Mechanism of Cationic Surfactant Adsorption at The Solid-Aqueous Interface

Advances in Colloid and Interface Science
103 (2003) 219–304
Mechanism of cationic surfactant adsorption at

the solid–aqueous interface
R. Atkina, V.S.J. Craigb, E.J. Wanlessc,*, S. Biggsd
a
School of Chemistry, University of Bristol, Cantock’s Close, Bristol BS8 1TS, UK
b
Department of Applied Mathematics, Research School of Physical Sciences and Engineering,
Australian National University, Canberra, ACT 0200, Australia
c
Discipline of Chemistry, School of Environmental and Life Sciences, The University of Newcastle,
Callaghan, NSW 2308, Australia
d
School of Process, Environmental and Materials Engineering, University of Leeds,
Leeds LS2 9JT, UK
Abstract
Until recently, the rapid time scales associated with the formation of an adsorbed surfactant
layer at the solid–aqueous interface has prevented accurate investigation of adsorption
kinetics. This has led to the mechanism of surfactant adsorption being inferred from
thermodynamic data. These explanations have been further hampered by a poor knowledge
of the equilibrium adsorbed surfactant morphology, with the structure often misinterpreted as
simple monolayers or bilayers, rather than the discrete surface aggregates that are present in
many surfactant–substrate systems. This review aims to link accepted equilibrium data with
more recent kinetic and structural information in order to describe the adsorption process for
ionic surfactants. Traditional equilibrium data, such as adsorption isotherms obtained from
depletion approaches, and the most popular methods by which these data are interpreted are
examined. This is followed by a description of the evidence for discrete aggregation on the
substrate, and the morphology of these aggregates. Information gained using techniques such
as atomic force microscopy, fluorescence quenching and neutron reflectivity is then reviewed.
With this knowledge, the kinetic data obtained from relatively new techniques with high
temporal resolution, such as ellipsometry and optical reflectometry, are examined. On this
basis the likely mechanisms of adsorption are proposed.
䊚 2003 Elsevier Science B.V. All rights reserved.
Keywords: Surfactant aggregates; Adsorption to silica; Surfactant adsorption; Adsorption mechanism;
Adsorption kinetics
*Corresponding author. Tel.: q61-2-4921-8846; fax: q61-2-4921-5472.

E-mail addresses: ewanless@mail.newcastle.edu.au (E.J. Wanless),
rob.atkin@bristol.ac.uk (R. Atkin), vince.craig@anu.edu.au (V.S.J. Craig),
s.r.biggs@leeds.ac.uk (S. Biggs).
0001-8686/03/$ - see front matter 䊚 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0001-8686(03)00002-2
220 R. Atkin et al. / Advances in Colloid and Interface Science 103 (2003) 219–304
Contents
1. Introduction ............................................................................................ 221

2. General surfactant and substrate properties ..................................................... 223
2.1. Silica surface chemistry ....................................................................... 223
2.2. Surfactant properties ........................................................................... 225
3. Adsorption isotherms ................................................................................ 225
3.1. Introduction ...................................................................................... 225
3.2. Traditional analysis ............................................................................. 225
3.2.1. The two-step model ..................................................................... 227
3.2.2. The four-region model .................................................................. 229
3.2.3. Similarities between models ........................................................... 230
3.3. The influence of surfactant chain length .................................................. 230
3.4. The role of surface charge ................................................................... 230
3.4.1. Increases in surface charge with adsorption ........................................ 231
3.4.2. The common intersection point ....................................................... 233
3.4.3. Adsorption model based on the cip .................................................. 235
3.4.4. The influence of surface preparation ................................................ 235
3.4.5. Comparison of adsorption mechanisms on raw and acid washed silica ..... 236
3.4.6. Surface charge and gemini surfactant adsorption ................................. 238
3.4.6.1. The importance of the spacer group ........................................... 238
3.4.6.2. Gemini surfactant adsorption isotherms ...................................... 240
3.5. Evidence for discrete aggregation from adsorption isotherms ........................ 242
3.6. Calorimetry ...................................................................................... 243
3.6.1. The importance of surface water ..................................................... 244
3.6.2. Calorimetry and adsorption mechanism ............................................. 244
3.6.3. Interactions between the hydrocarbon tail and the surface ..................... 246
3.7. Summary of adsorption isotherms .......................................................... 247
4. Atomic force microscopy ........................................................................... 248
4.1. Introduction ...................................................................................... 248
4.2. The earliest images of surfactant aggregation: CTAB on graphite .................. 249
4.3. Graphite strongly orientates surfactant aggregates ...................................... 251
4.4. Adsorption studies on mica .................................................................. 251
4.4.1. Alkyltrimethylammonium halides on mica ......................................... 252
4.4.2. The influence of electrolyte on aggregate morphology .......................... 252
4.4.3. Gemini surfactants on mica ............................................................ 253
4.5. Adsorption studies on silica .................................................................. 254
4.5.1. The influence of electrolyte and counterion type ................................. 254
4.5.2. Adsorption kinetics measured by AFM ............................................. 254
4.5.3. The influence of counterion polarisability .......................................... 256
4.5.4. Gemini surfactant aggregates on silica .............................................. 256
4.6. Model hydrophobic substrates ............................................................... 259
4.7. Summary of AFM investigations ........................................................... 262
5. Fluorescence quenching experiments ............................................................. 263
5.1. Introduction ...................................................................................... 263
R. Atkin et al. / Advances in Colloid and Interface Science 103 (2003) 219–304 221
5.2. Time resolved fluorescence quenching .................................................... 264

5.3. Determination of aggregation numbers .................................................... 265
5.4. The earliest fluorescence probe studies .................................................... 265
5.5. Time resolved fluorescence quenching of adsorbed aggregates ...................... 265
5.6. Summary of fluorescence quenching experiments ...................................... 266
6. Reflectance techniques ............................................................................... 268
6.1. Introduction and underlying principles .................................................... 268
6.2. Neutron reflectivity and adsorbed layer structure ....................................... 268
6.2.1. Limitation of NR ......................................................................... 268
6.2.2. Contrast control ........................................................................... 269
6.2.3. NR studies of cationic surfactants on silica ........................................ 269
6.3. Ellipsometry, optical reflectometry and adsorption kinetics............................ 272
6.3.1. Dynamic aspects of surfactant adsorption .......................................... 272
6.3.2. Principles of optical techniques ....................................................... 272
6.3.3. Hydrodynamic considerations ......................................................... 273
6.3.4. Ellipsometric measurements of nonionic surfactant adsorption ................ 273
6.3.5. OR studies of nonionic surfactant adsorption ...................................... 276
6.3.6. Adsorption kinetics of CTAB on silica ............................................. 277
6.3.6.1. Ellipsometry ......................................................................... 277
6.3.6.2. Optical reflectometry .............................................................. 278
6.3.7. The role of micelles in adsorption ................................................... 278
6.3.8. The influence of electrolyte on adsorption ......................................... 280
6.3.9. The influence of co-ion type on CTAC adsorption .............................. 282
6.3.10. Effect of chain length on adsorption ............................................... 283
6.3.11. The slow adsorption region .......................................................... 285
6.3.12. Adsorption of gemini surfactants to silica by OR ............................... 291
6.3.13. Adsorption of ionic surfactants to a charged hydrophobic substrate ........ 293
6.4. Summary of reflectance observations ...................................................... 296
7. Summary ................................................................................................ 298
7.1. Mechanism of adsorption and the adsorption isotherm ................................ 298
7.1.1. The electrostatic concentration span ................................................. 300
7.1.2. The electrostatic and hydrophobic concentration span ........................... 300
7.1.3. The hydrophobic concentration span ................................................ 300
7.2. Adsorption kinetics and the adsorption isotherm......................................... 301
References .................................................................................................. 301
1. Introduction
The adsorption of a solute at the solid–aqueous interface results in an increase in

the local concentration or surface concentration. When the interaction is favourable
the local concentration will exceed the concentration of the bulk solution. This is
commonly referred to as a surface excess. For simple solutes, adsorption behaviour
is generally uncomplicated, and can be modelled accurately on the basis of the
interactions between the adsorbing species and the surface of the substrate. This
type of adsorption is generally interpreted using the Langmuir isotherm, which

adequately describes adsorption behaviour up to a monolayer level of coverage.
The behaviour of amphiphilic surfactant molecules at such an interface is more
complex, and has been of considerable scientific interest since the concept of a
‘hemimicelle’ was first proposed by Gaudin and Fuerstenau w1x. This study showed
that the level of adsorption of both cationic and anionic surfactants on quartz
increased only slightly up to a certain critical concentration, but once this concen-
tration was exceeded, the surface excess increased markedly, indicating a cooperative
adsorption process. This increase was attributed to the formation of adsorbed
aggregates, termed hemimicelles, and the concentration at which a rapid increase in
the surface excess occurs became known as the hemimicelle concentration (hmc).
The aim of this manuscript is to review contemporary studies of surfactant
adsorption at the solid–aqueous interface in order to develop the most likely
adsorption mechanism. In classical chemistry, all but the simplest chemical reactions
are a consequence of several steps, or elementary reactions. The reaction mechanism,
which describes the process by which the reactants are converted into products,
generally consists of a series of such elementary reactions. For a given chemical
reaction, there may be several plausible reaction mechanisms. In order to determine
which mechanism best describes what actually occurs, the theoretical rate laws for
the proposed elementary steps and overall reaction are compared to experimentally
determined reaction rates. That is, the reaction mechanism is elucidated by studying
the reaction kinetics. Analogously, an understanding of the adsorption kinetics is
important to understanding the mechanisms of adsorption.
The fast kinetics associated with the formation of an adsorbed surfactant layer at
the solid–aqueous interface has, until recently, prevented accurate investigation.
This has led to the mechanism of surfactant adsorption being inferred from
thermodynamic data or, in the analogy of a classical chemical reaction, by
considering only the products. These explanations have been further hampered by a
poor knowledge of the equilibrium adsorbed surfactant structures (the products). In
many cases, these have been misinterpreted as simple monolayers or bilayers, rather
than the discrete surface aggregates that are present in many surfactant–substrate
systems.
To summarise, experimental limitations associated with kinetic and structural
measurement have, until recently, hindered any determination of a satisfactory
mechanism of surfactant adsorption at the solid–aqueous interface. Here we aim to
link the equilibrium and kinetic information in order to describe the adsorption
process. In order to accomplish this, we shall first examine traditional equilibrium
data and the most popular methods by which these data are interpreted. This is
followed by a description of the evidence for discrete aggregation on the substrate,
and the morphology of the aggregates formed. With this knowledge, the kinetic
data obtained from relatively new ellipsometric methods of investigation will be
examined, and on this basis the likely mechanism or mechanisms of adsorption will
be proposed.
To this end, particular attention will be given to literature that is representative
of the present understanding in the field. These results will be supplemented with
other relevant works where appropriate. Nonionic surfactant adsorption will only be
examined when the results give insight into the nature of ionic surfactant adsorption.
This generally occurs when the interactions between the hydrocarbon chains and a
hydrophobic surface are considered, but also may be of interest when examining a
specific area of investigation, such as the adsorption kinetics.
The head-group charge present on ionic surfactants results in a more complicated
adsorption process when compared to nonionic amphiphiles. Ionic surfactant adsorp-
tion is particularly sensitive to the interactions of counter- and co-ions with the
charged groups of the surface. Adjustment of the solution pH may also affect
several factors in the surfactantysubstrate system. These can include the level of
dissociation of surface groups, the degree of counterion binding to micelles, and the
overall ionic strength. If the affinity of co-ions for surface groups is sufficiently
high, then the co-ions can compete for adsorption sites at the surface. All these
factors have implications, not only for the surface excess, but also for the morphology
of the surface aggregates formed. For all of these reasons, systematic studies are
required to quantify the nature of the various factors that control surfactant
adsorption.
The structure of the adsorbed layer has been elucidated by innovative experimental
techniques, such as atomic force microscopy (AFM), neutron reflectivity (NR), and
fluorescence spectroscopy. Knowledge of the substrate structure allows the general
features of adsorption phenomena to be equated with the morphology of the
surfactant aggregate present on the substrate. The intermolecular energetics will
influence the type of structure formed and the macroscopic properties of the
interface, which in turn affects the suitability of the surfactant for practical
applications. These include ore flotation, stabilisation of foams and emulsions,
wetting control, and detergency, amongst others.
2. General surfactant and substrate properties
2.1. Silica surface chemistry
A significant proportion of the available literature concerning surfactant adsorption

at the solid–aqueous interface concerns amorphous silica w1–4x. As a result, we
will briefly discuss the chemistry associated with silica. Specific differences between
the silica surface and other substrates will be discussed when applicable. Note that
many of the features described here for silica are relevant to other mineral oxide
interfaces. Silica is by far the major constituent of the earth’s crust and as a result,
the chemistry associated with the silica surface has been widely studied w5x. Bulk
silica consists of siloxane units joined together in a tetrahedral lattice. Several
different functional groups can be present at the surface, depending on the
preparation of the surface and, if in solution, the nature of that solution. Functional
groups commonly associated with the silica surface are depicted schematically in
Fig. 1.
Like other mineral oxide surfaces, silica has a surface charge character that is
defined by the relative concentrations of Hq and OHy (the potential determining
Fig. 1. Schematic representation of the types of functional groups that occur on the silica surface. (a)
Hydrated and (b) anhydrous silanol groups are associated with the hydroxylated surface whereas (c)
siloxane-dehydrated groups occur mainly on the pyrogenic surface. Redrawn after Ref. w5x(a).
ions) in solution, as shown by the following equations.
SiOHqHqmSiOHq
2 (1)
K1
SiOHqOHymSiOyqH2O (2)
K2
It is the relative magnitude of the equilibrium constants K1 and K2 in Eqs. (1)

and (2) that determine the charge on the silica surface. The isoelectric point (iep)
for silica occurs at approximately pH 2 w5x, and is somewhat dependent on the
exact nature of the surface. The density of negative charges remains low until the
solution pH reaches 6, but increases sharply between pH 6 and 11 w6x. When
compared to other well-characterised mineral oxide surfaces, the charge vs. pH
curve for silica is unusual w2,6,7x, and modeling studies indicate that the surface
potential of silica as a function of pH is highly non-Nernstian w8x.
While solution depletion studies use silica particles (which typically have a high
sodium content) the silica surfaces used in reflective techniques and AFM studies
are often produced from silicon wafers. High purity silicon wafers are readily
available commercially. The simplest method for preparing oxide layers on the
surface of a wafer is to bake the wafer at high temperature in an oxygen atmosphere.
By controlling the length of time that the wafer is baked, the oxide film thickness
can be easily controlled. This process produces wafers of pyrogenic silica. Hydrox-
ylated silica surfaces are prepared by rehydrolysing the surface, either by soaking
the wafers in water or treatment with basic solution.
When analysing the silica surface charge, the structure of the oxide layer must
be considered. Hydroxylated silica has a high density of hydroxyl groups (;4.5
OH nmy2) w5x that are in close proximity to one another. This leads to hydrogen
bonding between the hydrogen of one hydroxyl group and the oxygen of the
neighbouring group, as depicted in Fig. 1b. Consequently, the hydroxyl hydrogen
atoms are strongly bound at normal pH levels, resulting in the hydroxylated silica
having a low surface charge. Conversely, pyrogenic silica has a lower density of
hydroxyl groups (;0.7 OH nmy2) w5x and a higher net charge than hydroxylated
silica. The presence of numerous siloxane-dehydrated groups (Fig. 1c) will render
the pyrogenic surface partially hydrophobic.
2.2. Surfactant properties
Table 1 lists the name, structural formula, the most commonly used abbreviation
and cmc of the surfactants covered in this review. In some cases, particularly for
the alkyltrimethylammonium bromide surfactants, more than one acronym is used
to refer to the same surfactant. In this review, the abbreviation used in the paper
under consideration will be used so that the text corresponds to the reproduced
figure.
3. Adsorption isotherms
3.1. Introduction
Adsorption isotherms are traditionally determined by solution depletion methods

w9x. Depletion experiments are accomplished by mixing a surfactant solution with a
given mass of adsorbate of known surface area. After equilibration, the surface
excess is determined by the change in the solution surfactant concentration. In order
to facilitate measurement of solution concentrations, surfactants containing spectro-
scopically active groups are often, but not always, employed. A series of experiments
conducted at appropriate surfactant concentrations allows the adsorption isotherm to
be resolved.
3.2. Traditional analysis
Much of the literature concerning adsorption isotherms predates in situ methods

of probing the adsorbed layer morphology w9x. As a consequence, models proposed
to reconcile the features of the isotherm, particularly the saturation surface excess,
often describe simple monolayers and bilayers. This is in stark contrast to more
recent data that in many cases suggests discrete surface aggregation. However, this
does not discount isotherm analysis in developing an understanding of the adsorption
process, particularly below the critical surface aggregation concentration (csac). In
this pre-aggregation region of the isotherm, even the most recent experimental
methods yield only inconclusive indications of adsorbed layer structure. Adsorption
isotherms can provide particularly useful information concerning the electrostatic
interactions that occur at low surfactant concentrations and also probe the manner
in which the surface charge adapts as the solution conditions and surface excess are
altered. In this section we will examine two of the more durable explanations for
adsorption at a charged interface: the ‘two-step’ and ‘four-region’ adsorption models.
Detailed attention will also be given to the influence of chain length, surface charge
effects, the relevance of the common intersection point (cip) between isotherms
226
R. Atkin et al. / Advances in Colloid and Interface Science 103 (2003) 219–304
Table 1
Characteristics of surfactants reviewed
Surfactant name Structural formula Acronymyabbreviation cmc (mM) cmc (mM)

10 mM salt
Cetyltrimethylammonium bromide C16H33NqMe3Bry CTAB or HTAB 0.9 0.15
Cetyltrimethylammonium chloride C16H33NqMe3Cly CTAC 1.1 0.3
Cetylpyridinium bromide C16H33 Nq (C2H2)2CHBry CPBr 0.7 0.1
Cetylpyridinium chloride C16H33 Nq (C2H2)2CHCly CPC 0.8 0.15
Tetradecyltrimethylammonium bromide C14H29NqMe3Bry MTAB, C14TAB or TTAB 3.6 2.1
Dodecyltrimethylammonium bromide C12H25NqMe3Bry DTAB or C12TAB 15.3 11
Dodecylpyridinium chloride C12H25 Nq (C2H2)2CHCly DPC 14.7 10.5
Sodium dodecylsulphate C12H25SO4yNaq SDS 8.1 6.5
Didodecyldimethylammonium bromide (C12H25)2NqMe2Bry DDAB 0.05 –
Benzyldimethyloctylammonium bromide C8H17NqCH2C6H5Me2Bry BDOAB – –
Benzyldimethyldodecylammonium bromide C12H25NqCH2C6H5Me2Bry BDDAB 5.6 –
Ethyl-a,v-bis (dodecyldimethylammonium bromide) C2H4(C12H25NqMe2 Bry)2 12-2-12 0.84 –
Propyl-a,v-bis dodecyldimethylammonium bromide) C3H6(C12H25NqMe2 Bry)2 12-3-12 0.9 –
Butyl-a,v-bis (dodecyldimethylammonium bromide) C4H8(C12H25NqMe2 Bry)2 12-4-12 1.09 –
Hexyl-a,v-bis (dodecyldimethylammonium bromide) C6H12(C12H25NqMe2 Bry)2 12-6-12 1.01 –
Octyl-a,v-bis (dodecyldimethylammonium bromide) C8H16(C12H25NqMe2 Bry)2 12-8-12 0.83 –
Decyl-a,v-bis (dodecyldimethylammonium bromide) C10H20(C12H25NqMe2 Bry)2 12-10-12 0.63 –
Dodecyl-a,v-bis (dodecyldimethylammonium bromide) C12H24(C12H25NqMe2 Bry)2 12-12-12 0.37 –
Methyl groups (CH3) are abbreviated to Me.
Fig. 2. Adsorption isotherms of DTAq (s) and Bry (h) ions measured on particulate silica at pH 8.
Note the adsorption of bromide ions only occurs once the second increase has commenced for the
DTAq ions. The solid and dashed lines were drawn by hand to guide the eye. The solution cmc is
indicated by a dashed vertical line. Reproduced from Ref. w10x.
measured at different salt concentrations and the consequences of different methods

of substrate preparation.
In general, adsorption isotherms are interpreted by discerning changes in the rate
of increase in the surface excess with concentration. This allows the isotherm to be
divided into regions, and the most likely conformation of adsorbed surfactant in
each region ascertained. The most common approaches for this type of interpretation
are the two-step and four-region adsorption isotherms. At first glance these models
may appear to be fundamentally different, but in actual fact they have much in
common. Both models divide the isotherm into four sections, and there is good
agreement regarding the orientation of surfactant adsorbed at the interface in most
regions. The primary difference between the models pertains to the region in which
hemimicellar aggregation is initiated. The four-region model predicts that hemimi-
celle formation takes place in the second region, whilst the two-step model has
hemimicelle formation occurring at higher solution concentrations, in the third
region.
In more recent studies, isotherm data are often combined with other information
allowing more precise determination of the nature of adsorption. The surface charge,
zeta potential, counterion concentration, solution pH and solution conductivity have
been monitored with surface excess. As we shall see below, studies that combine
techniques allow the adsorption mechanism to be commented upon with much
greater certainty.
3.2.1. The two-step model

