International Journal of Cosmetic Science, 2018, 40, 16–30 doi: 10.1111/ics.

12439

Review Article
A review of shampoo surfactant technology: consumer benefits,
raw materials and recent developments

P. A. Cornwell
Textile Research Institute (TRI), 601 Prospect Avenue, Princeton NJ 08540, USA

Received 14 July 2017, Accepted 27 October 2017

Keywords: claim substantiation in vivo/in vitro, formulation, hair+body care, polymers/surfactants

Abstract
Introduction
Surfactants form the core of all shampoo formulations, and con-
tribute to a wide range of different benefits, including cleansing, Surfactants form the ‘heart’ of most shampoo formulations and
foaming, rheology control, skin mildness and the deposition of ben- perform many different roles in these systems [1–4]. Their primary
efit agents to the hair and scalp. The purpose of this review was to function is to remove soils, such as sebum and solid particulates,
assist the design of effective, modern, shampoo surfactant technolo- from the hair, but they also are important for foaming, building
gies. The mechanisms through which surfactants help deliver their product viscosity, suspending actives and the solubilization of fra-
effects are presented, along with the appraisal techniques through grances. Surfactants also play a key role in the performance of
which surfactant options can be tested and screened for product cationic polymer-based deposition systems used to deliver actives
development. The steps that should be taken to select the most onto the hair and scalp. In addition to this, they have to be
appropriate blend of surfactants are described, and useful informa- selected and blended to be as mild to the skin, hair and eyes as
tion on the most widely used surfactants is provided. The review possible.
concludes with an examination of recent developments in ‘greener’ To anybody first entering the field of shampoo surfactants, the
surfactants, ‘sulphate-free’ technologies and structured liquid large number of materials that are available to choose from, and the
phases for novel sensory properties and for suspending benefit many claims made about their efficacy can be daunting. This review
agents. provides a broad overview of what is known about shampoo surfac-
tants to help formulators build the most effective products for their
target consumers. The first sections of this review analyse the five
Re
sume

key benefits associated with shampoo surfactants: cleaning, foaming,
Les agents tensioactifs sont les ingr
edients de base de la plupart
rheology control, skin mildness and polymer deposition. For each
des shampooings, et contribuent de nombreuses manieres a  leurs
area, the laboratory screening methods are described that can be
performances et sp
ecificit
es : qualit
e nettoyante, onctuosit
e de la
used to select the best performing surfactants. To help with the logi-
mousse, control de la rh
eologie, sensation cutan
ee ou bien d
eposi-
cal choice of surfactants for different benefits, structure–activity rela-
tion d’actifs sur les cheveux ou le cuire chevelue. Le but de cette
tionships, where they have been defined, are also examined. In the
revue est d’apporter une assistance pour l’
elaboration de surfac-
next section of this review, the steps that need to be taken to select
tants innovants pour le d
eveloppement de nouveaux produits
the most appropriate blend of surfactants for any given shampoo are
capillaires. Les m
ecanismes par lesquels les agents tensioactifs d
eli-
described. This is followed by detailed descriptions of widely used pri-
vrent leurs b
en
efices sont discut
es, ainsi que les diff
erentes techni-
mary and secondary surfactants, and by a review of specialized sur-
ques disponibles pour les tester et les s
electionner dans le cadre de
factants. The final sections of this review cover the new
l’
elaboration de nouveaux produits. Les diff
erentes
etapes qui dev-
developments in ‘greener’ surfactants, ‘sulphate-free’ approaches to
raient ^etre prises en consid
erations pour s
electionner les agents
shampoo formulation and structured liquid phases for novel sensory
tensioactifs les plus appropri
es y sont d
ecrites ainsi qu’une section
properties.
r
esumant les informations relatives aux agents tensioactifs les plus
A detailed explanation of the interfacial and colloid science
utilis
es actuellement. En conclusion, la revue pr
esente les d
evelop-
underlying shampoo surfactant properties and effects is outside of
pements r
ecents autour de nouveaux agents
ecologiques (ou
the scope of this review and can be found in textbooks [5, 6]. A
« vert »), des technologies « sans sulfate » et des technologies
comprehensive description of all the surfactants available to formu-
« structured liquid phases » qui procurent de nouvelles propri
et
es
lators is also covered elsewhere [7–10].
sensorielles ou de suspensions.

