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Colloids and Surfaces A: Physicochem. Eng.

Aspects 288 (2006) 96–102

Colloidal stability of di-chain cationic and ethoxylated nonionic


surfactant mixtures used in commercial fabric softeners
Mansur S. Mohammadi ∗
Unilever Research and Development, Fabric Conditioning and Care, Port Sunlight, Wirral CH63 3JW, UK
Received 21 October 2005; received in revised form 25 April 2006; accepted 5 May 2006
Available online 12 May 2006

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.

Keywords: Ester quats; Sugar surfactants; Flocculation; Coagulation rate theory

1. Introduction of a dispersion of liposomal particles (vesicles and multilamellar


vesicles), which have a periodic water layer and bilayer internal
Fabric conditioners are a dispersion of di-alkyl cationic sur- structure.
factants used in the last rinse during a washing cycle to soften Typical thickness of a bilayer with two C18 chains in all-
fabrics [1,2]. They adsorb onto fibres such as cotton, which in trans state measures about 46 Å. The water layers can be up to
the wash carry a negative surface charge, and coat them with 400 Å thick. This means that liposomes ‘encapsulate’ the aque-
a mono-molecular layer. This ‘boundary’ layer lubricates the ous phase and as a consequence of this the actual volume that
fibres reducing the fibre–fibre and fibre–skin friction giving the they occupy is much greater than that expected from the added
fabric a soft feel to the touch [3]. volume of the liposome forming surfactant. This has a strong
Fig. 1 represents the chemical structures of some di-chain influence on their rheological behaviour as Fig. 2 demonstrates
quaternary ammonium salts (ester quats) used in fabric condi- by comparing the expected viscosity of a hard sphere system
tioners [4] and compares them with the structure of a membrane with that of a di-alkyl cationic.
forming phospholipid. Like their phospholipids counterparts, From the graph it can be inferred that di-chain cationic surfac-
because of their insolubility in water, di-chain cationics prefer tants form viscous dispersions at concentrations above 10 wt%
to aggregate into lamellar planar structures when hydrated with and will not flow as required for dispensing from a container.
water. Therefore, an aqueous fabric conditioner liquid consists Low viscosity concentrated fluids can be produced by reduc-
ing the liposome size—either by mechanical high shear devices
or by osmotic compression of the water layers thickness using
∗ Tel.: +44 1516413118. electrolytes or polymers. These routes are prone to particle
E-mail address: mansur.mohammadi@unilever.com. aggregation and gelation stability problems. Alternatively the

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.

A. The level of nonionic needed to induce the three stage transi-


tion depends on the size and hydrophilicity of its headgroup.
For example, the mole fraction of C12 En needed to cause
vesicle rupture in a phospholipid is 0.30 (n = 8), 0.42 (n = 7),
0.58 (n = 6) and 0.80 (n = 5) at 25 ◦ C [18]. At elevated tem-
peratures a larger surfactant level is required as the ethylene
oxide chains become less hydrophilic. For example the rup-
ture mole fraction of C12 E8 varies from 0.24, 0.30, 0.55, to
Fig. 2. The relative viscosity against phase volume, φ, for a hard sphere dis-
0.68 at 10, 25, 50 and 75 ◦ C, respectively.
persion in water with an infinitely wide size distribution, φm = 1, according to
Kreiger–Dougherty expression, η/ηc = (1 − φ/φm )−2 . Comparison with the rel- B. The nonionic, because it prefers high curvature regions, pref-
ative viscosity against wt% for the dispersion of a typical di-chain cationic erentially partitions at the edges of the lamellar fragments
surfactant reveals the large volume that liposomal structures occupy. [7,25].
98 M.S. Mohammadi / Colloids and Surfaces A: Physicochem. Eng. Aspects 288 (2006) 96–102

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.

