazardly formed flocs settle
and pile up at the bottom of the vessel to form a
voluminous sediment. The large voids between
the particles are filled with solvent. Figure 3
shows different types of voluminous aggregates.
Spherical particles form a three-dimensional net-
work consisting of strings of particles tied to-
gether like strings of beads. Depending on the
experimental conditions and the charge distribu-
tion, platelike particles aggregate to band-type
structures (face/face contacts) or houses of cards
(edge/face contacts). The different types of ag-
gregation are very important in practical uses of
kaolins, bentonites, and clays [15, Chap. 12],
[28–32, 130–132].
The formation of a stable voluminous network
requires attractive forces between the particles.
Figure 3. Network structure of A) platelike particles
(house-of-cards), B) lath-shaped, and C) spherical particles
Vol. 9
These are the same electrostatic forces that cause
colloidal particles to coagulate and that are at-
tractive only in the presence of salt. The volume
of the aggregate can increase with an increase in
salt concentration above the critical coagulation
concentration because of the enhanced attractive
forces. Divalent counterions strengthen the
forces at the contact points which may increase
the stability and volume of the network. The salt
concentrations required are distinctly lower than
those for monovalent counterions. If the attrac-
tive forces are too strong, the volume-filling
network of particles contracts and fragments,
and distinct aggregates form [134]. Gels can
therefore be formed by increasing salt concen-
tration or by shifting the pH towards the point of
zero charge (see Chapter 6). In the latter case,
silica gels appear homogeneous whereas gels
produced by salt addition show inhomogeneities
[133]. Examples of sol–gel transitions of dis-
persed rod-shaped and needle-shaped boehmite
particles, see [135, 136] and of platelike gibbsite
particles, see [137]. Sol–gel processes are impor-
tant in industrial processes [138–141]. In partic-
ular cases, gels of larger particles can be formed
by depletion (see Chapter 5) of smaller particles
from the gaps between the larger ones [92].
Amorphous silica particles like Aerosil form
networks (Fig. 3) in many water-immiscible or
organic solvents. The particles are held together
by hydrogen bonds and by bridges of water. This
type of network formation is used practically for
thickening organic liquids [15, Chap. 12].
The term gel warrants discussion. Sometimes it
is used as a counterpart to sol (sol ¼ peptized
colloidal particles; gel ¼ coagulated dispersion).
However, coagulated dispersions do not usually
have those properties that one associates with
‘‘gel’’. Thus, gel should be used for voluminous
network structures that possess a certain degree of
stiffness (gel strength). Many hydrophobic col-
loids (SiO2 and Al2O3) form gels under certain
conditions. The voluminous band-type and house-
of-cards structures of the clay minerals show this
property very clearly [132]. Gelation is a general
phenomenon of lyophilic colloids [12].
Many practical applications are very sensitive
to the stability of the dispersion and the type of
aggregates formed [15, 17, 30, 31]. The delicate
adjustment of the stability conditions in paints is
an example (see ! Paints and Coatings, 1. In-
troduction, Chap. 5.). The dispersed pigments in
Colloids 527
paints settle slowly during standing. To avoid
compact sediments, the dispersion must be held
in some kind of flocculated condition, but the
stability parameters must be adjusted so that the
paint can be applied properly. On the other hand,
the formation of thin surface coatings by sedi-
mentation or electrodeposition (insulating films
and fluorescent coatings) demands compact se-
diments. Again, the compactness is adjusted by
varying the stability of the dispersion from which
the coating is obtained.
The widespread uses of clays are based on
their ability to form all types of aqueous and non-
aqueous colloidal systems ranging from highly
fluid dispersions to stiff gels with pronounced
thixotropy [17, 18, 31].
Filterability. The finely subdivided solid mat-
ter of colloidal dispersions cannot be separated
from the dispersion medium by filtration through
usual filters because of the small particle size.
Filter materials are now available with pore
diameters as small as a few nanometers, so that
larger colloidal particles can be retained (colloi-
dal filtration [143, 144]).
The behavior of dispersions of sodium smec-
tite (! Clays) is noteworthy. These dispersions
are difficult to filter, even through filters with
large pores. A thin filter cake forms at the very
beginning of filtration and makes the filter rather
impermeable. The clay mineral platelets become
aggregated parallel to each other and form a
dense sediment. For filtration, the dispersion
must be held in a coagulated or flocculated state,
for instance by adding Ca2þ ions, organic sol-
vents such as ethanol, or small amounts of poly-
meric materials. Flocculation by polyanions is
widely used in the processing of clays [17, 18, 31,
119]. On the other hand, engineering work takes
advantage of the formation of almost imperme-
able clay films to reduce the permeability of
rocks and soils. This ‘‘plastering’’ is also impor-
tant in drilling operations [17, 24, 119].
Sedimentation. When spherical colloidal par-
ticles in dilute dispersions move independently,
they settle under the influence of gravity [9, 23,
114, 143–147]. The particle falls through a dis-
tance h in time t,
18h0 h
t¼ s_ ð1Þ
ðr
r0 Þg d 2
with r, d: density and diameter of the particle,
r0,h0: density and viscosity of the dispersion
528 Colloids
Figure 4. Sedimentation under gravity (A) and under cen-
trifugal forces (B)
medium, and g: gravitational acceleration, 9.81
ms
2 (Fig. 4).
In water, 10-mm quartz particles (r
r0 ¼ 1.65
g cm
3, h0 ¼ 1.001  10
2g cm
1s
1, 20  C)
need t ¼ 18 min 34 s to fall a distance of 10 cm,
1-mm particles need t ¼ 30 h and 57 min. The
sedimentation time of too small particles (< 1 mm
for quartz or clay minerals) becomes so long that
sedimentation is disturbed by Brownian motion.
A centrifugal field must be used for sedimenta-
tion of such particles. The gravitational acceler-
ation in the Stokes equation (Eq. 1) is replaced by
the radial acceleration 4p2w2r ¼ 4p2(U/60)2r,
which can be increased to ca. 103g. The particles
then fall the distance h ¼ r–r0 (Fig. 4) in the
time t [148]:
Kc
t¼ ln r=r0
d2 U 2
where Kc ¼ 18h0602/4p2( r–r0) with U ¼ rpm
(rotations/min) and Kc in s. For U ¼ 5000, r ¼ 12
cm, r0 ¼ 10 cm, the sedimentation times of 0.1-
mm and 0.01-mm quartz particles in water at 20  C
are 12 min 7 s and 20 h 12 min.
The high centrifugal acceleration required for
sedimentation of particles < 0.01 mm in diameter
in reasonable times can only be realized in ultra-
centrifuges, in which the radial acceleration can
easily be increased to 105 g. This instrument is
used extensively for characterization and deter-
mination of the molecular mass of macromole-
cules, particularly those of biological origin such
as proteins, nucleic acids, and viruses.
When the particles are not spherical, the ap-
plication of the above formulas leads to Stokes
equivalent diameters [106, 107]. In the sedimen-
tation of nonspherical particles, the friction
Vol. 9
factor f is larger than that for spherical particles
(f0 ¼ 3 ph0d) and the viscous resistance is
increased. Thus the particles settle more slowly
than spherical particles of the same mass. The
same effect is produced by particle solvation. A
particle containing a given volume of dry mate-
rial has its smallest possible friction factor if it is
an unsolvated sphere [23, 114, 145].
Sedimentation under gravity and in the cen-
trifugal field finds practical application in sepa-
rating particles into fractions of different sizes
and for determination of particle size distribu-
tions. For commercial uses, the fractionation is
often confined to the removal of particles of too
large or too small dimensions. Fractionation by
sedimentation is applied particularly in proces-
sing clay minerals and pigments. Experimental
details for such laboratory techniques as frac-
tionation and determination of particle size dis-
tribution have been described [15, Chap. 6],
[148]. Several ‘‘particle size analyzers’’ are
available, but manual control experiments are
recommended.
Rheological Phenomena. In dilute colloi-
dal systems, the particles move independently of
each other and the system behaves as a Newto-
nian fluid [9]. With increasing particle concen-
tration, a gradual transition from Newtonian to
plastic or pseudoplastic behavior is generally
observed [23, 114, 116, 145, 149]. The transition
occurs when mutual interactions between the
particles become significant. This can be illus-
ð2Þ
trated by dispersions of silica (Aerosil) [149]. At
pH 3 the dispersion exhibits Newtonian flow up
to silica concentrations of ca. 10 wt%, above
which shear thickening at high shear rates and
increasing hysteresis effects are observed. At
pH 9, there is a gradual transition from Newtoni-
an to pseudoplastic flow as the silica content is
increased above 5 wt%. Figure 5 shows a plot of
the plastic viscosity (obtained from the slope of
the linear portion of the shear rate–shear stress
curves) at different pH values as a function of
particle concentration. Near pH 7 the viscosity
increases strongly above a particle concentration
of 8 wt%. At pH 9 and pH 3, higher particle
concentrations are required to obtain dispersions
of high viscosity.
At low pH, the surface charge density of the
silica particles is low (see Chapter 6), and the
particles aggregate to dense flocs [150] with
Vol. 9
Figure 5. Plastic viscosity of silica dispersions at different
pH as a function of solid content [149]
Newtonian flow behavior. Because of the low
surface charge density, the concentration of the
particles can be increased considerably without
significant viscosity changes. At high pH, the
increased negative surface charge density and
electric repulsion prevent the particles from
forming large dense flocs so that the number of
moving particles and small aggregates is in-
creased. This effect and the stronger electric
interaction lead to higher viscosities than those
at pH 3. In the neutral range, the particles interact
strongly through hydrogen bonds and form net-
work structures with considerable increase in
viscosity. The electric repulsion between the
particles is too weak to disrupt the network but
strong enough to prevent the formation of dense
flocs as at pH 3.
It should be noted that the viscosity of silica
dispersions depends on the nature of the silica
(fumed silica such as Aerosil and precipitated
silica such as Kieselgel) and the dispersing pro-
cedure (ultrasonication or not [150]).
The dependence of the viscosity of colloidal
silica dispersions on concentration, pH, and elec-
trolyte or polymer addition is widely used in
practical applications. Fumed silica serves as a
thickening and gelling agent for aqueous and
non-aqueous solvents. In polar solvents the thick-
ening is optimal in the neutral pH range. The
thickening efficiency of silica can be improved
by additives that stabilize the network structure.
Suitable additives for dispersions in unpolar
solvents are water, ethylene glycol, or ethylene
diamine [15, Chap. 12].
Gels are often thixotropic [142]. Thixotropy is
the property of dispersed systems to become
more fluid (lower viscosity) under the influence
Colloids 529
of mechanical forces (stirring, shaking, shearing)
and to regain the higher viscosity at rest. It is
caused by fragmentation of the network structure
by the mechanical forces. At rest, these frag-
ments are pushed into new contact positions by
the Brownian motion of the solvent molecules
and re-aggregate to the volume-filling network.
The process is reversible, the time scale for
stiffening can range from seconds to weeks,
depending on the system and the solid content.
The basic requirement for thixotropic behavior
is therefore a weak, not too strong attraction
between the particles. Thixotropy is required
in many applications, especially in ceramic
production, paints (to avoid sagging), paper coat-
ing, drilling fluids, civil engineering (slurry wall-
ing, underground sealing) but also in
foods (ketchup), cosmetic and pharmaceutical
products [9], [15, Chap. 12], [17, 18, 24–26,
31, 32, 119].
Electrokinetic Phenomena. [151] They are
observed when two phases move relative to each
other under the influence of an electric field.
Electrophoresis describes the motion of charged
particles or droplets in an applied electric field (for
other electrokinetic phenomena see [15, 23, 111,
112, 114, 145, 151]). A thin layer of liquid adheres
to the particle or droplet surface so that the
shearing plane is located anywhere in the liquid.
The potential at the shearing plane is called the
electrokinetic or zeta potential z. Because of the
unknown distance of the shearing plane from the
particle surface, electrokinetic phenomena are
often difficult to interpret.
The mobility u (¼ velocity v of the particles/
electric field strength E) of a particle in an
electric field E depends on the dimensions of the
particle and the atmosphere of counterions
around it, i.e., on ka (see Chapter 5; for details
see [15, 111, 112, 114, 145, 151, 152]):
ka
1.ka
1 (small particles with large diffuse
ionic layers, H€
uckel–Onsager equation)
u ¼ v=E ¼ 2""0 z=3h0 ð3Þ
with e: relative dielectric constant, e0: the electric
field constant, e0 ¼ 8.8541012 As V1 m1,
E: applied electric field strength, in V m1,
h0: viscosity of the dispersion medium, in
Pas ¼ kg m1 s1).
530 Colloids Vol. 9