Cleansing properties of surfactants

As already mentioned, the key benefits associated with shampoo
surfactants are as follows: cleaning, foaming, rheology control, skin
Correspondence: Dr Paul A. Cornwell, 45 Mount Way, Waverton, Che-
shire, CH3 7QF. Tel.: +44 1244 336118; e-mail: [email protected]
mildness and polymer deposition. Of these, the cleaning of hair is,

16 © 2017 Society of Cosmetic Scientists and the Soci
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A review of shampoo surfactant technology P.A. Cornwell

undoubtedly, the most important. Indeed, cleaning of the hair is gas chromatography. Using these protocols, Clarke et al. [21]
the main purpose behind using any shampoo. Most modern sham- have compared the detergency of three surfactants, sodium lau-
poos, based on alkyl ether sulphates, clean the hair very effectively. reth-2 sulphate, ammonium lauryl sulphate and sodium octeth-1/
As a result, formulators often pay little regard to shampoo cleans- deceth-1 sulphate. Their work suggests that sodium laureth-2 sul-
ing properties. However, consumer demands for new milder and phate is the most effective at removing sebum after one and ten
‘greener’ products mean that this area needs to be addressed again wash cycles. The study also showed that the ammonium lauryl
for a new set of technologies. The cleansing action of shampoo sur- sulphate and sodium octeth-1/deceth-1 sulphate selectively
factants has been reviewed by a number of authors [4, 11–14]. removed different sebum components from the hair. The authors
The detergent effects of surfactants are different for different types argue that the effectiveness of sodium laureth-2 sulphate is
of hair soils. To describe these different mechanisms, hair soils are related to its superior detergency, which, in turn, is driven by
broken down into four groups: (1) sebum, (2) skin cell debris, (3) its lower critical micelle concentration (CMC). The selective
solid air pollutants and (4) hair product soils. removal of different sebum components points to the micelle
For the removal of sebum, surfactants are proposed to work mechanism as being important for sebum removal. In a closely
through four mechanisms: (a) roll-up, (b) spontaneous emulsifica- related study, Clarke et al. [22] also show that sebum removal is
tion, (c) penetration and (d) solubilization. Although there is good more selective at higher washing temperatures. No explanation
evidence for each of these mechanisms, it remains unclear which for this effect was offered by the authors.
ones are most important. In reality, it is probably a combination of The relative solubilizing power of different surfactants with a
all the mechanisms that enable sebum removal. The first mecha- given hydrophobic tail usually follows the order non-
nism, the roll-up mechanism, was first proposed by Adam in 1937 ionics > cationics > anionics [5]. Nonionic surfactants, such as the
[15, 16]. Here, the driving force causing the oil separation from alkyl polyglucosides, with their low CMCs, are well known to be
the solid surface is the reduction in the interfacial tension at the very effective detergents for skin and sebum lipids. Unfortunately,
sebum/water and hair/water interfaces created by the surfactants. inclusion of alkyl polyglucosides, as the primary surfactants in
This allows the surface area of both interfaces to increase and shampoos, can make hair feel stripped and dry. Although they are
drives sebum lipids to roll up into round droplets and detach from very mild to the skin, they can also extract lipids and increase skin
the hair surface. Once removed, lipid soils will tend to stay in solu- dryness [23].
tion, as the wet hair, wetted with surfactants, is no longer an The removal of skin cell debris and solid air pollutants from the
attractive surface for oily materials to adhere to. Whilst attractive hair by detergents is widely believed to occur through surfactant
in theory, the roll-up mechanism relies on the soil to be a free- spreading forces, which force water into the soil/water interface
flowing liquid. In reality, sebum is more viscous and waxy, espe- and also through the formation of stable dispersions which prevent