surfactants. They have delayed the gelation and fragment growth


When observed under a light microscope the thickened dis- as pictured in Fig. 4f.
persions appeared to have developed ‘crystalline’ structures, see
Fig. 4e. This gave the impression that the thickening might have
stemmed from the crystallisation of the fatty acid impurities in 4. Discussion
the ester quat. This is a plausible hypothesis. However, a num-
ber of observations contradicted this hypothesis. For example, Inter-particle force measurements show that EO groups lose
fatty acid purified HEQ/nonionic dispersions still thickened at their steric repulsion at elevated temperatures [27,28]. This can
high temperatures but over a longer storage period and showed lead to the flocculation of particles stabilised by ethoxylate
similar ‘crystalline’ patterns. groups at elevated temperatures as has been observed in emul-
Cryo-SEM microscopy revealed that the thickened disper- sions [29]. The force–distance graph in Israelachvili’s book [27]
sions contain enlarged fragments and multi-layered sheets, see obtained for C12 EO5 anchored onto cationic bilayers shows
Fig. 4d. These enlarged fragments appear crystalline under light the change in the sign of the potential energy from positive
microscopy. The thickened dispersions also developed extensive (repulsive) to negative (attractive) as temperature increases. This
pearlescence, which can be explained based on the increase in the follows the shortening of EO group size with temperature from
size, number of layers and the refractive index of the fragments. 2.6 nm at 25 ◦ C to 1 nm at 37 ◦ C. The cross-over to attractive
The phase separation of aged dispersions by ultra-centrifugation interaction occurs between 25 and 30 ◦ C in this case. The liter-
enabled the direct measurement of the refractive index, n, of ature value for the cloud point of C12 EO5 is 28.9 ◦ C [30]. This
the neat liposome/fragment phase; n = 1.3726 (25 ◦ C), 1.3793 effect is the well-known cloud point (CP) phenomenon charac-
(37 ◦ C) and 1.3826 (45 ◦ C). This increase in n with storage tem- teristic of ethoxylated nonionics. A similar phenomenon may be
perature signifies the compaction of the d-spacing and reduction responsible for fragment coalescence in our system as schemat-
in water layer thickness. ically depicted in Fig. 7.
For fragment growth to occur the nonionic head group, sta- One objection to this model is that the temperature range
bilising the fragment edges against fusion, must lose their steric at which EO chains collapse depends on their size and for
repulsion at the elevated temperatures. This is feasible because cocoEO20 used here it is above 100 ◦ C whereas the gelation
of the tendency of ethoxylate chains to de-hydrated and shorten occurs at around 30 ◦ C. The presence of additives and impurities
in unfavourable environments (solvent or temperature). (perfume and fatty acid) in the formulation could be responsible
Using nonionic surfactants with a head group which remains for this considerable CP depression. The raw material impurities
hydrophilic at elevated temperatures could enable us to test and formulation additives play a strong and complex role in the
this fragment enlargement gelation hypothesis. Sugar surfac- kinetics of the thickening. Nevertheless, their apparent confus-
tants such as sucrose monostearate or APG as a replacement for ing role can be rationalised by the cloud point depression model
cocoE20 (at the equivalent molar level or higher concentrations) presented here. Those impurities that depress the cloud point
proved ineffective for liposome to fragment phase transition and lead to a faster gelation kinetics, those that elevate the cloud
to reduce the viscosity. The main reason for their inefficacy, as point slow down the gelation – fatty acid impurity, for example,
explained in Section 1, is the small head group size—an average de-stabilises the fragments via depression of the cloud point of
of 2.0 glucose units for the sucrose ester and 1.4 for the APG. nonionic. Table 1 provides some examples of this effect.
Sugar surfactants with larger number of sugar head group Against the CP data in Table 1 one can argue that fatty acids
were not commercially available therefore we used the avail- induce phase transition in a micellar solution of nonionics giving
able materials in combination with cocoEO20 to examine the larger micelles or lamellar structures which appear turbid and
concept. Our assumption here was that the partitioning of sugar hence the apparent lower CP. However, the CP lowering of fatty
surfactants into the nonionic rich regions can help to maintain acids has been studied under conditions more akin to our system
the hydration and the steric repulsion at the elevated tempera- where both NI and fatty acid molecules form a monolayer on oil
tures. Fig. 6 shows the visco-stability results with added sugar droplets [31].
M.S. Mohammadi / Colloids and Surfaces A: Physicochem. Eng. Aspects 288 (2006) 96–102 101