When expressed on a linear scale, adsorption isotherms typically display two
plateau regions w10x, and a sharp increase in the surface excess near the cmc. For a
classical example see Fig. 2.
Many descriptions of two-step isotherms are available in the literature for a wide
variety of surfactant–substrate combinations w11–16x. In works published before
the application of the AFM to imaging of adsorbed surfactant layers in 1994 w17x,
Fig. 3. The two-step model for cationic surfactants adsorbed to silica. (a) The general shape of the
adsorption isotherm. The x axis indicates residual surfactant concentration and the y axis indicates adsorp-
tion density. (b) The proposed model of adsorption. Adapted from Ref. w15x.
the shape of the isotherm is often interpreted as being indicative of a monolayer on

hydrophobic surfaces and a bilayer on hydrophilic surfaces e.g. Fig. 2.
A notable exception is the work of Gao et al. w15x. In their study of the adsorption
of alkylpyridinium halides to silica, they determined two plateau regions in the
adsorption isotherm. The plateau regions were at low surfactant concentrations (pre-
hmc) and the saturation level plateau observed above the cmc. This led to the
proposal of a two-step model for adsorption as shown in Fig. 3. The regions
suggested were a low surface excess region (I), a first plateau region (II), a
hydrophobic interaction region (III), and a second plateau (IV).
It was suggested that in region (I) the surfactant is adsorbing via electrostatic
interactions with the silica substrate. The surface excess is determined mainly by
the surface charge. Adsorption is sparse, so interactions between adsorbed surfactant
molecules are negligible. In region (II), the substrate surface charge has been
neutralised. However, the solution activity of the surfactant is not sufficient to lead
Fig. 4. The four-region or reverse orientation model of adsorption. Proposed adsorption isotherm and
surfactant aggregates on solid substrates. Adapted from Ref. w19x.
to any form of aggregation at the interface thus surfactants are still adsorbed as
monomers. The abrupt increase in adsorption at the hmc denotes the onset of region
(III). In this region, the solution surfactant concentration is sufficient to lead to
hydrophobic interactions between monomers. The monomers electrostatically
adsorbed in region (II) are thought to act as anchors (or nucleation sites) for the
formation of hemimicelles. In this article, a hemimicelle was defined as a spherical
structure with surfactant head-groups facing both towards the substrate and into
solution w15x. In more recent times this type of structure has been redefined as an
admicelle. In region (III) the admicellar structure was not necessarily fully formed,
allowing for further adsorption. Region (IV) occurred above the cmc, with the
formation of fully formed aggregates and saturation levels of surface coverage.
3.2.2. The four-region model

Whilst this type of ‘two-step’ analysis adequately explains many of the common
features of adsorption isotherms, it is not the only method of evaluation available.
Somasundaran and Fuerstenau proposed the four-region or reverse orientation model
for interpretation of surfactant adsorption isotherms when plotted on a log–log scale
w18x. This method has been shown to be particularly successful for modeling
adsorption behaviour on alumina and rutile w4,18x. The primary advantage of using
a log–log plot is that it amplifies the features of the isotherm at low surface excess
values. The general form of isotherms plotted in this manner, and the morphology
of adsorbed structures associated with each region are depicted schematically in Fig.
4.
In region I of the isotherm, surfactant monomers are electrostatically adsorbed to
the substrate, with head-groups in contact with the surface. Hydrocarbon tail-groups
may interact with any hydrophobic regions of the substrate. Region II involves
strong lateral interaction between adsorbed monomers, resulting in the formation of
primary aggregates. Using techniques such as Raman spectroscopy, fluorescence
spectroscopy, electron spin resonance and contact angle measurement, Somasundaran
et al. w19–22x have shown that the surfactants are adsorbed with head-groups facing
towards the surface while the hydrocarbon tail-groups protrude into solution. This
creates hydrophobic patches on the surface. In the four-region model, this type of
aggregate is known as a hemimicelle. Increases in the surface excess in region III
are thought to result from growth of the structures formed in region II, without any
increase in the number of surface aggregates. The presence of head-groups facing
into solution renders the surface hydrophilic once more. The transition between
region II and region III is thought to be due to neutralisation of the surface charge.
Finally, in region IV, the surface morphology is assumed to be a fully formed
bilayer. Further increases in the solution surfactant concentration do not lead to any
further increases in the surface excess.
3.2.3. Similarities between models

Clearly, these traditional types of analysis have a good deal in common. The
most obvious difference between the models is a lack of hydrophobic interaction in
the second region for the two-step model. Interestingly, in light of recent data, the
structures proposed in the four-step model below charge neutralisation, and the
admicellar structures predicted by the two-step model above charge neutralisation,
may yet prove to be correct.
3.3. The influence of surfactant chain length
As the hydrocarbon chain length of a surfactant molecule is increased, the

monomer is essentially rendered ‘more hydrophobic’. That is, an increased number
of clathrate bound water molecules are required to solubilise successively longer
tail-groups, which lowers the overall entropy of the system. As a result, surfactants
with longer hydrocarbon chains have a much greater driving force for aggregation,
and this dramatically reduces the solution cmc, cf. Table 1.
Chain length is also of critical importance in determining the adsorption behaviour
of a surfactant. Fig. 5 shows that increasing the chain length by four methylene
groups, from C12 to C16 (i.e. DPC to CPC) lowers the concentration at which the
features of the isotherm occur by approximately an order of magnitude, in line with
the reduction in solution cmc w23x. The ‘shifting’ of the isotherm to lower
concentrations for longer chained surfactants is a result of the increased hydropho-
bicity imparted by longer tail-groups. At the solid–aqueous interface, hydrophobic
interactions may exist between the surfactant and the surface, and also laterally
between adsorbed surfactants. Some evidence for this is apparent in Fig. 5. As the
increase in surface excess in regions II and III of the isotherm is dependent on
lateral hydrophobic interactions, it would be expected that the surface excess should
increase more rapidly with concentration for the surfactant bearing the longer
hydrocarbon chain. This is indeed what is observed in Fig. 5b, as the slopes of
regions II and III are clearly steeper for the C16 surfactant. In region IV the
saturation surface excess is clearly greater for CPC than for DPC, but whether this
was due to an increased level of hydrophobic interaction, or a change in the structure
of the aggregate formed at the interface, could not be ascertained from this study.
3.4. The role of surface charge
A major limitation of the solution depletion method for studying surfactant

adsorption was observed by Goloub et al. w2x, who argued that the silica surface
Fig. 5. Adsorption isotherms for CPC and DPC with 0.001 M KCl at pH 9. (a) Presents the data on a
log–log scale and the four-regions of the isotherm are indicated. (b) Shows the data on a linear-log
scale. 䉷 1997 ACS. Reproduced with permission from Ref. w23x.
charge varies not only with pH, but also with surfactant adsorption. Ionisation of
surface groups will alter the pH of the solution. This means that without careful pH
control, pH changes may occur not only from isotherm to isotherm, but also along
an isotherm. However, most studies report only the initial pH.
3.4.1. Increases in surface charge with adsorption

In order to overcome this difficulty, Goloub et al. conducted a systematic study
of the variation of surface charge with surfactant adsorption w2x. The solution pH
was adjusted throughout equilibration of the surfactant and substrate until no further
changes in pH were observed. The results obtained (an example of which is shown
in Fig. 6) give valuable insight into the mechanism of the adsorption process.
Fig. 6 shows that at both low electrolyte and low surfactant concentrations the
adsorption and surface charge isotherms are practically identical. The greatest
increase in surface charge occurs within this initial region of the isotherm and this
effect is more pronounced with increased pH. The correlation between surface
charge and adsorption at low concentrations suggests that whenever a surfactant is
adsorbed to the surface a proton is displaced, which indicates that the surfactant
head-group is in close proximity to the surface. The surfactant concentration at
which the substrate surface charge is neutralised is denoted as the charge compen-
Fig. 6. Adsorption of DPC and surface charge of silica at 0.001 M KCl as a function of the DPC
concentration at (a) pH 7 and (b) pH 9. To facilitate the comparison, the surface charge is expressed as
G0ss0yF, were F is the Faraday constant. In this way surface ‘charge’ and the adsorbed amount of
surfactant, Gs, are both expressed in micromole per square metre. 䉷 1996 ACS. Reproduced with per-
mission from Ref. w2x.
sation point (ccp). Increasing the surfactant concentration above the ccp had little
effect on the surface charge even though the surface excess continues to increase.
This suggests adsorption of a second layer on top of the electrostatically adsorbed
layer, with surfactant head-groups facing into solution.
This interesting result was expanded upon by examining a plot of the surface
charge vs. the surface excess of the surfactant, reproduced in Fig. 7, which shows
that at low surfactant concentrations the surface excess is less than the native surface
charge. In view of this it is somewhat surprising that the surface charge began to
increase as soon as surfactant adsorption commenced. That is, rather than surfactant
monomers first adsorbing to existing charged sites on the substrate, then creating
additional charges, the adsorption of surfactant molecules causes nearby hydroxyl
groups to immediately become more acidic, inducing further surface ionisation. As
the charge neutralisation point was approached (intersection with the line of unit
slope), the gradient of the surface charge isotherm was close to unity, which shows
Fig. 7. Surface charge of silica as a function of the surface excess of DPC measured at 0.001 M KCl
and pH 7 and 9, and the line of unit gradient. 䉷 1996 ACS. Reproduced with permission from Ref. w2x.
that the number of surfactant molecules adsorbing and the number of surface sites
created are nearly equal.
Somewhat different results were obtained at high electrolyte concentrations. In
100 mM KCl, the initial surface charge was much higher, and the increase in surface
charge on surfactant adsorption was much decreased. The surfactant ions were
competing for charged sites on the substrate with the potassium ions of the
electrolyte; hence adsorption did not reach measurable levels until much higher
solution surfactant concentrations compared with the low electrolyte case. However,
at high electrolyte concentrations, the Coulombic repulsions between the monomer
head-groups was greatly decreased. As a consequence, once adsorption is com-
menced the isotherm increased steeply. Other authors have reported similar results
w16x. The implications of high electrolyte concentration for the adsorbed morphology
will be elucidated below in the discussion of AFM imaging.
3.4.2. The common intersection point

De Keizer et al. w24x showed that the cip between adsorption isotherms measured
at different electrolyte concentrations was a useful method of analysing adsorption
isotherms. Further examples of the cip effect are provided in the work of Goloub
and Koopal w23x. An example of the cip for DPC at pH 7 at two salt concentrations
is presented in Fig. 8.
At the surfactant concentration at which the cip occurs, added electrolyte has no
effect on the surface excess. This condition may not hold in the case of longer
chain surfactants that adsorb strongly at low concentrations. In the case of DPC,
however, this observation allowed the effect of electrolyte on the adsorption process
above and below the cip to be commented upon. It was suggested that, providing
Fig. 8. Isotherms for DPC adsorption on silica at pH 7 for two salt concentrations on (a) a log–log and
(b) a linear-log scale. 䉷 1997 ACS. Reproduced with permission from Ref. w23x.
there are no specific interactions between the electrolyte and the substrate, the cip
corresponds to the iep of the substrate. In its simplest form, the cip represents the
point where the orientation of surfactants adsorbing at the surface changes from
heads facing towards the substrate to heads facing towards solution, forming
bilayered aggregates.
In order to test the validity of the cip as a means of identifying the iep of the
adsorbent, the variation in electrophoretic mobility in the presence of surfactant was
also investigated. This result is reproduced and shown in Fig. 9 for two pH values
and salt concentrations w23x. The iep results for DPC and its C16 analogue CPC
both correlate with the cip.
These data are directly comparable to the surface charge isotherm already
discussed in Section 3.4.1. Not only did the cip correspond to the iep, but also to
the ccp, cf. Fig. 6. The fact that these three points occurred at the same bulk
surfactant concentration showed that there is little or no specific adsorption of the
electrolyte to the substrate i.e. no adsorption beyond the level dictated by Coulombic
attraction. Thus, the cip represents the point where the electrostatic contribution to
the adsorption process changes from attractive to repulsive.
Fig. 9. Electrophoretic mobilities of silica particles as a function of DPC concentration at two salt
concentrations and (a) pH 7 and (b) pH 9. 䉷 1997 ACS. Reproduced with permission from Ref. w23x.
3.4.3. Adsorption model based on the cip

It has been postulated that, below the cip where adsorption is primarily electro-
statically driven, adsorption is decreased with increasing electrolyte concentration
because of competition between electrolyte co-ions and the surfactant monomers.
As with the other models described, surfactant adsorption in this region is orientated
with head-groups towards the surface due to electrostatic attraction. Above the cip,
hydrophobic interactions between surfactant tail-groups provide the driving force
for further adsorption. As electrolyte reduces the Coulombic repulsions between the
surfactant head-groups, increasing the electrolyte concentration above the cip
enhances surfactant adsorption. This can be observed in Fig. 9.
3.4.4. The influence of surface preparation

It has been shown that the solution conditions are not the only factors that
influence the surface charge of the substrate. The effect of different methods of
surface preparation was investigated by Chorro et al. w25x, who found that acid
treatment of the substrate prior to adsorption could reduce the maximum surface
excess by almost 50%. In this depletion study, differences in the adsorption isotherms
on raw and HCl washed particulate silica, designated SiNa and SiH, respectively,
were investigated for DTAB and the gemini surfactant 12-2-12. For the moment we
shall direct our attention towards the general implications of this study. A more
thorough treatment of gemini surfactant adsorption and surface charge will then be
undertaken in Section 3.4.6.
This study was performed under ‘free’ conditions i.e. no attempt was made to
control the solution conditions. Thus, the ionic strength of the major species in the
solution (surfactant ions, counterions, Hq , Naq and OHy) regulated the behaviour
of the system. This may appear to be precisely the type of study that Goloub et al.
w2x had described as flawed due to a lack of control over solution conditions.
However, in this case, as the level of surfactant adsorption increased, the properties
of the supernatant (pH, electrophoretic mobility, conductivity and counterion
concentration) were closely monitored. This allowed the effect of surfactant
adsorption on the system as a whole to be monitored and is therefore a valuable
means of investigation.
Upon immersion of the silica and surfactant in solution, the presence of sodium
ions was noted. It was shown that the sodium content for acid washed silica (7
ppm) was considerably less than that of raw silica (67 ppm). Thus, the HCl washing
technique was particularly successful for the removal of sodium from the surface
and the majority of residual sodium ions were strongly surface bound. These ions
were released during equilibration, and not during washing, due to the much longer
time period of the equilibration.
The adsorption isotherms for DTAB and 12-2-12 are reproduced in Fig. 10, with
the concentration axis presented as a function of the cmc. The cmc of DTAB in the
supernatant is 12.8 and 11.8 mM for the SiH and SiNa systems, respectively. For
12-2-12 the cmc is significantly reduced at 0.8 and 0.4 mM for the SiH and SiNa
systems. All of these cmc values are less than that of the corresponding surfactant
in pure water, reflecting the contribution of the released sodium ions to the solution
ionic strength. The most startling difference between the two substrates is that, for
both surfactants, almost double the surface excess was obtained on raw silica as
opposed to the acid treated silica. These differences were attributed to the different
charging properties of the surface. When sodium ions were released from the
surface, this resulted in the formation of ionised sites i.e. the raw silica surface is
considerably more charged than the acid washed substrate. The released sodium
ions also raised the ionic strength of both systems, but obviously this effect is much
greater for the raw silica system. The marked difference in plateau surface excess
values reflects not only the effect of increased ionic strength, but also the importance
of the number of initial surface charges on the adsorption process. This work
highlights the significant effects that changes in surface chemistry induced by
surfactant adsorption can have on adsorption behaviour and highlights a major
weakness in many depletion studies.
3.4.5. Comparison of adsorption mechanisms on raw and acid washed silica

Surfactant monomers initially adsorb to pre-existing charged sites electrostatically,
and these act as nucleation points for further surfactant adsorption. The acidity of
nearby hydroxyl groups increases, releasing Hq ions into solution i.e. adsorption
Fig. 10. The adsorption of DTAB and 12-2-12 on (a) SiNa and on (b) SiH reproduced from Ref. w25x.
that leads to ionisation of surface groups is detectable by a decrease in the solution

pH. This was observed for all surfactant–substrate combinations but was more
obvious for the acid washed silica due to the increased number of protons associated
with this substrate. Thus, when a free system is under investigation, the equilibrium
concentration of sodium ions in solution relates to the initial surface charge, while
changes in the Hq concentration are a measure of the number of surface charge
sites that are induced by surfactant adsorption.
The acid washed surface in Fig. 10b is obviously chemically different from the
silica used in the studies described previously. Nonetheless, the results obtained are
interesting, particularly when contrasted with the results for raw silica. For the
DTABySiH system, the pH of the supernatant was decreasing gently up to the point
where the surface excess reached 25% of the maximum value i.e. the end of the
first pseudo-plateau in the isotherm. Electrophoretic data indicated that the pzc was
reached at this surface excess and the adsorption of bromide ions at the surface was
shown to be very low. These data suggest that up to the end of the first pseudo-
plateau, the DTAB was adsorbed head-group towards the substrate due to electro-
static interactions.
In the region of rapid increase in surface excess, the fraction of surface bound
bromide ions increased. A rapid decrease in the supernatant pH accompanied this
bromide ion adsorption, but only until the solution Hq concentration reached 60%
of the maximum value. This suggests that above this surface excess, surfactant was
adsorbed with head-groups facing towards solution. Increases in the electrophoretic
mobility of the particles supported a change in the orientation of the adsorbing
surfactant at this surface excess. It was postulated that surface bound aggregates
were the most likely adsorbed morphology to account for these observations. These
aggregates could be loosely packed initially, but as saturation levels of coverage
were approached, aggregates would become tightly packed.
The major difference between the acid washed and raw silica surface was in the
ionisation of surface groups. For the raw silica surface, the solution pH reached a
plateau level at approximately 25% coverage of the surface i.e. the concentration
where surfactant is adsorbing exclusively with head-groups facing into solution is
reached much earlier for the raw silica system. Thus, the model for adsorption that
the data on raw silica implies shows good agreement with that described by Goloub
and Koopal w23x.
3.4.6. Surface charge and gemini surfactant adsorption

Gemini surfactants w26x are a relatively new genre of amphiphilic molecules, first
appearing in the literature in 1974 w27x. They have recently become a topic of
revived scientific interest, due in part to their effectiveness in the modification of
interfacial properties, but also because their unusual molecular geometries lead to
interesting aggregation structures.
A gemini surfactant consists of two identical surfactant molecules joined by an
alkyl spacer group. The spacer group can be flexible or rigid w28x, hydrophilic or
hydrophobic w29x and generally connects the two surfactant moieties at, or near, the
head-group. The attachment of the spacer group increases the hydrophobicity of the
dimeric surfactant relative to the constituent monomeric units. As a consequence,
the cmc of the gemini can be up to 100 times lower than that of the monomer units
w30x.
For simplicity, shorthand nomenclature of gemini surfactants is often employed,
based on the number of carbon atoms in the surfactant chain and the spacer group,
and is best illustrated by example. For alkanediyl-a,v-bis (dodecyldimethylammon-
ium bromide) dimeric surfactants with the alkanediyl spacer groups C2H4, or
C8H20, the corresponding surfactants are referred to as 12-2-12, and 12-8-12,
respectively. The molecular structure of a typical gemini surfactant is depicted in
Fig. 11. All discussion is limited to this family (12-s-12) of gemini surfactants.
3.4.6.1. The importance of the spacer group. The properties of gemini surfactants
are greatly dependent on the length of the spacer group. The spacer group controls
the separation between the two head-groups and may be greater or less than the
average separation of the corresponding monomers in an aggregate. This changes
Fig. 11. The structural formula of a typical gemini surfactant. The molecule represented is 12-4-12.
Counterions have not been included.
the mobility and the packing geometry of the gemini within a micelle, whether in
solution or at an interface.
Danino et al. w31x have demonstrated that the structure of the micelles formed in
solution varies significantly with spacer length. For quaternary ammonium surfac-
tants of the form 12-s-12, spacer groups of length less than or equal to five
methylene groups dictate that the head-groups are in close proximity. As the Bjerrum
length in water at 25 8C is equal to 0.7 nm w32x, for gemini surfactants with short
spacer lengths, charge condensation must occur, and the effective charge of the
surfactant is less than 2. The resultant monomer geometry leads to aggregates of
lower curvature than that of the corresponding monomer. For s values between 6
and 10, the distance between head-groups induced by the spacer is similar to that
of the monomer in a micellar aggregate, and similar structures result. For s values
greater than 14, it is suggested that the spacer adopts a looped conformation within
the aggregate, thus acting like additional hydrocarbon chains. The structure formed
in this case is similar to those of dimeric surfactants. More specifically, for ss2
worm-like micelles result, ss3 gives rise to extended micelles, while for s greater
than 4 essentially spherical micelles are formed w31,33–35x.
The effect of variation in the length of the spacer group has been extensively
investigated at the solution–air interface. Perhaps not surprisingly, it has been
demonstrated that the surface area occupied per surfactant molecule increases with
the size of the spacer for s between 3 and 10 w36x. The behaviour of gemini
surfactants at the solid–liquid interface has been shown to follow similar trends.
The first adsorption isotherms for a gemini surfactant at the solid–aqueous
interface were determined by Esumi et al. The adsorption of 12-2-12 was investigated
at the silica–aqueous interface w37x, the laponite clay–aqueous interface w38x and
the titanium–aqueous interface w39x. It was shown that the amount of 12-2-12
adsorbed at the silica–aqueous interface, was lower than that of the monomeric
analogue, DTAB. However, while some of the macroscopic properties of the
adsorbed aggregates were elucidated, no consideration was given to the adsorption
mechanism.
This initial study motivated subsequent research w25,40,41x. A systematic inves-
tigation of the effect of spacer length on the adsorption isotherm, and the mechanism
of adsorption was initially undertaken w40x. A subsequent paper dealt with the
effects of a variation in surface preparation, which has already been discussed in
Section 3.4.5 w25x. We shall review the effect of spacer length and mechanism of
adsorption first, before returning to the effects of acid washing the substrate prior
to adsorption of gemini surfactants.
3.4.6.2. Gemini surfactant adsorption isotherms. Adsorption isotherms for 12-2-12,