2. ka  1 (large particles with diffuse ionic
layers much thinner than the particle radius a,
Helmholtz–Smoluchowski equation)
u ¼ v=E ¼ ""0 z=h0
3: 0:1 < ka < 103
Eq. (3) and (4) represent limiting cases (ka  1
or ka  1) for calculating the zeta potential from
mobility data. Henry derived the corresponding
relation for all values of ka:
u ¼ v=E ¼ 2""0 z=3h0 f ðkaÞ
where f(ka) increases in an S-shaped manner
from 1 (ka < 1) to 1.5 (ka  1000) (Table 2).
For conducting particles, f(ka) decreases from 1
(ka < 1) to zero (ka ¼ 1000) [151]. It should be
noted that the Henry relation is valid only for
small zeta potentials ( 25/v mV, v ¼ valency of
the counterion). Henry also calculated the factors
for dielectric cylinders [151].
Table 3 illustrates the applicability of the
Equations (3)–(5) for different particle diameters
and electrolyte concentrations. Usually, particles
between 0.1 mm and 10 mm are observable in
electrophoretic cells so that the Helmholtz–
Smoluchowsky and Henry equations are more
applicable than the H€ uckel–Onsager equation. It
is certainly not correct to calculate in every case a
zeta potential from the mobility by the Helm-
holtz–Smoluchowski equation.
Corrections to these equations can be made to
account for the particle–particle interactions in
Table 2. Values of f(ka) (Eq. 5) for nonconducting colloidal particles
ka f(ka)
0.1 1 H€uckel-Onsager equation
1 1.03
10 1.24
100 1.45
1000 1.5 Helmholtz-Smoluchowski equation
dispersions that contain more than 5 wt% solid
particles [151, Chap. 4]. In such dispersions the
mobility of the particles is reduced, and too small
zeta potentials would be obtained without the
ð4Þ
corrections.
Further corrections are needed for electropho-
retic retardation and relaxation [151, 153–155].
Since the counterions with their hydration shells
tend to move in an opposite direction from the
particles, the movement of the particles is retard-
ed. Furthermore, the double layer must be con-
tinually restored in front of the particle and
ð5Þ dispersed behind the particle. This restoration
takes a finite time (relaxation). The double layer
is therefore shifted somewhat with respect to the
particle and a field is created that opposes the
applied electric field and reduces the mobility.
For practical purposes, the corrections can only
be neglected for low particle concentrations and
small zeta potentials. Retardation is considered
in the above equations but the relaxation effect is
difficult to calculate. The serious consequences
are that for zeta potentials > 25 mV u is no longer
proportional to z for 0.1 < ka < 1000 [15, 153].
The theory of O’BRIAN and WHITE [156] also
reveals the deviation from linearity between u
and z and the mobility as a function of z shows
maxima (depending on ka) at 5 < z <7.
Recently, the influence of surface conduction
on the mobility has become evident [15, Chap.
10], [151, Chap. 4], [157].
The electrokinetic mobility is an important
quantity in colloid chemistry and is a fundamen-
tal property of colloidal particles. It gives impor-
tant information such as the sign of the surface
charge, the way in which the charge changes
when experimental parameters are changed, and
the conditions that establish the isoelectric point.
It responds to the addition of inorganic com-
pounds and monomeric and polymeric organic
materials, thus providing information about the

Table 3. Applicability of the Helmholtz–Smoluchowski, Henry, and H€uckel–Onsager equations (Eqs. 3–5) for determining zeta potentials

Approximate particle diameter (nm) for which the equations are valid

Normality of solution Helmholtz–Smoluchowski Henry H€uckel–Onsager

1 80 0–80 —
0.1 200 0–200 —
0.01 800 1–800 0–1
0.001 1800 2–1800 0–2
0.0001 8000 10–8000 0–10
0.00001 16 000 20–16 000 0–20
Vol. 9 Colloids 531

interaction of the colloid particles with these dispersed particles or droplets tend to reduce the
materials. Mobility measurements can also be large interfacial area by aggregation to a contin-
used for some kinds of quality control. For uous phase. The coarsening process may be slow,
example, commercial TiO2 pigments, both ana- but it is inexorable. If special stabilization me-
tase and rutile, can exhibit isoelectric points chanisms are absent, the particles or droplets
between pH 1 and 7, depending on the way they aggregate spontaneously (Fig. 6). Two mechan-
have been prepared. The variation is caused by isms are known for stabilizing the colloidal state,
adsorption of anions, mainly sulfate and phos- electric stabilization and steric stabilization.
phate anions, which are introduced during indus- Electric stabilization occurs when the surface of
trial production. The isoelectric point of pure the particle or droplet carries an electric charge.
TiO2 (both modifications) is near pH 6.0. Mea- The particles are surrounded by atmospheres of
surements of zeta potentials can also be used to counterions and an electric repulsion is created
obtain information on the flotability of minerals between these atmospheres. As long as the re-
in flotation processes [23, 158, 159]. The yield pulsion VR exceeds the van der Waals attraction
stress of many colloidal dispersions displays a VA between the particles, the colloidal dispersion
linear relationship with the square of the zeta is stable. When the van der Waals attraction
potential [160]. overcomes the electric repulsion, the system
The electrokinetic mobility usually is mea- becomes unstable. This occurs when the concen-
sured by microelectrophoresis and laser-doppler tration of salts added to the dispersion exceeds a
electrophoresis (commercial instruments are critical value.
available). In the 1990s the instrumentation and
theory of the electroacoustic characterization of
colloidal dispersions and emulsions made great
strides. An important advantage is that the dy-
namic mobility can be determined in dispersions
of essentially any concentration above about
1 wt%. Apparatus is available to measure particle
sizes in the range 0.1–10 mm and the zeta poten-
tial of particles down to nanometer dimensions
[109, 110]. The moving boundary method [145,
161–163] is simple and does not require large and
expensive instrumentation. HORN and DITTER
[164] describe a self-made laser interferometer
for mobility measurements of pigment particles
in organic solvents.
Most commercial instruments calculate the
zeta potential from the mobility data by the
Helmholtz–Smoluchowski equation (Eq. 4). As
discussed above, conversion of mobility data
to zeta potentials is not without arbitrariness
[15, 151]. It is recommended to report the
electrokinetic mobility instead of possibly false
zeta potentials, in particular when the zeta
potential is high and the particles are anisometric
or hairy.

