International Journal of Cosmetic Science, 2010, 32, 193–203 doi: 10.1111/j.1468-2494.2010.00540.

Liquid crystal colloidal structures for increased

silicone deposition efficiency on colour-treated hair

M. A. Brown*, T. A. Hutchins*, C. J. Gamsky*, M. S. Wagner , S. H. Page  and J. M. Marsh 

*Sharon Woods Innovation Center, The Procter & Gamble Company, 11511 Reed Hartman Highway, Cincinnati, OH
45241 and  Miami Valley Innovation Center, The Procter & Gamble Company, 11810 East Miami River Road,
Cincinnati, OH 45252, U.S.A.

Received 12 March 2009, Accepted 9 May 2009

Keywords: hair, liquid crystals, oxidative damage, poly(diallyldimethyl ammonium chloride)

tion efficiency of silicone conditioning ingredients.

Synopsis
An approach is described to increase the deposi-
tion efficiency of silicone conditioning actives from
a shampoo on colour-treated hair via liquid crystal
(LC) colloidal structures, created with a high
charge density cationic polymer, poly(diallyldim-
ethyl ammonium chloride) and negatively charged
surfactants. LCs are materials existing structurally
between the solid crystalline and liquid phases,
and several techniques, including polarized light
microscopy, small angle X-Ray analysis, and differ-
ential scanning calorimetry, were used to confirm
the presence of the LC structures in the shampoo
formula. Silicone deposition from the LC-contain-
ing shampoo and a control shampoo was mea-
sured on a range of hair substrates, and data from
inductively coupled plasma optical emission spec-
troscopy analysis and ToF-SIMS imaging illustrate
the enhancement in silicone deposition for the LC
shampoo on all hair types tested, with the most
pronounced enhancement occurring on hair that
had undergone oxidative treatments, such as col-
ouring. A model is proposed in which the LC
structure deposits from the shampoo onto the hair
to: (i) provide ‘slip planes’ along the hair surface
for wet conditioning purposes and (ii) form a
hydrophobic layer which changes the surface
energy of the fibres. This increase in hydrophobic-
ity of the hair surface thereby increases the deposi-
Correspondence: Jennifer Marsh, The Procter & Gamble
Company, Sharon Woods Technical Center, 11511 Reed
Hartman Highway, Cincinnati, OH 45241, U.S.A. Tel.:
513-627-0055; e-mail: marsh.jm@pg.com
Zeta potential measurements, dynamic absorbency
testing analysis and ToF-SIMS imaging were used
to better understand the mechanisms of action.
This approach to increasing silicone deposition is
an improvement relative to conventional condition-
ing shampoos, especially for colour-treated hair.
Résumé
Structures colloı̈dales à cristaux liquides pour
améliorer l’efficacité de dépôt de silicone sur les
cheveux colorés
Une approche est décrite pour augmenter l’effi-
cacité de dépôt de silicone, agents conditionneurs
d’un shampooing pour cheveux colorés via des
structures colloı̈dales de cristaux liquides (LC),
créées avec un polymère à haute densité de charge
le poly(Diallyldimethyl Ammonium Chloride) et
des tensioactifs chargés négativement. Les LCs sont
des structures existant entre les phases cristallines
solides et les phases liquides. Plusieurs techniques,
y compris la microscopie à lumière polarisée,
l’analyse aux rayons X et la calorimétrie différenti-
elle ont été utilisées pour confirmer la présence des
structures LC dans les formules de shampooings.
Les dépôts de silicone à partir du shampooing con-
tenant des LC et d’un shampooing contrôle ont été
mesurés sur une gamme de substrats de cheveux.
Les données de spectroscopie d’émission plasma
(ICP-OES) et l’image par spectrométrie de masse
d’ions secondaires à temps (ToF-SIMS) illustrent la
majoration du dépôt de silicone sur tous les types
de cheveux évalués, avec une majoration plus