12-4-12, 12-6-12 and 12-10-12 on acid washed silica are presented in Fig. 12 w40x.
As the size of the spacer group increased the maximum surface excess of surfactant
was decreased. Corresponding results have been reported at the air–water interface
w36x, and have been attributed to increasing head-group area. Similarly, at the silica–
aqueous interface it is likely that the adsorbed morphology alters as the spacer
length is varied. This will be demonstrated in Section 4.5.4. Interestingly, although
Esumi et al. w37x did not pre-treat their surface to remove sodium ions, the maximum
surface excess attained for 12-2-12 was similar in both studies. This suggests that
all of the surface bound sodium ions were exchanged by the surfactant.
Electrophoretic data showed that the silica was substantially negatively charged
at the beginning of adsorption, and that the amount of surfactant adsorbed at the
point of zero charge was the same irrespective of the spacer length and corresponded
to an area occupied per surfactant of 25 nm2. This equates to an average distance
between monomers of 5 nm. As this value is much larger than the length of a fully
extended spacer group (;1.4 nm for 12-10-12) each surfactant can only neutralise
one surface charge site. The observed zero net charge implied that the second head-
group, which is not surface bound, had a bromide ion associated with it. Alterna-
tively, the close proximity of the unattached head-group may have resulted in the
formation of a charged site at the surface, which was then associated with the head-
group. A third possibility is that the number of unassociated surfactant head-groups
matched the number of free charged sites on the surface, thereby achieving
electroneutrality.
All of the gemini surfactant adsorption isotherms exhibited a plateau after the
point of zero charge was reached. As can be seen in Fig. 12, this plateau was much
narrower for 12-10-12 than for the other surfactants. Surprisingly, the surface excess
of gemini surfactant required for charge neutralisation was 5 times less than that for
DTAB cf. Fig. 10. Recall that both electrostatic and hydrophobic interactions were
involved in the first step of the adsorption process for DTAB. This result suggests
that the surface charge is indeed redistributed once gemini surfactants with short
spacers were adsorbed to the surface. Thus, for spacer lengths less than or equal to
Fig. 12. Adsorption isotherms of 12-2-12 (circles); 12-4-12 (triangles); 12-6-12 (squares); and 12-10-
12 (diamonds) on silica at 25 8C. The surface excess is expressed in micromole of surfactant per gram
of silica. The concentration scale has been normalised by the appropriate surfactant cmc. Solid lines are
guides for the eye. The surface area per gram was determined by the BET method to be 29 m2. Repro-
duced from Ref. w40x.
6, the adsorption mechanism operating in the first step is different to that of the
monomeric analogue. Once the gemini is adsorbed at the surface, the second charged
head-group is brought into close proximity with the surface, an effect which becomes
more pronounced as the spacer length is decreased. The acidity of nearby silanol
groups is increased, raising the likelihood of local ionisation. As a decrease in the
solution pH was not noted at this time, it was postulated that the charged sites were
created by desorption of surface bound sodium ions that were not removed during
the washing process.
Increasing the spacer length allows the second head-group to be positioned further
from the surface. In this case, the second head-group is more likely to be neutralised
by a bromide ion. Thus, gemini surfactants with long spacer groups behave more
like their monomeric analogue, with an overlap between the first and second steps
in the adsorption process. The decreased size of the first plateau for 12-10-12
suggested that it was acting more like a monomeric surfactant than its counterparts
with shorter spacer lengths.
The second step in the adsorption process is thought to be due to lateral
hydrophobic interactions. As the solution surfactant concentration is increased,
interactions between electrostatically adsorbed monomers and the adsorbing surfac-
tants are more likely, which leads to aggregate formation. It was expected that the
concentration at which the surface excess rises appreciably should be lowest for the
surfactant with the lowest solution cmc. This is indeed what was observed, with the
steeply rising region of the isotherm occurring in the order 12-10-12-12-2-12-
12-6-12f12-4-12, cf. Table 1. A drop in the pH of the supernatant accompanied
this step, which showed that the high positive charge density of the surfactant
Fig. 13. Physicochemical characteristics of 12-2-12 adsorption on SiH: the degree of surface coverage
u; the conductivity of the equilibrated supernatant, the pH, and the degree of bromide ion association
to the surface b are plotted against the concentration of surfactant in the equilibrated supernatant. Repro-
duced from Ref. w25x.
aggregates induced the formation of surface charge sites. Recent optical reflectometry
(OR) studies reported somewhat different findings as will be discussed in Section
6.3.12.
We now return to the adsorption of 12-2-12 on acid washed and raw silica. As
the study described above was for acid washed silica, the mechanism for the SiHy
12-2-12 system has already been outlined above. Variation in the physicochemical
properties of the SiHy12-2-12 system with solution surfactant concentration can be
seen in Fig. 13. It is important to note that along with the decrease in solution pH
that accompanies the sharp increase in surface excess, the degree of bromide ion
adsorption reaches a plateau at approximately 0.5 mM. This value is similar to that
obtained for 12-2-12 micelles in solution w42x, and is indicative of an adsorption
process that was hydrophobically driven.
12-2-12 was proposed w25x to have the same mechanism of adsorption on raw
silica. The quantitative differences in the adsorption isotherms are thought to be due
mostly to the greater capacity of the raw silica surface to release sodium ions,
thereby increasing the ionic strength of the supernatant. The pzc for the SiNay12-
2-12 system was significantly higher than that of the SiH surface, and corresponded
to a smaller area per adsorbed molecule (only 2.7 nm2). However, once the initial
charged surface sites were neutralised, there was no further decrease in the pH of
the supernatant. This shows that the second adsorption step had already begun and
aggregation was occurring at the surface.
3.5. Evidence for discrete aggregation from adsorption isotherms
Adsorption isotherms yield significant information concerning the nature of the

interactions between the surface and the surfactant, particularly in the initial stages
of adsorption. However, it is difficult to infer adsorbed structures from this type of

data, and the traditional monolayerybilayer interpretation has been the favoured
model until recently. Despite this, some indirect evidence for admicelle structures
may be inferred from adsorption isotherms. When one compares isotherms obtained
with different surfactants, counterions, and degrees of surface modification, it
becomes difficult to rationalise the results simply in terms of mono- and bi-layer
aggregation. Furthermore the surface excess values obtained usually do not correlate
with the levels that would be expected for complete monolayers or bilayers. This
has been rationalised as being due to ‘patchy’ coverage, which of course in itself
infers a more discrete structure.
Some of the most persuasive isotherm data for the presence of interfacial
aggregates is that obtained with the salicylate ion. Several studies have shown that
the surface excess of surfactants with pyridinium-based head-groups on silica
depends strongly on the counterion. Leimbach et al. w43x first demonstrated for
tetradecylpyridinium that a sixfold increase in the plateau surface excess occurs
when the counterion is changed from the weakly binding chloride ion to the strongly
binding salicylate ion. Although this result may be deceptive due to the reported
specific interactions between the salicylate ion and pyridinium head-groups w44–
47x, it is nonetheless very difficult to explain this type of increase only in terms of
mono- and bi-layer aggregation. However, it is relatively easy to envisage a situation
of increased aggregate growth around electrostatically bound surfactants, given the
well-known increase in solution aggregation number as the degree of counterion
binding is increased.
Further support for this aggregation model can be found in isotherm data obtained
on hydrophobically modified silica. Leimbach and Rupprecht w48x covalently
attached a low concentration of octadecyl groups to a silica surface, thereby creating
anchor sites for surface aggregation. The concentration of the hydrophobic groups
was such that only 7% of surface hydroxyl sites were occupied. Thus the surface
was negatively charged and hydrophobic. The adsorption of the anionic surfactant
SDS to the treated and untreated silica was investigated. On the untreated silica,
SDS did not adsorb to detectable levels. However, on the modified silica a one step
isotherm was obtained both with and without added electrolyte. The saturation
adsorption density was 0.4 and 1.4 mmol my2 for the no added electrolyte and 0.1
mM NaCl system, respectively. The increase in adsorption density in electrolyte was
justified on the basis of decreased repulsions between adsorbed surfactant head-
groups, and the surfactant and the substrate, which carried the same charge. This
model provides convincing evidence for electrostatically adsorbed surfactant mono-
mers acting as nucleation sites for further adsorption. This hypothesis will be further
probed in Section 5.
3.6. Calorimetry
Adsorption isotherms can be complemented by measurement of the heat of

adsorption (calorimetry w49x). This allows the energetics of adsorption to be
monitored throughout an adsorption isotherm. Much useful information has been
obtained by calorimetry concerning the mechanism of adsorption, without actually

revealing a definitive surface structure. Comparative measurements can allow the
nature of the exchange of cations, the conformation of adsorbed water and the
orientation of the surfactant with respect to the surface to be commented upon,
amongst other issues.
There are several methodologies by which heats of adsorption may be obtained
w50–52x. Flow calorimetry w52x is one technique that illustrates the fundamentals
associated with the measurement of adsorption energetics, and is basically an
extension of ion exchange chromatography. The surfactant solution is passed through
a column containing the powdered form of the substrate, for example silica or
alumina. This column is contained within a microcalorimetry chamber, and a
constant temperature is achieved by means of a feedback loop that controls the
power supply to a heating coil. Initially the column is equilibrated under flow of
pure solvent; then a known quantity of surfactant is passed into the column. The
magnitude of the energy required to maintain the temperature of the column is
monitored, and a plot of heat flow vs. time deduced. The net heat transfer is simply
the area under this curve. As this process is isothermal, this area directly equates to
the heat of adsorption, which can be converted to the molar enthalpy of adsorption
by dividing by the molar surface excess.
3.6.1. The importance of surface water

The role of water in the energetics of adsorption cannot be underestimated. In
order to adsorb to a substrate, an incoming surfactant may need to displace water
of hydration at the solid surface. The influence of the solid on the arrangement of
the adjacent water molecules will depend upon the properties of that surface. For
example, sodium cations specifically bound at the substrate attract free water
molecules. This leads to a local ordering of the water molecules at the interface.
The ability of small metal ions in bulk solution to induce structure in nearby water
molecules has been recognised for some time w53x. The likelihood of an analogous
effect at the solid–liquid interface has also been discussed w54x. Thus, endothermic
contributions to the heat of adsorption will depend on the co-ion concentration both
at the surface and in the bulk. Other specific interactions between water and silica
may limit the ability of the surfactant to adsorb to the surface other than by
Coulombic interactions.
3.6.2. Calorimetry and adsorption mechanism

Fig. 14a shows the adsorption isotherms for DTAq and TTAq ions on silica at
pH 8.3 w55,56x. It is worth noting that the TTAq isotherm was shifted to the left
relative to DTAq, but the general shape of the isotherm was similar. This shift was
due to the longer tail-group of TTAq. A longer hydrocarbon chain provides a
greater driving force for aggregation (evidenced by a lower solution cmc cf. Table
1), and results in the entire isotherm being compressed relative to DTAq. Both
surfactants reach their saturation surface excess slightly below their respective
solution cmc values. The corresponding heats of adsorption are presented in Fig.
14b.
Fig. 14. The adsorption of DTAq (squares) and TTAq (circles) ions measured on silica at 25 8C and
pH 8.2. (a) The adsorption isotherms; and (b) the heats of adsorption. The solid lines were drawn by
hand to aid the eye. 䉷 1994 ACS. Reproduced with permission from Ref. w55x.
The change in enthalpy during the adsorption process was dependent on the
properties of the bulk and adsorbed phases. Fig. 14b shows that the enthalpy initially
decreased as the surface excess increases. This was due to the displacement of
surface cations and water molecules from successively more strongly bound sites.
As the surface excess increased two important effects came into play. Firstly, the
rate of ion exchange was reduced, as there were fewer exchangeable ions present
on the surface. Secondly, strong lateral interactions between the tail-groups of the
adsorbed surfactants led to a perpendicular orientation of the hydrocarbon chains
relative to the surface. These two effects led to the observed minimum, then
subsequent increase in the heat of adsorption. The energetic state of interfacial water
molecules was less affected and the overall heat of adsorption eventually became
endothermic.
The region of monotonic increase of enthalpy with the degree of surface coverage
corresponds well with the sharply increasing region of the adsorption isotherm.
Adsorption in this region is entropically driven and is dominated by intermolecular
interactions, similar to those that lead to micellisation in the bulk. Bulk micellisation
is also an endothermic process for most surfactants, with the driving force derived
from the entropy gained upon aggregation w57x. This entropy increase is acquired
from the release of clathrate bound water molecules associated with the tail-groups
into the bulk solution upon micellisation. In some cases it has been shown that the
heat of adsorption at moderate to high concentrations is remarkably similar to that
of bulk micellisation w58x. Moreover, at high surface excess values, the temperature
variation in the adsorption enthalpy mirrors that of the micellisation enthalpy w59x.
These results have been used to argue for the presence of surface bound micelles.
Fig. 15. The influence of the hydrophobic tail length on the adsorption energetics for benzyldimethy-
lalkylammonium bromides onto precipitated silica from aqueous solutions at 298 K with an initial pH
of 8.3: the differential molar enthalpies of displacement against the quantity of adsorption in a limited
adsorption range. 䉷 1996 ACS. Reproduced with permission from Ref. w60x.
3.6.3. Interactions between the hydrocarbon tail and the surface

Zajac et al. w60x investigated the effect of surfactant chain length on the enthalpy
of adsorption at low surface excess values. Specific interactions between the
surfactant tail-groups and the substrate brought about the desorption of structured
interfacial water. This provided a significant endothermic contribution due to the
heat of adsorption. The heats of adsorption of benzyltrimethylammonium bromide
(BTMAB), benzyldimethyloctylammonium bromide (BDOAB) and benzyldime-
thyldodecylammonium bromide (BDDAB) are reproduced in Fig. 15.
For surface excess values of up to 20 mmol gy1, enthalpies of adsorption of the
C8 tailed BDOAB and its head-group BTMAB were negative and indistinguishable.
This suggested that the short C8 alkyl chain did not interact with the silica surface
and the most likely orientation for the tail-group was perpendicular to the substrate.
Conversely, the C12 BDDAB had a positive enthalpy of adsorption throughout the
same range of surface excess values. It was suggested that interactions between the
longer C12 tail-group and the substrate led to disruption of the structured interfacial
water. This de-wetted the silica and made a significant contribution to the energetics
of the adsorption process. These interactions were made possible by the additional
conformations available to a C12 tail-group over a C8 chain. Thus, at low surface
coverage values, the C12 tail-group is oriented parallel to the surface to some degree.
It would be expected that the surfactant tail-group would interact more strongly
with a hydrophobic graphite substrate. The recent calorimetric study of Kiraly and
Findenegg w59x used heat of adsorption data to determine whether the most likely
conformation of C12TAB adsorbed to graphite was the classical reorientation model
(where the adsorbed surfactant molecules are reoriented from horizontal to a vertical
position, accompanied by further adsorption from solution), or that of an interfacial
aggregate (formation of hemicylindrical admicelles templated by an epitaxially
bound surfactant monolayer). The calorimetric evidence, based on the displacement
of water from the interface, showed that the adsorption process had two distinct
phases. The first phase, in which the surfactant molecules are horizontally adsorbed
as a monolayer, was strongly exothermic and, surprisingly, appeared to be independ-
ent of the ambient temperature (in the range 288–318 K) and the surface coverage.
The second phase was less exothermic than the first phase and weakly dependent
on the level of surface coverage. The second stage was, however, inversely dependent
on temperature. This important result strongly suggests a high degree of intermole-
cular cooperativity between neighbouring adsorbate molecules, which was extremely
difficult to reconcile on the basis of the reorientation model. On this basis, the
authors concluded that the most concordant aggregate morphology was of hemicy-
lindrical aggregates, as suggested by AFM imaging studies. These AFM studies,
and more detail of the structure of the adsorbed surfactant layer at the graphite–
water interface is discussed below in Section 4.3.
3.7. Summary of adsorption isotherms
The study of adsorption isotherms by depletion methods continues to be an

effective means of studying surfactant adsorption at the most fundamental level,
however, future efforts must in all cases consider the possibility that changes in the
surface chemistry during surfactant adsorption will influence the bulk concentration
of various species and this in turn will influence the surfactant adsorption. Models
have been available for some time to explain the features of adsorption isotherms,
and it would seem that the most durable is the ‘four-region’ model for surfactant
adsorption. However, in light of recent evidence the interpretation of the final step
in the four-step isotherm must be modified to account for aggregate formation.
Based on the data reviewed in Section 3, the ‘two-step’ model proposed by Gu et
al. w15,16x (cf. Fig. 3) would seem to be invalid, as it fails to account for the
increase in surface charge and lateral hydrophobic interactions that occur in the
second region of the isotherm.
It was demonstrated in Section 3.3 that increasing the hydrocarbon chain length
of the surfactant, which increases the hydrophobicity of the monomer, displaces the
adsorption isotherm to lower bulk concentrations. The rate of increase of surface
excess with concentration in regions II and III of the isotherm, in which adsorption
is partially or wholly hydrophobically driven, respectively, is more rapid for
surfactants with longer tail-groups. Both of these effects become more pronounced
as the surfactant chain length is successively increased.
The critical intersection point (cip) between isotherms of the same surfactant at
different salt concentrations denotes the bulk concentration at which the electrostatic
contribution to adsorption changes from attractive to repulsive. At this concentration
the orientation of adsorbing surfactant molecules switches from head-groups facing
towards the substrate to head-groups facing into solution. Below the cip, the addition
of electrolyte lowers adsorption by competing with monomers for charged surface

sites. Above the cip added electrolyte lowers the electrostatic repulsions experienced
between surfactants in aggregates, permitting tighter packing. This increases the
surface excess relative to the no added electrolyte case. Acid washing of the silica
substrate prior to surfactant adsorption lowers the number of charged surface sites
and decreases the number of surfactant molecules adsorbed in region I. Thus, there
are fewer nucleation sites for continued adsorption lowering the saturation surface
excess for the acid washed substrate.
Gemini surfactants are a relatively new class of surfactants that exhibit interesting
adsorption behaviour. Most importantly, the saturation surface excess has been
shown to be strongly dependent on the length of the spacer group, with shorter
spacer length gemini surfactants having the highest saturation surface excess values.
The adsorption mechanism for gemini surfactants differs from that of their mono-
meric analogue only in the initial stages (region I). For spacer lengths greater than
6, it appears that the gemini surfactant is adsorbed to the substrate by one head-
group, with the other head-group electrostatically bound to a bromide co-ion some
distance from the interface. For spacer lengths less than 6, the second head-group
is held in sufficiently close proximity to the substrate to induce ionisation of a
surface hydroxyl group, and both head-groups are bound to the substrate.
Calorimetric investigations show that the first step in the adsorption process
involves significant displacement of adsorbed water. The energetics of subsequent
surfactant adsorption involve a significant cooperative hydrophobic interaction, such
that the heat of adsorption is similar to bulk micellisation. Calorimetry also shows
that surfactant molecules with chain lengths of 12 or more carbon atoms interact
with ‘hydrophobic’ areas on the silica substrate presumably by adopting a flat
conformation on the surface at low coverage levels.
While some indirect evidence for the presence of discrete surface aggregates can
be obtained from adsorption isotherms and calorimetry, the major disadvantage of
these techniques is the lack of information they provide concerning the adsorbed
morphology. Without knowledge of the adsorbed layer structure, surfactant adsorp-
tion models must always be somewhat speculative. The remainder of this review
will essentially deal with techniques that aid in elucidating the precise nature of the
adsorbed aggregate. With this knowledge, the most likely adsorption mechanism
and the structures present in each region of the isotherm will be presented in
Section 7.
4. Atomic force microscopy
4.1. Introduction
Perhaps the greatest advance in the study of surfactant adsorption at the solid–
liquid interface of the last decade is the development of techniques to obtain in situ
images of the adsorbed aggregates using the AFM. Imaging has allowed adsorption
isotherms to be analysed with knowledge of the aggregate morphology and
complemented model dependent techniques such as neutron reflectivity to provide
greater accuracy. AFM is particularly well suited to detecting the periodicity of

discrete surface aggregates i.e. a peak to peak separation. However, AFM is not
without its limitations. In order to image aggregates, a surfactant layer must have
head-groups facing solution to provide a repulsive force. Thus meaningful AFM
data are generally obtained only above the csac, and most AFM experiments are
carried out at concentrations greater than the cmc. As only the adsorbed layer facing
solution is scanned, for a bilayered aggregate the nature of the underlying layer
remains speculative. AFM provides no information concerning the surface excess
and the density of adsorption between aggregates is also open to speculation. As a
consequence, several possible morphologies can adequately justify a given image,
particularly for bilayered aggregates. However, when AFM results are analysed with
information from other forms of adsorption data, the most likely structure can be
predicted with reasonable confidence. Thus, AFM is most useful when used in
conjunction with other measurements.
Traditionally, the AFM has been used with the probe in contact with the substrate.
While this is suitable for the imaging of a hard surface, it is inappropriate for
imaging adsorbed surfactants. Surfactant aggregates are generally fragile and hard
contact measurements will destroy the adsorbed morphology. However, the sensitivity
of the AFM is such that it is possible to sense the repulsive electrical double layer
associated with the adsorbed species. By using a ‘fly height’ of approximately 1
nm above the adsorbed layer, sufficient contrast is obtained to image the aggregate
structure. This type of imaging has been termed soft contact w61x and lowers, but
does not eliminate, the risk of aggregate deformation.
A considerable volume of surfactant adsorption research predates AFM. Some
AFM experimentation has been aimed at better understanding known surface and
solution effects. For example, for decades it has been observed that the addition of
salt increases the surface excess of surfactant, and the AFM has been used to
elucidate the precise response of the adsorbed aggregates to electrolyte. However,
other AFM investigations have been motivated solely by a desire to manipulate
aggregate morphology, accomplished by studying surfactants with unusual geome-
tries or by specific surface modification. Both types of experimentation have greatly
added to our understanding of adsorption phenomena.
The size, shape and spacing of adsorbed surfactant aggregates are dependent upon
the intermolecular and surfactant–substrate interactions w62x. These interactions are
strongly influenced by solution conditions such as the ionic strength and pH. The
solution micellar size and shape is strongly related to the geometry of the monomer,
however at a surface this structure must be reconciled with the confinements
imposed by the substrate. Nonetheless, the arrangement of aggregates at an interface
is often analogous to solution structure observed at higher concentrations w63x.
4.2. The earliest images of surfactant aggregation: CTAB on graphite
The first direct imaging of interfacial aggregation concerned the adsorption of