5. Colloid Stability
Origin of Colloid Stability. No finely sub-
divided material dispersed in a continuous phase Figure 6. Electrostatic (A) and steric (B) stabilization of
is ever stable in a thermodynamic sense. The colloidal dispersions and emulsions
532 Colloids Vol. 9

The dispersion also becomes unstable when

the surface charge disappears. This occurs when
the concentration of protons or other potential-
determining ions (see Chap. 6) is changed or
when counterions are introduced that are strongly
absorbed.
Long-chain molecules or macromolecules ad-
hering to the particle surface cause steric stabili-
zation. Envelopes of organic matter around the
particles prevent the particles from aggregating.
Such dispersions are often difficult to destabilize
because salts exert little influence. Destabiliza-
tion can be achieved by changing the temperature
or the quality of the solvent, thus changing the
polymer–solvent interaction.
Liquid particles in emulsions have the same
kinds of interactions as solid colloidal particles.
They can be stabilized electrically by surface
charges or sterically by macromolecules (!
Emulsions). Important emulsifiers are nonionic
surfactants like alkyl poly(ethylene oxides). Ion-
ic surfactants are used in combination with non-
ionic surfactants [15, Chap. 7]. Stabilization by
solid particles is one of the pathways that lead to Figure 7. Diffuse ionic layers around and between spherical
emulsions which are generally very stable with- and platelike colloidal particles
out the need of surfactants (Pickering emulsions)
P
[102–104], [165–173]. k2 ¼ F2 v2i ci =""0 RT ½m
2
ð6Þ
3
The Ionic Layer. [15, 98, 111, 112, 114, with the concentration ci in mol/m , vi valency of
145, 151, 174] When particles, for instance, with the ions, F ¼ 96 485.29 As mol
1 and the
a negative surface charge density s0, are dis- dielectric field constant e0 ¼ 8.854  10
12As
persed in a continuous liquid phase with the V
1 m
1, R ¼ 8.315 J K
1 mol
1.
relative dielectric constant e, an electric potential When only one type of salt is present with
y ¼ f(x) develops that decays from y ¼ y0 vþ ¼ v
¼ v (for instance: NaCl, KNO3, MgSO4)
(surface potential) at x ¼ 0 to y ¼ 0 far away P
v2i ci ¼ 2v2 c and k 2 ¼ 2F 2 v2 c=""0 RT ð7Þ
from the surface (x ! ¥) (Fig. 8 and Fig. 18). A
cation (counterion) at position x is then attracted The reciprocal length k is of general importance
by the surface, but the electric force is counter- and is widely used in colloid science instead of
acted by the thermal motion of the ions, and
the distribution of the counterions is determined
by the Boltzmann equation. The concentration
of counterions, therefore, decreases from a
value at x ¼ 0 to the bulk concentration at
x ! ¥ (Fig. 8). Anions (co-ions) are repelled
from the surface.
The counterions and the co-ions are not ar-
ranged in a distinct pattern on the particle surface
but are distributed within an atmosphere sur-
rounding the particle. The dimension of this
Figure 8. Concentration of monovalent counterions (nþ)
diffuse (or Gouy–Chapman) layer can be sub- and co-ions (n
) around platelike particles or large spheres
stantial (Fig. 8). The thickness of the diffuse layer at different electrolyte concentrations (surface potential
is given by 1/k, the Debye–H€ uckel length  50 mV). k in cm
1
Vol. 9 Colloids 533

Table 4. Values of k and 1/k as a function of the electrolyte (vþ ¼ v
¼ 1) lyte concentration, the atmosphere of counter-
concentration
ions is extended, and particles are widely sepa-
Concentration k (m
1) 1/k (nm) rated. Higher electrolyte concentrations com-
(mol/L) press the diffuse layer, and the particles approach
10
5 1.04107 96.2
more closely (Fig. 9). At k ¼ 107 cm
1(c ¼ 10
1
510
5 2.32107 43.1 mol/L, v ¼ 1), the particles can approach to ca. 5
10
4 3.29107 30.4 nm until they ‘‘feel’’ the mutual repulsion.
510
4 7.35107 13.6 The electric repulsion between two particles
10
3 1.04108 9.6
510
3 2.32108 4.3
can be calculated by the approximation:
10
2 3.29108 3.0
510
2 7.35108 1.4 VR ¼ 32pa""0 ðRT=vFÞ2 g 2 e
kH ½J
ð9Þ
10
1 1.04109 0.96
510
1 2.32109 0.43 where H is the nearest distance between two
3.29109
1 0.30
particles (Fig. 7), and the expression for g is
g ¼ ðez=2
1Þ=ðez=2 þ1Þ with z ¼ vFy0 =RT
the concentration. For water e ¼ 78.5 at 25  C) ð10Þ
one obtains with c expressed in mol/L: z ¼ 1!y0 ¼ 25:7 mVðv ¼ 1; 25 CÞ

pffiffiffi
k ¼ 32:87_s108 v c ½m
1
ð8Þ It should be noted that g approaches 1 at higher

5
3
1
For 10 , 10 , and 10 mol/L solutions k is surface potentials (y0  150 mV). The electric
ca. 107, 108, and 109 m
1, respectively (v ¼ 1) repulsion then becomes independent of the sur-
(Table 4). face potential. The electric repulsion is therefore
The reciprocal value 1/k is generally consid-
ered a measure of the thickness of the diffuse
ionic layer. For large or platelike particles, the
potential is reduced to y0/e ¼ 0.37y0 at the
distance x ¼ 1/k from the surface. The ionic
layer extends further into the continuous phase,
and y becomes 0.01 y0 at x ¼ 4.6 1/k.
The extension of the ionic layer is very sensi-
tive to salt addition. This is seen from the varia-
tion of 1/k with the salt concentration (Eq. 6–8).
As the concentration of salt (v ¼ 1) is increased
by a factor of 10 or 100, the thickness of the ionic
layer 1/k is reduced by the factors 0.32 and 0.1,
respectively. At a salt concentration c ¼ 10
5
mol/L, the thickness of the ionic layer is 1/k100
nm. Increasing the concentration to 10
3 and
10
1 mol/L compresses the double layer to 1/
k10 and 1/k1 nm (Table 4).
Polyvalent ions exert a similar effect (Eq. 6–
8). Di- and trivalent ions compress the diffuse
layer thickness by a factor of 2 and 3,
respectively.
Figure 9. Electrostatic repulsion VR between spherical
DLVO Theory. The DLVO theory (DLVO: particles (radius 100 nm) at different electrolyte concentra-
DERJAGUIN, LANDAU, VERWEY, and OVERBEEK) tions,
describes the interplay between electric repul- vþ ¼ v
¼ 1, surface potential:  50 and 100 mV, H: see
sion and van der Waals attraction [15, 23, 111, Fig. 7
112, 114, 145, 151, 174–177]. The compression a) z ¼ 2 (c0  50 mV), k ¼ 105 cm
1 (10
5 mol/L);
b) z ¼ 4 (c0  100 mV), k ¼ 106 cm
1 (10
3 mol/L);
of the double layer has dramatic effects on the c) z ¼ 2 (c0  50 mV), k ¼ 106 cm
1 (10
3 mol/L);
stability of colloidal dispersions. At low electro- d) z ¼ 2 (c0  50 mV), k ¼ 107 cm
1 (10
1 mol/L)
534 Colloids Vol. 9

strongly dependent on the surface potential at

low charge densities but almost independent on
the charge density at high surface potentials.
The van der Waals attraction is nearly inde-
pendent of the salt concentration. A good ap-
proximation for spherical particles [178] is
0 1
A @L HA
VA ¼
þ2ln with L ¼ aþ0:75H ð11Þ
12 H L

The Hamaker constant A is dependent on the

chemical composition of the particles. Typical
values for aqueous dispersions follow [15, 179,
180]:
Metals:
A  ð15
30Þ  10
20 J