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Liquid crystal shampoo
prononcée pour les cheveux ayant subit des traite-
ments oxydatifs, comme la coloration. Il est ainsi
proposé un modèle dans lequel les dépôts de LC à
partir du shampooing sur les cheveux : 1) fournis-
sent des ‘‘slip planes’’ le long de la surface du che-
veu pour des conditionneurs en milieu humide et
2) forment une couche hydrophobe qui modifie
l’énergie de surface des fibres. Cette augmentation
d’hydrophobie de surface favorise ainsi l’efficacité
du dépôt de silicone comme agent conditionneur.
Des mesures de potentiel Zeta, des analyses
d’absorption dynamique et l’analyse d’image par
ToF-SIMS ont été utilisées pour mieux comprendre
les mécanismes d’action. Cette approche pour aug-
menter le dépôt de silicone est une amélioration
quant aux shampooings conditionneurs conven-
tionnels, et particulièrement pour les cheveux col-
orés.
Introduction
It is estimated that over 70% of women in the
developed world have used hair colour, and a
large proportion of those do so regularly. There
are two chemical processes that occur during the
permanent dying process: oxidation of the melanin
pigments and previously deposited dyes and the
oxidation of the dye precursors to form the col-
oured dyes. This oxidative process causes both
physical and chemical changes to take place on
and within the hair fibre. The protective, outer-
most lipid layer (F-Layer), 18-methyleicosanoic
acid (18-MEA), of the hair fibre is removed during
the hair colouring process (Fig. 1) and strength-
giving disulphide bonds in cystine are oxidized to
create cysteic acid [1, 2]. It is the combination of
the hydrogen peroxide with the high pH of a hair
colourant that causes these changes to occur and
thus occurs with all Levels 2 and 3 products
to some extent [3]. The exact mechanism of the
F-Layer removal has not been well documented in
the literature but it is thought to be due to perhy-
drolysis of the thio ester which links the 18-MEA
ª 2010 The Procter & Gamble Company. Journal compilation
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194
M. A. Brown et al.
to the ultra high sulphur protein backbone at the
surface of the hair [4]. The result is a more hydro-
philic, anionic and porous surface that weakens
the hair fibre making it more susceptible to
mechanical and environmental damage.
Traditional dry hair conditioning approaches
tend to be less effective on colour-treated hair than
on untreated hair. Polydimethylsiloxanes (PDMS)
are often employed as conditioning materials in
both shampoo and conditioner applications to
improve dry hair feel. However, it is known that, in
the case of more hydrophilic, damaged hair, large
particle (>5 lm) PDMS deposition is greatly
reduced and cannot provide the same benefit in
hair conditioning as for undamaged or virgin hair
[5]. Large particle silicone relies on the surface
energy of hair for the silicones to adhere and spread
on hair. For these silicones, the general approach
to improve the conditioning on colour-treated hair
is to increase the silicone concentration, but this is
expensive and inefficient. An alternative approach
has been to use small particle silicones (<5 lm)
and to deposit these via isotropic flock coacervates.
However, to achieve these small particle sizes a
microemulsion is generally required and because
these microemulsions tend to need more expensive
surfactants and need additional processing this can
add costs to the formulation [6, 7].
This paper describes an approach to increase
the efficiency of conditioning on colour-treated
hair. A liquid crystal colloidal structure has been
created in a shampoo formulation with the use of
a high charge density cationic polymer, poly
(diallyldimethyl ammonium chloride) [poly(DAD-
MAC; Fig. 2], supplied by Rhodia, combined with
oppositely charged surfactants such as ammonium
lauryl sulphate and ammonium laureth-3 sul-
phate. This unique colloidal structure has been
demonstrated to enhance the deposition of silicone
conditioning actives such as PDMS from the
shampoo. A model is proposed in which the liquid
crystal structure of the shampoo deposits onto the
hair to form a hydrophobic layer which changes
Figure 1 Change in hair structure
upon oxidative-colouring process.
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Liquid crystal shampoo M. A. Brown et al.

