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Article 4 PDF
Article 4 PDF
Abstract
Mixed surfactant systems find extensive use in laundry for fabric cleaning and fabric conditioning and in personal products as shampoos and
hair conditioners. This paper studies the colloidal stability of a system containing co-exiting liposome and bilayer fragment phases used in fabric
conditioners.
Di-chain cationic surfactants form L liposomal structures in water, which on addition of ethoxylated nonionic surfactants transform into
intermediate L bilayer fragments or disks and eventually to mixed micelles. Co-exiting liposome-fragment structures show a smaller phase
volume compared to liposomal dispersions and therefore have lower viscosities and better flow properties.
In contrast to the colloidal forces that control the stability of liposomes the stability in fragment containing dispersions is mainly controlled by
the steric repulsion provided by the ethoxylate chains that are partitioned at the edges of the fragments to reduce their hydrophobic edge tension.
We show here that the gel formation phenomenon observed in fragment containing dispersions at elevated temperatures is a manifestation of the
well-known ‘cloud point’ depression effect associated with the de-hydration of ethoxylate chains. This shortens the range of the steric repulsion
between the chains leading to the edge-to-edge coalescence of the fragments and hence the gelation and viscosity increase on ageing.
© 2006 Elsevier B.V. All rights reserved.
0927-7757/$ – see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.colsurfa.2006.05.005
M.S. Mohammadi / Colloids and Surfaces A: Physicochem. Eng. Aspects 288 (2006) 96–102 97
Fig. 1. The structure of di-alkyl cationic surfactants (ester quats) used in fabric conditioners compared to a phospholipid. The alkyl tail, R, can be based on
hydrogenated tallow (2:1 ratio of C18 :C16 ).
low viscosity can be achieved by using high HLB ethoxylated treated. The surfactants studied include polyethylene Cn EOm
nonionic surfactants. These micelle-forming surfactants reduce series [5,16], octylphenyl polyethoxylated nonionics of Triton
the particle size by opening the liposomes into smaller fragments X100 series [5,8,9,11,12,17], octylglucosides [5,7,9,15], anionic
and disks. Low viscosity dispersions containing fragment struc- alkyl sulphates [10], single chain cationics [14], phospholipids,
tures also suffer from a stability weakness, which is the subject and non-lipids [7,9,10,12,14,18]. A few studies detail the mech-
of this paper. However, before treating this subject it is helpful anism of the phase transformation [5,6,15,19–22] and two recent
to briefly review the literature on the mixtures of liposome- and papers from our group consider the microstructure and physical
micelle-forming surfactants. stability of di-chain cationics and nonionic surfactant mixtures
The surfactant–liposome interaction has been extensively [23,24] but none, to our knowledge, considers the rheology and
investigated in the related but distinct field of membrane research colloidal stability of the resulting structures.
where aspects such as surfactant induced release of liposome The phase behaviour of surfactant–liposome mixtures can
content [5,6], solubilisation of membranes by surfactants [7–13], be understood in terms of a ‘three-stage model’ as depicted in
and liposome-to-micelle phase transition [15–18] have been Fig. 3.
The accepted mechanism for the phase transitions is based
on the spontaneous curvature model where the incorporation of
a nonionic surfactant with a conic molecular shape increases
the curvature of the planar bilayers forcing them into smaller
units. Further discussion of this can be found in [19,21,25] and
goes beyond the scope of this study. However, the following key
points are noteworthy for later discussion.
Fig. 3. The three stage model for a vesicle (reproduced from permission from reference [21]). With increase in nonionic surfactant concentration the structure evolves
from a mixed bilayer phase to a co-existence phase with opened bilayers and lipid saturated fragments or disks, and finally to a mixed micellar phase with surfactant
saturated micelles. The viscosity and particle size decrease in that order with a concomitant change in optical appearance from turbid to turbid with pearly lustre to
pearly translucent and finally to transparent in the mixed micellar phase. The pearlescence originates from the reflection of light by the fragment microstructure.
2. Experimental cosity loss. This gel–liquid transition and its onset temperature
we believe signifies the fragmentation process;
This section outlines the materials and methods used to inves-
tigate the nature of the stability problem of a model concentrated Critical fragmentation temperature/◦ C 45 50 53 55
system containing a fixed 13.5 wt% level of the ester quat HEQ [Nonionic] wt% 0.0 0.75 1.50 3.00
(see Fig. 1 for its structure) and varying levels of a coco(EO)20 Nonionic/cationic mole ratio 0.0 0.05 0.10 0.20
nonionic with and without perfume. All the materials were of
technical grade and used as received. The HEQ (from Hoechst) The viscosity drop for the liposome system without non-
contained 67.1% hard tallow ester quat, 11.2% hard tallow fatty ionic was negligible. The fragmentation threshold temperature
acid, 8.9% glycerol and 12.8% isopropyl alcohol. Hard tallow relates to the onset of the L␣ to L phase transition of the mixed
is a mixture of ∼2:1 C18 :C16 . The fatty acid is a synthesis by- cationic/nonionic system as evidenced by DSC measurements.