cially with ageing [11]. Lochhead [4] also points out that the roll- the re-deposition of soils once they have been removed [13]. It is
up mechanism is probably best suited to damaged hair that has a well known that anionic surfactants increase the negative potential
more hydrophilic surface. of the electrical double layers on the soil particles and hair, and so
The second mechanism, spontaneous emulsification, is an exten- increase repulsive forces between the surfaces. This tends to stabi-
sion of the roll-up mechanism. In this case, it is argued that the lize the dispersion during washing and prevent re-deposition of the
reduction in the lipid/water surface tension makes it possible for soil particles. Cationic surfactants are much less effective at clean-
the surface area of the interface to expand and for buds of lipid soil ing solid soils than anionic surfactants as they cause, what is
to be formed from larger soil deposits [16]. These buds sponta- known as, an inversion of the cleansing action, that is a cleansing
neously form emulsified lipid droplets that can be easily removed. action less than that of pure water [13].
The emulsification mechanism is better suited to explain the emul- Hydrodynamic forces are very important in the removal of solid
sification of oils from large areas of lipid soil, which are too big to soil particles. These are most effective at removing larger soil parti-
just roll up. However, this mechanism still relies on the soil being cles. However, as streaming velocities reduce closer to the hair sur-
mobile and fluid. face, there comes a point when Van der Waals forces of attraction
The third mechanism, the penetration mechanism of detergency, between soil particles and the hair surface outweigh the displace-
was first proposed by Lawrence in 1959 [17, 18] after he observed ment forces from the water. Soil particles smaller than about
that many soaps and surfactants can penetrate into insoluble lipid 0.1 lm cannot be easily removed from textile materials or hair by
soils and produce liquid–crystalline phases at the soil–water inter- detergents [13, 14]. In textiles, this leads to irreversible greying of
face. Agitation of the system is believed to pull away the loosened fabrics. In hair, it suggests that soils such as fine sand (90 lm in
material, revealing a fresh layer of oily soil underneath, and so on. diameter) may be easy to remove from the hair, but that ultra-fine
Finally, the fourth mechanism, the micelle mechanism of soil airborne particulate pollution from, for example, combustion engi-
removal involves the transfer of lipid soil molecules from the sur- nes (<2.5 lm, known as PM2.5) may be harder to remove. The lack
face of the soil into micelles adhering to the water/oil interface. of published work suggests further work should be carried out on
This mechanism relies on the kinetics of micelle adsorption to the the effectiveness of shampoos in removing solid soils of different
hair surface, lipid transfer into the micelle and, finally, detachment sizes, and particularly pollution particles.
of the filled micelle back into the bulk solution [19]. The micelle The mechanisms through which shampoos remove hair product
mechanism is the only mechanism that can easily account for the soils are not very well defined, and there do not seem to be any
selective removal of lipid soils, as it allows for the removal of lipid rules governing surfactant choice. However, it is understood that,
soils at a molecular, not a bulk, level. unlike sebum, the conditioning surfactants, polymers and silicones
Laboratory tests for shampoo detergency involve the dosing of used in hair products may sometimes not be easily removed by
hair switches with synthetic sebum. Thompson et al. [20] describe washing with a standard anionic surfactant-based shampoo. Rob-
useful protocols for the artificial soiling of hair, various cleaning bins et al. [24], for example, show that monofunctional cationic
processes and the analysis of the lipids remaining on the hair by surfactants are not completely removed by washing with anionic