Table I Shampoo formulations

Liquid
Shampoo formulation crystal Control

Ammonium laureth sulphate (AE3S) 6.00 6.00

Ammonium lauryl sulphate (ALS) 10.00 10.00
Laureth-4 alcohol 0.90 0.90
Poly(diallyldimethyl ammonium chloride)1 0.25 0.00
Trihydroxystearin2 0.10 0.10
Fragrance 0.60 0.60
Figure 2 Poly(DADMAC) structure.
Sodium chloride 0.40 0.40
Citric acid 0.04 0.04
the surface energy of the fibres. This increase in Sodium citrate 0.40 0.40
Sodium benzoate 0.25 0.25
hydrophobicity of the surface increases the deposi-
Ethylene Diamine Tetra Acetic acid 0.10 0.10
tion of the silicone conditioning actives. Dimethicone3 1.00 1.00
DI water (QS to 100%)

Materials and methods 1

Materials
Virgin hair and bleached hair were purchased
from International Hair Importers & Products Inc.
(Glendale, NY, U.S.A.). Poly-DADMAC (trade name
Mirapol 100) was sourced from Rhodia, Inc.
(Cranbury, NJ, U.S.A.). The virgin hair was treated
with a permanent hair colourant (medium brown
shade) to produce the colour-treated hair, and the
virgin hair was treated with a retail perm product
to produce the permed.
Method of manufacture
Table I shows the formulations for the liquid crys-
tal shampoo and the control non-polymer contain-
ing shampoo that were used in all the testing. The
compositions, in general, were made by mixing
together at elevated temperature, e.g. about 72C,
water and surfactants along with any solids (e.g.
amphiphiles) that need to be melted, to speed mix-
ing into the personal cleansing composition. The
ingredients are mixed thoroughly at the elevated
temperature and then cooled to ambient tempera-
ture. Additional ingredients, including electrolytes,
polymers and particles, may be added to the cooled
product. The silicone may be emulsified at room
temperature in concentrated surfactant and then
added to the cooled product.
All exemplified amounts are listed as weight per-
cents and exclude minor materials such as dilu-
ents, preservatives, colour solutions, imagery or
conceptual ingredients, botanicals and so forth,
unless otherwise specified. The (LP) silicone oil
Poly(DADMAC) (Rhodia) (charge density = 6.2 meq g)1,
molecular weight 175 000.
2
Thixcin R (Rheox).
3
Viscasil 330 M (Momentive).
droplets have a volume average particle diameter
of about 24–35 lm as measured using the
LA-910 Particle Size Analyzer, manufactured by
Horiba (Irvine, CA, U.S.A.). All shampoo composi-
tions discussed herein were processed with the
same emulsified silicone oil premix and in such a
way as to not significantly alter the droplet size of
the pre-emulsified silicone oil.
Treatment of hair switches
To treat hair with shampoo, 4 g hair switches
were pre-wetted with water (38C, 1.5 gal min)1,
with water hardness ranging from 0.12 g L)1 to
0.22 g L)1) for 30 s. After removing excess water,
0.4 mL of shampoo was applied to the front side
of each hair switch. The shampoo was brushed
into each hair switch for 30 s before each hair
switch was rinsed with water for 30 s. After
removing excess water, the back side of each hair
switch was treated in the same manner. The hair
switches were then air-dried.
The above-steps, with the exception of the pre-
wetting step, were repeated four times for each
hair switch for a total of five applications.
Polarized light microscopy
Polarized light microscopy was used to confirm the
presence of crystalline matter within a particular