product and affects the packing of the quat in the lamellar phase It appears that the nonionic surfactant opens the liposomes after
and contributes to its softening performance. The solvents lower the chains in the bilayers have frozen in the L state and lost their
the melting temperature of the raw material and hence, help in fluidity and lateral motion. This suggests that the fragments are
the handling issues during transport and production. It is impor- in the L state (except for the edges stabilised by the anchored
tant to note that the HEQ ester quat itself is not purely a di-ester nonionic molecules). The increase in the critical fragmentation
as suggested in Fig. 1 but contains some mono-ester too. The temperature with nonionic is surprising. One expects the mixing
molecular weight of the di-ester quat is 678 g/mol. The non- of C18 :C16 bilayers with C12 :C14 nonionic to lower the phase
ionic (Genapol C200 from Clariant) had a coco alkyl chain transition temperature and hence be reflected in a lower criti-
which is a mixture of mainly 3:1 C12 :C14 with an average of cal fragmentation temperature. One hypothesis for this reverse
20EO groups and an average molecular weight of 1081.7 g/mol. effect is that the nonionic surfactant ‘purifies’ the bilayers from
The perfume (from Givaudan) was a commercial mix con- its fatty acid and mono-ester quat impurities by fractionating
taining over 50 individual components. The additives used to these components into the edges. Di-alkyl bilayers without sin-
test the gelation hypothesis included sugar surfactants sucrose gle chain impurities pack better and have a much larger phase
monostearate (S-1670 from Mitsubishi), a tallow glycoside APG transition temperature. This ‘purification’ might be of a tempo-
(Rho-AH-6335/28, an experimental material from Henkel) with rary nature so that with time a re-mixing could occur.
an average of 1.4 glucose units, a coco7EO nonionic (Genapol The dispersions containing bilayer fragments display a pearly
LA07 from Hoechst) and an ester oil (ethylstearate, Estol 1545 lustre, which is enhanced when they flow. A study using small
from Uniqema). Tallow alkyl chain contains approximately a angle neutron scattering technique in combination with a Cou-
1.8:1.8:1 C18 :C18:1 :C16 mixture where C18:1 stands for a single ette flow cell in our group showed that flow anisotropy, fragment
double bond in the chain. alignment, develops only after the critical fragmentation temper-
The model dispersions were prepared at 200 ml scale in a ature is crossed [26].
bench mixer with a three-stage agitator and a jacketed vessel The samples generated according to the above process were
for temperature control. The cationic and the nonionic surfac- stored at different temperatures for the study of their stability
tants were melted together and added to the water in the vessel using an array of techniques including rheology, differential
at 70 ◦ C while mixing at 800 rpm. This ensured thorough mix- scanning calorimetry (DSC), small angle X-ray scattering, ultra-
ing. After about ten minutes mixing the vessel was cooled to centrifugation (at 40k rpm), light microscopy and cryo-scanning
35–40 ◦ C for the addition of perfume if appropriate. The disper- electron microscopy (SEM). The physical stability, phase sep-
sions were equilibrated at ambient temperature for 24 h before aration, aspects of such dispersions have been studied by small
any measurement. angle neutron scattering and reported elsewhere [24].
It is worth recording that at the high processing temperature Viscosity is an important product attribute for fabric softener
the dispersions were a viscous gel as expected from a lamellar dispersions and can be used as a sensitive measure of stability.
liposome microstructure. As the vessel was cooled and temper- Fabric softener dispersions are strongly shear thinning like most
ature dropped to about 50 ◦ C the gel became a thin liquid. The high phase volume colloids. The viscosities reported here were
larger the amount of nonionic the larger was the extent of vis- measured at a shear rate of 106 s−1 . A dispersion with a viscos-
M.S. Mohammadi / Colloids and Surfaces A: Physicochem. Eng. Aspects 288 (2006) 96–102 99
ity between 50 and 150 mPa s at 106 s−1 shows good flow and shielding the cationic charge and hence reducing the d-spacing
dispensing properties. (bilayer + water thickness). It is also conceivable that part of the
phase volume reduction stems from the osmotic compression
of water layers by the presence of some nonionic surfactant in
3. Results the continuous phase. Small angle X-ray scattering data gave a
d-spacing of 258 Å for 13.5% HEQ compared to 217 Å for the
This section focuses on the stability of the model system mixed 13.5/0.75 HEQ/NI system.
