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Materials and Structures

DOI 10.1617/s11527-015-0603-9

ORIGINAL ARTICLE

Competitive adsorption of surfactant foaming agents


to nanoclays added to cement foams for enhanced strength
Benjamin J. Naden

Received: 28 January 2015 / Accepted: 18 March 2015


RILEM 2015

Abstract The adsorption affinity of a surfactant


foaming agent (SFA), a-olefin sulphonate (AOS)
used for generation of foam for low density concrete
to organically-modified montmorillonite (OMMT) has
been investigated. OMMT has been proposed as an
additive to cement and concrete for improved strength
and durability. Similar thermodynamic processes are
involved in the generation and stabilisation of foam
and in the compatibilisation and stabilisation of
organic particles in aqueous environments, so interaction between SFA and OMMT particles is likely.
Association of foaming agent molecules with organoclay may lead to poor foaming performance and
potential instability of the nanoparticles due to
displacement of dispersants from the particle surface
by foaming agent. Adsorption isotherms determined
using a combination of ion-pair reverse phase high
performance liquid chromatography (RP-HPLC) and
gravimetric methods revealed that there is a relatively
high affinity of AOS for the organoclay particles. This
is a dynamic process, with smaller molecules adsorbing quickly but being displaced by larger
molecules at higher surfactant loading. From the
adsorption isotherm it was possible to calculate the
minimum AOS addition that will ensure the full

B. J. Naden (&)
Chemistry & Biotechnology. Pera Technology Ltd, Pera
Business Park, Nottingham Road, Melton Mowbray,
Leicestershire LE13 0PB, UK
e-mail: b.naden@peratechnology.com

foaming performance in the cement formulation.


Relative adsorption affinity and competitive adsorption at the particle surface of AOS with non-ionic and
anionic surfactants commonly used as wetting and
dispersing agents, was studied. The dispersants displayed considerably higher relative adsorption onto
the organoclay than AOS, particularly in the case of
the anionic species. There is evidence that some AOS
adsorption takes place in particle systems stabilised by
non-ionic dispersants; displacement of high adsorption affinity dispersants by the lower affinity AOS
from the OMMT particle surface was not observed.
Keywords Surfactant foaming agent  Organicallymodified montmorillonite  Cement  Adsorption
isotherm  Competitive adsorption  Nano-functional
additive
Abbreviations
SFA
AOS
OMMT
RP-HPLC
HLB
MB2HT-MMT

AE

Surfactant foaming agent


a-olefin sulphonate
Organically-modified
montmorillonite
Reverse phase high performance
liquid chromatography
Hydrophiliclipophilic balance
Methylbenzyl di-hydrogenated
tallow ammonium chloride
modified montmorillonite
Fatty alcohol polyoxyethylene

Materials and Structures

AAS
UV
MPI

Anionic alkyl-aryl sulphonate


Ultraviolet
N-methylpyridinium iodide

1 Introduction
Surfactant foaming agents are added to cement and
concrete formulations for the production of low
density materials, often used in applications that
require low strength void filling. Surfactants are
amphiphilic molecules that reduce the interfacial
tension between hydrophilic and hydrophobic phases
and increase contact surface area, enabling association
of these otherwise incompatible phases. The behaviour of a surfactant at the interface can be predicted
by the hydrophiliclipophilic balance (HLB), a semiempirical scale based on the relative molecular mass
of hydrophilic functionality compared to lipophilic
groups. A surfactant with a high HLB will have a large
hydrophilic group compared to the hydrophobic
component and this will influence its behaviour at an
oil (or hydrophobic solid particle)/water (or hydrophilic particle) phase boundary, although this
partitioning is independent of the overall size of the
molecule.
Surfactants promote the production of foams in
aqueous media by stabilizing the interface of the
hydrophobic gas phase and the hydrophilic aqueous
phase (Fig. 1). A surface tension gradient is established by the presence of the surfactant at the interface,