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A review of shampoo surfactant technology P.A. Cornwell

surfactants. Hannah et al. [25] have shown that coacervates lather from a loose structure to more dense foam. However, it
formed between polyquaternium polymers and anionic surfactants seems that the inclusion of foam boosters is more of an ‘art’ than a
during shampoo use can resist removal from the hair from subse- science. Rieger [2] argues that the mechanisms for foam boosting
quent shampoo washes. This can cause build-up problems if sham- are essentially unknown. It may, in part, be related to how they
poo products are not carefully formulated. Haake et al. [26] have influence the bulk viscosity of the shampoo. The most commonly
shown that the silicones deposited by typical 2-in-1 shampoos are used foam boosters in shampoos at present are alkanolamides, such
only removed gradually after a number of washes in aqueous solu- as cocamide monoethanolamide, and betaines, such cocamido-
tions of sodium lauryl ether sulphate. In some cases, only 50% of propyl betaine. Fatty alcohols, commonly found as impurities in
the deposited silicone was removed after three washes. It is widely alkyl sulphate surfactants, also boost foam [2]. In order to get the
understood that amodimethicones and silicone quats have the best foam, alkanolamides and betaines are often added to the main
greatest substantivity to the hair (in comparison with non-polar anionic surfactant at a ratio of 10 parts anionic to 1 part foam
dimethicones) [27]. As a consequence, there is a greater risk of booster [3]. A typical shampoo would, for example, contain, for the
build-up with these ingredients and formulators need to use them purposes of foam creation: 10% w/w sodium lauryl ether sulphate
with great care. and 1% w/w cocamidopropyl betaine. Of course, as will be dis-
cussed below, different ratios can also be used to boost viscosity
and product mildness. In addition to the above approaches, it is
Foaming properties of surfactants
well known that low levels (<0.5% w/w) of high molecular weight,
Whilst cleaning is the main function of surfactants in a shampoo, water-soluble polyethylene glycol polymers (e.g. PEG-800) can, at
it is actually the foaming properties that more often drive con- relatively low cost, give shampoos a denser, more creamy foam
sumer preference. Foams are an important cue for product quality. [28]. Cationic conditioning polymers, introduced at low levels (0.1–
This is, of course, ironic, as technically speaking, the foam is not 0.3% w/w) to provide hair conditioning benefits, can also have, as
necessarily linked to the cleansing power of the product. Despite an added bonus, positive effects on shampoo foam quality.
this, consumers demand that shampoos foam easily and produce Laboratory tests for shampoo foam performance are very diverse
lots of creamy foam. and are often different from one laboratory to the next [29]. The
The science behind the creation of foam for personal care prod- Ross Miles test [30] dates back to 1941 and is the technique most
ucts is reviewed by Rieger [2]. The creation of foams from sham- frequently used by detergent manufacturers. It involves dropping a
poos has also been reviewed by Lochhead [4]. Surfactants help dilute surfactant solution from a fixed height into a pool of the
generate foam because they are able to concentrate at the air/wa- same dilute solution and measuring the height of the foam thus
ter interface and reduce surface tension. During hair washing, generated. The strength of the method is that cross-comparison
small air bubbles, each surrounded by liquid, are formed. These with literature data is possible; however, the great drawback it
bubbles stretch the surface area of the air/water interface. Without bears very little relation to how shampoos actually foam on con-
surfactants present, the strong surface tension of water would sumers’ hair. The cylinder shake method is the most frequently
quickly pull the bubbles closed. However, with surfactants present, used in the cosmetics industry for evaluating foam in shampoos
the bubbles are stabilized and remain for longer. A fully formed and shower gels [29]. It involves placing diluted shampoo solution
foam consists of the bubble walls (or lamellae) and the triple-bubble in a graduated cylinder, sealing the cylinder and then rotating it a
junctions (or plateau borders). The lamellae are stabilized by sur- number of times to create the foam. The test can be used to mea-
factants concentrated at the air/water interface. Foams degrade sure flash foam, foam volume and drainage time. Introduction of
either through drainage of the liquid phase or through puncture of artificial sebum can also be used to investigate how well a sham-
the lamellae. poo may perform on very soiled hair. Many more laboratory meth-
The relationship between surfactant structure and foam creation ods exist to test shampoo foam and are reviewed by Klein [29]. In
and sustainability is complex. It is widely understood that most Klein’s opinion, the most effective method to date is the blender
surfactants with low CMCs foam well. However, non-ionic surfac- foam volume/drainage test developed by Henkel Corporation. In
tants (which have low CMCs) generally foam less well as they have this test, 4 g of a 10% solution of shampoo is added to 146 g of
difficulty with lateral packing at the air/water interface. Generally water (50 ppm hardness) at 29°C. The solution is agitated for 10 s
speaking, very pure surfactants, even if they have the ideal struc- at a medium speed in a blender. The foam is poured into a 1000-
ture, do not produce good foams. The best foams are produced mL graduated cylinder and the volume measured. After 3.5 min,
when blends of surfactants are used and when foam boosters are the position of the foam–water interface is recorded. This gives a
introduced. Beyond these rather general observations, there do not measure of foam drainage. Additionally, the time of agitation may
seem to be any detailed rules for predicting which surfactants or be decreased to 5 s to determine flash foam.
surfactant blends produce the best foam. It is, unfortunately, a Automated foam testers have been introduced into the market to
matter of trial and error. assist formulators. The SITA Foam Tester R2000 (Messtechnik
Foams can be stabilized in a number of different ways. Thicken- GmbH) offers repeatable and automated monitoring of foam char-
ing of the liquid phase can help the lamellae resist deformation and acteristics of diluted shampoos. Other devices include the FoamS-
puncturing. In addition, thickening the liquid phase can slow drai- can foam analyser (Teclis Instruments) and the DFA100 Dynamic
nage and help maintain the foam for longer. Formulators can sta- Foam Analyzer (Orbit Research Associates Private Limited).
bilize foams in this way, with a wide range of polymeric rheology
modifiers and thickeners. Thickening the liquid phase of a sodium
Surfactant phase behaviour and the role of
lauryl sulphate- or sodium lauryl ether sulphate-based shampoo
surfactants in rheology control
with sodium chloride will also help with stabilizing the foam. Some
amphoteric and non-ionic surfactants can be included in sham- In addition to having a good cleansing and foaming action, a
poos, as secondary surfactants to boost foam and to modify the good-quality shampoo needs to have a well-balanced rheological