Oxides, silicates:
A  ð1
5Þ  10
20 J

Inorganic salts:
A  ð0:3
5Þ  10
20 J

Polymers (latices): Figure 10. Schematic representation of the interactions be-

20
A  ð0:3
1:4Þ  10 J
A more precise value for latices has been re-
ported [181].
The van der Waals attraction decays more
rapidly with particle distance than does the dou-
ble layer repulsion. It becomes operative only
when the double layer is sufficiently compressed
so that the particles can approach closely. Under
these conditions the attraction overcomes the
double layer repulsion, the particles attract each
other and coagulation is initiated. Figure 10
illustrates schematically how the attraction curve
VA (negative sign) and the repulsion curve VR
(positive sign) are superimposed to give the total
interaction curve VT ¼ VA þ VR. With decreas-
ing particle distance, VT increases from a shallow
minimum (secondary minimum) at a great dis-
tance to a maximum and then falls off sharply.
When the particles come into direct contact, Born
repulsion VB prevents further approach. Super-
imposition of VB and VT creates the primary
minimum.
Because the repulsion VR varies with the
salt concentration, VT responds sensitively to
salt addition. Calculated curves are shown in
tween colloidal particles
VR electrostatic repulsion; VA van der Waals attraction; VB
Born repulsion
Figure 11 for latex particles with surface poten-
tials of z ¼ 1 and z ¼ 2. As long as a maximum Vm
separates the secondary and primary minima, the
colloidal dispersion is stable. When Vm is re-
duced below ca. 10 kT, the particles aggregate
and the dispersion becomes unstable. The salt
concentration that initiates this process is the
critical coagulation concentration cK.
If coagulation really occurred at the primary
minimum, it would be impossible to repeptize the
colloidal particles by removing the salt. Howev-
er, the particles rarely come into direct contact as
required for coagulation at the primary mini-
mum. Instead, two or more water layers remain
between the particles, so that the ‘‘distance of
closest approach’’ is larger and the coagulated
particles do not assume the high negative
interaction energies of the primary minimum.
Figure 12 shows that repeptization is then possi-
ble [175, 182].
The above formulas refer to spherical parti-
cles. For platelike particles the energy of repul-
Vol. 9 Colloids 535

Figure 11. VT, VR, and VA for latex dispersions at different concentrations of electrolyte (vþ ¼ v
¼ 1) and surface potentials z
A) z ¼ 2 (c0 ¼ 51.4 mV), Hamaker constant A ¼ 10
20 J; k as cm
1
a) VR, k ¼ 107 (0.1 mol/L); b) VT, k ¼ 107 (0.1 mol/L); c) VT, k ¼ 1.80  107 (0.3 mol/L); d) VT, k ¼ 3.16  107 (0.9 mol/
L); e) VT, k ¼ 4.66  107 (2 mol/L); f) VA
B) z ¼ 1 (c0 ¼ 25.7 mV), Hamaker constant
A ¼ 10
20 J; k as cm
1
a) VT, k ¼ 107 (0.1 mol/L); b) VT, k ¼ 1.47  107 (0.2 mol/L); c) VT, k ¼ 1.80  107 (0.3 mol/L); d) VA

sion can be calculated from the following

expression
VR ¼ 32""0 ðRT=vFÞ2 kg 2 e
2kd ½Jm
2
ð12Þ

The energy of van der Waals attraction is

obtained from
" #
A 1 1 2
VA ¼
þ
ð13Þ
48p d2 ðdþDÞ2 ðdþD=2Þ2

(d, D see Fig. 7) [114, 174–177]. The calculation

Figure 12. Energy diagram leading to coagulation (A) and to procedure for clay minerals is described in detail
repeptization (B) [175] by VAN OLPHEN [119]. See also [134, 183–185].
536 Colloids
Stability Ratio. Whether coarsening of col-
loidal dispersions by coagulation occurs rapidly,
slowly, or hardly at all depends on the forces
between the colloidal particles. In the absence of
repulsion forces, the frequency of Brownian en-
counters determines the rate of coagulation,
which is the maximum rate possible (rapid co-
agulation). Repulsion forces reduce the rate. The
maximum Vm of the interaction curve (Fig. 10)
acts as an activation energy that decreases the
ratio of coagulation [175]. The stability ratio
(stability factor) W is defined as the ratio between
the rate constant (k0) in the absence of repulsion
forces and in their presence (k): W¼ k0/k.
When repulsion forces are absent, k ¼ k0 and
W ¼ 1; then rapid coagulation occurs. Increasing
repulsion decreases the frequency of particle col-
lisions (decreasing k), and W increases. For the
influence of the hydrodynamic effect, see [15,
Chap. 2], [187, 188]. Colloidal dispersions
ð16Þ
are considered stable when W > 105. This corre-
sponds to a maximum of Vm > 15 kT [174, p. 167].
The dependence of W on the energy of inter-
action of two spherical particles (in water, 25  C)
is given by [189]:
ð17Þ
7 2 2
d logW=d logc ¼
2:15_s10 ag =v
(a: particle radius in cm). Equation 14 is very
useful because the surface potential y0 or yd (see
Chapter 6) can be derived easily without knowl-
ð18Þ
edge of the van der Waals interaction parameter
(Hamaker constant).
The dependence of W on the salt concentration
can be measured by a simple photometric proce-
dure [189]. When salt is added to a colloidal
dispersion, the optical density (D ¼ log I0/I)
Figure 13. Experimental determination of the stability ratio W (D optical density) A) Optical density as a function of time at
different salt concentrations; B) and C) log (dt/dD) (from A) and log W (from B) as a function of salt concentration
Vol. 9
increases, as shown schematically in Figure 13.
The increase of D with time at the very early states
of coagulation (initial linear section of the curves
in Figure 13 A) is related to W:
logðdt=dDÞc ¼ logW
K ð15Þ
(K ¼ constant). The values of log W as a function
of log c are obtained when log (d t/d D) is plotted
against log c (Fig. 13 B, C). This method is
widely used for measuring the stability ratio of
colloidal dispersions [15, Chap. 11].
Critical Coagulation Concentration. The
critical coagulation concentration cK is of funda-
mental importance in colloid chemistry. It can be
obtained directly from a series of VT curves
constructed for different salt concentrations.
A useful approximation for spherical particles
is [174, 178]:
cK ¼ 49_s63ð4p""0 Þ3 ðRTÞ5 g 4 =ðF6 A2 v6 Þ½mol=L
A ¼ Hamaker constant (in J); at 25  C, e ¼ 78.5
(water):
cK ¼ 3:837_s10
39 g 4 =ðA2 v6 Þ½mol=L
ð14Þ
Corrections that may be introduced are discussed
in [178].
For platelike particles, the expression is
ck ¼ 8_s308_s10
39 g 4 =ðA2 v6 Þ½mol=L
As discussed before (see ‘‘Stability’’), cK is highly
dependent on the valency v (Schulze–Hardy rule)
[15, Chap. 3]. Equation 16–18 may give the
impression that cK varies with v
6. This is true
for high surface potentials (g ! 1), but does not
Vol. 9
hold at lower surface potentials because v is also
included in g. The critical coagulation concentra-
tion cK then changes with v
5, v
3, or v
2 at
potentials of 100, 50, and 25 mV, respectively
[15, Chap. 3].
Critical coagulation concentrations are gen-
erally measured by two methods [15, Chap. 11].
The test-tube method is simple but sensitive.
Increasing amounts of salt are added to a certain
amount of the colloidal dispersion in a series of
test tubes. The tubes are shaken and then allowed
to stand for a certain time, usually 24 h. By visual
inspection it is determined which dispersions are
stable and which are coagulated. The particle
concentration must be kept low so that formation
of voluminous networks is avoided, concentra-
tions below 0.1 wt% are generally required.
When the stability factor is determined as
described in ‘‘Stability Ratio’’ and Figure 13,
the critical concentration is obtained immediate-
ly as the lowest salt concentration at which log W
becomes zero or has a minimum. The stability of
colloidal dispersions should be studied by both
methods because the experiments are based on
different time scales. The test-tube investigations
reveal the changes that occur over several hours,
whereas the photometric turbidity measurements
record the initial stages of coagulation. Thus,
different critical concentrations are determined
in complex systems by the two methods. The
differences can be helpful in understanding dif-
ferent coagulation processes. The test-tube meth-
od should not be considered obsolete because of
the lack of electronic equipment. It is particularly
recommended for testing industrial products be-
cause it responds sensitively to many experimen-
tal parameters and stability changes can be
detected over long time periods by visual inspec-
tion. When deviations from ‘‘ideal’’ behavior
occur, the test-tube tests provide information that
may not be noticed by other methods.
The critical coagulation concentration is in-
dependent on the particle concentration as
long as the solid content is low, usually
< 0.1 %. It often increases with the particle
concentration, caused by counterion adsorption
on the particle surface (Stern layer) (see ‘‘Coun-
terion Adsorption’’) [15, 190–192].
Selective Coagulation. In particular cases
dispersions of two types of colloidal particles can
be selectively coagulated, i. e. the different parti-
Colloids 537
cles are separated by coagulation (see Chapter 7),
[15, 183, 193, 194]. Colloidally dispersed oxides
may be separated by choosing appropriate pH
values. For example, in quartz–rutile dispersions,
both types of particles are negatively charged at
pH  9.5 but can be separated by making the
dispersion 0.015–0.050 mol/L in NaCl [193].
Non-DLVO forces. In particular cases inter-
actions other than electric repulsion and van der
Waals attraction (DLVO theory) are discussed
[15, 195]: Ion–ion correlation [17, 31, 196, 197],
attractive hydrophobic forces between hydropho-
bic surfaces [198], protrusion forces leading
to repulsion between amphiphilic surfaces in
water [199], and repulsive hydration forces
between hydrophilic surfaces [198–203] ‘‘It
may be fair to say that (the hydration force) is
probably the most important yet the least under-
stood of all forces in liquids’’ (ISRAELACHVILI,
p.281 in [195]).
Steric Stabilization. The stabilizing action
of polymers is significant in many aqueous and
non-aqueous systems. The principles of steric
stabilization are well understood [15, Chap. 4],
[176, 204]. If large molecules or polymers
are absorbed on or bound to the particle surface
(Fig. 14), a repulsion between the particles is
created. When two particles with their envelopes
of organic chains approach, the chains in the gap
between the particles lose conformational entro-
py and resist a further approach (volume restric-
tion effect or entropic stabilization). In any case,
there is also a local increase in concentration of
organic material between the particles (region of
the dotted line, Fig. 14A) and an osmotic effect is
produced that exerts a repulsive force between
the particles (for terminology see [204]). The
osmotic term (mixing term) determines the sta-
bility of the dispersion. The polymer–solvent
interaction is therefore decisive (Table 5). The
dispersion is only stable at better-than-theta con-
dition. In a good solvent, interpenetration of the
chains is disfavored, promoting stabilization.
Conversely, interpenetration is thermodynami-
cally favored in a worse-than-theta-solvent, and
the dispersion is destabilized. Figure 15 illus-
trates how sensitively stability responds to the
polymer–solvent interaction parameter a.
The interaction energy due to steric stabiliza-
tion can be easily calculated by pragmatic formu-
 538 Colloids Vol. 9