CTAB on the cleavage plane of highly ordered pyrolytic graphite w17x. Graphite is
a frequently used substrate for AFM investigations because it is available in
Fig. 16. Adsorption of CTAB on graphite (a) an AFM image obtained in soft-contact mode using the
double layer forces between the tip and sample. The adsorbed layer structure appears as stripes which
are spaced 4.2"0.4 nm apart (about twice the length of the adsorbed surfactant). Image size 240=240
nm2, z-range 1.2 nm. (b) The proposed hemicylindrical structure of CTAB on graphite in cross-section.
The base molecules (shaded) were probably strongly bound epitaxially by the graphite surface, while
the rest of the monomers in the hemimicelle are more labile. 䉷 1994 ACS. Reproduced with permission
from Ref. w17x.
atomically smooth crystalline form, making it ideal for AFM investigations, and
graphon, a form of particulate graphite, is an often-used hydrophobic adsorbate. The
graphite lattice consists of three equivalent symmetry axes and the interactions
between graphite and surfactants are primarily hydrophobic. The images obtained
(one of which is reproduced in Fig. 16a) showed parallel stripes spaced 4.2 nm
apart for CTAB concentrations between 0.8 and 5 mM. The orientation was
perpendicular to the symmetry axes of the substrate. As the period between the
stripes was slightly greater than twice that of the extended monomer, the authors
suggested that the most likely surface conformation of the surfactant was a
hemicylindrical arrangement, as reproduced schematically in Fig. 16b. Adsorption
isotherm data acquired more than 30 years prior to the AFM investigation had
revealed a two-step adsorption isotherm w64x. Without knowledge of the adsorbed
structure it was proposed that the shape of the isotherm resulted from the monomer
being adsorbed with its alkyl chain extended in the substrate plane at low
concentration, and as the concentration increased the monomers interacted laterally
to orient themselves perpendicularly to the substrate. This was thought to result in
monolayer formation. However, with knowledge of the ultimate equilibrium struc-
ture, the new mechanism proposed by Manne et al. of hemimicelle formation has
rightly gained widespread acceptance, this is described below w17x.
4.3. Graphite strongly orientates surfactant aggregates
The first step in the isotherm results from surfactant monomer binding strongly
to the surface via the hydrophobic interaction, forming a film that has a relatively
low rate of exchange with solution surfactants. The adsorbed surfactants align
themselves with the graphite symmetry axis, with the tail-groups oriented towards
the interior of the hemimicelle. This first layer acts as a template for subsequent
surfactant adsorption, as the solution concentration is increased. Aggregation is
driven by hydrophobic interactions between the exposed surfactant tail-groups and
the tail-groups of surfactants in the bulk.
Graphite exhibits the highest degree of control over adsorbed aggregate structure
of any substrate investigated to date, due to its large interaction area with the
surfactant. Hemicylindrical aggregation has been observed on graphite for ionic
w17,62,63,65,66x (conventional and gemini), nonionic w67–69x and zwitterionic w70x
surfactants on graphite with hydrocarbon tail-groups longer than 12 carbon atoms.
Surfactants with tail-groups of 10 or fewer carbon atoms in length form a featureless
monolayer on graphite. This is most likely due to the tail length failing to reach a
critical length to successfully adsorb epitaxially and act as a template for hemicy-
lindrical aggregation.
4.4. Adsorption studies on mica
Considerably different aggregate morphologies have been determined for the

crystalline mica substrate. As mica is hydrophilic, it is the head-group of surfactant
monomers that interact strongly with the substrate and thus, relative to graphite, the
area of interaction per surfactant molecule is greatly reduced. Mica has exchangeable
surface cations, the presence of which can bring about higher levels of coverage
than the less charged silica substrate. The density of the charges on the mica
substrate (0.48 nm2) w61x is such that surfactants are adsorbed to the surface with
their head-groups closer together than the equilibrium bulk separation (for compar-
ison, the head-group area for CTAB in a micelle is 0.64 nm2) w26x. This leads to
adsorbed aggregates having a lower degree of curvature than the corresponding
solution micelles. The negative surface sites on mica are arranged precisely in the
Fig. 17. Adsorption of CTAB on mica in the presence of 10 mM KBr. (a) AFM image in 1.8 mM
CTAB. (b) Schematic representation of the cylindrical structure of adsorbed CTAB. Part of the cylinder
on the right has been cut away to reveal the interior. The cylinders may be flattened on the bottom
because of an attractive electrostatic interaction between the surfactant head-groups and the mica. 䉷
1999 ACS. Reproduced with permission from Ref. w72x.
surface lattice of the substrate, which is expected to influence aggregate morpholo-

gies. However, relative to graphite, the mica surface only weakly orients the axial
directions of any adsorbed aggregates w47,61,62x.
4.4.1. Alkyltrimethylammonium halides on mica

DTAB, MTAB and CTAB have been shown to form flattened cylindrical
aggregates on mica. The period of these aggregates is similar to the diameter of a
solution micelle, whilst the length of the aggregate was much larger w62,71,72x. The
long axis of neighbouring aggregates was aligned locally in one of three directions,
presumably due to the crystallinity of the substrate, giving a striped appearance.
Interestingly, it was shown that for CTAB at twice the cmc the cylindrical structures
observed 2 h after surfactant was passed into the fluid cell had been transformed
into a bilayer after approximately 24 h. Addition of 10 mM KBr had little effect on
the type of aggregate formed initially, but with added electrolyte the cylindrical
structure was stable up to at least 30 h. An AFM image of adsorbed CTAB and a
schematic representation of the structure of the aggregate have been reproduced in
Fig. 17.
4.4.2. The influence of electrolyte on aggregate morphology

Ducker and Wanless w72x investigated the effect of added electrolyte on aggregate
shape. AFM imaging was used to demonstrate that the thermodynamically stable
flat bilayer formed by CTAB was transformed to cylinders on the addition of
electrolyte (KBr). As the electrolyte concentration was increased further, the long
axis of the cylinders was shortened, resulting in the formation of discrete aggregates
with no directional orientation. It was postulated that the addition of salt affected
Fig. 18. AFM images (150=150 nm2) of gemini surfactant aggregates on the cleavage plane of mica.
(a) Spherical admicelles of the asymmetric gemini surfactant 12-3-1 (3.0 mM solution). (b) Cylindrical
aggregates of the symmetric gemini surfactant 12-4-12 (2.2 mM solution, or 2= cmc); (c) Adsorbed
bilayer of the symmetric gemini surfactant 12-2-12 (1.0 mM solution, or 1.3= cmc). 䉷 1997 ACS.
Reproduced with permission from Ref. w63x.
aggregation in two ways. Firstly, once the co-ion concentration reached sufficiently
high levels, it competes effectively with surfactant cations for surface charged sites.
Additionally, the free counterion was electrostatically attracted to the head-groups
of the surfactant, lowering the tendency of the surfactant to bind to the surface.
This released sufficient surfactant from the surface to reduce, then eliminate, the
templating effect. This explanation is supported by the fact that more defects are
produced in the layer with increasing potassium ion concentration. Additionally, the
addition of Hq, which is known to be more strongly surface binding than Kq,
produces a greater number of defects at the same concentration.
4.4.3. Gemini surfactants on mica

Gemini surfactants have proved particularly useful in the investigation of the
relationship between surfactant geometry and substrate interaction on aggregate
structure. Gemini surfactants offer the opportunity to systematically vary surfactant
geometry by changing chain andyor spacer lengths, which allows the importance of
surfactant geometry on aggregate shape to be investigated. Manne et al. w63x studied
the adsorption of gemini surfactants of various geometries to graphite and mica
with interesting results. On the strongly orientating graphite, where adsorption occurs
via hydrophobic interactions, hemicylindrical aggregates formed regardless of the
surfactant geometry. As with conventional surfactants, these structures were orien-
tated perpendicular to the underlying symmetry of the substrate. However, on
crystalline mica, the surfactant geometry was shown to have a stronger influence
on the aggregate formed. This is shown eloquently in Fig. 18.
The spherical structures formed by the asymmetric gemini 18-3-1 were also
present for 16-3-1 and 12-3-1, although the spacing between aggregates decreased
with chain length. Cylinders formed in the presence of 12-4-12 and 12-6-12.
However, a reduction in the spacer length to 2 resulted in the formation of a

featureless bilayer. These results show the same general trend as solution aggregates
(where the curvature of aggregates is lowered as the spacer length is decreased),
and demonstrate the dependence of structure morphology on geometry, even when
the surface exerts a templating effect.
4.5. Adsorption studies on silica
In contrast to the study of adsorption isotherms relatively few AFM studies have
employed amorphous silica, perhaps primarily because it is more difficult to obtain
clear images. In general, straight chain cationic surfactants have been shown to
form essentially spherical admicelles with no long range ordering on the silica
substrate w62,73–75x. This morphology agrees well with the mechanism predicted
by adsorption isotherms: that electrostatically adsorbed monomers act as nucleation
sites for further surfactant adsorption. As with other substrates, factors that affect
aggregation in solution often have consequences for structures at the silica–water
interface.
4.5.1. The influence of electrolyte and counterion type

The influence of surfactant and electrolyte concentration and type of counterion
on the adsorbed morphology was investigated by Velegol et al. w73x. For CTAB,
when the surfactant concentration was increased from 0.9= cmc to 10= cmc the
adsorbed morphology changed from short rods to ‘worm-like’. This occurred
regardless of whether 10 mM KBr was present or absent, although added electrolyte
did reduce the aggregate period. When the counterion was changed from bromide
to chloride, the aggregate morphology was predominately spheroidal for both
concentrations, and once again the presence of electrolyte did not significantly
change the aggregate structure. These results are reproduced in Fig. 19.
Fig. 19 clearly shows the dependence of adsorbed layer morphology on the type
of counterion. These results were rationalised by the greater binding efficiency of
bromide over chloride allowing bromide to better stabilise the lower curvature
cylindrical structures. Using OR, it was shown that the change in structure from
spheroids to ‘worm-like’ (for CTAC and CTAB, respectively) corresponded to the
surface excess increasing by a factor of two thirds.
4.5.2. Adsorption kinetics measured by AFM

In a recent study of the coadsorption of surfactants and polymers, Liu et al. w74x
made an interesting observation concerning the adsorption and desorption kinetics
of CTAC. Although the kinetics of adsorption were not measured directly, force
curves were analysed to give some indication of the adsorption rate. Immediately
after surfactant solution was passed into the AFM cell a steep repulsive force and
adhesion was evident. This indicated the presence of bilayered surfactant aggregates,
which were successfully imaged. When the cell was rinsed with water, the repulsive
barrier disappeared, and was replaced by an attractive force and larger adhesive
force. The length of time that these forces persisted was found to be dependent on
Fig. 19. AFM images of a range of cationic surfactants on silica: (a) CTAB 10= cmc. (b) CTAB 0.9=
cmc. (c) CTAC 10= cmc (d) CTAC 0.9= cmc, with push through the adsorbed layer to the underlying
silica substrate shown in the bottom of the image. The peak-to-peak distance between CTAC aggregates
with and without 10 mM kBr is 10"2 nm at 10= cmc and 13"2 nm at 0.9= cmc. For CTAB, the
peak to peak distances are 10"1 nm without salt and 8"1 nm with 10 mM KBr at 10= cmc. 䉷 2000
ACS. Reproduced with permission from Ref. w73x.
how long the CTAC solution was exposed to the substrate. The general features of
this effect are shown in Fig. 20.
These results suggested that the molecules that serve to reverse the surface charge
are easy to desorb; whereas those that are electrostatically bound to the surface are
retained by the surface much longer upon rinsing. The time dependence of this
process was justified using a model proposed by Chen et al. w76x. This adsorption
model proposed that the surfactant ion is initially adsorbed with a counterion bound,
and that this counterion is expelled from the film over time, allowing the surfactant
to be electrostatically bound to the surface. The electrostatic nature of this adsorption
serves to extend the desorption process. Desorption was found to proceed more
Fig. 20. Schematic representation of the desorption of CTAC from silica, showing the dependence on
the length of exposure of the surfactant to the surface. 䉷 2001 ACS. Reproduced with permission from
Ref. w74x.
slowly at higher pH values. As increasing the pH should increase the level of

electrostatic binding, this result supports the proposed model.
4.5.3. The influence of counterion polarisability

Subramanian and Ducker w75x investigated the effect of counterion on the adsorbed
structure of CTAq on the basis of the ‘hardness’ of the ion. It was found that soft,
polarisable (e.g. Bry) ions were more effective than hard counterions (e.g.
CH3COOy, Cly) at inducing shape changes in admicelles, namely a sphere-to-
cylinder transition. It was suggested that as hard anions strongly bind water they
are relatively unavailable for binding to surfactant ions. Soft counterions, which
weakly interact with water, associate more readily with surfactant. Binding of
counterions lowers the repulsive force between head-groups, permitting the formation
of the less curved cylindrical aggregates. This study reported that surface micelles
were clearly observed at 0.5= cmc in the absence of electrolyte. This is because
electrostatic adsorption of surfactant to the substrate lowers the activation energy of
aggregate formation and permits the formation of admicelles below the solution
cmc.
4.5.4. Gemini surfactant aggregates on silica

The adsorbed morphology of gemini surfactants at the silica–aqueous interface
has been investigated by Atkin et al. w77x. An image of 12-2-12 at approximately
2= cmc is presented in Fig. 21 revealing flattened ellipsoidal structures. Similar
structures were imaged for 12-3-12. The adsorption density was found to be
approximately 150 aggregates per 10 000 nm2 and the aggregate thickness is
Fig. 21. An AFM image of the silica–solution interface immersed in an aqueous solution of 2= cmc
12-2-12 revealing adsorbed aggregates with approximately circular profiles in the upper portion of the
image. The slow scan direction is down the page. The underlying silica surface is imaged in the lower
portion of the page when a higher imaging force is applied. 䉷 2003 ACS. Reproduced with permission
from Ref. w77x.
estimated to be 3.5 nm, from the push through distance obtained in the force curve.
As these surfactants have been shown to form worm-like aggregates in solution, the
smaller surface aggregates must be attributed to the influence of the substrate. The
physical dimensions and spacing of the admicellar structures presented here are
similar to those observed for monomeric quaternary ammonium surfactants on silica
(Section 4.5.1).
In this study we reported that obtaining clear images of 12-3-12 was considerably
more difficult than for 12-2-12. This was attributed to the decreased adsorption
density of 12-3-12. The number of adsorbed molecules of 12-3-12 was 25% lower
than that of 12-2-12. As the spacer length increased, the adsorption density continued
to fall as per Fig. 12. For s)3, AFM images of the adsorbed surfactant layer could
not be obtained. This was a consequence of the change in the nature of the
interaction force between the AFM tip and the surface, resulting from proximal
desorption of surfactant.
Proximal adsorption or desorption describes a change in surface excess as a
function of surface separation. Ducker et al. w78,79x recently demonstrated that the
magnitude of proximal desorption was significant for cationic surfactants adsorbed
to silica surfaces. At concentrations where the surface charge is reversed due to

surfactant adsorption, surfactant monomers desorb from the surfaces upon approach
in order to lower the electrostatic repulsion. Subramanian and Ducker has shown
that, for CTAB concentrations slightly higher than the cmc, the proximal desorption
increases dramatically at surface separations of less than 10 nm w78x. At approxi-
mately 9 nm the change in adsorption is ;0.25 molecule nmy2. If the change in
adsorption was similar for gemini surfactants then this represents a significant
proportion of the total surface excess, up to 50% for the larger spacer groups (as
there is a significant decrease in surface excess with increasing spacer length, cf.
Fig. 12 and Section 6.3.12). Thus, fewer surfactant monomers are required to desorb
from the substrate for the longer spacer sizes in order to expose a hydrophobic
surface. Additionally, the electrostatic repulsion is greater for the longer spacer
lengths, therefore the driving force for desorption is likely to be greater. Both of
these influences strongly suggest that proximal desorption during imaging will have
a greater effect on the adsorbed structures as the spacer length increases.
This proximal desorption process is depicted schematically in Fig. 22. It is
expected that solution-facing monomers will be more likely to desorb from the
interface as the tip approaches. As a consequence, a portion of the tail-groups of
the monomers adsorbed with head-groups facing the silica substrate will be exposed.
This will produce hydrophobic surfaces and consequently the surfaces jump together
under the influence of the long-range hydrophobic attraction, which precludes
imaging of surface structures. As similar force vs. distance data were obtained for
spacer lengths between 4 and 12, a similar process is likely occurring for all of
these spacer lengths.
As images of the adsorbed structures for spacers of length greater than 3 could
not be obtained, the likely structures of the adsorbed aggregates were inferred from
the images of the 12-2-12 aggregates and the linear increase in the area per adsorbed
molecule w77x with spacer size. It is known that the same surface excess in terms
of number of monomers is required to neutralise the surface charge for the gemini
surfactants (cf. Section 3.4.6). Further it is generally accepted that surface aggregates
form around electrostatically adsorbed monomers (cf. Section 3). Therefore approx-
imately the same number of surface aggregates should be formed for 12-2-12 up to
12-12-12. This was supported by AFM imaging of the 12-2-12 and 12-3-12 gemini
surfactants, which reveal similar numbers of aggregates per unit area despite a 25%
difference in surface excess. As the same number of aggregates were present per
unit area, and the surface area occupied by the aggregates did not change with
spacer length, by assuming the mass density of the aggregates does not change, the
aggregate volumes and shapes for s)3 were determined. It was shown that the
adsorbed aggregates become more flattened as the spacer length is increased.
Schematic representations of the variation in adsorbed structure with spacer length
are shown in Fig. 23. Clearly as the head-group area increases (larger s), the
surfactant chains interdigitate to a greater degree in order to maximise chain–chain
interactions. This leads to the flattening of the surface aggregates. These flattened
aggregates appear to be less than optimal in terms of surfactant packing as they are
very easily disrupted.
Fig. 22. Schematic representation of the release of gemini surfactant molecules from an adsorbed aggre-
gate upon approach of the AFM tip apex (represented by a large filled triangle) for spacer lengths of
four or more. The surfactant concentration is sufficient to lead to surface aggregation. No attempt has
been made to represent counterions or surfactants that are not adsorbed either at the silica substrate or
AFM tip in the first instance, and for simplicity all surfactants are represented in the cis conformation
with straight hydrocarbon chains. In (a) the tip is effectively far from the interface, at a separation of
;100 nm. The AFM senses an electrostatic repulsion, but this repulsion is not sufficient to induce
release of surfactant from the adsorbed aggregate. (b) Depicts the situation as the AFM tip continues to
approach the interface. At these smaller separations the magnitude of the electrostatic interaction is
sufficient to force surfactant monomers out of the admicelle. However, the overall electrostatic force is
greater than the hydrophobic attraction at these separations. (c) Represents the situation immediately
prior to the jump into contact. The outer layer of the surfactant aggregates on both the AFM tip and the
substrate have largely diffused into solution, resulting in the residual electrostatic repulsion being con-
siderably reduced relative to the initial situation, and a significant amount of hydrophobic material being
exposed. The hydrophobic attraction between the surfactant adsorbed to the AFM tip and the substrate
leads to the jump to contact observed in the force curve, the magnitude of which is indicated by the
arrow. (d) Shows the expected configuration of surfactant adsorbed to the tip and the substrate in the
constant compliance region. Depending on the stiffness of the adsorbed layer, the AFM tip may push
through to contact directly with the silica substrate. The situation depicted also leads to the significant
adhesion observed for all spacer sizes greater than 3 as the AFM tip is retracted from the substrate. 䉷
4.6. Model hydrophobic substrates
Model substrates can be used to study the influence of factors such as surface
charge, roughness, crystallinity and hydrophobicity on the adsorption process.
Grant et al. w80x systematically investigated the influence of substrate hydropho-
bicity on the adsorption of a nonionic surfactant, namely octa(oxyethylene) n-
dodecyl ether (C12E8). In the absence of a charged head-group, the driving force
for the adsorption of nonionic surfactants is derived from hydrophobic and van der
Waals attractions. In this study, altering the ratio of chemisorbed hexadecane thiol
and thiohexadecanol to a gold substrate controlled the substrate hydrophobicity. As
Fig. 23. Schematic representation of the variation in the adsorbed gemini surfactant layer as the spacer
sizes increased. The diagrams presented are two-dimensional cross sections of three-dimensional aggre-
gates present at the interface. Counterions are not represented. The lateral dimensions of the aggregate
are similar at all spacer sizes, and it is the increased size of the surfactant head-group as the spacer
length increases that results in reduced aggregation numbers, a lower surface excess and a reduced
aggregate thickness. As the adsorbed aggregates cannot be imaged for spacer sizes of four or more, the
structures depicted are proposed on the basis of area per molecule and force data. 䉷 2003 ACS. Repro-
duced with permission from Ref. w77x.
the relative amount of thiohexadecane was increased, so was the substrate hydro-
phobicity. This allowed the preparation of five increasingly hydrophobic surfaces.
The contact angle varied almost linearly with the proportion of chemisorbed
hexadecane thiol, from 258 at 0%, to 1108 at 100% hexadecane thiol (the three
other surfaces prepared were 25, 50 and 75% hexadecane thiol). Force curves and
images were collected at a solution surfactant concentration of 2= cmc.
Analysis of AFM images and force curves allowed the variation of substrate
hydrophobicity on the structure of the adsorbed layer to be commented upon. The
general results are summarised in Fig. 24 w80x. On the most hydrophilic surfaces (0
and 25% CH3 terminated) the force curves showed that the surfactant was easily
displaced from the surface. This indicated that the interactions between the surfactant
and the substrate are relatively weak. On these surfaces, there were many sites at
which water could be hydrogen bonded, allowing water to effectively compete for
the surface. Imaging of the adsorbed layer indicated diffuse micellar coverage, with
an aggregate period of approximately 10 nm. Adsorption was attributed to hydro-
phobic interactions and a comparatively weak van der Waals contribution, shown in
Fig. 24a.
On the 50% methyl terminated surface, the adsorbed aggregate period was
decreased to 6 nm. A more stable repulsive barrier was present in the force curve,
indicating a layer thickness of 6 nm. This value compared well to the solution
micellar diameter of 6.2 nm. Increasing the substrate hydrophobicity had increased
the strength of the hydrophobic interactions between the surface and the surfactant.
The morphology of the surfactants was found to be close packed micellar aggregates
Fig. 24. Schematic representation of the influence of the variation in the percentage of CH3 terminated
alkyl chains on C12E8 adsorption. The remainder of the surface is composed of CH2OH terminated
groups. 䉷 2000 ACS. Reproduced with permission from Ref. w80x.
(Fig. 24b). When the degree of methyl group termination was increased to 75%
force imaging could reveal no discrete aggregation. However, once again the force
curve indicated that the adsorbed layer was 6 nm thick. In this case the adsorbed
layer morphology was interpreted to be a classical bilayer, represented in Fig. 24c.
When the degree of alkyl termination was increased to 100%, a featureless layer
was also imaged. However, in this case the layer thickness interpreted from the
force curve was approximately 4 nm. This indicates the presence of a surfactant
monolayer on the surface, see Fig. 24d.
These results also serve to demonstrate the importance of interfacially adsorbed
water. The degree of water hydrogen bonded to the surface increases as the level of
alkyl termination is reduced from 100 to 0%. Where water is not bound at the
interface in great amounts, as on the 100 and 75% alkyl terminated surfaces, mono-
and bi-layered aggregation results. The 50% alkyl terminated surface provides a
greater quantity of sites for water binding, and discrete aggregates are observed.
One could interpret this result on the basis of the adsorbed water preventing the
bilayered aggregation, leading to the formation of curved aggregates. The 0 and
25% alkyl terminated surfaces were even more hydrophilic, which allowed water to
compete more strongly for surface area. This led to the aggregates being spaced
further apart and suggested a lower surface excess. Thus, increasing the level of
substrate hydrophobicity not only increases the attraction between the surface and
the surfactant, it also lowers the level of water interacting with the surface. Both of
these factors have implications for structure of the adsorbed surfactant.
Several other AFM studies have used modified hydrophobic substrates and have
generally reported adsorption of single layered aggregates with adsorption dominated
by substrate tail-group interactions. Briefly, Grant and Ducker w81x have investigated
nonionic surfactant aggregation at an amorphous hydrophobic surface, prepared by
covalently attaching diethyloctylchlorosilane (DEOS) to a silica substrate. The
repulsive forces observed, together with AFM imaging of the adsorbed surfactant,
were deemed to be consistent with the formation of a uniform monolayer at the
surface, with head-groups facing solution and the surfactant tail-groups and DEOS
interacting hydrophobically. Wolgemuth et al. w82x studied the adsorption of various
ionic, nonionic and zwitterionic surfactants to an amorphous silica surface, hydro-
phobised by the covalent attachment of trimethylchlorosilane (TMCS). It was found
that the interfacial aggregates formed were roughly hemispherical, in contrast to the
half-cylindrical structures formed on crystalline hydrophobic substrates. Similar
surfactant morphologies were observed regardless of the type of head-group, leading
the authors to suggest that adsorption is driven by hydrophobic interactions between
the substrate and the surfactant tail-groups. SDS adsorption was not noted consis-
tently on the TMCS treated substrate, which was attributed to a residual negative
charge associated with the silica after reaction with TMCS.
4.7. Summary of AFM investigations
AFM has provided direct evidence for the presence of discrete aggregates at the
solid–aqueous interface and has led to a slow revolution in our interpretation of
surfactant adsorption data from all sources. AFM imaging is only useful above the
csac, where surfactant head-groups are facing towards solution, imparting a repulsion
(electrostatic for ionic surfactants) that allows soft contact imaging to be accom-
plished. The clarity of the AFM images obtained varies with the surfactant and the
substrate under investigation. As the AFM is most useful at detecting periodicity,
surfactant–substrate combinations that produce highly regular morphologies produce
the clearest AFM images.
The hydrophobic cleavage plane of graphite orients the adsorbed surfactant
structures more strongly than any other substrate. This is primarily due to a high
level of (hydrophobic) interaction with initially adsorbing monomers, which tem-
plates the subsequently formed hemicylindrical structures for surfactant chains with
greater than 10 carbon atoms. Chains of less than 10 carbon atoms are not templated
by the substrate and result in a laterally featureless adsorbed layer.
The hydrophilic, crystalline mica substrate also orients the adsorbed surfactant
structures, but not as strongly as graphite. The alkyltrimethylammonium surfactants
form cylindrical aggregates, which were in some cases transformed into a featureless
layer. However, the addition of electrolyte stabilises the cylindrical admicelles. The
adsorbed morphology of gemini surfactants on mica can be manipulated by altering
the geometry of the surfactant monomer.
Surfactants are less strongly oriented on silica surfaces, due to a lower surface
charge and the amorphous state of the substrate and perhaps also due to an increase
in surface roughness. The adsorbed structure of CTAB and CTAC on silica has
been investigated. The adsorbed configuration of CTAB was concentration depend-