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International Journal of Cosmetic Science, 40, 16–30
A review of shampoo surfactant technology P.A. Cornwell

fingerprint. This fingerprint needs to deliver different benefits at and liquid crystals. Of course the PC is an oversimplification, and
various stages in the product’s use. If we first consider a more stan- the relative size of the head-group region can often be altered by
dard shampoo, then, in-store and in the bathroom, if presented in changes in pH or by the levels of various counter-ions. Surfactant
clear bottles, it needs to flow well as the bottle is tipped from side packing can also be modified through the use of co-surfactants.
to side to cue product quality. In the shower, or at the basin, it However, the PC is still a good place to start and helps explain
needs to be easy to dispense into the hand, without any stringiness, many common phenomena, and can help as a basic guide for sur-
particularly if it is pump dispensed. It also needs to have to right factant selection.
appearance and consistency in the hand and needs to be easy to Surfactant phase behaviour is often driven by surfactant concen-
spread into the hair. If we next consider a more unusual shampoo tration. Many anionic surfactants tend to go through a similar
with structured surfactant technology, then this might have a dif- sequence of phases as their concentration is increased [1]. At low
ferent fingerprint, with, for example, a lotionlike feel in the hand, concentrations, above their CMC, they tend to form low-viscosity,
but with a good ease of spread in the hair. In addition to sensory isotropic solutions of micelles. As the concentration is raised, the
benefits, shampoos also often need to suspend materials such as micelles elongate into rods that eventually stack to form a high vis-
pearlizers, silicones, anti-dandruff agents and encapsulated actives. cosity hexagonal phase. As the concentration rises further they
This creates new demands on the rheological fingerprint of prod- form a lower viscosity, liquid crystalline lamellar phase, then
ucts as they will need to have a high yield point over a wide range inverse hexagonal phase and, finally, inverse micelles. This descrip-
of storage temperatures. tion of concentration effects is, of course, an oversimplification,
At the heart of the rheology of a shampoo is the phase beha- many different liquid crystals, or mesophases, have been described
viour of the surfactants included in the formulation. In other in the literature, and they will vary with the blend of the surfac-
words, the way the surfactants pack together and form three- tants used, the concentration, the temperature and various other
dimensional structures in the product. The subject of surfactant factors. However, the sequence of phases shown here tends to hold
phase behaviour is large and complex, and outside the scope of this for many anionic shampoo surfactants, such as alkyl sulphates and
review. However, there are two key insights that will help formula- alkyl ether sulphates. As we will see later, this sequence of phases
tors select the best surfactants for a particular sort of phase beha- explains the problems often encountered with the dilution of con-
viour. Firstly, it is understood that a key parameter involved in the centrated solutions of surfactant used as raw materials. It also
formation of different surfactant structures is the geometrical struc- means that it is hard to create ‘concentrated’ shampoo products, as
tures of the molecules themselves [31]. The critical packing param- high viscosities at high surfactant concentrations make pouring
eter (PC) is a conceptual tool used to describe different surfactant and diluting these products difficult.
structures in numerical terms. It is calculated using the cross- Three types of measurements can be used to define the rheologi-
sectional area of the surfactant head-group and the tail volume cal fingerprint of a shampoo. Firstly, the viscosity of the product at
and length. Figure 1 shows that surfactants with a PC of <0.5 pre- different shear rates is usually characterized using a flow curve
fer to form micellar structures in water with their alkyl chains [32]. Most shampoos exhibit non-Newtonian flow characteristics
facing inwards. The anionic surfactants most commonly used in and have higher viscosities at low shear rates. This is usually
shampoos tend to fall into this category and act as good detergents. advantageous, since higher viscosities at low shear rates (e.g. dis-
In contrast, surfactants with a PC = 1 can form lamellar phases pensing the product into the hand) cue product quality. However,

Figure 1 Schematic illustrating the effects of

changes in critical packing parameter (Pc) of
surfactants and the effects on aggregation
structures.