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International Journal of Cosmetic Science, 32, 193–203 195
Liquid crystal shampoo
composition. A ZEISS Axioskop microscope with a
40· objective was used, yielding micrographs at a
magnification of approximately 500·. Eight micro-
litres of shampoo was sampled for analysis.
X-ray analysis
The small angle data were collected with a Bruker
Nanostar small-angle X-ray scattering instrument.
The generator was operated at 40 kV, 30 mA,
using a fine focus Cu X-ray tube. The sample to
detector distance was 105.1 cm and the detector
was a GADDS 2-dimensional wire detector.
The wide angle data were collected with a Scin-
tag ·1 powder X-ray diffractometer. The generator
was operated at 40 kV/45 mA, powering a normal
focus copper X-ray tube. A solid-state detector was
used. The X-ray beam was collimated using inci-
dent beam slits of 2 and 4 mm and diffracted
beam slits of 0.5 and 0.2 mm. Data were collected
using a step-scan mode from 1.1 to 70 2h at
1 s/step with a step size of 0.04. The undiluted
shampoo was used for the measurements.
Differential scanning calorimetry
Differential scanning calorimetry (DSC) data were
collected using a DSC Q100 V7.3 Build 249 (TA
Instruments, New Castle, Delaware, U.S.A.).
Sample size of neat shampoo used was 34.15 mg.
Zeta potential and particle size measurements
Zeta Potential measurements were conducted
using a (Brookhaven) ZetaPALS instrument to
determine surface charge of the liquid crystals at
various shampoo dilutions (Fig. 7). The analyte
(supernate) was collected after centrifugation
(1078 g for 90 min) of the shampoo at each dilu-
tion and analysed via ZetaPALS. A Zeta Sizer (Mal-
vern, Worcestershire, U.K.) was used to identify
the liquid crystal particles present at the various
shampoo dilutions.
Surface energy measurements
A Dynamic Contact Angle and Absorption Tester
(FTA 200 dynamic contact angle analyser from
First Ten Angstroms, Portsmouth, VA, U.S.A.) was
used to measure the surface energy of the hair
samples before and after treatment. Two hairs
were positioned 18.0-lm apart parallel to each
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196
M. A. Brown et al.
other and horizontal to the ground. A 0.2 lL drop
of solvent (either >99% hexadecane or ultrapure
water) was carefully lowered onto the surface of
the two hairs and the needle was retracted from
the drop. Video imaging of the drop making con-
tact with hairs, detaching and sitting on the hair
up to 15 s after detaching from the needle at 10
images per second was recorded. Imaging was per-
formed looking across the length of the parallel
hairs with zero look down angle on the drop. The
contact angle of the solvents on the hair was
determined from the image, at 0.3 s following drop
placement, using commercially available software
(First Ten Angstroms, Software version 2.0, Build
number 303) in the non-spherical mode for drop-
shape analysis. Fowkes equation of state was used
to convert contact angles into apparent surface
energies [8]. A minimum of five measurements
was made for each data point.
ToF-SIMS
Positive ion secondary ion images of hair fibres
were acquired using an ION-TOF IV (ION-TOF
GmbH, Munster, Germany) time-of-flight second-
ary ion mass spectrometer (ToF-SIMS) equipped
with a 25 keV Bi3+ primary ion source and oper-
ated under static SIMS conditions (primary ion
dose < 1013 ions/cm2). The primary ion beam was
operated in the single crossover (‘burst alignment’)
mode, resulting in a primary ion beam diameter of
0.5 lm. For this analysis, single hair fibres were
oriented parallel to the direction of the impinging
primary ion beam and were affixed to an alumin-
ium sample holder by immobilizing the ends of the
hair fibres using adhesive tape. Charge neutraliza-
tion of these samples was accomplished by means
of a low energy electron flood gun. A minimum of
five fibres per sample were examined and a repre-
sentative image taken of one fibre.
Silicone deposition efficiency
Inductively coupled plasma optical emission spec-
troscopy was used to measure silicone deposition
efficiency. 1.5 g of hair was placed in a 20 mL
scintillation vial. To extract the silicone from the
hair, 6 mL of 50 : 50 toluene : methylisobutyl
ketone was added to each vial, then the vials were
agitated on a pulsed vortexer for 30 min. ICP
calibration standards of known silicone concentra-
tion are made using the same or a structurally
International Journal of Cosmetic Science, 32, 193–203
Liquid crystal shampoo M. A. Brown et al.