ent, with short rods at 0.9= cmc and worms at 10= cmc. These structures were
insensitive to the presence or absence of electrolyte. For CTAC, the adsorbed
morphology was insensitive to both the surfactant concentration and the presence
or absence of electrolyte, with spheroidal structures present at both 0.9= cmc and
10= cmc in the presence and absence of electrolyte. In all cases there was little or
no long range ordering of the adsorbed aggregates. Similar structures have been
observed for MTAB and DTAB on silica.
By altering the substrate hydrophobicity the adsorbed morphology of nonionic
surfactants can be controlled. By sequentially increasing the substrate hydrophobicity
the structure of adsorbed nonionic surfactants can be changed in a controlled manner
from diffuse adsorbed micelles on the least hydrophobic surface, to densely packed
micelles, to a bilayer, to a monolayer on the most hydrophobic interface.
It is clear that adsorbed aggregate structures are often formed upon surfactant
adsorption at the solid–aqueous interface, and that the properties of the substrate
may exert a high degree of influence on the type of aggregate formed. These
structures can be reconciled with the adsorption isotherm data presented in Section
3, and this will be discussed in Section 7. The intervening discussion is aimed at
more completely characterising the structure of the adsorbed layer.
5. Fluorescence quenching experiments
5.1. Introduction
Fluorescence quenching studies statistically analyse the fluorescence emission of

a micelle bound probe molecule. A second molecule, known as a quencher,
suppresses this emission. Fluorescence quenching is a well accepted method for the
determination of micelle aggregation numbers in bulk solution w83,84x. The fluoro-
phore probe, typically pyrene, is excited at a particular wavelength and the
fluorescence intensity monitored at a second wavelength. All fluorescence quenching
studies assume that both the probe and quencher molecules are entirely contained
within micelles, that there is no exchange between aggregates, and that the micelles
are unperturbed by the presence of the probe and quencher.
A random distribution of the fluorophore and the quencher throughout the system
under investigation is assumed. Therefore, some aggregates will contain both the
probe and the quencher, some contain either the probe or the quencher, and some
aggregates will contain neither. Statistical analysis will allow the average number
of quencher molecules per micelle in the system to be calculated. As only micelles
containing the fluorophore are probed, the aggregation number of the micelles can
be determined from the intensities of the fluorescence emission in the absence and
presence of a known concentration of quencher. This relatively simple analysis is
known as the static emission method and for this method to be successful it is
essential that quenching is rapid. It is assumed that there is no fluorescence from
micelles containing quencher, thus any emission from these micelles alters the
aggregation number determined. This effect is expected to be more pronounced for
Fig. 25. Representative fluorescence decay curves for pyrene fluorescence from admicelles on silica.
Two curves are shown for each surfactant: one with no quencher present and one in the presence of
quencher. The concentration of surfactant is as follows TTAB (Cs1.01 mM) and CTAB (Cs0.801
mM). The amount of pyrene in each sample is approximately 1 pyrene per 50 surface-bound micelles.
䉷 2000 ACS. Reproduced with permission from Ref. w85x.
large aggregates, where the rate of quenching will be dependent on the diffusion
rate of the probe and quencher throughout the micelle core.
5.2. Time resolved fluorescence quenching
The time resolved fluorescence quenching experiment is not as dependent on the

assumption of rapid quenching. This experiment uses a delta pulse excitation of the
probe molecules and the decay of the fluorescence emission with time is recorded.
As the rate of quenching is dependent on molecular collisions between the probe
and the quencher molecules, this gives rise to a fast initial decay, followed by a
slower unquenched decay. Examples of the form of these curves are presented in
Fig. 25, reproduced from Strom ¨ et al. w85x. These curves were obtained from
admicelles on a silica surface.
For time resolved fluorescence quenching experiments, the aggregation number
can be determined from the curved portion of these data, or by extrapolation of the
long time data back to ts0. This gives the intensity at time 0 in the presence and
absence of quencher molecules, and allows the aggregation number to be determined
in the same manner as for the static emission method.
5.3. Determination of aggregation numbers
In order to determine aggregation numbers, the concentration of aggregate bound

surfactant must be known. In solution, this can be determined from the cmc. When
studying the properties of aggregates adsorbed at an interface, the surface concen-
tration must be determined by other methods, and it is assumed that all surfactant
is aggregate bound. If aggregates are present in solution and at the interface, the
probe molecule will be distributed through both solution and surface aggregates,
leading to results that are inaccurate. However, if the surfactant concentration is
chosen such that it is below the solution cmc, but above the concentration at which
aggregates form on the surface (csac), then the probe molecule will be fully surface
bound. This allows the adsorbed aggregates to be probed directly.
5.4. The earliest fluorescence probe studies
The first fluorescence probe studies of adsorbed aggregates were performed by

Levitz et al. w86,87x, using the static emission method. The adsorption of nonionic
surfactants such as Triton X-100, were investigated. It was shown that the
aggregation numbers for adsorbed surfactant determined by fluorescence emission
followed similar trends to bulk micelles. It was thus concluded that the most likely
form of surface aggregate was that of a small surface admicelle. Fan et al. w19x
performed similar studies for ionic surfactant adsorption. The aggregation of
alkyltrimethylammonium bromides on an alumina substrate was investigated and
the presence of small surface bound aggregates was also determined. The size of
these aggregates appeared to grow as the surface excess of surfactant increased.
This result is shown in Fig. 26.
These results agree well with the adsorption model for ionic surfactants to an
oppositely charged substrate suggested by the adsorption isotherm data described in
Section 3. That is, electrostatically adsorbed monomers act as nucleation sites for
further surfactant adsorption, leading to the formation of surface aggregates. This
accounts for the observed increase in aggregation number. These data also show
that fluorescence probe quenching gives insight into the structure of the adsorbed
layer at surface excess values below that where aggregates are fully formed, and
are thus not readily investigated using AFM.
5.5. Time resolved fluorescence quenching of adsorbed aggregates
The first time resolved fluorescence quenching study of adsorbed aggregates was
performed by Strom ¨ et al. w85x. The adsorption of DTAB, TTAB, CTAB and
dodecyl-1,3-propylene-pentamethyl-bis(ammonium chloride) or DoPPDAC, a diva-
lent cationic surfactant, was studied. The quencher molecules used in this study
were alkyl pyridinium surfactants. This choice was deemed suitable in light of the
structural similarity between the quaternary ammonium surfactants under study and
the alkyl pyridinium quencher, which minimised the degree to which the system
was perturbed. Emission data typical of that obtained by this study are shown in
Fig. 26. Aggregation numbers for adsorbed surfactant aggregates on alumina formed using alkyltrime-
thylammonium bromide surfactants of three different chain lengths. The aggregation numbers corre-
sponding to a given surface excess are given on the figure for the steeply increasing region of the
isotherms. 䉷 1997 ACS. Reproduced with permission from Ref. w19x.
Fig. 25. In particular, note the initial curved decay, which results from micelles
containing both quencher and probe molecules, and note that the exponential portion
of the curve, due to micelles containing probe only, has the same slope as the result
recorded without quencher present. These features provide strong evidence for the
formation of discrete surface aggregates, which was the principal finding of this
study. This result agrees well with AFM imaging results, and cannot be rationalised
simply in terms of mono- and bi-layer aggregation. The evolution of aggregation
number with surfactant concentration and with increasing electrolyte concentration
is reproduced in Fig. 27. It was judged that the uncertainty in these values was at
most 20%.
The increase in aggregation number with surface excess observed in Fig. 27a
supports the trend observed by Fan et al. for the adsorption of alkyltrimethylam-
monium bromides on alumina w19x. Increasing the electrolyte concentration was
also shown to increase the aggregation number. This was rationalised on electrostatic
grounds, with added electrolyte decreasing the electrostatic repulsions between
monomers within adsorbed aggregates. This facilitates tighter packing within
admicelles, leading to the observed increase in aggregation number.
5.6. Summary of fluorescence quenching experiments
For the purposes of this review, fluorescence quenching experiments provide two
important results. Firstly, fluorescence quenching provides strong evidence for the
Fig. 27. Aggregation numbers of micelles on silica for DTAB (circles), TTAB (squares), DoPPAC
(triangles), and CTAB (cross). Aggregation numbers are presented as a function of (a) bulk concentra-
tion and (b) as a function of added electrolyte. 䉷 2000 ACS. Reproduced with permission from Ref.
w85x.
presence of discrete aggregates. This supports the results obtained using AFM, that
discrete admicellar structures are present at the substrate as summarised in Section
4. Perhaps more importantly, several fluorescence quenching studies have shown
that the aggregation number of the adsorbed structures increases with surface excess.
This result provides the strongest evidence for the nucleation mechanism of
surfactant adsorption, described previously in Section 3.
6. Reflectance techniques
6.1. Introduction and underlying principles
The principle of reflectivity is essentially the same with respect to scattering,

regardless of whether light, X-rays or neutrons are used as the radiation source.
Whereas X-rays are sensitive to the electron density, and hence the atomic number
of the species under investigation, the scattering of neutrons is dependant on the
nuclear properties of the molecules being probed. Optical techniques such as
ellipsometry and optical reflectometry (OR) derive their sensitivity from the
dependence of reflection and refraction on refractive index and interference effects
that give phase information. These effects allow calculation of the adsorbed layer
thickness or surface excess. The significantly shorter wavelengths associated with
X-rays and neutrons allow the structure of the adsorbed layer to be examined more
intimately.
6.2. Neutron reflectivity and adsorbed layer structure
NR provides sufficient resolution to study the orientation of surfactant molecules

in the adsorbed layer, as different nuclei scatter neutrons with different amplitudes.
In the case of protons and deuterons, neutrons are scattered with opposite phases,
which allows contrast variation to be achieved by use of a combination of protonated
and deuterated adsorbates. This type of substitution alters the reflectivity of the
adsorbed layer, but leaves the surfactant morphology unaltered. Additionally, by
careful adjustment of the proton to deuterium ratio of the solvent, the contrast
between the solvent and the surface can be set to 0, resulting in the recorded
reflectivity profile being dependent only on the adsorbed layer. The resolution, or
the smallest length scale able to be probed, is a function of the wavelength. The
short wavelength of neutrons gives increased resolution over that of optical
techniques. This, combined with the contrast control available using isotopic
substitution, allows NR to elucidate concentration profiles close to the surface, and
even the orientation of the adsorbed species.
6.2.1. Limitation of NR
The major limitation of NR is that interpretation of the results is model dependent.
Conventionally, the adsorbed layer is treated as a laterally unstructured film w88x.
This allows the interference fringe that results from the reflections at the solid–
layer and layer–solvent interfaces to be characterised by a thickness and a scattering
length density profile w89x. In practice, the adsorbed film is often more complicated
than a homogenous layer, and the only satisfactory method for determination of the
perpendicular composition profile is to divide the adsorbed film into a series of
layers with separate density profiles using the optical matrix formulation of
reflectivities. Each layer is characterised by its scattering length density, thickness,

and if necessary an interfacial roughness factor. The division of layers generally
reflects the different scattering length densities of the surfactant head-groups and
alkyl chains.
6.2.2. Contrast control

The additional contrast achieved by isotopic substitution provides information
that aids in selecting the most appropriate model. In spite of this detail, a determined
profile is not necessarily a unique solution i.e. several models of the adsorbed layer
structure may fit the experimental result. For the most part, neutron reflection results
for surfactant layers have been interpreted as a monolayer on hydrophobic solids
and bilayered or a patchy bilayer morphology on hydrophilic substrates.
Whilst these results are somewhat surprising in light of AFM imaging, if one
takes into account the limitations of the technique, useful information can be derived
from these studies. Neutron reflection gives the most direct measurement of the
thickness of adsorbed aggregates, and provides the orientation of molecules perpen-
dicular to the surface. However, it provides no data concerning the lateral ordering
of molecules, and hence one cannot make definitive statements concerning the in-
plane dimensions of aggregates w90x.
6.2.3. NR studies of cationic surfactants on silica

Several NR studies have examined the adsorption of CTAB to silica w89–91x.
The consensus of these studies is that the surface is incompletely covered. This is
rationalised by either a defective bilayer, or by the adsorption of discrete micelle-
like aggregates. The AFM and fluorescence data presented above indicate that the
admicelle morphology is the correct interpretation.
McDermott et al. w92x showed that whilst the fraction of the surface covered
increased from 51% at 1y3= cmc to 65% at 1= cmc, the layer thickness of 3.4
nm was consistent at both concentrations. From this result the authors suggested
that the increase in the level of surface coverage was unlikely to be derived from a
change in the aggregate structure. Due to the incomplete coverage of the surface it
was postulated that the water and surfactant occupy separate domains on the surface,
with ‘islands’ of surfactants suggested. It was noted that these islands would most
likely have head-groups protruding from the sides in order to shield the alkyl chains
from the water intermittent to the islands. It was shown that when the dimensions
of these islands were sufficiently small the head-groups at the sides of the aggregates
would become important to the fitting of a consistent optical model, in that both
head-groups and chains would be present in the midplane of the aggregates.
Secondly, inclusion of the intermittent water in the optical model suggested a lateral
size of 9 nm at the higher surfactant concentration. This result is consistent with
the dimensions observed using AFM in Section 4.5.1. Further, the fluorescence
quenching studies show that the aggregation number increases with surface excess.
This result is inconsistent with the above interpretation.
These results were clarified by Fragneto et al. w90x, who also concluded that if
the adsorbed aggregates were micelle-like, then they must be strongly flattened.
This result has been corroborated by several authors using various techniques, and
has now become well accepted. This study also investigated the effect of surface
roughness on adsorption. As does surface preparation, surface roughness could
contribute to the variation in results for surfactant adsorption on silica substrates.
The authors reached several important conclusions. Firstly, the level of surfactant
adsorption decreased as the surface roughness increased. This result may seem
counter-intuitive, as increasing roughness should increase the available surface area.
It was suggested that this effect could be derived from an inability of the rougher
surface to match the curvature of the adsorbed aggregate. Additionally, the thickness
of the surfactant aggregates was increased on the rougher surface. This could be
attributed to reduced electrostatic interactions between the substrate and the aggregate
leading to a greater aggregate curvature. Alternatively the surface roughness could
add to the thickness of the layer by varying the position of the centre of the
aggregate relative to the surface.
It has been consistently noted that adsorption studies using two or more
experimental techniques have a far greater probability of producing unequivocal
results. This is also the case with NR. On the basis of the numerous discrete
adsorbed aggregates determined by AFM imaging, Schulz et al. w93,94x have
recently produced reflectivity models using unit cells consisting of spheres and
cylinders. The authors point out that adsorbed films consisting of discrete aggregates
will naturally produce a level of surface coverage that is less than 100%. This is an
important observation, as the ‘patchy bilayer’ or ‘island’ interpretations suggested
by many NR studies are simply corrections made to account for fractional surface
coverage, with little supporting evidence and can be seen as originating from
outdated interpretations of adsorption isotherms where surface excess values consid-
erably below that required for bilayer adsorption were interpreted as ‘patchy
bilayers’.
The most recent investigation of Schulz et al. combined AFM and NR studies of
surfactant adsorption onto crystalline quartz and showed that NR can correctly
distinguish between adsorbed morphologies by using bulk solution contrast variation
w94x. Three surfactant-quartz combinations were studied, and the structure of the
adsorbed layer was determined using AFM imaging. At concentrations above the
solution cmc, TTAB was shown to form spherical admicelles, TTAB with 200 mM
NaBr formed cylindrical structures and the double chained surfactant DDAB
produced a laterally unstructured film. These morphologies are consistent with the
solution structures, where spheres, cylinders and bilayers have been determined for
TTAB, TTAB and 200 mM NaBr, and DDAB, respectively.
The authors produced theoretical scattering models for spherical, cylindrical and
bilayer morphologies for each surfactant. The best fit parameters used for each of
the models is reproduced in Table 2. While each model had a unique scattering
length density profile, it was not possible to determine the structure of the adsorbed
layer solely on the basis of goodness of fit, as all structures seemed equally likely
for each surfactant.
However, the structure of the adsorbed surfactant layer can be ascertained by
comparing surface excess values obtained in pure D2O, and in a system where the
Table 2
Fits to adsorbed layer structure for cationic surfactant systems on quartz from neutron reflectometry
NR in D2O NR in contrast matched D2OyH2O AFM