Figure 15. Steric interactions as a function of the solvent

parameter a [209]. d0 is the normalized distance H/(r2)1/2
where (r2)1/2 is the root-mean-square end-to-end length of the
polymer coil in solution.
color
fig
Figure 14. Steric (A) and electrosteric (B, C) stabilization.
cal application has been exploited continuously.
Industrial applications now comprise polymer
dispersions, including latices, emulsions of all
lae [205]. However, it is difficult to find the correct types, paints, inks, oils, lubricants, laundry pro-
input data, for instance, the segment density ducts, and many others.
distribution of the macromolecules or the contour Typical requirements for steric stabilization
length of the macromolecular envelope. are as follows:
In several systems, particularly biological
systems, a combination of electric and steric 1. Steric stabilization requires threshold concen-
stabilization occurs when particles carry surface trations of polymers. At low concentrations,
charges or when the adherent macromolecules sensibilization occurs (see ‘‘Polymers’’).
are polycations or polyanions (Fig. 14B, C). 2. The amounts of absorbed polymer required
Steric stabilization has been used by people for stabilization decrease with the molecular
since ancient times (Egyptian ‘‘instant’’ ink, mass of the polymer.
paints, and peptizing agents for clays). Its practi- 3. The macromolecules must be firmly bound to
the surface byadsorptionor grafting[206–208].
4. The interaction between the macromolecules
Table 5. Polymer-solvent interaction parameters and the solvent molecules is decisive. Stable
dispersions require better-than-theta condition.
2nd virial 5. The dispersion becomes unstable and floccu-
coefficient of
Flory-Huggins Expansion osmotic
lates at the theta point (Fig. 15).
parameter factora pressure 6. Change of temperature can favor or disfavor
steric stabilization and therefore stabilize or
Worse-than-theta c >0.5 a<1 B<0
Theta point c ¼ 0.5 a¼1 B¼0 destabilize the dispersion (cf. Table 5).
Better-than-theta c < 0.5 1 < a < 1.5 B>0 7. The dispersions can only be destabilized by
a
a ¼ root mean square end-to-end length of the polymer coil in changing the theta-condition, i.e. the temper-
solution/root mean square end-to-end length at the theta point ature or the quality of the solvent.
Vol. 9
8. Destabilization is generally reversible; chang-
ing the temperature or the quality of the
solvent leads to redispersion and stabilization.
Steric stabilization is widely exploited in indus-
trial processes [210] because of the following
advantages:
1. Sterically stabilized dispersions are relatively
insensitive to electrolytes.
2. Flocculation (destabilization) is generally re-
versible; the particles are redispersed by ad-
dition of a good (better-than-theta) solvent.
Even after drying, the particles redisperse in a
good solvent.
3. Steric stabilization at high concentration of
solid materials does not produce a comparable
increase in viscosity, as occurs in electric
stabilization. In the latter case, gels of consid-
erable strength are often formed.
4. Whereas electric stabilization is less effective
in non-aqueous dispersion media, steric sta-
bilization can be as effective in aqueous as in
non-aqueous solvents. Steric stabilization is
therefore the preferred method of stabilization
in organic solvents.
Steric stabilizers for industrial products are
found empirically. Amphipatic block or graft
copolymers are widely used as steric stabilizers.
They are made up of monomer units that anchor
the polymer to the particle and other units that
provide stabilization. The anchor unit is one that
would not be soluble in the dispersion medium
and that has affinity for the particle surface. The
stabilizing unit is one that would be soluble in
the medium and that imparts mutual repulsion to
the dispersed particles. For example, aqueous
dispersions can be stabilized by styrene/ethylene
oxide block copolymers in which the styrene
units act as the anchor and the ethylene oxide
units provide stabilization. Conversely, a non-
aqueous dispersion is stabilized by styrene/acry-
lonitrile copolymers in which the acrylonitrile
units provide the anchor and the styrene units
provide stabilization.
Depletion Effects. Dissolved, non-adsorb-
able macromolecules can destabilize colloidal
dispersions by depletion effects [15, Chap. 4],
[211, 212]. The surface of the dispersed particles
is surrounded by a depletion zone of thickness D
Colloids 539
in which the polymer concentration is smaller
than in the bulk. The reason is that the reduced
conformational entropy of non-adsorbable
macromolecules at the surface is not compensat-
ed by the adsorption enthalpy. When the particle
distance H becomes smaller than 2D (Fig. 16), the
macromolecules are displaced from between the
particles. Solvent molecules also leave the inter-
particle space, so that H decreases, DG becomes
more negative, and the colloidal dispersion is
destabilized by phase separation or flocculation,
although the solvent is a better-than-theta-sol-
vent for the dissolved macromolecules [213,
214]. The theory claims that in certain cases
restabilization can occur at very high polymer
concentrations [205, 211, 214]. The typical form
of the potential curve is shown in Figure 16. The
depletion interaction energy can be calculated by
pragmatic formulae [205, 215, 216].
Many systems, particularly practical disper-
sions like latex dispersions contain particles
surrounded by macromolecules and dissolved
polymers, and both steric stabilization and
depletion effects have to be considered. Also,
electric stabilization can be relevant. Stability
diagrams are calculated from the corresponding
Figure 16. Depletion interaction. The macromolecules leave
the space between two approaching particles when the dis-
tance H is smaller than 2 D; the particle – particle interaction
becomes attractive. f2 is the polymer concentration between
the particles, D is the thickness of the depletion zone [205];
from [15]
The curve shows the depletion potential Vdep as a function
of H.
540 Colloids Vol. 9

equations by assuming the different interactions

(electric, van der Waals, steric, depletion) to be
additive, which may not always be the case. For
examples of such calculations see [217–221].

6. Factors Controlling Colloid

Stability
Surface Charge. The imperative require-
ment for electric stabilization is the presence of
electric charges on the particle surface. There are
several mechanisms for producing these charges:

1. In many silicates, including clay minerals and

zeolites, isomorphous substitutions (most
common is Al3þ for Si4þ) and cation vacan-
cies produce negative surface charges. The
surface charge density is invariantly deter-
mined by the substitutions and vacancies and
does not change with experimental conditions
(concentration, pH, etc.).
2. Oxides like SiO2, Al2O3, Fe2O3, and TiO2
carry OH groups on the surface that can
dissociate or adsorb protons. Silanol groups,
for instance, are protonated at very low pH
(< 2) and the surface is positively charged.
With increasing pH, the surface charge density
decreases and becomes increasingly negative
above the point of zero charge (pzc) because of
the dissociation of silanol groups (Fig. 17).
Analogously, SH groups impart surface
charges to colloidal sulfides. In both cases the
surface charge density changes with pH.
3. Sparingly soluble salts such as silver iodide
may have an excess of Agþ or I
ions on the
surface depending on the Agþ or I
concen-
trations in the solution. (The concentrations of
Agþ and I
ions in solution are related to
each other by the solubility product L: pAg þ
pI ¼ pL ¼ 16). The silver and iodide ions act
as potential-determining ions; thus AgI par-
ticles are positively charged at Agþ concen-
trations above the pzc (at pAg0 ¼ 6) and are
negatively charged at Agþ concentrations
below pAg0 ¼ 6.
4. Colloidal metal particles are usually charged
by absorption of ions, for instance Cl
and
citrate anions on Au and Pt particles [15, 35].
5. Commonly, latex particles carry –SO4H,
–SO3H or –COOH groups on the surface. Sul-
fate and sulfonate groups dissociate the proton
Figure 17. Variation of surface charge of oxides with pH
in 0.1 mol/L (- - - -) and 1 mol/L KCl (—) solutions at 20  C
a) Precipitated silica [222]; b) TiO2 [223]; c) Hematite
[223]
at low pH so that in pH ranges of practical
applications the surface charge density is in-
variant with pH. The weakly acidic –COOH
groups dissociate at pH > 4, so that the surface
charge increases considerably at pH > 4.
Consequences of Surface Charge
Changes. Above several systems are described
in which the surface charge density changes with
experimental conditions (pH and concentration
of potential-determining ions). When parameters
are chosen so that the particle charge disappears
(point of zero charge), the dispersion becomes
unstable and coagulates. The stability factor has a
sharp minimum (cf. Fig. 32A) because the sur-
face is recharged by crossing the pzc, and the
system restabilizes. Thus, small pH changes near
the pzc can have dramatic effects on the stability
of colloidal dispersions.
Counterion Adsorption. The simplest
model, developed by STERN (1924), assumes that
the number of ions adsorbed on a particle surface
is restricted by their size (including their hydra-
tion or solvation shell). The adsorption of the
counterions basically is determined by electric
Vol. 9
Figure 18. Stern layer and diffuse ionic layer around colloi-
dal particles
interactions with the surface charges. In addition,
specific adsorption (as defined by LYKLEMA) can
occur as the consequence of chemical and entro-
pic contributions [8, Chap. 9,], [151, 225–227,
192, 228–232]. The aqueous part of the ionic
layer is divided into a Stern layer and a diffuse or
Gouy–Chapman layer. The ‘‘Stern surface’’ is
drawn through the centers of the ions that are
assumed to be adsorbed on the particle surface;
the potential is assumed to decrease linearly from
y0 at the particle surface to yd at the Stern
surface and then exponentially in the diffuse
layer (Fig. 18).
The thickness of the Stern layer is usually
assumed to be about 0.4 nm (two water layers).
Some generalizations can be made:
1. For an appropriate discussion of colloid sta-
bility it is mandatory to include Stern layers.
In many cases not only electric but also
chemical and entropic contributions have to
be considered [230].
2. The existence of the Stern layer does not
invalidate the expressions for the diffuse part
of the double layer. The double layer inter-
actions are determined by the Stern potential
yd. This potential has to be used instead of y0
in Equations 9, 10, 12, 14, 16, 17, 18.
3. When the adsorption in the Stern layer in-
creases, yd is reduced and the interparticle
repulsion is diminished. In the limiting case
where the counterions are strongly absorbed,
yd  0, and the system becomes unstable.
4. As the electrolyte concentration increases,
adsorption in the Stern layer increases and
Colloids 541
reduces yd, even if specific interactions are
absent.
5. yd varies only slightly with the energy of
specific interactions until this energy is rela-
tively large.
6. LYKLEMA and DUVAL [230] have shown that
the interaction of constant diffuse double
layer potential or – charge works only at
larger distances of separation. At smaller
distances charge regulation (the charge den-
sity changes with the distance between the
particles) has to be considered.
Several other models were developed to de-
scribe the behavior of the ions at the surface [15,
Chap. 9], [151]. The triple-layer model is often
used. On the basis of such models, equilibrium
constants of the reactions of the surface groups
were evaluated from potentiometric titrations.
However, these values should be considered
cautiously [228, 233].
Solvent Effects. Solvent parameters are of
decisive importance for sterically stabilized sys-
tems (see ‘‘Steric Stabilization’’). This section
describes the changes that occur when, under
conditions of electric stabilization, water is re-
placed by or mixed with polar organic solvents. A
dependence of the critical coagulation concentra-
tion on the relative dielectric constant e is gener-
ally observed but does not follow the relation cK 
e3 as required by Equation (16) [186, 234, 235].
The principal effect of organic solvents (with
e < 80) is to press the counterions into the Stern
layer, thus reducing yd and the stability of the
dispersion toward salts. The effect can be quite
strong for multivalent counterions. In an extreme
case, ‘‘equivalent coagulation’’ occurs [235].
When the di- or trivalent counterions are added
to the dispersion, the surface charges are neutral-
ized, the particles become uncharged and the
dispersion coagulates. The critical counterion
concentration is then distinctly lower than that
for coagulation by compression of the double
layer and decreases with the concentration of the
particles.
In some cases, high content of organic solvent
suppresses the dissociation of the surface groups
and the surface remains almost uncharged. Very
low concentrations of monovalent counterions
then coagulate the dispersion ( 0.001 mol/L for
Ag and a-FeO(OH) particles in acetone [235]).
542 Colloids
The effect of organic solvents is therefore not
sufficiently described by changes in the dielectric
constant. For instance, isopropanol and acetone
affect the colloid stability more strongly than
methanol and ethanol although their dielectric
constants are not much lower. The effect of the
organic solvent on the structure of the continuous
phase, on the dissociation of surface groups, and
on the solvation of the ions and their distribution
between the Stern and the diffuse layer are
important to the stability of dispersions in organ-
ic solvents or their mixtures with water.
Stabilization by charges can also occur in
unpolar solvents [15, Chap. 2]. As the concentra-
tion of charges is extremely low in such solvents,
k is very small (Eqs. 6–8) and the ionic layer very
large, that is, the potential decreases very slowly
with increasing distance from the surface. There-
fore, high zeta potentials are often observed in
such dispersions.
Effect of pH. Changes in pH can consider-
ably influence the stability of colloidal disper-
sions when the surface charge density is pH-
dependent. This is particularly true for oxides,
sulfides, and latices with surface COOH groups.
The influence of pH on the stability of PTFE latex
dispersions is illustrated in Figure 19. Because of
Figure 19. Stability ratio of PTFE latex as a function of pH in NaCl solutions [224]
Vol. 9
the increased surface charge density the disper-
sion tolerates a tenfold higher salt concentration
at pH ¼ 5.8 than at pH < 2.5 before becoming
destabilized. The behavior of TiO2 dispersions is
shown as a further example (Fig. 21). The coun-
terions are anions at pH below the zero point of
charge, and cations at pH > 3. The above-men-
tioned influence of the ions of homologous series
is clearly evident.
The influence of pH on the stability of silica
sols is striking (Fig. 20) [236]. The decreasing cK
for NaCl and CaCl2 in the alkaline range is
opposite the behavior expected from Figure 17.
This behavior is important in practical systems
but is not understood completely. Deformation
and decomposition of a hydration layer around
the SiO2 particles by the increased negative
charge density is a plausible explanation.
Repulsive and attractive hydration forces are
discussed in Non-DLVO Forces. It is known
for a long time that aqueous dispersions of small
silica particles (around 10 nm) are completely
stable at low pH. Recently, KOBAYASHI et al.
[238] have shown that additional non-DLVO
repulsive forces may be related to hairy layers
on the silica surface. Smaller deviations from
the DLVO theory are expected for larger par-
ticles. The increase of the cK values of the TiO2
Vol. 9
Figure 20. Specific ion effects for the coagulation of rutile
(TiO2) dispersions: the critical coagulation concentration cK
as a function of pH. At pH < 3 anions are the counterions; at
pH > 3 cations are the counterions [237]; from [15]
dispersions in the presence of alkali metal ions
(Fig. 21) is not as strong as would be expected
from Fig. 17, and this may be for similar reasons.
The flow behavior (viscosity, yield value) of
dispersed oxides is also pH-dependent. Both
properties often show maximum values at the
Figure 21. Dependence of the critical coagulation concen-
tration cK on pH for silica sol (Ludox sol, 0.2 g SiO2 /100 mL)
[236]
Colloids 543
point of zero charge (Fig. 22) [239, 240] because
the disappearance of the electric repulsion pro-
motes aggregation of the particles. This behavior
is very important for practical applications. Some-
times, undesirable thickening or thinning of dis-
persions can be reduced by changing the pH. The
viscosity and yield value at a given pH can also be
decreased by adsorption of appropriate anions.
Adsorption of polyacrylate, for instance, shifts the
maximum yield value of ZrO2 dispersions to
lower pH values (Fig. 23). Similar changes were
observed with many other anions (phosphate,
citrate, benzenecarboxylic acids, etc.) [241].
Multivalent Ions. [229] Colloidal systems
respond very sensitively to multivalent cations
(Schulze–Hardy rule). Aluminum and iron ions
are thus the preferable counterions for coagulat-
ing colloidal systems. Multivalent cations, in
particular tri-and tetravalent ions, can influence
the colloid stability in a way different from the
behavior expected from the Schulze–Hardy rule
for v ¼ 3 or 4:
1. First, aqueous solutions of these cations are
acidic and change the pH of the system, so that
pH effects as described can occur, in particu-
lar when the pH is near pzc.
2. Hydrated multivalent cations condense to
form oligo- and polymeric complexes with
a high charge, which decreases the stability
[242, 243]. The stepwise decreasing critical
concentration of aluminum sulfate and nitrate
at pH 4–5 in AgI dispersions is explained on
this basis [236].
3. The specific adsorption of counterions in the
Stern layer is more pronounced for multiva-
lent ions than for monovalent ones. In extreme
cases, the surface charges are neutralized by
the multivalent counterions so that the system
reacts very sensitively to such ions (‘‘equiva-
lent coagulation’’ see Solvent Effects).
4. An excess of multivalent counterions on the
surface recharges the surface, for instance for
a molar exchange of monovalent by divalent
cations:
544 Colloids Vol. 9

Figure 22. Yield value t 0 of some dispersions as a function of pH at 25  C a) Alumina (Type C, Degussa, solid content
10 wt %). b) Titania (P25, Degussa, 7.5 wt %). c) Silica (Aerosil 200, Degussa, 8 wt %) [239]; from [15]