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

References

[1] R.C. Laughlin, Fabric softening, in: D.N. Rubingh, P.M. Holland (Eds.),
Cationic Surfactants: Physical Chemistry, Marcel Dekker Inc., New
York, 1991 (Chapter 9).
[2] J.H. Clint, Surfactant Aggregates, Blackie, London, 1992 (Chapter 8).
[3] D.J. Tildesley, in: M.J. Adams, et al. (Eds.), Dynamics of Complex
Fluids, Imperial College Press, 1998 (Chapter 15).
[4] G. Kruger, et al., Esterquats, in: Novel Surfactants’ Surfactant Science
Series, K. Holmberg (Ed.), Marcel Dekker Inc, New York, vol. 74,
1998 (Chapter 4); also see O. Ponsati, Cationic surfactants based on
Triehanolamine Esters, Commun. Jorn. Com. Esp. Detergent (1992) 23
167–179.
[5] J. Ruiz, et al., Biochim. Biophys. Acta 937 (1998) 127–134.
[6] K. Edwards, M. Almgren, Langmuir 8 (1992) 824–832.
[7] M. Seras, et al., Langmuir 12 (1996) 330–336.
Fig. 9. Simulation using Eq. (1) of viscosity evolution for a monodispersed [8] M.A. Partearroyo, et al., J. Colloid Interface Sci. 178 (1996) 156–
hard sphere colloidal system as dimers, trimers and n-mers form with time for 159.
φ = 0.45, U = 0, and dimensionless time τ = (D/a2 )e−U/kT t. [9] A. De la Maza, J.L. Parra, Colloid Polym. Sci. 275 (1997) 821–829.
[10] A. De la Maza, J.L. Parra, Langmuir 12 (1996) 6218–6223.
[11] A. De la Maza, J.L. Parra, Colloid Polym. Sci. 272 (1994) 721–730.
grows linearly with time (the first term in Eq. (1)) but with [12] A. De la Maza, et al., J. Colloid Interface Sci. 184 (1996) 155–162.
increase in the size of particle clusters to ‘trimers’ and beyond the [13] R. Nagarajan, Curr. Opin. Colloid Interface Sci. 2 (1997) 282–293.
viscosity increase becomes non-linear. This qualitatively agrees [14] D. Danino, et al., J. Colloid Interface Sci. 185 (1997) 84–93.
with the behaviour shown in Fig. 5. [15] S. Almog, et al., Biochemistry 29 (1990) 2592–4582.
[16] K. Beyer, Progr. Colloid Polym. Sci. 103 (1997) 78–86.
[17] A. De la Maza, J.L. Parra, Biochem. J. 303 (1994) 907–914.
5. Conclusions [18] F. Ricoul, et al., Progr. Colloid Polym. Sci. 105 (1997) 351–359.
[19] H. Heerklotz, et al., J. Phys. Chem. B 101 (1997) 639–645.
This paper offered a hypothesis for the high temperature [20] M. Silvander, et al., J. Colloid Interface Sci. 179 (1996) 104–113.
gelation and viscosity rise of concentrated cationic/nonionic dis- [21] M. Olllivon, et al., Biochemistry 27 (1988) 1695–1703.
[22] T. Inoue, et al., J. Colloid Interface Sci. 168 (1994) 94–102.
persions, which contained a mixed phase liposome/fragment
[23] J.F. Penfold, et al., Fiber Diff. Rev. 11 (2003) 68.
structure. The evidence pointed to the edge-to-edge floccula- [24] J.F. Penfold, et al., J. Phys. Chem. B 109 (2005) 1810–18116.
tion of small fragments as the cause of the instability. The steric [25] P. Fromherz, in: P.L. Luisi, B.E. Straub (Eds.), Reverse Micelles, Plenum
repulsion of ethoxylate chains stabilises the lamellar fragment Press, 1982.
edges against fusion. This repulsion weakens at elevated ambient [26] I. Tucker, et al., A poster presentation at ISIS2003 Science Highlights,
Oxford University.
temperatures. The effect that impurities and formulation addi-
[27] J. Israelachvili, Intermolecular and Surface Forces, second ed., academic
tives such as perfume, fatty acid, fatty alcohol, salt or solvent Press, London, 1994, p. 285.
have on the steric repulsion interaction was unified here in a [28] P.M. Claesson, et al., J. Chem. Soc. Faraday Trans. I 82 (1986)
familiar cloud-point depression framework. Surfactant or com- 2735–2746.
ponents that elevate the cloud point prolong the stability, those [29] K. Tajima, et al., Colloid Polymer Sci. (1992), pp. 270–759–767.
[30] P.D.T. Huibers, et al., J. Colloid Interface Sci. 193 (1997) 132–136.
that depress the cloud shorten the stability.
[31] S. Magdani, et al., J. Dispersion Sci. Technol. 11 (5) (1990) 518–519.
[32] D. Attwood, A.T. Florence, Surfactant Systems, Chapman and Hall,
Acknowledgement London, 1983, p. 280.
[33] L. Marszall, J. Colloid Interface Sci. 59 (2) (1977) 376–377.
I thank Unilever Research and Development Port Sunlight for [34] N. Kanei, et al., J. Colloid Interface Sci. 218 (1999) 13–22.
[35] M.S. Mohammadi, et al., A method of stabilising fabric softening com-
permission to publish this work, Ian Tucker and John Hubbard
positions, WO2001046360 A1.
for the x-ray scattering results and discussion, Patrick Warren [36] W.B. Russel, et al., Colloidal Dispersions, Cambridge University Press,
for the coagulation rate theory and Kirsty Sinclair for the SEM Cambridge, 1991 (Chapter 8).
microscopy. [37] P. Warren, M. Lal, unpublished work.

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