Fig. 1 Optical micrograph of stabilised aqueous foam

creating an elastic surface due to the flow of surfactant


molecules and liquid from the bulk to the interface.
This restoring GibbsMarangoni effect prevents thinning of the liquid film between the gas bubbles and
stabilizes the foam [1]. Instability due to drainage of
liquid under gravity from the interfacial region can be
resisted by high viscosity liquid and the production of
small, stiff-walled bubbles.
Foamed cement and concrete materials can provide
enhanced acoustic and thermal insulation properties
compared to non-foamed mineral structures [2] but are
generally inappropriate for load-bearing applications
or in circumstances where high mechanical strength is
required. This inherent weakness may be addressed by
increasing the strength of the foam cement concrete
matrix by the use of additives such as binders and
fibres. Foam pore walls can be reinforced, although
this requires the use of molecules that are significantly
smaller than the thickness of the gas-cement interfacial region. One such approach investigated previously has been the addition of carbon nanotubes, the
inclusion of 0.05 wt% of which showed an increase in
compressive strength of non-autoclave cement foam
concrete of up to 70 % [3].
A number of studies have reported enhanced
structural properties of concrete with the addition of
nanoclays [47], organically-modified clay minerals
displaying nanostructural properties. The FibCem
project, an EU FP7 part-funded collaborative project
to develop nanotechnology-enhanced extruded fibrereinforced foam cement, intends to incorporate nanoclays to provide mechanical property improvements.
To achieve compatibility and stability of organoclays
with an aqueous cement environment it is necessary
that a surfactant is used, the absence of which will
result in particle agglomeration and the loss of any
reinforcing nano effect. Surfactants used to produce
emulsions and particle dispersions consist of a small
number of units and they mostly are reversibly
adsorbed at surfaces. Adsorbed amount is a function
of molecular weight, solubility in the solvent (and
therefore relative solubility parameters), affinity for
the surface of the adsorbing functional group(s), and
poor solubility and hence rejection from the solvent of
this functional group.
The adsorption of surfactants on hydrophobic
surfaces such as organically modified nanoclay is
governed by hydrophobic interaction between the
alkyl chain of the surfactant and the hydrophobic

Materials and Structures

surface (Fig. 2). Immobilisation at the particle surface


results in a loss of entropy which must be compensated
for by the enthalpic and entropic gains implied by the
thermodynamics involved in association of functional
groups of the adsorbing molecule and those at the
particle surface and the liberation from the particle
surface of adsorbed solvent molecules. Since adsorption depends on the magnitude of the hydrophobic
bonding free energy, the amount of surfactant adsorbed increases directly with increasing alkyl chain
length [8].
In the application of particle dispersions, the
addition of other formulation ingredients, including
surface active components and dilution with solvent
can act to compromise dispersion stability. The same
mechanisms that are involved in the adsorption of the
stabilizing surfactant to the organic surface of the
nanoclay will also affect the amphiphilic surfactant
foaming agent. As a consequence, there is a very real
possibility of interaction between the foaming agent
and nanoclay, resulting in a reduction in foaming
capacity and foam stability. In addition, the adsorption
amount dependence upon molecular weight and the
reversible nature of the adsorption mechanism means
that competitive adsorption may occur in mixed
surfactant systems, involving the displacement of
stabilizing surfactant molecules by the foaming agent
and a consequent destabilizing effect. The result of the
competitive adsorption between two non-interacting
molecules depends on their relative affinity for the
surface, although other factors, including relative
solubility discussed above, need to be considered.
Thus, it is not sufficient simply to compare hydrophobic anchor chain composition of competing surfactant
molecules in order to predict displacement of adsorbed
stabilising molecules in the presence of, in this case, a
surfactant foaming agent.

Adsorption of solutes at the solidliquid interface is


usually described through isotherms, expressed as
amount of adsorbate on the adsorbent in relation to
equilibrium concentration in solution. Adsorption
isotherm curves can exhibit different shapes but are
generally composed of three different regions (Fig. 3):
(1) initially low adsorbate concentration is characterised by high adsorption rates of isolated molecules;
(2) this is followed by an increase in the surface
adsorption density and then (3) by a third plateau
region which is independent of the concentration of
adsorbate in solution and corresponds to complete
surface coverage.
The shape of the isotherm can provide insight into
the nature of the adsorption process. For example,
monodisperse molecular adsorption isotherms show a
sharp transition between a steep adsorption rate at
incomplete surface coverage to a plateau value at full
surface coverage. A polydisperse distribution of
molecules produces a more rounded isotherm due to
the complete adsorption of molecules at low concentration, but as concentration increases and the surface
becomes saturated the longer chains in solution are
able to displace the shorter chains on the surface [9].
Comparison of the adsorption isotherms for the
surfactant systems can provide useful information
regarding any likely competition at the surface. It may
also be possible to measure directly surfactant
displacement.
The objective of this study was to investigate
the nature of the interaction between a typical
surfactant foaming agent and organically-modified

Fig. 2 Schematic of surfactant adsorption at organoclay


particle surface in aqueous medium

Fig. 3 Typical Langmuir-type adsorption isotherm curves


showing regions of adsorption behaviour

Materials and Structures

montmorillonite nanoclay (OMMT) that has been


dispersed in water for incorporation into a cement
formulation as a nano-functional additive.