G d t G d t d
(mmol my2) (nm) (nm) (mmol my2) (nm) (nm) (nm)
TTAB Spheres 6.6"0.6 5.3"0.3 4.6"0.4 6.5"0.4 5.2"0.3 4.6"0.3 6.9"0.5
Cylinders 6.1"0.6 5.1"0.5 3.6"0.4 6.4"0.3 6.0"0.3 4.0"0.2
Bilayer 5.4"0.5 2.7"0.3 6.4"0.3 3.3"0.1
TTABq200 mM NaBr Spheres 7.3"0.3 5.2"0.2 4.7"0.1 6.9"0.3 4.7"0.2 4.4"0.2
Cylinders 7.0"0.4 5.5"0.3 4.0"0.2 6.9"0.3 5.2"0.2 3.9"0.2 4.9"0.5
Bilayer 6.3"0.4 3.0"0.2 6.8"0.3 3.2"0.1
DDAB Spheres 4.7"0.3 3.0"0.2 3.2"0.2 4.9"0.2 3.5"0.2 3.6"0.2
Cylinders 4.5"0.3 2.5"0.2 2.6"0.2 4.8"0.2 3.3"0.1 3.1"0.1
Bilayer 4.2"0.2 2.1"0.2 4.8"0.2 2.6"0.1
Consistent fits to NR and AFM images for each system are set in bold, showing agreement between adsorbed amounts in the D2O and quartz contrast-
matched D2OyH2O measurements. Also listed are the film thicknesses t and nearest-neighbour spacings d, from NR fitting and AFM images, showing
agreement between the two techniques for the best fit NR case. Redrawn from Ref. w94x.
271
solution is contrast matched to the quartz substrate. This is achieved by varying the
ratio of H2O to D2O in the bulk. For the correct model, the surface excess (and the
fitted parameters) must be equivalent at both contrasts. As can be seen in Table 2,
the surface excess values (G) are indeed independent of the model used when the
quartz and the bulk solution are contrast matched. In the unmatched system, the
surface excess values show considerable variation. The interfacial model which best
fits these data, between these limits in contrast, is shown in bold in Table 2. The
results obtained agree well with those obtained with AFM imaging. This led the
authors to suggest that this method of adsorbed layer structure determination may
be of particular use when the necessary conditions for soft contact AFM images
cannot be obtained. This elegant work indicates that AFM and NR data are
compatible provided an appropriate model is employed to interpret the NR data.
6.3. Ellipsometry, optical reflectometry and adsorption kinetics
The evolution of the adsorbed layer structure with concentration is often

commented upon when studying surfactant adsorption using equilibrium techniques.
These studies imply a series of processes that occur as the interfacial concentration
increases. As we have seen previously for ionic surfactants, the general consensus
is that surfactant adsorption is by electrostatic means at low concentrations, and as
the surface excess increases lateral hydrophobic interactions lead to induction of
surface charge and hemimicelle formation. This is followed by the formation of
aggregates at higher surface excess values. This interpretation is quite well estab-
lished and accepted. However, whether these processes occur kinetically is open to
question. That is, for a concentration where aggregates result, is the surface charge
first neutralised, followed by hemimicelle formation, then by bilayered aggregate
formation, or do these processes occur simultaneously? Additionally, the contribution
or otherwise of micelles to the adsorption process is often questioned. Investigations
of surfactant adsorption kinetics should elucidate these issues.
6.3.1. Dynamic aspects of surfactant adsorption

In contrast to equilibrium adsorption characteristics, the dynamic aspects of
surfactant adsorption have been far less studied and are consequently not as well
understood. This is in spite of the importance of adsorption kinetics to many real-
world applications such as wetting, lubrication and spreading. The difficulty in
monitoring the expected fast kinetics of the adsorption process is the primary reason
for the lack of investigation of adsorption rates. However, the recent development
of ellipsometric techniques with high temporal resolution has made it possible to
study the kinetics of adsorption and desorption with adequate precision.
6.3.2. Principles of optical techniques

OR and ellipsometry both monitor the variation in the reflectivity of an interface
upon adsorption. These variations are induced by the change in the refractive index
profile of the substrate upon the adsorption of a surfactant layer. Both techniques
use a linearly polarised light source that is reflected off the substrate to which
adsorption takes place. The polarisation characteristics of the reflected light are
monitored. These polarisation changes are highly sensitive to the presence of a
surfactant layer. Ellipsometry allows the average thickness and refractive index of
the layer throughout the adsorption process to be calculated by monitoring the
ellipsometric angles c and D with time. For an extensive explanation of ellipsometry,
see Ref. w95x. OR records the amplitudes of the perpendicularly polarised compo-
nents of the reflected beam. Upon adsorption, the ratio of these two intensities is
altered and this allows for calculation of the surface excess. OR is described in
detail in Ref. w96x. Unlike NR, reflectance techniques using light as the radiation
source cannot give information concerning the molecular structure of the adsorbed
layer.
6.3.3. Hydrodynamic considerations

In order to make quantitative statements concerning the adsorption kinetics it is
critical that the hydrodynamics of the measurement be well defined. Whether the
adsorption process is transport-limited or limited by the rate of layer organization
cannot be discerned unless the rate of diffusion of surfactant to the substrate is
known. Several studies have suffered from a lack of hydrodynamic control w97–
101x. This has complicated the accompanying attempts at modeling the observed
kinetics. However, the qualitative results obtained are still of value. When hydro-
dynamic conditions are well defined, such as that provided by use of a stagnant
point flow w102x, the character of the adsorption process can be commented upon
with much greater certainty.
6.3.4. Ellipsometric measurements of nonionic surfactant adsorption

Several ellipsometry studies have investigated the adsorption of nonionic surfac-
tants w98–101x. Whilst the hydrodynamics of the interface were not well controlled,
interesting results were nonetheless obtained. For a nonionic surfactant adsorbing to
silica, only weak interactions are expected between the surfactant and the substrate.
In this case, a transport limited adsorption process is expected, and the results
obtained were in good agreement with this.
Tiberg et al. w98x used in situ ellipsometry to study the adsorption and desorption
kinetics of polyethylene glycol alkyl ethers at the silica–aqueous interface. A typical
adsorptionydesorption cycle was determined that comprised of five separate kinetic
regions. It was found that the rate of adsorption was strongly dependent on the bulk
surfactant concentration. The rate of adsorption continued to increase above the
cmc, clearly demonstrating the involvement of micelles in the adsorption process.
Representative results are presented in Fig. 28.
The increasing section of the adsorption profile was divided into two separate
regions: first, a linear region where adsorption increases monotonically with time,
followed by a transition region where the adsorption rate decreases. The linear
region of the result was attributed to the rate of diffusion of monomers and micelles
from the bulk through the stagnant layer in the immediate vicinity of the surface
being lower than the rate of adsorption to the substrate. That is, in this portion of
the data the adsorption rate was thought to be transport limited. As the surface
274
Fig. 28. Left: Time evolution of the surface excess (G, open diamonds) and mean optical thickness (df , filled diamonds) for C14 E6 at concentrations, from
bottom, 0.007, 0.009 and 0.01 mM. All concentrations are below the cmc. Right: Time evolution of the surface excess (G, open diamonds) and mean optical
thickness (df, filled diamonds) for C14E6 at concentrations, from bottom, 0.025, 0.1 and 0.25 mM. All concentrations are above the cmc. 䉷 1994 ACS.
Reproduced from Ref. w98x.
Fig. 29. Desorption kinetics from silica for three different hexaethylene glycol monoalkyl ethers:
C12E6, (filled diamonds); C14E6 (open diamonds); C16E6 (filled triangles). The inset shows the corre-
sponding process for different polyethylene glycol monododecyl ethers: C12E5 (open triangles); C12E6
(filled triangles); C12E8 (open diamonds). 䉷 1994 ACS. Reproduced with permission from Ref. w98x.
excess increased, the concentration gradient between the surface and the bulk
decreased. This lowered the rate of adsorption to the surface and led to the curved
region of the adsorption data. Throughout this transition region, the rate of adsorption
steadily decreased, presumably as the surface became more saturated. This eventually
led into the plateau region of adsorption. For surfactant concentrations above the
csac, it was shown that the equilibrium surface excess increased as the size of the
hydrocarbon moiety of the surfactant increased. Similar results have been reported
for ionic surfactants by solution depletion methods cf. Section 3.3.
Interestingly, for all surfactant concentrations studied, the measured mean optical
thickness was found to rapidly increase to a steady value of approximately 4.7 nm.
This was interpreted as indicating that the adsorbed layer was built up of micellar
like structures, which had a well-defined thickness even in the initial stages of the
adsorption process. Higher surface excess values were achieved by the formation of
more surface aggregates that eventually saturated the surface, or by increasing the
packing density of monomers in the existing aggregates.
When the adsorption plateau was reached using a bulk concentration above the
cmc, no desorption was apparent until the solution surfactant concentration fell
below the csac. This demonstrated the cooperative nature of nonionic surfactant
adsorption. The general features of the desorption kinetics are given in Fig. 29,
showing the effect of alkyl chain length and head-group size.
Two regions were also identified in the desorption results. The surface excess
initially decreases in a linear fashion with time. It was suggested that the rate of
diffusion away from the surface was the rate-limiting step in this region. As shown
in Fig. 29, the rate of desorption increases by an order of magnitude when the
length of the alkyl chain is increased by two carbon atoms. However, variation in
Fig. 30. Reversibility of the adsorption–desorption cycle of C12 E5 adsorbed on polystyrene coated silica.
C1s0.17 mM. First desorption upon dilution with C2s0.0006 mM. Further desorption with water.
Second cycle: adsorption of a 0.17 mM surfactant solution. Desorption by water. The soluteysolvent
switches are indicated by arrows. 䉷 2000 ACS. Reproduced with permission from Ref. w103x.
the head-group size had only a slight effect on the desorption rate. These effects
were thought to be directly correlated with the corresponding changes in the csac.
That is, as surfactant diffuses away from the surface, the adsorbed equilibrium
adjusts such that in the region of the solution immediately adjacent to the surface
the surfactant concentration is kept constant at the csac. The lower csac of the
surfactants with longer tail-groups was therefore able to bring about the shorter
desorption times observed. The increased strength of hydrophobic interactions
between adsorbed surfactants was not considered.
The decrease in surface excess eventually becomes non-linear. This slowing of
desorption suggested that the monomer concentration could no longer be maintained
at the csac. This shows that as the surface excess decreases, the rate of dissociation
of surface micelles becomes the rate-determining step.
6.3.5. OR studies of nonionic surfactant adsorption

The adsorption of nonionic surfactants to synthetic hydrophobic substrates has
also been investigated. Geffroy et al. w103x used OR with stagnant point flow
hydrodynamics to study the adsorption of ethylene oxide surfactants to a polystyrene
coated silica surface. Interestingly, it was shown that a portion of the surfactant
layer was irreversibly bound to the substrate.
The hydrodynamics associated with the stagnant point flow make it particularly
suitable for cycling experiments, where solvent, then surfactant solution is succes-
sively flowed toward the substrate. An example of such an experiment is shown in
Fig. 30, which shows that the initial adsorption with a surfactant concentration of
0.17 mM rapidly leads to a surface excess of ;1 molecule nmy2. This was first
desorbed with a much lower concentration of surfactant, 0.0006 mM, which led to
the surface excess being reduced to ;0.4 molecule nmy2. When pure water was
passed into the cell, no change in the surface excess was detectable. Upon
reintroduction of the higher surfactant concentration the original surface excess was
obtained, and rinsing with water returned the surface excess to the lower adsorption
density. This led the authors to suggest that an adsorbed amount of ;0.4
molecule nmy2 would be obtained at very low surfactant concentrations. The authors
suggested that this irreversibly bound surfactant was adsorbed flat at the surface
based on the form of the desorption kinetics and molecular area considerations.
In this study the kinetics of adsorption were relatively fast, and the equilibrium
surface excess values were reached within a few minutes. Below the cmc, the rate
of adsorption increased linearly with concentration. Above the cmc the rate of
adsorption continued to increase albeit more slowly. In this system, it was not
expected that the micelles would adsorb to the surface directly, as the head-groups
are quite hydrophilic. Nonetheless, the observed increase in the rate of adsorption
above the cmc suggested that the micelles were acting as a source for monomers
adsorbing to the surface, which increased the adsorption rate.
6.3.6. Adsorption kinetics of CTAB on silica

Several studies have investigated the adsorption kinetics of CTAB at the silica–
aqueous interface. The presence of the charged head-group should provide a greater
initial driving force for adsorption. However, the native charge associated with the
silica surface will be neutralised at low surface excess values. Goloub et al. w2x
have shown that the surface charge will compensate for the charge associated with
the adsorbed surfactant to a significant extent, but the maximum potential of the
surface has been reached well below the saturation surface excess. Thus, for a
surfactant concentration above the csac, adsorption is against an electrostatic
repulsive barrier throughout most of the adsorption process.
6.3.6.1. Ellipsometry. Eskilsson and Yaminsky w104x used in situ ellipsometry to

study the adsorption of CTAB to silica. The adsorption isotherms were determined
for both CTAB and CTAq, reproduced in Fig. 31. These isotherms showed that the
level of surfactant adsorption began to increase significantly at approximately 0.1
mM, with the most rapid increase in the level of adsorption occurring between 0.4
and 0.8 mM. In this concentration range the surface excess rose from 1 to 4
mmol my2, which was the saturation surface excess. At the beginning of this region
of sharp increase in surface excess, the level of counterion adsorption became
appreciable. This indicates that surfactant is starting to be adsorbed with the head-
group facing away from the surface. These results are in reasonable agreement with
those obtained by Goloub et al. w2x for a similar cationic surfactant.
For solution surfactant concentrations above 0.4 mM the thickness of the adsorbed
layer was determined to be approximately 2.5 nm. This value did not increase with
surfactant concentration, even though at this concentration the surface excess was
only 25% of the saturation value. It was suggested that the Coulombic repulsions
between adsorbed surfactant serve to orientate the surfactants normal to the surface.
Fig. 31. Adsorption isotherms for CTAB (crosses) and CTAq (circles) at the silica–aqueous interface.
䉷 1998 ACS. Reproduced with permission from Ref. w104x.
The kinetics of adsorption were found to be strongly dependent on the bulk

concentration. For surfactant concentrations less than 0.1= cmc up to 2 h was
required for equilibrium to be obtained at the surface. However, as the surfactant
concentration approached and exceeded the cmc, adsorption was complete within
minutes. For all surfactant concentrations studied, the rate of desorption was fast,
complete within a few minutes and no concentration dependence was found.
Examples of adsorption and desorption experiments are shown in Fig. 32.
6.3.6.2. Optical reflectometry. Pagac et al. w105x investigated the adsorption of

CTAB to silica using OR with laminar flow hydrodynamics. Unfortunately, this
study was influenced by a trace impurity that caused large overshoots in the surface
excess values for surfactant concentrations below the cmc. This impurity was later
shown to be due to leaching from PVC tubing contained within a peristaltic pump
w73x. Results obtained above the cmc appear to be unaffected, and display kinetics
similar to those obtained by Eskilsson and Yaminsky w104x. The equilibrium was
reached within approximately 1 min of adsorption commencing. Once again, the
involvement of micelles in the adsorption process was indicated by an increase in
the rate of adsorption above the cmc.
6.3.7. The role of micelles in adsorption

The role of micelles in the adsorption process for CTAB w106x and CPBr w107x
was elucidated by our group using an optical reflectometer with stagnant point flow
hydrodynamics. The well defined hydrodynamic flow fields associated with stagnant
point flow permits the measured initial rate of adsorption to be compared to the
Fig. 32. Surface excess vs. time during adsorption from 1 mM CTAB solution. The surfactant is injected
at time 0. Rinsing of the sample cell with pure water is initiated at ts1420 s. The inset shows the
adsorption from 0.1 mM CTAB. 䉷 1998 ACS. Reproduced with permission from Ref. w104x.
theoretically derived diffusion limited flux to the surface w102x. The quotient of
these two values is recorded as the sticking ratio w106x, and is simply the number
of surfactant molecules that are adsorbed to the surface normalised by the
theoretically derived diffusion limited flux to the surface. Note that this is an
oversimplification of the actual process, as adsorbed surfactant molecules are freely
exchanging with surfactant in the bulk. However, trends in the sticking ratio can
give valuable insight into the nature of the adsorption process. An increase in
sticking ratio with concentration indicates cooperativity, a decreasing sticking ratio
suggests competitive adsorption, while a constant sticking ratio infers that surfactant
molecules are adsorbing independently.
The sticking ratios for CTAB and CTAB with 10 mM KBr are shown in Fig. 33.
In this figure the concentration of surfactant has been normalised by the cmc for
each system (1.25=10y4 M with 10 mM KBr, w108x, 9.0=10y4 M without salt
w109x). For concentrations above the cmc the theoretical flux consists of two
components, the flux due to monomers and the flux due to micelles. Any increase
in the concentration above the cmc is reflected only in the flux due to micelles as
the monomer concentration is assumed to be constant.
The important result from Fig. 33 is the marked increase in the sticking ratio for
both systems at the cmc, indicating an increase in the efficiency of the adsorption
process above the cmc. If surfactant molecules were competing for adsorption sites,
this would be reflected in a reduction in the sticking ratio. In the absence of salt,
the sticking ratio is essentially constant up to the cmc indicating that the monomers
are adsorbing independently. With 10 mM KBr present the sticking ratio is higher
Fig. 33. The sticking ratio (determined from the initial rate of adsorption) vs. concentration for solutions
of CTAB, normalised by the corresponding cmc, with (squares) and without (diamonds) added 10 mM
KBr. The sticking ratio increases at the cmc for both systems. 䉷 2000 ACS. Reproduced with permission
from Ref. w106x.
than in the absence of salt and is seen to gradually increase even below the cmc,
indicating that adsorption of monomers is cooperative in this case. Cooperative
adsorption is clearly aided by the screening of the head-group charge by electrolyte.
Perhaps such screening allows hydrophobic interactions to play a greater role in
adsorption? The sticking ratio increases sharply at the cmc, both in the presence
and absence of electrolyte, which clearly indicates that above the cmc adsorption
has become cooperative. Similar trends were determined for CPBr w107x.
The most obvious explanation for cooperativity is that micelles are directly
adsorbing to the surface, either partially or wholly. For this to lead to the observed
trend in sticking ratio the increased success with which micelle bound monomers
adsorb to the substrate must be due to more effective penetration of the electrical
double layer of the interfacial layer by micelles compared to monomers. Opposing
adsorption is the electrostatic repulsion of this double layer, and as a micelle has a
significant number of counterions associated with it, we propose that surfactant
contained within a micelle will more effectively penetrate the double layer than a
monomer. This is due to the reduced charge per monomer contained in a micelle.
6.3.8. The influence of electrolyte on adsorption

The effect of changing the counterion from bromide to chloride on the surface
excess, kinetics of adsorption and adsorbed layer structure was investigated using
OR and AFM in the study of Velegol et al. w73x. The implications for the adsorbed
layer structure have already been discussed in Section 4.5.1. For now we shall
concern ourselves primarily with the adsorption kinetics. Below the cmc, the surface
excess reached 80% of its maximum value within 2 min, while above the cmc,
equilibrium was attained within this time interval. When the surface was rinsed with
water, the surfactant was completely desorbed within seconds.
Fig. 34. Response of the adsorbed layer to a change in the type of counterion in solution. All solutions
contain 2 mM C16TAq Xy in 10 mM KX where X is either Bry or Cly . The composition is varied as
follows: (1) CTAB in KBr; (2) CTAC in KCl; (3) CTAC in KBr; (4) CTAB in KCl; (5) CTAB in
KBr. The surface excess for the upper curve is calculated from the optical data by using the refractive
index increment of CTAC and for the lower curve by using the refractive index increment of CTAB. 䉷
The suitability of OR for performing cycling experiments is demonstrated by Fig.