comparable type of silicone raw material as the are formed in the neat, aqueous shampoo phase
products being tested. Four hair samples were used and behave similarly to other hydrophobic parti-
for each data point and the average ± one stan- cles within the shampoo (e.g. dimethicone). Above
dard deviation are reported. the critical micelle concentration (CMC) the liquid
crystals acquire a coating of the unbounded anio-
nic surfactants, as shown in the schematic in
Results and discussion
Fig. 3.
Figure 4 shows a freeze-fracture cryo-SEM of the
Shampoo formulation
liquid crystal structure in the neat shampoo and
A series of shampoo formulations were made con- illustrates the order of the lamella phases in one of
taining different cationic polymers and anionic the three directions.
surfactants. It was found through extensive Several additional analytical techniques were
screening of different polymers that a highly used to further confirm the presence of the liquid
charged cationic polymer was required for the
liquid crystal formation, and poly(DADMAC) was
found to give the appropriate colloidal properties
with no negatives in terms of rheology and final
hair feel. The polymer had a cationic charge den-
sity of 6.2 meq g)1 and a molecular weight of
175 kD (as reported by manufacturer). The high
cationic charge of poly(DADMAC) enables it to
attract anionic surfactant into localized regions of
high concentration, at which concentration the
surfactant naturally forms a lamellar phase and
ultimately a liquid crystal phase. The surfactant
lamellar phase is impacted by concentration, tem-
perature and steric properties of the particular sur-
factant chosen so it is important that the
appropriate surfactants and surfactant/polymer
ratios are chosen. To form the required lamellar Figure 3 Schematic of the liquid crystal structure in the
and subsequent liquid crystal structure, the surfac- neat shampoo.
tants ammonium lauryl sulphate and ammonium
laureth-3 sulphate were chosen. When the poly-
mers and surfactants are formulated in the correct
ratios, a multi-lamellar, lyotropic, liquid crystal
microstructure is formed. The test shampoo was
formulated to also contain 1.0% of a PDMS
dimethicone as a conditioning active. Table I
shows the formulation details for the liquid crys-
tal-containing shampoo and control formulations
used throughout the study.

Characterization of the shampoo microstructure

The term ‘liquid crystal’ is applied to a material
existing structurally between the solid crystalline
phase and the liquid phase. It has phases that are
ordered and/or crystalline in one of their three
possible crystallographic directions, a property that
causes it to appear birefringent under cross-polar-
ized light, except for cubic phases [9, 10]. In this Figure 4 Freeze-fracture cryo-SEM image of the liquid
shampoo formulation, the insoluble liquid crystals crystal particle.

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International Journal of Cosmetic Science, 32, 193–203 197
Liquid crystal shampoo
crystal structures. Polarized light microscopy was
used to show the expected birefringent nature of
the liquid crystal structures. The liquid crystals
appeared as Maltese crosses in the cross-polarized
light because of their multi-lamellar nature.
X-ray scattering was used to confirm the crystal-
line matter within the composition and to confirm
that the liquid crystal structure was lamellar.
A basal reflection was found in the small angle
X-ray scattering pattern corresponding to a d-spac-
ing of 44 Å. The wide angle X-ray scattering
diffraction pattern showed smaller reflections at 22
and 15 Å which confirmed the lamellar nature of
the liquid crystal structure.
Finally, differential scanning calorimetry analy-
sis of the neat shampoo shows no melt transition
temperature between 20C and 90C, confirming
the liquid nature of the Poly(DADMAC) crystals.
Silicone deposition
The silicone deposition from the shampoo formu-
lation was measured on a range of different hair
substrates from the liquid crystal containing
shampoo and a control shampoo containing cat-
ionic polymers and no liquid crystal structure.
Both shampoos contained 1.0% of dimethicone
(polydimethylsiloxane). Table II shows the silicone
deposition from these two shampoos after five
repeat shampoo applications. The data illustrate
that the liquid crystal-containing shampoo
enhances silicone deposition onto all of the differ-
ent hair types but the enhancement is signifi-
cantly higher on the substrates previously treated
with oxidative products (e.g. colourants, perms
and bleaches). This enhancement is in part
because of the very low deposition levels seen on
these substrates from the non-cationic polymer
shampoo.
Visualization of the deposited silicone condition-
ing agent was performed using positive ion mode
Silicone deposition (ppm)
Untreated Permed
Liquid-crystal shampoo 648 ± 141 427 ± 52
Non-polymer control 465 ± 56 91 ± 40
1
Below detection limit of method (<10 ppm).
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198
M. A. Brown et al.
ToF-SIMS imaging. ToF-SIMS can be used to
semi-quantitatively image the distribution of these
polymers on hair surfaces by creating a two-
dimensional image with a complete mass spectrum
at each pixel in the image. The secondary ions
uniquely related to the silicone can then be
selected from the mass spectra and the intensity of
these secondary ions at each pixel used to demon-
strate the distribution of the silicone on the hair
surface. Figure 5 shows images of the silicone on
the surface of hair fibres treated with the liquid
crystal shampoo and with the control shampoo.
The silicone secondary ion image is the sum of the
intensities of several silicone-related secondary
ions [Si(CH3)3+ at m/z = 73, Si2(CH3)5O+ at
m/z = 147, Si3(CH3)5O3+ at m/z = 207 and
Si3(CH3)7O2+ at m/z = 221]. The total ion image is
also shown in Fig. 5, and is the sum of the intensi-
ties of all of the secondary ions generated in each
pixel. The total ion images primarily show where
the hair fibre is located within the image field of
view. The silicone images were scaled by the total
secondary ion intensity followed by a square root to
improve quantification of the image [11]. To facili-
tate comparison between samples, both silicone
images use the same intensity scale. The field of
view of these images is 100 lm x 100 lm.
Mechanism of action
A proposed mechanism of action of the liquid crys-
tal shampoo is shown in Fig. 6. In the neat sham-
poo, at low dilution and above the CMC of the
surfactant, it is proposed that the liquid crystals
act as a typical hydrophobic particle in a shampoo
matrix. Even where silicones are included in the
formulation the liquid crystals will remain as com-
pletely separate entities from the silicone droplets.
In the neat shampoo the liquid crystals will inter-
act with the excess surfactant and acquire a
mono-layer coating of the unbound, anionic
Table II Silicone deposition from
liquid crystal shampoo vs. control
shampoo
Colour-treated Bleached
211 ± 5 353 ± 30
<10* <101
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International Journal of Cosmetic Science, 32, 193–203
Liquid crystal shampoo M. A. Brown et al.