Thus when increasing amounts of multivalent

ions are added to a dispersion, the system can
pass from stabilization to destabilization (charge
neutralization) and again to stabilization (rechar-
ging). Recharging and restabilization of SiO2
sols with increasing concentrations of La3þ are
perceptible in Figure 20. One might expect that
recharging by aluminum salts is optimal at low
pH when Al3þ ions are present. Figure 24, how-

Figure 24. Zeta potential of PVC latex (0.003 wt %) as a

Figure 23. Yield value t0 of ZrO2 dispersions in the presence function of pH in the absence and presence of Al(NO3)3
of polyacrylic acid (M ¼ 2000) as a function of pH. m ¼ (Arrows indicate the isoelectric points. All systems contained
amount of polymer (g/100 g ZrO2) [241]; from [15] 110
3 mol/L NaNO3.) [236]
Vol. 9 Colloids 545

Surface Active Agents. Surfactants with

counterionic charge are strongly adsorbed at the
particle surface [245]. Charge neutralization
(yd ¼ 0) with rapid destabilization of the colloidal
system requires specific concentrations because
recharching and restabilization can take place by
adsorption of an excess of surfactant ions together
with their counterions (Fig. 26). This process is
promoted by the tendency of the long-chain ions
to aggregate to monomolecular or bimolecular
films. In the case of low surface charge densities,
the surfactants form small surface aggregates
Figure 25. Dependence of zeta potential on pH in the
presence of hydrolyzable multivalent metal cations of con-
[246]. Adsorption of surfactant counterions on
centration c1 < c2 < c3 A) Oxide in absence of metal cations; oxidic surfaces is often accompanied by charge
B) Colloidal metal hydroxide regulation. For example, after compensation of
The dispersion becomes unstable at zeta potentials lying the positive surface charges by surfactant anions,
between the dotted lines [244]; from [15]
adsorption of further anionic surfactants causes
the adsorption of protons by surface OH groups,
so that the density of the positive surface charges
ever, shows that recharging occurs at higher pH
(pH 4–5, depending on the aluminum salt con-
centration). It is assumed that recharging is
brought about by the adsorption of ‘‘hydrolyzed
metal ions’’ (correctly: poly(hydroxo metal)
ions) [236]. At higher pH precipitation of the
metal oxyhydroxide or hydroxide is initiated.
Surface precipitation usually occurs under con-
ditions different from precipitation in homoge-
neous solution. As a consequence of surface
reactions, the zeta potential can change in a
complex manner (Fig. 25) [244].
Poly(hydroxo metal) cations can also stabilize
colloidal dispersions by a mechanism different
from recharging when the adsorption of the poly
(hydroxo metal) cations causes a shift of the
charge carrying surface over some distance into
the solution [136].
Multivalent anions (e.g., sulfate, phosphate,
oxalate) are often strongly adsorbed by oxides or
incorporated into the surface instead of oxygen or
hydroxyl ions with considerable changes of the
pzc [237].

Complexing Agents. [46, 229, 236] Com-

plexing of countercations by anions often causes
antagonistic effects. Thus, fluoride and sulfate
ions (at pH < 4) can decrease the coagulation
power of aluminum ions (increasing cK). An
opposite effect is observed when the counterions
are adsorbed as complexes. Addition of small
amounts of complexing agents can then decrease
the cK by orders of magnitude.
Figure 26. Adsorption of surfactant counterions at hydro-
philic surfaces A) charge neutralization; B), C) Recharging by
an excess of surfactant counterions at high (B) and low (C)
surface charge density; D) Adsorption of surfactant cations on
the positively charged TiO2 surface in the presence of sulfate
ions [246], [248], [249].
546 Colloids
increases and the zero point of charge increases
with increasing pH [247].
The charge reversal by adsorption of alky-
lammonium ions on quartz is illustrated in
Figure 27. Longer alkyl chains shift the pzc to
lower surfactant concentrations by orders of
magnitude. The effect of a particular surfactant
depends on pH, which determines whether the
surface of the oxide is positively or negatively
charged. Thus, dodecyl sulfate causes charge
reversal and restabilization of Al2O3 sols only
at a pH below the pzc of pure Al2O3 sols (pH < 8)
when the surface is positively charged. The
importance of the way in which oxides are pro-
duced industrially can be exemplified by TiO2.
TiO2 prepared in the absence of sulfate or phos-
Figure 27. Influence of salts and surfactants on the zeta
potential A) Ammonium acetate (- - -) and alkylammonium
acetates (—) of various chain lengths on quartz (n of alky-
lammonium ions Cn H2nþ1 NHþ
3 as indicated) [25];
B) Sodium chloride (- - -) and dodecylsulfate (—) on corun-
dum at different pH [251]
Vol. 9
phate ions adsorbs tetradecylpyridinium ions
only at pH > 5. In the presence of sulfate ions,
which are strongly held on the surface, the sur-
factant is adsorbed throughout the whole pH
range, with a minimum at pH  6, and a complex
surfactant layer is formed Fig. 26 [248, 249].
Core-Shell Particles. Core-shell particles
can show enhanced colloidal stability due to
reduced van der Waals interaction when the
Hamaker constant of the shell As approximates
the Hamaker constant Am of the medium because
the total Hamaker constant [15, 252] is
pffiffiffiffiffi pffiffiffiffiffiffi
A ¼ ð As
Am Þ2 ð19Þ
The difference between As and Am will be small
when loosely packed hairy layers around the core
of the particles form lyospheres of the solvent, as
in the case of hairy latex particles or small silica
particles (see ‘‘Effect of pH’’). Similar effects are
observed for dispersions in mixed solvents when
one component is enriched on the surface
[253–256].
Polymers. Polymers influence the stability
of colloid dispersions in different ways (Fig. 28)
[15, Chap. 4], [98], [204], [245]. Usually, low
concentrations of macromolecules decrease the
stability of colloidal dispersions (sensibilization)
whereas higher concentrations stabilize the col-
loidal state, in many cases in extreme ways. The
stability factor W as a function of polymer con-
centration proceeds through a minimum that
indicates the highest degree of sensibilization
(Fig. 29). Besides the stabilization effect, the
adsorption of polymers can change the behavior
of the systems to salts. PVA-stabilized silica
responds sensitively to Na2SO4 and KCl but is
not coagulated by CaCl2 [257].
Sensibilization at low polymer concentration
is brought about by charge neutralization or by
macromolecules bridging between the particles.
Charge neutralization can occur site by site (each
polyion charge compensates a surface charge)
(Fig. 30A) or patchwise (Fig. 30C). In this case
the total charge of the adsorbed polyions is equal
to the total surface charge but the macromole-
cules are not equally distributed on the surface so
that domains with positive and negative excess
charge are formed. Electric attraction can occur
Vol. 9
Figure 28. Stabilization and destabilization of colloidal dispersions by macromolecules [204]
between a domain on one particle and a domain
of opposite excess charge of a neighboring
particle.
To bridge the particles (Fig. 30B), the mac-
romolecular charge must not be opposite to the
surface charge; it is only required that the mac-
romolecule can attach itself at some sites at the
surface so that large parts of the macromolecule
remain free to form bridges between different
particles. Practical applications prefer sensibili-
zation by particle bridging because charge
neutralization requires a careful adjustment of
parameters to prevent charge reversal and resta-
bilization. Polyanions are therefore widely
used as flocculating agents for clay materials
[17, 18, 31, 258].
Figure 29. Variation of the stability ratio with the concen-
tration of polymers
Colloids 547
Formation of flocs by polymer addition can
retard the adsorption equilibrium because sol-
vent remains trapped within the flocs. The
amounts adsorbed then depend on the manner
of mixing, stirring, shaking, etc., and reproduc-
ibility of the measurement can be poor [259].
Stabilization at higher polymer concentra-
tions is caused by steric stabilization. This pro-
cess is often the only process that allows
stabilization in non-aqueous solvents.
With highly anisometric particles the sensi-
bilization region can be preceded by a stabiliza-
tion region at very low polymer concentrations so
Figure 30. Destabilization of colloidal dispersions by
macromolecules A) Flocculation by charge compensation;
B) Bridging flocculation; C) Flocculation by charge pattern
interactions (mosaic model). The domains with adsorbed
polycations receive a positive excess charge, which is com-
pensated by the negative charge of the uncovered surface
patches
548 Colloids
that, with increasing polymer concentration, the
sequence stabilization ! sensibilization ! sta-
bilization is observed as shown for the interaction
of polyacrylamide with kaolinite [260].
Mechanical Effects. In laboratory experi-
ments, colloid stability usually is measured under
perikinetic conditions, that is, the particles col-
lide owing to the Brownian motion of the solvent
molecules. In practical applications, the disper-
sions are shaken, stirred, or transferred by pump-
ing. The mechanical forces intensify the particle
flux, which depends on the third power of the
collision diameter of the particles [145]. Ortho-
kinetic aggregation is therefore more important
for larger than for smaller particles. Thus, ortho-
kinetic destabilization can be very effective
for emulsions.
Under orthokinetic conditions, hydrodynamic
forces are in interplay with the forces between the
colloidal particles [15, Chap. 3], [261–266]. It is
difficult to predict the behavior of colloidal dis-
persions under shear. The stability and destabi-
lity regions depend on the rate of shear, the
particle size and size distribution, and the inter-
particle forces in a complicated way. Even small
changes in parameters can strongly influence
stability at low and high shear rates. A calculated
diagram is shown in Figure 31. The dispersion is
unstable (log W < 5) at low but also at high shear
rates. At low shear rates the dispersion coagulates
in the secondary minimum (see Fig. 10), at high
shear rates in the primary minimum [267]. In
many technical processes coagulation occurs
under turbulent flow but not much is known about
this process [262].
Figure 31. Influence of shearing on colloid stability. Stabili-
ty factor W versus rate of shear for particles of 1 and 10 mm
diameter. Stern potential 25 mV, k ¼ 108 m
1, Hamaker
constant A ¼ 10
20 J [267]; from [15]
Vol. 9
Stability against shearing plays an important
role in industrial processes such as coating and
production of thin-layer ceramic films. Further,
dispersions should not destabilize during shaking
(transport), stirring, or pumping. Sometimes, a
dispersion is stable for years but coagulates in a
short time on shearing. Because of the compli-
cated dependence on the particle size, two latex
dispersions with different particle sizes can be
stable against shearing but the mixture can be
unstable. To avoid undesirable shear coagulation
the stabilization mechanisms, particle shape, size
and size distribution and the chemical parameters
(pH, salt content, presence of organic com-
pounds) must be critically evaluated. Dispersions
of oxides often coagulate under shear when pH is
near the zero point of charge (see ‘‘Effect of pH’’).
Adsorbed stabilizer ions or macromolecules
can be desorbed by shearing. Emulgator mole-
cules can be removed from the surface of latex
particles by centrifugation [15, Chap. 6] which
reduces the stability of the dispersions.
Shearing can change the structure of adsorbed
macromolecules, and this can also reduce stabil-
ity. OTSUBO and WATANABE [268, 269] observed,
at low shear rates, a stepwise increase of the
viscosity of silica particles stabilized by adsorbed
polyacrylamide. Depending on the molecular
mass, the solvency of the solvent, the solid mass
content, and the particle size, macromolecular
bridges were formed between colliding particles
during shearing and increased the viscosity.
Macromolecules which are desorbed by
shearing can cause flocculation by depletion
effects.
Temperature Effects. Temperature effects
are most pronounced for sterically stabilized
systems. It depends on the type of stabilization
— mainly enthalpic or mainly entropic — wheth-
er a dispersion flocculates on cooling or heating.
When enthalpy effects dominate, the system
flocculates on heating. If entropic effects are
important, the sol flocculates on cooling. Exam-
ples of water-in-oil and oil-in-water emulsions
are given in Table 6 [270]. Every sterically
stabilized system flocculates under theta-condi-
tions and at the theta-temperature (see ‘‘Steric
Stabilization’’) [15, Chap. 4], [204].
Electrically stabilized dispersions are not very
sensitive to temperature provided structural
changes do not occur. When such changes take
Vol. 9 Colloids 549