34. This experiment utilised a 2 mM surfactant solution with 10 mM electrolyte,
which was continuously flowed over the substrate. The composition of the solution
was varied between combinations of CTAB, CTAC, KBr and KCl. In any combi-
nation, the added electrolyte provided 83% of the total counterions in solution. For
CTAC with 10 mM KBr, the surface excess obtained is the same as that of CTAB
with 10 mM KBr. However, when the chloride concentration was greater than that
of bromide, as with CTAB with KCl, the surface excess is intermediate to that
reached for CTAC with KCl and CTAB with KBr. These results show that when
both the chloride and bromide counterions are present, there is competition for
binding to the aggregate surface, both in solution and adsorbed at the interface. This
influenced the surface excess obtained. The results obtained in this experiment were
consistent with the bromide ion having a much higher affinity for the aggregate
than the more hydrated chloride ion. This was evident in the higher surface excess
values obtained for the bromide counterion.
Fig. 35. Adsorption Isotherms for CTAC; without added electrolyte (closed diamonds), with 10 mM
KCl (open diamonds), with 10 mM NaCl (open triangles) and with 10 mM LiCl (open circles). For
more information see Ref. w112x.
6.3.9. The influence of co-ion type on CTAC adsorption

We have also investigated the effect of variation in the co-ion type on adsorption
behaviour. The CTAC system was used to investigate this effect, as it has been
demonstrated w73,75,110,111x that the concentration of chloride ions has little
influence on the surface aggregate structure formed upon adsorption of CTAC.
Thus, if variation in adsorption is observed, it is likely to be a consequence of
altering the electrolyte co-ion.
The adsorption isotherms for CTAC and CTAC in 10 mM NaCl, KCl and LiCl
(henceforth referred to as CTAC and CTACqNaCl, CTACqKCl and CTACqLiCl,
or collectively as CTACqXCl) are presented in Fig. 35. The adsorption isotherms
are shifted to lower concentrations in the presence of electrolyte. Importantly, the
size of this shift is independent of the co-ion identity. In fact, the adsorption
isotherms for the different salts are remarkably similar, indicating that the co-ion
has little effect on the surface excess above or below the cmc. It is possible that
the different co-ions cause different adsorption behaviour at very low surfactant
concentrations where electrostatics provide the driving force for adsorption. How-
ever, the surface excess values at these adsorption levels are below the sensitivity
of the reflectometer. The rates of adsorption for the three electrolyte types were also
alike at all surfactant concentrations, indicating that the co-ion has little effect on
the adsorption rate.
These results agree well with the AFM study of Subramanian and Ducker w78x
(Section 4.5.3) that suggested that the addition of LiCl up to a concentration of 500
mM had little effect on the adsorbed aggregate morphology of CTAC. The results
obtained here extend this finding, and show that KCl, NaCl and LiCl have no
Fig. 36. (a) Adsorption isotherms for CTAB (open squares), MTAB (closed diamonds) and DTAB
(open triangles) in the presence of 10 mM KBr (b) demonstrates the similarities in the form of the
adsorption isotherms when the same data are plotted as a function of the solution cmc. For more infor-
mation see Ref. w112x.
measurable effect on the saturation surface excess up to 10 mM XCl. Thus, it could

be expected that similar surface aggregate structures would be present for CTAC in
the presence or absence of 10 mM XCl.
6.3.10. Effect of chain length on adsorption

We have also studied the influence of the length of the hydrocarbon chain of
quaternary ammonium surfactants using OR w112x. The isotherms in Fig. 36
demonstrate that the data are qualitatively similar for DTAB, MTAB and CTAB in
the presence of 10 mM KBr. At concentrations below 0.1= cmc, where surface
Fig. 37. Initial adsorption rate for CTAB (open squares), MTAB (closed diamonds) and DTAB (closed
triangles) in the presence of 10 mM KBr. The dashed vertical lines represent the solution cmc for each
surfactant system. Reproduced from Ref. w112x.
excess values are low, the isotherms are essentially the same within instrumental
limitations. For concentrations greater than 0.1= cmc the isotherms separate, with
the surface excess increasing in the order DTAB-MTAB-CTAB for a given
fraction of the cmc. The increase in the surface excess is too large to be simply due
to the increased mass of individual surfactants i.e. the number of surfactant molecules
adsorbed at the interface increases in the order DTAB-MTAB-CTAB.
The kinetics of adsorption for DTAB, MTAB and CTAB in 10 mM KBr are
presented in Fig. 37. The general form of the data are the same for the three
surfactants. Below the cmc the rate of adsorption increases steadily with concentra-
tion. In the vicinity of the solution cmc there is an abrupt increase in the rate of
adsorption, as noted previously in Section 6.3.7. This is due to the direct adsorption
of micelles, which facilitates rapid and effective surface aggregate formation.
Comparison of the adsorption kinetics for the three surfactants is not as simple
as it may at first appear. If one chooses a surfactant concentration and compares the
adsorption rates, unless all three surfactants are below or above their cmc values,
different surface and bulk structures will be present. This will affect the rate at
which the adsorbed layer is created and thus the initial adsorption rate. It may seem
that the solution to this problem is to normalise the data by the solution cmc so
that the surface structures and hydrophobic driving force at a given fraction of the
cmc are similar. However, in doing this the absolute concentration of the surfactants
being compared will be vastly different, which will have a similarly large effect on
the flux of surfactant to the substrate. This obviously hampers any comparison.
However, it is possible to make some direct comparisons in certain regions of the
isotherms, and several more general observations.
Below 0.02 mM, where the surfactants are far below their solution cmc values,
the initial adsorption rates are low for all three surfactants. At these concentrations
it is expected that electrostatic interactions between the surfactant and the substrate
provide the driving force for adsorption and that hydrophobic interactions between
the tail-groups will have little, if any, effect on the adsorption rate. Thus, the initial
adsorption rates are all quite similar.
At 0.1 mM the three surfactants are still below their respective cmc values, but
there is a clear trend with the adsorption rate increasing in the order DTAB-
MTAB-CTAB. If one examines the adsorption isotherms (Fig. 36) at this
concentration, we note that the surface excess values increase in the same order.
That is, not only does an increased hydrophobic driving force lead to the assembly
of a more complete adsorbed layer, it also leads to significantly faster adsorption
rates.
Above 1 mM CTAB and MTAB are both above their solution cmc values. Once
again CTAB has the faster adsorption rate. The increased rate of CTAB adsorption
in this case is most likely due to the fact that the CTAB solution will have a much
higher proportion of its surfactant contained within micelles. As micelles are
considerably more effective at covering the substrate than monomer units w106,107x,
this brings about a faster adsorption rate. Above the cmc for DTAB no data were
obtained for CTAB. However, it is still possible to compare data for DTAB and
MTAB. The same effect occurs in this case, with MTAB having a significantly
faster adsorption rate for the concentration corresponding to the DTAB cmc.
In general, once the surface excess is appreciable (i.e. above 0.2 mM) the rate
of adsorption is always greater for the surfactant with the longer hydrocarbon chain.
When the surfactants are all below their solution cmc values it is the increased
hydrophobic interactions between monomers that leads to the faster adsorption rate.
A longer tail-group surfactant will also have a greater proportion of surfactant
contained within micelles (when present). As micelles are more effective in creating
an adsorbed layer on the substrate, this means that the longer chain surfactant will
also always have a faster adsorption rate above the cmc. Thus, at any concentration,
the adsorption rate always increases in the same order as the tail-group size.
6.3.11. The slow adsorption region

Our OR investigations have revealed a concentration range in the vicinity of the
csac where long-term increases in adsorption are observed w106,107,111,112x. This
region is known as the slow adsorption region (SAR), and was first noted for 0.6
mM CTAB in the absence of salt, where the adsorption of surfactant occurred over
a period of several hours. This is shown in Fig. 38. The surface excess rapidly
increased up to ;0.6 mg my2, but then proceeded very slowly until it reached the
final equilibrium adsorption value of ;1.6 mg my2 which was equivalent to that
reached at all higher concentrations of CTAB. Similar long-term increases in surface
excess have also been elucidated for CTAC w111x for surfactant concentrations
between 0.6 and 0.9 mM.
These unusual results were investigated in more detail using CPBr. As CPBr is
UV active, solution surfactant concentrations could be determined with high
precision spectrophotometrically. This allowed the effect of small increases in
surfactant concentration on slow adsorption phenomena to be ascertained. As shown
Fig. 38. Surface excess of CTAB at the pyrogenic silica–solution interface vs. time for 0.6 mM CTAB.
Adsorption occurs over a much greater time period than for other concentrations. The surface excess
initially increases rapidly to 0.6 mg my2 (which equals the equilibrium excess achieved at slightly lower
concentrations) then over a number of hours adsorption increases to the plateau level obtained for slightly
higher concentrations. At these higher concentrations equilibrium adsorption levels are obtained within
minutes Upon introduction of pure water at 12 000 s the adsorption returns to baseline levels. Reproduced
with permission from Ref. w106x.
in Fig. 39, solution CPBr concentrations of 0.2 and 0.55 mM were sufficient to lead
to a plateau coverage of 0.4 and 1.6 mg my2, respectively. It was between these
two boundaries, and only between these boundaries, that long-term increases in
CPBr adsorption were noted.
For CPBr concentrations between 0.274 and 0.306 mM, the surface excess rapidly
increased to approximately 0.4 mg my2, and then continued to increase at a greatly
reduced rate. Changes in solution CPBr concentrations of only 0.01 mM were
sufficient to bring about notable increases in the rate of the secondary adsorption.
The rate of this secondary increase in adsorption was proportional to the surfactant
concentration. Increasing the solution surfactant concentration to 0.336 mM CPBr
led to a fast increase in the level of surface coverage to 0.9 mg my2, followed by
a similar slow increase in the level of adsorption. The rate of the secondary
adsorption in this case was decreased over that observed for concentrations between
0.274 and 0.306 mM. For each of these experiments the surface excess had not
reached plateau levels after 30 h. Limitations associated with data collection
prevented longer observation times.
These results suggest that in the secondary phase of the adsorption process
adsorbing surfactants are filling surface adsorption sites stochastically. As the
concentration is increased, the probability of a monomer adsorbing is also increased,
leading to a faster rate of secondary adsorption. The initial level of surface excess
is higher for 0.336 mM (0.9 mg my2), which suggests that the adsorbed surfactant
layer is more complete in the initial stages of adsorption than that obtained with
slightly lower bulk concentrations. Consequently, there was a reduced number of
Fig. 39. Measured surface excess of CPBr at the hydroxylated silica–solution interface vs. time for CPBr
concentrations of 0.202 (filled circles), 0.274 (filled diamonds), 0.284 (filled squares), 0.306 (filled
triangles), 0.315 (open squares), 0.336 (open diamonds) and 0.554 mM (open triangles) with no added
electrolyte. Adsorption occurs over a much greater time period than for concentrations outside this range.
The surface excess initially increases rapidly to 0.4 mg my2 (or 0.9 mg my2 for 0.336 mM CPBr) then
continues to increase over many hours. 䉷 2000 ACS. Reproduced with permission from Ref. w107x.
adsorption sites available on the surface, which led to the observed reduced
secondary rate of adsorption at this concentration.
In this work AFM imaging was used to investigate the structural changes that
must accompany these slow increases in adsorption. AFM images of the silica
surface were obtained 20 min and 22.5 h after the injection of 0.3 mM CPBr. After
20 min had elapsed there was no evidence of any structure present in the adsorbed
layer on the silica surface, despite a surface coverage of ;0.4 mg my2 obtained by
reflectometry. However, after 22.5 h the presence of an adsorbed layer structure
consisting of elongated admicelles is clear w107x. Changes in the force vs. distance
data collected over this time period were also consistent with the slow formation of
surface aggregates.
It appears that the SAR is a consequence of kinetic barriers to the formation of
the thermodynamically stable arrangement of adsorbed surfactant. As the SAR
occurs at concentrations below the solution cmc, adsorption is due only to monomers.
These monomers must participate in an aggregation process at the interface that
results in the formation of surface structures analogous to bulk micelles. During this
process, a monomer may have to sample many sites before it is successfully
incorporated into a surface aggregate. Additionally, an incoming monomer must also
overcome an electrostatic barrier to reach the surface, as the surface excess of 0.4
mg my2 is sufficient to cause charge reversal of the silica surface. Thus, we
concluded that the SAR is a result of kinetic barriers to the adsorption process, in
the form of structural and electrostatic components.
The boundaries of the SAR were determined by both the surface structure and
coverage, and by the aggregate structure of surfactant in solution. At concentrations
below the SAR the concentration in bulk is not sufficient to raise the chemical
potential of the monomer to a level where surface aggregation is favourable. The
surface excess therefore indefinitely remains below that required to give rise to
surface aggregates. At concentrations above the SAR surface aggregates are clearly
forming and are doing so rapidly. One explanation is that at concentrations above
the SAR but below the cmc a number of transient semi-formed aggregates are
present in solution and these premature aggregates adsorb to the surface, negating
any requirement for monomer units to slowly pack into a preformed aggregate
structure. Alternatively, as the bulk substrate concentration is increased the electro-
static repulsion between the monomer and the surface will be screened more
effectively. This will decrease the energy barrier to adsorption for monomers and
facilitate more rapid accumulation at the surface.
The electrostatic screening interpretation is supported by the presence of a SAR
for CTAC in the presence of 10 mM LiCl w112x. This important result shows that
long-term increases in adsorption can occur in the presence of electrolyte, provided
the electrolyte does not influence the surface structure. Recall that the addition of
10 mM XCl to CTAC solutions has little effect on the equilibrium surface excess
w112x (cf. Fig. 35) or the adsorbed structure (cf. Section 4.5.3). Thus, while the
presence of 10 mM XCl diminishes the electrostatic repulsion an adsorbing monomer
experiences in the secondary adsorption phase, the same structural barriers to
adsorption remain in the presence of electrolyte. This permits long-term increases
in adsorption for CTACq10 mM LiCl and indicates that it is the structural barrier
to adsorption that is critical for the evolution of slow adsorption effects.
Using OR in conjunction with AFM, similar secondary increases in surface excess
have been observed for low surfactant concentrations at high pH w111x. The
adsorption kinetics were monitored using OR, and it was shown that for 0.11 mM
CTAB at pH 9.4, a rapid increase in adsorption occurred in the first 10 s, followed
by a slow rise (2–3 h) after which the equilibrium surface excess was reached.
This result was complemented by variation in force vs. apparent separation data as
a function of time and AFM imaging. Immediately after surfactant was passed into
the AFM cell, the substrate-tip interaction was dominated by an attractive jump into
contact starting from an apparent separation of approximately 10 nm. This originates
from a hydrophobic attraction between the tail-groups of the surfactant adsorbed to
the tip and surface. With additional time, a steeply repulsive force was observed,
typically from a separation of approximately 5 nm. This permitted images of the
adsorbed aggregates to be obtained, suggesting an adsorbed morphology similar to
that obtained at much higher surfactant concentrations, cf. Section 4.5.1.
These results show that a critical density of surfactant molecules adsorbed at the
interface is required to initiate spontaneous aggregation on the surface, rather than
a certain bulk surfactant concentration. Increasing the pH of aqueous solutions in
contact with silica leads to a substantial increase in surface charge. This promotes
the adsorption of cationic surfactants from dilute solution. Once a certain surface
excess is reached (0.6 mg my2 for CTAB on silica), the density of hydrophobe on
the surface is such that bilayered aggregation is initiated i.e. the adsorption of more
surfactant via hydrophobic interactions. The successful imaging of these aggregates
indicates that the csac for silica at pH 9.6"0.4 is in the vicinity of 0.055 mM
Fig. 40. Surface excess of CTAB on hydroxylated silica vs. time for (a) sequentially increasing and (b)
sequentially decreasing CTAB concentrations in the absence of electrolyte. A stable baseline was
obtained in water; the surfactant solutions were passed into the cell in series. Surfactant concentrations
used were 0.05 mM (filled circles), 0.15 mM (open diamonds), 0.3 mM (open triangles), 0.5 mM (open
circles), 0.6 mM (closed squares), 0.7 mM (closed diamonds), and 0.8 mM (open squares). Note the
long-term increase observed for 0.6 mM. Surfactant concentrations of 1, 3 and 5 mM were also used.
These concentrations all produced an equilibrium surface excess of 1.4 mg my2 within experimental
limitations and are not shown here for clarity. Water (crosses) is passed into the cell at 16 500 s and
the non-zero surface excess obtained is due to baseline drift. Only representative data points are provided.
However, the line to guide the eye provides a reasonable indication of the form of the experiment.
Reproduced from Ref. w113x.
CTAB, about an order of magnitude lower than at neutral pH w111x. As such it is

no longer logical to normalise the csac as a function of the bulk concentration but
to acknowledge that a certain surface concentration of adsorbed surfactant is
required to initiate surface aggregation. This approach not only considers the
surfactant–surfactant interactions which are correlated with the bulk behaviour but
includes the influence of the substrate.
OR enables different surfactant concentrations to be consecutively analysed, this

allowed the SAR to be further probed by cycling experiments w113x. Fig. 40a shows
the increasing concentration cycle and Fig. 40b the decreasing concentration cycle,
where surfactant concentrations were sequentially equilibrated at the interface. As
expected, a stepwise increase in surface excess is noted for all concentrations in the
increasing concentration cycle, except for 0.6 mM, where long-term increases in
surface excess are noted. In the decreasing concentration cycle of this experiment
the surfactant solutions were passed into the cell in reverse order and a stepwise
decrease in surface excess results. When water was passed into the cell at 16 500 s,
a surface excess of approximately 0.15 mg my2 results. This reflects drift in the
baseline over the course of the experiment, rather than residual surfactant adsorbed
at the surface. We note that the drift in these experiments is greater than for others
as the temperature control is adversely influenced by the large number of solution
changes.
The long-term increase for 0.6 mM observed in this concentration cycling
experiment (Fig. 40a) is somewhat different to that described above in Fig. 38, as
in this case the surface excess does not reach saturation levels of coverage. Whilst
this may seem problematic, there are important differences between the experiments
presented in Figs. 38 and 40a. In the first case, 0.6 mM CTAB is introduced to a
substrate which is initially bare and a fast increase in surface excess to 0.6
mg my2 results. It is assumed that, in the period of fast adsorption, the surfactant
adsorbs in a manner which is favourable for continued adsorption, albeit slow. This
allows the adsorption to continue, and saturation surface excess is eventually
reached. In the concentration cycling experiment, when the 0.6 mM surfactant is
passed into the cell, it encounters a pre-adsorbed surfactant concentration of 0.6
mg my2 that has been sequentially built up over a period of approximately 1 h.
Thus, in the cycling experiment when 0.6 mM is passed into the cell, the structure
initially present at the interface is the equilibrium structure for 0.5 mM CTAB. This
pre-adsorbed structure leads to a different structural adsorption path that becomes
kinetically trapped at a surface excess below the equilibrium surface excess. Because
of this, it is not until the surfactant concentration reaches 0.8 mM that saturation
levels of coverage are reached.
Surprisingly the desorption cycle reveals an increase in surface excess for
concentrations below 0.5 mM. Some of this discrepancy can be attributed to the
drift in the baseline of ;0.1 mg my2, but not all of it. This suggests that in the
increasing cycle, equilibrium is not achieved at the lower concentrations despite the
observation that the surface excess is stable. Perhaps this is an extreme case of
kinetically trapped conformations and suggests that the SAR may be indicative of a
more general effect at low concentrations and that accurate equilibrium adsorption
isotherms may only be obtained by desorption from higher concentrations.
These results highlight the importance of the surfactant structure in slow
adsorption, and also serve to illustrate the folly of implying kinetic information
from equilibrium data.
Fig. 41. The adsorption of 12-s-12 gemini surfactants at the silica–solution interface at 1= cmc: 12-2-
12 (filled diamonds), 12-3-12 (closed squares), 12-4-12 (closed triangles), 12-6-12 (closed circles), 12-
8-12 (open squares), 12-10-12 (crosses) and 12-12-12 (open triangles). A typical adsorption result for
1 mM CTAB (open circles) is included for comparison. The surfactant solution is first passed into the
cell at ;15.5 s leading to surfactant adsorption. The plateau level of adsorption is maintained whilst
the surfactant solution is flowing into the cell. 䉷 2003 ACS. Reproduced with permission from Ref.
w77x.
6.3.12. Adsorption of gemini surfactants to silica by OR

The adsorption kinetics of 12-s-12 gemini surfactants to silica has been investi-
gated w77x, and is presented in Fig. 41. The surfactant concentrations shown are
;1= cmc. For a given spacer length there was no variation in the form of the data
over the range of surfactant concentrations studied. For each surfactant a baseline
was obtained for ;15 s prior to surfactant being introduced into the cell, at which
time the surface excess rapidly increases. For all spacer lengths, equilibrium
adsorption levels are attained within 4 s of adsorption commencing. The surface
excess rises rapidly to approximately 70% of the equilibrium surface excess,
followed by a slower increase to the final value. The equilibrium surface excess
remained constant whilst the surfactant concentration was maintained. For compar-
ison, the adsorption curve of CTAB, also at 1= cmc, is included. CTAB has a
longer alkyl chain (C16) than the gemini surfactants under investigation here, but a
similar cmc (0.9 mM), and is therefore an appropriate comparison. The form of the
adsorption for CTAB is similar to that of all the gemini surfactants and identical to
that obtained for 12-3-12. Upon water being passed into the cell, desorption was
complete and rapid for all surfactants (not shown).
This study reported the most complete set of adsorption isotherms obtained for
gemini surfactants at the silica–aqueous interface, with adsorption isotherms for
seven different spacer sizes investigated, presented in Fig. 42. Below 0.3= cmc,
the adsorption isotherms are coincident. This indicates that electrostatic interactions
between the substrate and the adsorbed surfactant play a dominant role in the
adsorption process up to this concentration. The saturation surface excess decreases
Fig. 42. Adsorption isotherms for 12-s-12 gemini surfactants at the silica–solution interface with the
concentration axis as a function of the cmc: 12-2-12 (filled diamonds), 12-3-12 (closed squares), 12-4-
12 (closed triangles), 12-6-12 (closed circles), 12-8-12 (open squares), 12-10-12 (crosses) and 12-12-
12 (open triangles). Below 0.3= cmc there is no apparent variation in surface excess with spacer size.
Above 0.3= cmc the isotherms begin to separate, and the saturation surface excess decreases with
increasing spacer size. 䉷 2003 ACS. Reproduced with permission from Ref. w77x.
with increasing spacer size. The implications of this decrease for the adsorbed
morphology are detailed in Section 4.5.4.
There are two important differences between the data obtained in this study and
the depletion studies examined in Section 3.4.6. Firstly, solution depletion studies
(cf. Fig. 12) show a substantial increase in surface excess above the solution cmc,
an effect that was more pronounced for short spacers. No evidence of this effect
was detected in the current study for any spacer length. The isotherms for all spacer
lengths reached saturation at or slightly below the solution cmc. The same behaviour
is found for conventional cationic surfactants adsorbing to silica w106,107x. The
cause of the discrepancy between this study and those previous is unclear. The
second discrepancy relates to the concentration required to lead to the second
adsorption stage. Previous adsorption isotherms reported that the second adsorption
stage for the longest spacer investigated (12-10-12) commenced at lower concentra-
tions than for those with shorter spacer groups. This was attributed to the increased
hydrophobicity of the longer chain surfactant. In this study the concentration leading
to the second adsorption step was independent of the spacer length. The difference
between the two studies may be related to a change in the ionic strength of the
solution on surfactant adsorption that can occur in depletion studies. Surfactant
adsorption to charged surface sites on silica can induce nearby hydroxyl groups to
become more acidic w2x. For longer spacer groups this may result in both head-
groups interacting with the substrate and a consequent increase in solution ionic
strength w41x. An increased ionic strength will result in the solution cmc being
decreased, shifting the features of the adsorption isotherm to lower concentrations.
Fig. 43. Adsorption isotherms for CTAB (closed squares), DTAB in no added electrolyte (closed tri-
angles) and DTAB in 10 mM NaBr (open triangles) on the AAPP substrate. The filled lines are drawn
to guide the eye. The dashed lines separate the regions of the adsorption isotherms. Within instrumental
limitations, the adsorption isotherms for CTAB and DTAB with no added electrolyte are indistinguishable
below 0.1 mM, as are the DTAB no added electrolyte and DTAB with 10 mM NaBr isotherms above
approximately 3 mM. 䉷 2003 ACS. Reproduced with permission from Ref. w114x.
In the experiments using the reflectometer, the ionic strength of the solution is
unaffected by surface ionisation.
6.3.13. Adsorption of ionic surfactants to a charged hydrophobic substrate