2 Experimental
2.1 Materials
The organoclay used in this study was a methylbenzyl
di-hydrogenated tallow ammonium chloride modified
montmorillonite (MB2HT-MMT) provided by Laviosa
Chimica Mineraria S.p.a. (Livorno, Italy). Powders
were dried at 70 C for a minimum of 24 h.
The following technical grade surfactants were
used for organoclay stabilisation in water:
Nonionic C10 fatty alcohol polyoxyethylene(6)
(AE)
from
Croda
Chemicals,
UK.

Nonionic emulsifier polyethylene(10) oleyl ether


(Brij O10 ) from Sigma Aldrich, UK.

sample jar were transferred to centrifuge tubes and


centrifuged at 8500 rpm for 30 min. The supernatant
from each tube was carefully removed and filtered and
the equilibrium concentration of dispersant determined by the various techniques described below. The
amount of surfactant adsorbed at the particle surface
was derived from the concentration of the nonadsorbed surfactant in solution.
2.2.1 Reverse phase ion-pair UV detection HPLC
A method for analysis of the AOS surfactant was
developed based on a technique described by Zahrobsky and co-workers [10] using RP-HPLC with indirect
photometric detection. Pyridinium salt N-methylpyridinium iodide (MPI) was used to form an ion-pair
complex with the sulphonate surfactant, allowing UV
detection. Surfactant solution samples of 25 lL were
injected into a mobile phase comprising 60 vol%
water and 40 vol% acetonitrile and 0.15 mM MPI.
Mobile phase elution rate was set at 1 mL/min through
a 5 lm C18 reverse phase column fitted to an Agilent
1100 series HPLC using diode array detector at
258 nm wavelength.

Anionic alkyl-aryl sulphonate (AAS) from Croda


Chemicals, UK.

2.2.2 Gravimetric analysis

The surfactant foaming agent used was an anionic


a-olefin sulphonate (AOS) supplied by Sika S.A.U.,
Spain at actives concentration of 40 wt%.

Non-adsorbed surfactant concentration was determined by loss of mass of the centrifuge supernatant
at 150 C. Approximately 510 g of sample was
placed in the pan of a thermal balance (MS-70
moisture analyzer, A&D Weighing) and reduction of
mass was monitored until rate of loss was less than
0.1 % per minute. The remaining weight was used to
determine equilibrium concentration and subsequently
adsorbed amount using mass balance calculations.

3 Results and discussion


2.2 Methods
3.1 RP-HPLC calibration
To determine the adsorption isotherm for each of the
systems studied, various weights of surfactant were
diluted to approximately 9.5 g in deionised water in
screw-top 15 mL vials and fully dissolved. Approximately 0.5 g of nanoclay was added to each vial,
each of which was sealed and then sonicated for
45 min in a sonic bath. The samples were stored at
room temperature overnight. The contents of each

The elution chromatograms for standard solutions of


AOS surfactant are presented in Fig. 4. A large
negative peak was observed early in the run, with the
same retention time as the ion-pair reagent (approximately 2 min). Later in the chromatogram another
large, broad, negative peak was observed; these
negative system peaks were present in all surfactant

Materials and Structures


Fig. 4 HPLC elution
spectra of a-olefin
sulphonate surfactant with
MPI ion-pair reagent

elution chromatograms and may be caused by depletion


of the UV-active reagent from the mobile phase when
the sample is injected. When the surfactant material
was eluted from the column, the second system peak
area increased with surfactant concentration.
A number of retention peaks that are representative
of the surfactant composition appear in the elution
profile. These peaks can be attributed to the range of
molecular weights of compounds within the sample.
The larger the adsorbing alkyl tail of the surfactant, the
more lipophilic the molecule and the longer the
residence time in the reverse phase column. Any
branching of the tail results in a more compact alkyl
chain and may be expected to reduce lipophilicity of a
compound compared to the linear equivalent with the
same number of carbon atoms [11].
At high surfactant concentration, the large negative
system peak at *6 min dominated the chromatogram
at higher retention times, rendering any peaks occurring in this region unsuitable as representative peaks
for surfactant concentration determination. It was
found that the peak appearing at elution time between
3.0 and 3.2 min provided a linear response in the
detector with respect to the concentration of surfactant
in the injected sample over a range of more than two
orders of magnitude (Fig. 5). This peak was present
over the full range of surfactant concentration

Fig. 5 Calibration curve for peak area at retention time


between 3.0 and 3.2 min with concentration of a-olefin
sulphonate

measured and was therefore used as being representative of the concentration of the surfactant sample.
3.2 Adsorption isotherms
Isotherms for the adsorption of AOS to MB2HTMMT, determined by RP-HPLC and by gravimetric