Table 6. Effect of the stabilizing moieties on emulsion stability [270]

Type of Stabilizing Anchor Dispersed Dispersion Flocculation Type of Critical flocc. Q-Temp., K
emulsion moiety polymer phase medium on stabilization temp., K

O/W PEO PVAc toluene 0.39 M MgSO4 heating enthalpic 318 318
O/W PVA PVAc toluene 2 M NaCl heating enthalpic 297 299
O/W PAM PVAc toluene 2.1 M (NH4)2SO4 cooling entropic 297 298
O/W PAA PVAc toluene 0.2 M HCl cooling entropic 298 287
W/O PLM PAA water n-pentanol cooling entropic 301 303
W/O PS PEO water cyclohexane cooling entropic 308 307
PEO ¼ Poly(ethylene oxide); PVA ¼ Poly(vinyl alcohol); PAM ¼ Poly(acrylamide);
PAA ¼ Poly(acrylic acid); PLM ¼ Poly(lauryl methacrylate); PS ¼ Polystyrene;
PVAc ¼ Poly(vinyl acetate)

place, the dispersion becomes sensitive to tem-
perature and can destabilize within a narrow
temperature range. Thermosensitive poly(N-iso-
propyl acrylamide) latices (NIPAM latices) were
studied in detail [57–60, 271–273]. The van der
Waals attraction increases when the particles
shrink above 30  C and reduce the stability of
the dispersion [274]. Temperature sensitivity can
also be attained by choosing as counterions
complex ions that decompose at higher tempera-
ture, for instance [SiF6 ]2
counterions.
7. Heterocoagulation
The calculation of hetero-interactions refers to
particles of different surface charge density, may
be of the same sign or of opposite signs, for
instance mixed dispersions of oxides of different
pzc. Calculations [15, Chap. 2], [275, 276] led to
the surprising results that in certain cases the
interaction between particles with the same sign
of charge can be attractive without considering
the van der Waals force and repulsive when the
surface charges have opposite signs. Some ex-
perimental observations support this conclusion
[15, 230]. LYKLEMA and DUVAL [230] have re-
cently shown that transition from long-range
repulsion to short-range attraction can occur for
hetero-interaction as a consequence of charge
regulation (see ‘‘Counterion Adsorption’’).
If the different particles carry opposite surface
charges, heterocoagulation occurs in specific pH
ranges. This is illustrated for TiO2–Al2O3 dis-
persions in Figure 32 A. At any pH between the
pzc of TiO2 and Al2O3, the TiO2 particles are
negatively charged whereas the Al2O3 particles
are positive, and heterocoagulation takes place.
Thus, TiO2 can be selectively separated from
mixed dispersions only at a pH below the pzc of
TiO2 and, correspondingly, Al2O3 above the pzc
of Al2O3. Experimental observations (Fig. 32B,
[277]) confirm the expected behavior, but only if
coagulation is initiated immediately after the
TiO2 and Al2O3 dispersions are mixed. If the
mixed dispersion is allowed to stand before
coagulation, it behaves like a pure Al2O3 disper-
sion. Soluble aluminum species are adsorbed by
the TiO2 particles, so that the particles become
coated by Al2O3 and behave like Al2O3 particles.
This example demonstrates that the stability of a
colloidal dispersion of two or more different
particles can be considerably affected by the
adsorption of soluble species. RASA et al.
[278] described recharging of negative silica
particles by poly(hydroxo aluminum) ions (not
‘‘aluminate ions’’!) desorbed from positively
charged alumina-silica particles.
When aluminum nitrate is added to a PVC
latex, distinct regions of stabilization and desta-
bilization are observed (Fig. 33, [279, 280]).
Since the anionic PVC latex has the isoelectric
point at pH 3, domains a and g represent stable
negative sols of PVC (a) and PVC þ Al2O3 (g). In
domain b the latex particles are coagulated by
Al3þ ions. In region f, the latex particles absorb
poly(hydroxo aluminum) ions (‘‘hydrolyzed alu-
minum ions’’), become positively charged (re-
charging, cf. Fig. 24), and form a stable disper-
sion. In region c, PVC and Al2O3 coprecipitate,
probably because recharging of the PVC latex
ceases (cf. [244]) so that heterocoagulation oc-
curs between negative PVC and positive Al2O3
particles.
Heterocoagulation has also been studied with
amphoteric latices [281]. By variation of the ratio
of –COOH and –NH2 groups, latices with a
different pzc can be prepared. The stability ratio
550 Colloids Vol. 9

Figure 33. Stability diagram of a PVC latex (0.005 g/100 ml)

in presence of Al(NO)3; (- - -) variation of point of zero
charge; (   ) precipitation boundary of aluminum hydrox-
ide; a) – g) see text [280]

of mixtures of latices with a different pzc follows

the theoretical prediction. The behavior of nega-
tive latices in the presence of negative ampho-
teric latices toward salts exhibits some interest-
ing features. The negative latex appears to be
more easily coagulated in the presence of a
negative amphoteric sol.
In practical applications heterocoagulation
can occur during mixing of two different types
of dispersions. To obtain a stable mixture, one
kind of particle must be recharged by addition of
suitable compounds like trivalent metal ions,
complexed metal ions, or ionic surfactants.
A novel application of heterocoagulates is the
stabilization of oil-in-water emulsions by clay
minerals and layered double hydroxides without
any surfactant emulsifier [96, 103, 104, 166, 173].

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Figure 32. Coagulation of Al2O3– TiO2 dispersions
A) Variation of surface potential and stability ratio with
pH, schematically (—pure sols, – – – Al2O3– TiO2 sol);
B) Experimental results in 10
4 mol/L KNO3 at 15 s and
24 h after mixing [277]
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Further Reading
K. S. Birdi (ed.): Handbook of Surface and Colloid Chemis-
try, 3rd ed., CRC Press, Boca Raton 2009.
T. Cosgrove (ed.): Colloid Science, 2nd ed., Wiley, Chiche-
ster 2010.
J. W. Goodwin: Colloids and Interfaces with Surfactants and
Polymers, 2nd ed., Wiley, Chichester 2009.
L. L. Schramm: Colloids, ‘‘Kirk Othmer Encyclopedia of
Chemical Technology’’, 5th ed., vol. 7, p. 271–303, John
Wiley & Sons, Hoboken, NJ, 2004, online: DOI:
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