For comparison, surfactant adsorption at a negatively charged, hydrophobic,
plasma polymer substrate was used to study the influence of the substrate on
adsorption behaviour w114x. The acetaldehyde plasma polymer (henceforth denoted
AAPP) surface used is similar to silica in charge density but differs in that the
regions between the charge sites are hydrophobic. The adsorption isotherms for
CTAB, DTAB and DTAB with 10 mM NaBr are presented in Fig. 43 and for SDS
and SDS with 10 mM NaBr in Fig. 44. The isotherms can easily be divided into
four-regions. Region I is a low surface excess region where the level of adsorption
was independent of the bulk concentration. Regions II and III occurred where the
surface excess was increasing linearly with concentration, the latter increasing more
steeply, and a final plateau region where no further adsorption is observed as the
bulk concentration of surfactant is increased (region IV). It was noted that the first
region was absent for the anionic surfactant systems. This difference was attributed
to the negative surface charge on the AAPP substrate, which drives electrostatic
adsorption of cationic surfactant and hinders adsorption of anionic surfactant.
In Fig. 43 it can be seen that up to a surfactant concentration of ;0.02 mM the
adsorption isotherms of CTAB and DTAB are indistinguishable. This indicates that
the adsorption in the first region is independent of the hydrophobicity of the
surfactant monomer, and is thus driven purely by Coulombic attractions between
Fig. 44. Adsorption isotherms for SDS in no added electrolyte (closed circles) and in 10 mM NaBr
(open circles) on the AAPP substrate. The lines are drawn to guide the eye with regard to the trend in
the data series. The dashed lines separate the regions of the adsorption isotherms. Note that region I is
absent. Within experimental limitations, the isotherms are indistinguishable above 3 mM. 䉷 2003 ACS.
Reproduced with permission from Ref. w114x.
the surfactants and the charged sites on the surface. In the DTABq10 mM NaBr
system the surface excess is much lower in this region of the isotherm. We attribute
this difference to screening of the surfactant–substrate electrostatic interaction andy
or reduction in the number of charged sites suitable for adsorption on the surface
due to adsorption of Naq ions. Similar effects have been observed on silica for the
adsorption of CPBr w107x. Note no measurable adsorption occurs for the SDS
systems. That is, the first region is absent in Fig. 44.
For all isotherms, further adsorption beyond region I takes place against a
repulsive electrostatic interaction and therefore must be driven by hydrophobic
interactions. The concentration which separates the first and second regions of the
isotherm is analogous to the cac w115x for surfactant–polymer interactions in
solution and is denoted the surface cac. In region II, all systems exhibit a linear
increase of surface excess with the log of concentration above the surface cac. The
slope of the isotherm in this region is indicative of the magnitude of the favourable
hydrophobic surface–monomer interactions. The slope of the CTAB isotherm
exceeds that of the DTAB isotherm. This is a direct consequence of the greater
hydrophobicity of the C16 vs. C12 hydrocarbon chain. Importantly, all the systems
remain linear until the same surface excess of ;0.3 mg my2 is reached. Saturation
of this adsorption process occurs at this concentration and strongly suggests that the
arrangement of surfactants on the surface is the same in all systems. It is postulated
that coverage of the substrate in this region is by random sequential adsorption.
Adsorbed surfactant chains are confined to the plane of the surface by hydrophobic
interactions whilst the head-groups may protrude from the surface in order to
maximise hydration. For the cationic surfactants, the surfactants adsorb opposite a
surface charge, orientated with head-groups electrostatically bound to the charged

surface group, and hydrocarbon chains adsorbed to the substrate. Between the
charged substrate groups, surfactants are adsorbed with hydrocarbon chains against
the hydrophobic surface, while the head-groups may be orientated towards solution.
For SDS, it is anticipated that the surfactant will be adsorbed in the same manner
as for DTAB and CTAB but lie between charged surface sites.
The next sub-region occurs for surface excess values from 0.3 mg my2 up to the
saturation level of coverage for each system (;0.5 mg my2 for C12 systems and
0.7 mg my2 for CTAB). The surface excess is now too large for all the surfactant
monomers to be confined to a prostrate layer against the substrate; a more complex
structure must exist. This region of the isotherm exhibits the greatest rate of increase
in surface excess with increasing bulk concentration. This rapid increase is a
consequence of cooperative hydrophobic interactions between adsorbed and adsorb-
ing monomers. The end result of this process is the plateau region of the adsorption
isotherm, and further increases in concentration have no effect on surface excess.
The level of adsorption beyond the prostrate monolayer coverage achieved at the
end of region II is not large (;40% of the total). The proposed structure is one of
monomers adsorbed to the most hydrophobic patches of the prostrate monolayer.
This will leave the more hydrophilic charged sites exposed to water. Thus the
overall structure is one of a prostrate monolayer with a partially (;65%) complete
second prostrate monolayer attached to it. The sparseness of the ‘second’ layer
ensures that head-group interactions are not important. Note the ‘second’ layer
should not be considered a distinct layer as it will be anchored in the prostrate layer
and very incomplete. The disorder in the structure ensures that AFM images cannot
be obtained.
The times to obtain equilibrium for surfactant adsorption on the AAPP substrate
were also reported. In regions II, III and IV of the isotherms when electrolyte is
absent, the adsorption of both SDS and DTAB to the AAPP substrate typically
required approximately 2500 s to achieve equilibrium. On the addition of electrolyte,
these equilibration times were considerably reduced, to approximately 100 s. It is
suggested that the presence of added salt permits more rapid coverage of the
substrate by reducing the range of electrostatic repulsions between head-groups.
Lengthening the hydrocarbon chain from 12 to 16 carbon atoms (i.e. DTAB to
CTAB) resulted in a similar reduction in equilibration time. In this case, the
reduction could only be due to the increased hydrophobicity of the monomer
imparted by a longer tail-group, as electrostatic influences are not expected to be
significantly different between DTAB and CTAB in the absence of electrolyte.
The initial adsorption rates were investigated, and it was shown that CTAB had
the fastest initial adsorption rate of the surfactants studied. This was also attributed
to the greater hydrophobic driving force imparted by a longer tail-group. The
adsorption rates for the DTAB, DTABq10 mM NaBr and SDSq10 mM NaBr
systems were quite similar at all concentrations. The SDS no added electrolyte
system had the lowest initial adsorption rate, due to the electrostatic repulsions
between the substrate and the monomer.
6.4. Summary of reflectance observations
Results from NR provide the most accurate measure of the thickness of the
adsorbed layer of CTAB on silica, of approximately 3.5 nm, as well as a lateral
size of discrete aggregates of approximately 9 nm. It was suggested that if these
aggregates were micelle-like, then they must be strongly flattened. This result agrees
well with push through distances measured using AFM, and the flattening of the
aggregate is most likely due to the surface charge of the substrate.
SAR on silica have been identified for CTAB and CPBr at normal (unadjusted)
pH in the absence of electrolyte, for CTAC both in the presence and absence of
added electrolyte, and for CTAB at pH 10 using OR. We propose that the nature of
the surfactant arrangement in solution and on the surface at equilibrium determines
if an SAR region is likely. An SAR can only occur if the packing constraints of a
monomer in a surface aggregate is very much greater than the packing constraints
in solution. In the absence of electrolyte, the equilibrium surface structure present
is small micelle-like surface aggregates adsorbed on the surface, whereas in solution
only monomers are present. It is this process of building order at the surface that
gives rise to the slow kinetics. The presence of electrolyte increases the aggregation
in solution and at the same time results in surface aggregates with less curvature,
thus removing the mismatch in packing constraints between the bulk and the surface.
The evolution of these structures were followed by AFM. As the SAR corresponds
to the first concentration where aggregates are formed at the interface, the lower
concentration boundary of the SAR is equivalent to the csac. Slow adsorption effects
have not been elucidated in the presence of the electrolyte of a strongly binding co-
ion i.e. the addition of 10 mM KBr to CTAB or CPBr solutions. Slow adsorption
effects have been observed in the presence of the weakly binding chloride counterion.
This supports a structural interpretation for the origin of slow adsorption. The
gemini surfactants did not exhibit slow adsorption for any spacer size.
For surfactants in the presence of the electrolyte of a strongly binding co-ion,
equilibrium is rapidly reached at all surface excess values and increases in the
surface excess above the cmc are noted. This is a result of a higher packing density
of the surface aggregates and a change in aggregate morphology. Thus, for these
systems, the csac is actually greater than the cmc. In these systems aggregates occur
in bulk before they are present on the surface indicating that the energy cost of the
geometrical constraints of the surface on the aggregate structure exceed the
adsorption energy.
In both the presence and absence of electrolyte, chloride surfactants exhibit
similar features to bromide surfactants in the absence of electrolyte, due to the
chloride ion having a much lower affinity for surfactant aggregates than the bromide
ion. The decreased binding efficiency of the chloride ion results in the saturation
surface excess of the chloride system being approximately 50% less than that of the
corresponding bromide surfactant. For concentrations up to 10 mM, the identity of
the electrolyte co-ion does not influence adsorption behaviour within the experimen-
tal limitations of OR.
For constant solution conditions, lengthening the hydrocarbon tail-group of the

surfactant monomer leads to two important effects. Firstly, the entire adsorption
isotherm is ‘shifted’ to lower concentrations, in line with the reduction in solution
cmc, and the width of the increasing region of the isotherm is decreased. Secondly,
the saturation surface excess is increased for the longer chain surfactants. Calculation
of the number of surfactant monomers per unit area reveals that this increase in
surface excess is due to the presence of a greater number of molecules adsorbed at
the interface, and not merely a result of the increased mass of the monomer units.
For 12-s-12 gemini surfactants adsorbing at the silica–aqueous interface it has
been shown that below 0.3= cmc, the surface excess is independent of the spacer
size. At these concentrations attractive electrostatic interactions between the adsorbed
surfactants and the substrate determine the level of adsorption. At increased
surfactant concentrations further adsorption is due to hydrophobic interactions
between adsorbed monomers. The saturation surface excess is a function of the
spacer size, with the shortest spacer size producing the largest saturation surface
excess.
Whereas the equilibrium surface structures determined for cationic surfactants on
silica have been shown to be elongated spherical structures, the adsorbed morphology
of the surfactant layer on the AAPP substrate is a prostrate monolayer with a
partially (;65%) complete second prostrate monolayer attached to it. The ‘second’
layer is not a distinct layer as it will be anchored in the prostrate layer and very
incomplete. CTAB has the highest saturation surface excess of the surfactants
investigated on this substrate. However, the area per molecule data shows that
approximately the same numbers of molecules are adsorbed for all surfactant–
substrate combinations at saturation and so the increase in surface excess is due to
the increased mass of the CTAB monomer. On this substrate, DTAB and SDS have
the same saturation surface excess both in the presence and absence of added 10
mM NaBr, despite the surface having a substantial negative charge. This demon-
strates the dominance of hydrophobic interactions for surfactant adsorption onto
hydrophobic substrates.
Studies of surfactant adsorption kinetics give insight into the mechanism of
surfactant adsorption. Comparison of the measured kinetics of adsorption (for
cationic surfactants adsorbing to silica) to the theoretical diffusion limited flux of
surfactant to the substrate has revealed a cooperative character in the adsorption
process above the solution cmc. This cooperativity is due to the direct adsorption
of micelles to the substrate.
The kinetic aspects of gemini surfactant adsorption have been shown to be similar
to that of conventional surfactants. The adsorption process is complete within
seconds for all spacer sizes, at all concentrations. Thus the slightly slower micellar
monomer exchange rates for gemini surfactants has little influence on the adsorption
kinetics.
For a constant head-group type, a longer tail-group will have a higher initial
adsorption rate at any concentration, on both silica and the AAPP substrate. This is
due to the increased hydrophobicity of the monomer providing a greater driving
force for adsorption at pre-aggregate concentrations. This increased hydrophobicity

is evidenced by the fact that longer tail-group surfactants form micelles at lower
concentrations. As micelles facilitate more effective substrate coverage, this leads
to faster adsorption rates.
The addition of electrolyte to surfactant solutions increases the rate of adsorption
at a given concentration for both the silica and AAPP substrate. In addition to
screening electrostatic interactions the addition of electrolyte lowers the solubility
of the hydrocarbon chain, rendering the surfactant molecule more hydrophobic. This
results in the adsorption rate being increased as described above. As the increase in
the rate of adsorption is not dependent on the binding efficiency of the counterion
to the surfactant, in the absence of specific interactions, the species of the electrolyte
does not influence the rate of adsorption.
In general, the kinetics of adsorption is slower on the AAPP substrate than for
silica. This is most likely due to the difference in the adsorbed conformation on the
two substrates. The mixed nature of the surface may also play a role, in that
favourable electrostatic and hydrophobic interactions are possible on the AAPP
surface but the strength of these interactions may be reduced. The adsorption of
DTAB and SDS in the absence of electrolyte to the AAPP substrate is comparatively
slow to reach equilibrium, but does not correspond to a SAR. For these systems,
adsorption at all concentrations is slow, not just in a discrete portion of the isotherm.
Secondly, the increase in surface excess with time does not correspond to a structural
transition in the adsorbed aggregates. The role of the substrate in the pace of
adsorption should not be underestimated.
7. Summary
Adsorption isotherms are the traditional method for investigating surfactant

adsorption phenomena, and they continue to yield much valuable information. By
comparing isotherm data with the more recent structural information provided by
techniques such as AFM, calorimetry, fluorescence probe studies, NR, and ellipso-
metry, changes in the interfacial conformation of the surfactant as a function of the
solution concentration can now be determined. In a further advance, analysis of
adsorbed aggregate structures in the light of new and detailed kinetic data indicates
that it is the type of aggregates that form on the surface that determines both the
surface excess and the rate of adsorption.
7.1. Mechanism of adsorption and the adsorption isotherm
The new knowledge now available allows us to comment on the adsorption

process with greater precision than ever before. This is particularly true for cationic
surfactants on oxide surfaces. Adsorption is controlled by electrostatic and hydro-
phobic interactions. The relative influence of these interactions is determined by
both the properties of the substrate and the nature and concentration of the surfactant.
We divide the adsorption isotherm into three concentration spans. In each span a
new adsorption process is possible. The spans are named on the basis of the
Fig. 45. Proposed Mechanism of surfactant adsorption. Each span is described in detail in Section 7.
adsorption mechanism that is newly available in that concentration range. They are,
in increasing concentration, the electrostatic concentration span, the electrostatic–
hydrophobic concentration span and the hydrophobic concentration span. The
mechanism of adsorption in each span differs and is depicted schematically in Fig.
45. Note that the hydrophobic concentration span may be further divided into above-
cmc and below-cmc spans to reflect the direct adsorption of micelles. We provide
our description of the adsorption mechanisms in order of increasing concentration
but this should not be taken to imply that the kinetics of adsorption operate in this
manner. That is, adsorption at a concentration in, for example, the hydrophobic span
does not imply that the adsorption process occurs sequentially through the electro-
static span, the electrostatic–hydrophobic span then the hydrophobic span. Rather
in the hydrophobic span the mechanisms applicable to all regions may be operating
simultaneously and at different rates. For example, as we have evidence that micelles
adsorb directly to the surface, in this case the hydrophobic interactions are essentially
in operation before the micelle approaches the surface, at which time the electrostatic
mechanisms begin to operate. The mechanism we have assigned to each span is
available to surfactant adsorption at greater concentrations but not at lesser
concentrations.
7.1.1. The electrostatic concentration span

In the first span surfactant molecules are electrostatically adsorbed to the charged
surface sites. The presence of a positively charged head-group at the interface
renders nearby hydroxyl groups more acidic, which induces more charged sites in
the vicinity of the initial charge site.
7.1.2. The electrostatic and hydrophobic concentration span

Surfactant tail-groups will interact with any hydrophobic regions that are present
on the substrate. Regardless, the hydrophobic tails of the surfactant, along with the
newly induced sites of surface charge, act as nucleation points for further surfactant
adsorption. The adsorption is thus driven both by hydrophobic interactions and
electrostatic attraction. Throughout the second span the charge on the underlying
substrate continues to increase. At the end of this concentration span the adsorbed
morphology is described as a ‘teepee’ structure, the substrate ionisation is at a
maximum and the overall surface charge is neutralised.
7.1.3. The hydrophobic concentration span

Any further adsorption is purely hydrophobically driven, and will be against a
repulsive electrostatic barrier that arises as a result of overcompensation of the
surface charge by the adsorbed surfactant. Thus span three is characterised by the
hydrophobic adsorption of surfactant molecules to the ‘teepees’ present at the
interface, with head-groups oriented away from the surface. In the third concentration
span, the level of counterion adsorption becomes appreciable. The kinetic evidence
evaluated in this review suggests that the explanation of the hydrophobic concentra-
tion span is relevant for all surfactant concentrations above charge neutralisation.
The only variation in the adsorption mechanism is the direct adsorption of micelles
above the solution cmc.
Not all systems will exhibit different adsorption regions corresponding to the
three concentration spans described. We have seen that for an anionic surfactant
adsorbing to a partially hydrophobic anionic surface w114x, there is no electrostatic
adsorption, as such the first span is not present in this isotherm. Highly hydrophobic
surfaces give a similar result.
7.2. Adsorption kinetics and the adsorption isotherm
We have demonstrated that the adsorption process can continue over long periods
due to ‘kinetic trapping’. The concentration range over which this occurs is called
the SAR. The SAR spans concentrations that are sufficient to lead to aggregate
levels of coverage on the substrate, but where no aggregates are present in solution
and is a consequence of kinetic barriers to the formation of the thermodynamically
stable arrangement of adsorbed surfactant. This phenomenon may yet prove to be
widespread. We have seen that adsorption levels obtained on dilution exceed those
that are reached when the surfactant concentration is increased in a step-wise
manner. Further, the adsorption levels obtained by increasing the concentration in a
stepwise fashion were less than those obtained when the concentration is increased
directly, in one step. These differences exist despite the fact that in all cases the
surface excess had stabilised and apparent equilibrium had been reached. The fact
that stepwise introduction of surfactant led to values of surface excess less than
those seen at the same concentration for stepwise reductions in surfactant concen-
trations can be interpreted as evidence that equilibrium has not been reached in the
former case, and that this is due to kinetic trapping akin to that which gives rise to
the SAR. However in this case the kinetic trapping is so severe that continued
adsorption has ceased. Thus, equilibrium adsorption isotherms that are determined
by stepwise changes in surfactant concentration should always be conducted under
a dilution regime to prevent false equilibrium values being obtained.
An assessment of the available literature on the adsorption of cationic surfactants
to silica surfaces has led to a new understanding of the mechanisms operating
during adsorption. The mechanisms available are determined by which concentration
span of the adsorption isotherm the solution surfactant concentration lies in. The
adsorbed surfactant morphology determines both the kinetics of adsorption and the
surface excess. The influence of the kinetics of adsorption can be dramatic, leading
to very slow adsorption processes and possibly complete kinetic trapping at surface
excess values below the true equilibrium surface excess.
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Mechanism of Cationic Surfactant Adsorption at The Solid-Aqueous Interface

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Advances in Colloid and Interface Science

103 (2003) 219–304

Mechanism of cationic surfactant adsorption at

*Corresponding author. Tel.: q61-2-4921-8846; fax: q61-2-4921-5472.

1. Introduction ............................................................................................ 221

5.2. Time resolved fluorescence quenching .................................................... 264

The adsorption of a solute at the solid–aqueous interface results in an increase in

type of adsorption is generally interpreted using the Langmuir isotherm, which

2. General surfactant and substrate properties

2.1. Silica surface chemistry

A significant proportion of the available literature concerning surfactant adsorption

ions) in solution, as shown by the following equations.

It is the relative magnitude of the equilibrium constants K1 and K2 in Eqs. (1)

2.2. Surfactant properties

Adsorption isotherms are traditionally determined by solution depletion methods

3.2. Traditional analysis

Much of the literature concerning adsorption isotherms predates in situ methods

Surfactant name Structural formula Acronymyabbreviation cmc (mM) cmc (mM)

measured at different salt concentrations and the consequences of different methods

3.2.1. The two-step model

the shape of the isotherm is often interpreted as being indicative of a monolayer on

3.2.2. The four-region model

3.2.3. Similarities between models

3.3. The influence of surfactant chain length

As the hydrocarbon chain length of a surfactant molecule is increased, the

3.4. The role of surface charge

A major limitation of the solution depletion method for studying surfactant

3.4.1. Increases in surface charge with adsorption

3.4.2. The common intersection point

3.4.3. Adsorption model based on the cip

3.4.4. The influence of surface preparation

3.4.5. Comparison of adsorption mechanisms on raw and acid washed silica

that leads to ionisation of surface groups is detectable by a decrease in the solution

3.4.6. Surface charge and gemini surfactant adsorption

3.4.6.2. Gemini surfactant adsorption isotherms. Adsorption isotherms for 12-2-12,

3.5. Evidence for discrete aggregation from adsorption isotherms

Adsorption isotherms yield significant information concerning the nature of the

of adsorption. However, it is difficult to infer adsorbed structures from this type of

Adsorption isotherms can be complemented by measurement of the heat of

obtained by calorimetry concerning the mechanism of adsorption, without actually

3.6.1. The importance of surface water

3.6.2. Calorimetry and adsorption mechanism

3.6.3. Interactions between the hydrocarbon tail and the surface

3.7. Summary of adsorption isotherms

The study of adsorption isotherms by depletion methods continues to be an

of electrolyte lowers adsorption by competing with monomers for charged surface

4. Atomic force microscopy

greater accuracy. AFM is particularly well suited to detecting the periodicity of

4.2. The earliest images of surfactant aggregation: CTAB on graphite

The first direct imaging of interfacial aggregation concerned the adsorption of

4.3. Graphite strongly orientates surfactant aggregates

4.4. Adsorption studies on mica

Considerably different aggregate morphologies have been determined for the

surface lattice of the substrate, which is expected to influence aggregate morpholo-

4.4.1. Alkyltrimethylammonium halides on mica

4.4.2. The influence of electrolyte on aggregate morphology

4.4.3. Gemini surfactants on mica

However, a reduction in the spacer length to 2 resulted in the formation of a