Silicone image Total ion image

Control shampoo 1.6 8
1.4 7
1.2 6
1 5
0.8 4
0.6 3
0.4 2
0.2 1
0

Liquid crystal shampoo 1.6 10

1.4 9
8
1.2
7
1 6
0.8 5
0.6 4
3
0.4
2
Figure 5 ToF SIMS images of con- 0.2
1
trol shampoo vs. control shampoo. 0

Si
LC
LC Si Si
LC
Si

Figure 6 Schematic of proposed en-

hanced silicone deposition mecha- Liquid crystals deposit on hair Increased silicone deposition
nism. making surface more hydrophobic on hydrophobic surface

1.00E – 04 1.00E – 03 1.00E – 02 1.00E – 01 1.00E + 00 1.00E + 01 1.00E + 02 1.00E + 03 1.00E + 04 1.00E + 05
0

–20 Dilution five

Dilution four

Dilution one
Surface charge (mV)

–40
Dilution three

–60

–80 Dilution two

–100 CMC
of shampoo

Figure 7 Zeta potential measure- –120

ments of liquid crystal shampoo. Surfactant concentration (mg L–1)

surfactant. This coating of surfactant will increase
the stability of these particles in the shampoo
matrix and give the particles a negative charge.
On application of the shampoo to the hair (i.e. at
low dilution), the liquid crystals will be trapped by
the hair via a filtration mechanism and adhere to
the hair as a result of van der Waals forces over-
coming any charge repulsion between the particles
and the hair.
Upon rinsing, the shampoo is diluted to a point
where the surfactants are near or below the CMC.
At this time, the unbound surfactant surrounding