Materials and Structures

methods are presented in Fig. 6. Samples were


prepared with ratios of AOS to organoclay up to
0.11 for RP-HPLC measurement and 0.13 for the
gravimetric method. Similar adsorption per unit mass
of nanoclay and maximum adsorbed amount were
observed for both gravimetric and RP-HPLC techniques. This correlation at low surfactant:nanoclay
ratio of the two techniques provides confidence that
there is no desorption of MB2HT modifier from the
nanoclay which would influence the results of the
gravimetric measurement. Beyond an adsorption ratio
of approximately 0.08 the gravimetric method showed
independence of adsorbed amount to concentration of
surfactant remaining in solution, indicating that
adsorption saturation was reached. The RP-HPLC
method, on the other hand, showed a reduction in
adsorbed amount with increasing equilibrium concentration beyond this point. Taken in isolation, the RPHPLC result would indicate desorption of AOS from
the particle surface. However, the gravimetric results
for the same experiment do not show this behaviour.
This discrepancy in the shape of the isotherm provides
evidence that the surfactant sample is composed of an
homologous series of molecules with varying alkyl
chain length. This polydispersity has been observed
elsewhere for similar technical grade surfactants
[12] and the multiple peaks observed in the HPLC
chromatogram (Fig. 4) implies a distribution of
molecular weights within the sample; surfactants with
monodispersed well-defined chain length are only
synthesized for research purposes. The gravimetric
method measured directly the mass of surfactant

Fig. 6 Comparison of a-olefin sulphonate/nanoclay adsorption


isotherms measured by RP-HPLC and by gravimetric methods.
Connecting lines have been added to guide the eye

molecules remaining in solution after adsorption had


occurred, allowing the surface-adsorbed component to
be calculated from simple mass balance. By contrast,
the chromatographic method assumed that the molecules eluting from the column at 3.1 min were
representative of all surfactant molecules in the
sample. This was true at low surfactant-to-nanoclay
ratio, when all of the surfactant molecules adsorbed
onto the surface. However, at high surfactant concentration when the number of molecules exceeded
particle surface saturation, competition between
molecules for surface adsorption resulted in the
displacement of the small molecules (represented by
the 3.1 min elution time) by larger molecules from
solution, as predicted by the thermodynamic adsorption process described earlier. Thus, at high surfactant
addition, desorption of these smaller molecules from
the surface increased their relative concentration in
solution, giving the impression of reduced surface
adsorption at high surfactant concentration; the larger
molecules were not detected due to the limitations of
the method.
Knowledge of the amount of surfactant adsorbing at
the organoclay surface can provide guidance on the
quantity of additional AOS foaming agent required to
generate the desired foaming effect. In this case
saturation of AOS at the particle surface was reached
at equilibrium concentration *500 mg/L. It can be
determined that, to achieve the full effect from the
foaming agent, AOS addition should exceed *80 mg
per gram of MB2HT-MMT organoclay in the cement
formulation. An understanding of how adsorption at
the organoclay surface is affected by the molecular
weight distribution of the AOS foaming agent can also
help select surfactant concentration to balance rate of
foam formation (low molecular weight surfactant
molecules adsorb at a higher rate at the foam
interfacial region than their larger counterparts) and
enhanced foam stability provided by larger molecules.
Adsorption affinity of the surfactants selected to
provide stabilisation of the organoclay in water was
investigated and the isotherms are presented in Fig. 7.
AE showed higher adsorbed amount onto MB2HTMMT than AOS. Brij O10, like AE, is non-ionic but is
a larger molecule than, although its behaviour at the
phase boundary can be expected to be similar (HLB
12.4 for Brij O10 compared to 12.6 for AE). This was
confirmed by the similarity of the adsorption isotherms, indicating that adsorption affinity is a function

Materials and Structures

Fig. 7 Adsorption isotherms for particle stabilising surfactants


to MB2HT-MMT organoclay. Also plotted is the isotherm for aolefin sulphonate foaming agent for comparison. Lines have
been drawn through the points to guide the eye

Fig. 8 Comparative elution spectra for a-olefin sulphonate;


peak magnitude is inversely proportional to adsorption amount
of the foaming agent to MB2HT-MMT organoclay in the
presence and absence of AE stabilizer at the particle surface

of overall molecular properties, rather than simply that


of the adsorbing moiety. All of the stabilising surfactants displayed lower rate of adsorption at low addition
than AOS. This was particularly pronounced for AAS
which displayed relatively low mass adsorption at low
surfactant concentration, producing a comparatively
gentle slope to the isotherm, but overall adsorbed
amount at maximum surface coverage was far greater
than that of the non-ionic surfactants or AOS.