13.5/0.75/0.9 HEQ/nonionic/perfume with a mixed liposome- Less viscous concentrated dispersions in mixed cationic/
fragment microstructure as shown in Fig. 4b and c. The nonionic systems makes formulation of concentrated fabric soft-
viscosity of this fragment containing dispersion measured at eners possible but they must maintain their low viscosity during
50 mPa s compared to its liposomal counterpart at 500 mPa s. their shelf-life under ambient conditions. Accelerated stability
This viscosity loss stems from the lower phase volume of the experiments, where a sample is stored at different temperatures
fragment microstructure. The opening of the liposome struc- over a few weeks period, are designed to simulate their long-term
tures releases the trapped aqueous phase. Nonionic surfactants stability behaviour, see Fig. 5. Fragment containing dispersions
can reduce the phase volume by a secondary pathway too – by are freeze-thaw stable but thickening at elevated temperatures.
Fig. 4. Cross-polar and cryo-SEM microscopy images of dispersions of the di-chain cationic HEQ:(a) liposome;(b) co-existing liposome/fragment, the individual
fragments align to create the collective birefringence pattern seen here; (c) SEM of b; (d) SEM of b after ageing at 45 ◦ C for 4-week; (e) cross-polar of d; and (f)
45 ◦ C, 4-week aged dispersion as in b with 1% additional APG surfactant.
100 M.S. Mohammadi / Colloids and Surfaces A: Physicochem. Eng. Aspects 288 (2006) 96–102
Fig. 6. Change in viscosity (4-week – initial), for the model mixed frag-
Fig. 5. The stability of the model mixed liposome/fragment system ment/liposome system 13.5/0.75/0.90 HEQ/nonionic/perfume with and without
13.5/0.75/0.90 HEQ/nonionic/perfume aged at three ambient temperatures. The sugar surfactants sucrose monostearate (SMS) and APG.
viscosity was measured after samples equilibrated at 25 ◦ C.
Fig. 7. A schematic presentation of the proposed gelation mechanism. The collapse of nonionic ethoxylate chains at high temperatures leads to the enlargement of
fragments by edge-to-edge flocculation.
Other formulation additives such as (long chain) fatty alco- change with time [37];
hols can have as strong an influence on the CP as fatty acids [32].
η(t) φ2 D
The general rule appears to be that fatty alcohols and fatty acids = 1 + 3A e−U/kT t + Ot 2 + · · · (1)
with Cn < 4 increase the CP whereas those with Cn > 4 decrease η(0) (1 − (φ/φm ))a2
it [33].
where η(t), η(0), φ, φm , a, A, D, U, t, and kT are the viscosity after
Perfume is an indispensable component in fabric soften-
time t, initial viscosity, phase volume of the particles, maximum
ers and its influence on cloud point of nonionics should be
phase volume, particle size, aggregate shape factor, particle dif-
considered here. Perfume contains a mixture of many individ-
fusion coefficient, depth/height of potential energy, time, and
ual components characterised by their hydrophilic–hydrophobic
temperature factor. The pre-t2 factor, O, contains second order
nature. As a general rule the hydrophilic perfume components
expressions of the above parameters.
increase the CP and the hydrophobic ones, particularly benzene-
This expression allows us to simulate the viscosity change for
containing ones, decrease it. Kanei et al discuss these aspects of
a dispersion of spherical particles as they aggregate with time
perfume–CP interaction in ref. [34]. Fig. 8 exemplifies the CP
to form ‘dimers’, ‘trimers’ and so on. Fig. 9 typifies one such
depression efficiency of perfume and how this influence may
simulation based on a number of simplifications and shows that
be manipulated by additives [35]. The cocoEO20 of interest
viscosity requires a gestation period before it can rise rapidly.
could not be used in this experiment because of its cloud point
During this period when ‘dimers’ are forming the viscosity
(>100 ◦ C).
The phenomenon of viscosity rise with ageing in colloidal
systems is universal. Particles ultimately cross their potential
barrier and flocculate into the secondary or primary minimum.
The coagulation rate theory provides a deeper insight into the
kinetics of this gelation and the physical factors involved [36]. In
a version of this theory the Kreiger–Dougherty viscosity equa-
tion, the DVLO theory and the Smoluchwski coagulation rate
theory are combined to provide an expression for the viscosity
Table 1
Effect of fatty acid on the cloud point of nonylphenyl nonionics [30,31]
Percent oleic acid NPEO12 /◦ C Percent oleic acid NPEO9.5 /◦ C
0.0 84 0.0 65
0.3 60 0.25 45
0.5 32 0.30 35 Fig. 8. The cloud point of a 2% solution of coco EO7 with additives. The sugar
0.7 0 0.50 25 surfactant sucrose monostearate (SMS) and an ester oil (Estol) that can solubilise
the perfume have elevated the cloud point in the presence of perfume.
102 M.S. Mohammadi / Colloids and Surfaces A: Physicochem. Eng. Aspects 288 (2006) 96–102
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