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International Journal of Cosmetic Science, 32, 193–203 199
Liquid crystal shampoo
the liquid crystal is washed away exposing the
outermost hydrophobic tails surface of the surfac-
tant bound to the liquid crystal. This leaves parti-
cles on the hair surface, which has a lower
negative charge and a higher hydrophobicity. For
coloured hair, the consequence is that these liquid
crystal deposits increase the hydrophobicity of the
colour-treated hair surface, which brings the sur-
face properties of the hair closer to that of virgin
hair. It is believed that on deposition, the surfac-
tant bi-layers within the lamellae of the liquid
crystal provide ‘slip planes’ along the hair surface
that provide some wet conditioning benefits from
the particles themselves. In addition, this increased
hydrophobicity increases the efficiency of deposi-
tion of the silicone conditioning ingredients in the
shampoo and also from the conditioner. The abil-
ity of conditioning agents and other substances to
adsorb to hair fibres depending on the charge and/
or hydrophobicity of the adsorbing species and the
surface has previously been reported [12] and is
important to this proposed mechanism. The intro-
duction of liquid crystals is a unique approach to
those previously reported [12] for depositing cat-
ionic polymer on hair from a shampoo. Herein,
unlike conventional cationic polymers (PQ-10,
Guar), the cationic polymer forms a stable, insolu-
ble complex with surfactant because of its suffi-
ciently high cationic charge which does not
resolubilize at high dilutions. Additionally, this
coacervate complex reduces the surface energy of
chemically damaged hair whereas conventional
coacervates do not.
Zeta potential measurements, which can mea-
sure the surface charge about particulate matter
within solution, provide some evidence of this pro-
posed mechanism following measurements from
neat shampoo through successive shampoo dilu-
tions. In neat shampoo, the liquid crystals are
coated with unbounded anionic surfactant, yield-
ing a negative surface charge surrounding the
liquid crystals (Fig. 3). This outer, unbounded sur-
factant layer is removed from the liquid crystal
surface during shampoo dilution, exposing a liquid
crystal surface that is hydrophobic and less nega-
tively charged than when present in neat sham-
poo; this process occurs during shampooing
(lathering and rinsing) of hair. To simulate the
change in surface charge about liquid crystals that
occurs during typical product usage, a series of
shampoo dilutions were made and then measured
for zeta potential. In these experiments, a simpli-
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200
M. A. Brown et al.
fied shampoo formulation was made with no sili-
cone so the only particles present in the system
were the liquid crystal particles.
The dilution sample preparation was carried out
as follows: )20.0 g of water was added to 20.0 g
of neat shampoo and mixed thoroughly until
homogeneous. Thirty-seven grams of the diluted
shampoo was centrifuged at 1078 g for 90 min to
isolate the majority of dispersed liquid crystals
present within solution, thus yielding a visually
clear supernate. 36.5 g of the supernate was col-
lected from the centrifuged sample (first rinse). A
second rinse sample was obtained by dispersing
the 0.5 g of liquid crystal precipitate, obtained
from the first rinse, in 36.5 g of deionized water
followed by centrifugation and collection of the
supernate; three additional rinse samples were
acquired accordingly. The five rinse samples were
then analysed via ZetaPALS to measure the sur-
face charge about the liquid crystals at the various
dilutions. Figure 7 shows the measured charge on
the particles as a function of the surfactant con-
centration (i.e. as the shampoo is diluted). The
chart shows that the surface charge about the
liquid crystal particles changes and becomes less
negative as a function of increased shampoo dilu-
tion after the second dilution. The first dilution is
above the CMC of the surfactant (526 mg/L) and
is thought to be also measuring the charge on the
surfactant micelles. The shampoo dilutions were
chosen to be close to the dilution profile of a
shampoo during product usage. It is difficult to
accurately measure the dilution of shampoo
incurred during rinsing because of the dynamic
state of the environment about the hair. Rinsing
removes (washes away) much of the surfactant
present within solution about the hair thus lower-
ing the concentration of the surfactant that
remains, having a proposed concentration (10–
0.01 mg/L) that is consumer relevant. This is
approximately between the third and fifth dilution
in this testing thus is in a region where the sur-
face charge is clearly becoming less negative.
In addition to measuring liquid crystal surface
charge, a Zeta Sizer (Malvern) was used to mea-
sure the size of particulate matter present within
the rinse samples. This technique was useful in dif-
ferentiating between liquid crystal particles and
micelles at high shampoo concentration as well as
confirming the absence of other particulate matter
within the supernate. Figure 8 shows the results
from the particle size analysis at rinses 1 and 4.
International Journal of Cosmetic Science, 32, 193–203
Liquid crystal shampoo M. A. Brown et al.