approach of large AOS molecules is sterically hindered;


adsorption of the small molecules represented by the
selected elution peak will be less impeded. Consequently, adsorption of these small AOS molecules between
molecules of AE will be favoured over the higher
molecular weight components. In the absence of AE at
the surface, the free energy balance favours the
adsorption of large AOS molecules at this surfactantto-organoclay ratio, resulting in a higher relative
concentration of low molecular weight molecules
remaining in solution, as described above. Further
investigation into this phenomenon is advised as
selective adsorption of low molecular weight foaming
agent molecules may affect foaming characteristics
with regards to rate of foam formation and foam
stability, as discussed above. An alternative RP-HPLC
detection method, such as refractive index detection,
may allow for the characterization of the full molecular
weight distribution of the surfactants and hence the
adsorption behaviour. The effect this has on foaming
effects should be investigated also.
Competitive adsorption of AOS foaming agent
with AAS stabilizer to MB2HT-MMT was investigated by comparison of RP-HPLC elution profiles of
AAS prior to and following the addition of AOS
(Fig. 9). The aromatic functionality of AAS is chromophoric with UV absorption over a wide spectral
range, including the 258 nm wavelength used to detect
ion-pair modified AOS. Adsorption behaviour of the
AAS stabilizer to organoclay appeared to be consistent

3.3 Competitive adsorption


Competition between AOS foaming agent and stabilising surfactants AE and AAS for adsorption at the
surface of MB2HT was investigated. Particle suspensions were prepared using each of the stabilising
surfactants at a mass ratio to organoclay of 0.25, to
which AOS was added at a ratio of foaming agent to
organoclay of 0.20.
For competition with AE, the RP-HPLC elution
chromatograms of suspension samples containing AOS
in the absence and in the presence of AE were compared
(Fig. 8). The higher free AOS concentration for the
sample prepared in the absence of AE suggests that the
presence of dispersant promotes AOS adsorption at the
particle surface. This may be a result of the molecular
weight selective feature of the RP-HPLC method.
Adsorption of AOS does not mean that AE was
desorbed; this was not demonstrated by this experiment.
If AE molecules remain in place at the surface, the

Materials and Structures

Fig. 9 Comparison of elution spectra for equilibrium solution


of AAS stabilised organoclay in the presence and absence of
AOS foaming agent

regardless of AOS presence. It was not possible to


determine if the adsorption of AOS to MB2HT-MMT
occurred using this technique. The structural similarities of the AOS and AAS molecules means that the
residence time in a chromatography column will be
similar (and also the adsorption to the particle
surface), making differentiation between them difficult using this technique. Radiolabelling of the AOS
molecules by synthesizing with e.g. the 14C isotope
will allow identification of those molecules by
radioactive beta decay detection. The concentration
of non-adsorbed AOS molecules can then be determined and hence the adsorbed amount by mass
balance calculation. To determine the influence of
molecular weight upon adsorption it will be necessary to carefully synthesize a range of labelled
monodisperse AOS molecules and carry out a number
of experiments to determine adsorbed amount for each
size of molecule.

4 Conclusions
A-olefin sulphonate, a surfactant frequently used as a
foaming agent for cement and concrete, displays a
relatively high adsorption affinity for organically
modified nanoclay that is added to the cement
formulation for enhanced strength of the cured material. Although the maximum adsorbed amount of AOS
at the organoclay surface is considerably less than
those of the surfactants used as dispersing agents, this

will inevitably have implications for foaming efficacy


when organoclays are present and should be taken into
consideration when setting surfactant foaming agent
concentration. Increasing foaming agent loading to
account for the non-availability of the organoclayadsorbed component will certainly increase material
costs. Desorption of dispersing agents due to competitive adsorption of the foaming agent will lead to
instability of dispersed particles; there is no explicit
evidence of dispersant displacement in the experiments described here, however. A minimum
addition ratio of AOS to organoclay was determined
to account for any adsorption at the particle surface
and thus ensure the full foaming performance effect.
Acknowledgments The author would like to acknowledge the
European Commission funding under the 7th Framework
Programme for the project FIBCEMNanotechnology Enhanced
Extruded Fibre Reinforced Cement Based Environmentally
Friendly Sandwich Material for Building Applications (Grant
agreement no. 262954). Thanks to project partners Laviosa Chimica
Mineraria and to the Lithuanian Energy Institute for powder supply
and characterisation, and Sika SAU for foaming agent supply.
Thanks also to Croda Chemicals Europe for supply of surfactants.

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