At the first rinse (1 : 1 shampoo/water dilution),
the surfactant concentration was sufficiently high
to enable surfactant micelle formation (20 nm in
size) and thus two peaks were observed, one for
the surfactant micelles and one for the liquid crys-
tals; no other particulate matter was known to
exist within the product. Particle size data col-
lected at higher shampoo dilutions (e.g. fourth
rinse) show the absence of a peak attributed to
micelles within the supernate. A non-polymer con-
taining shampoo (no liquid crystals present) was
also tested in this study. Only the surfactant
micelle peak was observed at the low shampoo
dilution, whereas no peaks were observed at the
higher dilutions. These data demonstrate the
presence of only liquid crystal particles at high

1st
Dilution rinse

4th
Dilution rinse

Figure 8 Particle size measure-

ments of liquid crystal shampoo.

1.6

1.4
Bleached hair
1.2
Polar (mJ m–2)

0.8

0.6

0.4
Liquid crystal
0.2 treated bleached
hair Virgin hair
Figure 9 Surface energy of hairs
0
determined by the DAT system 18.5 19 19.5 20 20.5 21 21.5 22
showing the effect. Nonpolar (mJ m–2)

ª 2010 The Procter & Gamble Company. Journal compilation

ª 2010 Society of Cosmetic Scientists and the Société Française de Cosmétologie
International Journal of Cosmetic Science, 32, 193–203 201
Liquid crystal shampoo
Conventional shampoo Liquid crystal shampoo
1 1
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0 0
Image field of view: 100 µm x 100 µm
shampoo dilution, while having considered a
range of shampoo concentrations above and below
the critical micelle concentration.
Dynamic absorbency testing (DAT) was used to
assess the surface energy of the hair after treat-
ment with the liquid crystal shampoo. DAT uses
high-speed videography to monitor the time it
takes for a 0.2 lL drop of solvent (>99% hexade-
cane and ultrapure water) to absorb into two
strands of hair that have been positioned and held
parallel to one another a distance of 18 lm apart.
The more hydrophilic the hair is, the faster the
droplet absorbs into the hair. The contact angle of
the solvents on the hair was determined from the
image and Fowkes equation of state was used to
convert contact angles into apparent surface
energies. DAT analysis of liquid crystal shampoo-
treated hair showed a marked reduction in the
polar component of surface energy as compared
with colour-treated hair. The polar component of
LC-treated hair was comparable with uncoloured,
virgin hair as shown in Fig. 9.
Visualization of the deposited poly(DADMAC)
polymer was performed using positive ion mode
ToF-SIMS imaging in the same way as was per-
formed for the silicone deposition. Figure 10
depicts the secondary ion image of C3H8N+, which
is generated by the poly(DADMAC) polymer depos-
ited on hair after treatment with the liquid crystal-
containing shampoo. Within the limitations of the
lateral resolution of the ToF-SIMS measurement,
poly(DADMAC) appears to coat the surface of the
hair fibre uniformly at this length scale. The con-
ventional shampoo, which does not contain
poly(DADMAC), provides a negative control show-
ing that the C3H8N+ secondary ion image can be
used to uniquely visualize the distribution of
poly(DADMAC) on the hair surface.
ª 2010 The Procter & Gamble Company. Journal compilation
ª 2010 Society of Cosmetic Scientists and the Société Française de Cosmétologie
202
M. A. Brown et al.
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1 Figure 10 ToF SIMS image of the
C3H8N+ peak, generated by the Poly
(DADMAC) polymer.
Conclusion
Oxidatively damaged hair, above others, needs
effective conditioning to protect the hair from envi-
ronmental and mechanical damage as the oxidative
process has left it more prone to damage. However,
the surface characteristics of the colour-treated hair
make formulating a conditioning shampoo a chal-
lenge. It has been found that creating a liquid crys-
tal colloidal structure in a shampoo formulation
can significantly enhance the deposition of silicone
conditioning actives onto oxidatively damaged
colour-treated hair. It is proposed that the liquid
crystal structure promotes the deposition of a
hydrophobic polymer/surfactant layer on the hair
surface. This increase in hydrophobicity changes
the surface energy of the hair and allows for more
effective deposition of the silicones.
Acknowledgements
Funding provided by Procter & Gamble Beauty.
Thanks to our analytical partners for help in gen-
erating the data included in this publication – Dan
Silbersack, Jamal Berry, Matt Lynch, Fred Wireko,
Amanda Ritter, Shashi Jain.
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