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A review of shampoo surfactant technology P.A. Cornwell

low viscosities at high shear rates (e.g. spreading the product on Aqueous solutions of alkyl sulphate and alkyl ether sulphate sur-
the hair) make the product easier to apply. High viscosities at low factants, thickened with salt, are also viscoelastic. They usually
shear rates may also help suspend materials in the product. Vari- behave like Maxwell fluids, with viscous and elastic properties [35].
ous methods can be used to calculate the yield point required to Balzer et al. [35] show that understanding the balance of viscosity
suspend materials of different sizes and relative densities [33, 34]. and elasticity can explain the stringiness of the product as it is
Flow curves can be measured on a wide range of viscometers [32], dispensed.
including rotary and cone-and-plate instruments. The second type The addition of low molecular weight, non-ionic or amphoteric
of measurement used in the rheological fingerprint is the character- surfactants to an alkyl sulphate- or alkyl ether sulphate-based
ization of the viscoelasticity of the system, or how easily the pro- shampoo can also thicken the product. These secondary surfactants
duct can regain its viscosity after being exposed to shear [32]. Most are sometimes termed hydrophobic thickeners because their alkyl
shampoos show pseudo-plastic behaviour and have an elastic ele- chains form the largest proportion of their mass [37]. They include
ment to their flow properties [35]. This is important, as products cocamide MEA and cocamidopropyl betaine. These hydrophobic
that are too elastic may thicken too quickly after shearing and thickeners generally act to create more wormlike micelles and
become stringy, or may suck back into the bottle when being dis- encourage more non-Newtonian flow behaviour. In practice, they
pensed. Product viscoelasticity can be measured on a range of oscil- also act to push the salt curve to the left. This means they can
latory viscometers [32], including cone-and-plate instruments. The increase the product viscosity at low salt levels, making the product
third type of measurement in the fingerprint relates to the stringi- easier to thicken with brine.
ness of the shampoo when it is dispensed. Stringiness has been High molecular weight, polymeric non-ionic surfactants can also
characterized using a thread-drawing apparatus [36]. be added to an alkyl sulphate- or alkyl ether sulphate-based sham-
An added factor in the characterization of the fingerprint is that poo to increase viscosity. These are known as hydrophilic thicken-
shampoos can be sensitive to temperature. A product that flows ers because their highly extended, ethoxylated head groups form
perfectly at 20°C, may, for example, become thick and jellylike in a the largest proportion of their mass [37]. They include PEG-120
cold bathroom. Another product that suspends pearl effectively at methyl glucose dioleate and PEG-7 glyceryl cocoate. These thicken-
20°C may be unstable at high summer temperatures. It is impor- ers can increase the micelle size or bridge neighbouring micelles
tant, therefore, to make measurements over the temperature range and encourage more Newtonian-like flow [37].
that the product may be stored or used at.
The rheological properties of alkyl sulphates and alkyl ether sul-
Surfactant mildness
phate surfactants are well known. These surfactants are commonly
used for low-cost viscosity build. It has been shown that aqueous Mildness to the skin and eyes is another key benefit that shampoos
solutions of alkyl sulphates and alkyl ether sulphates, with low need to deliver to consumers. Unfortunately, there is no one scien-
levels of added sodium chloride, have spherical micelles, and flow tific definition of mildness. It is, instead, defined by the absence of a
like Newtonian liquids (i.e. their viscosity is independent of the series of negatives [38]. Mildness is most commonly associated with
shear rate) [1, 4]. This behaviour, as discussed already, is driven the absence of skin irritation, that is redness, heat, swelling and
by their low PC. The addition of salt to these surfactants reduces pain. Medically, skin irritation is described as irritant contact der-
the ionic repulsion between the head groups, which encourages matitis (ICD). ICD is classified as an immediate biological response
the micelles to transition to wormlike rods [1, 4]. The salt effec- to irritation from a chemical, such as a surfactant, or abrasion of
tively reduces the size of the head groups and raises the PC, and the skin. The in vivo skin patch test is the gold standard for screen-
changes the packing behaviour. The wormlike micelles behave like ing products for an irritant response [39]. It usually involves the
polymers in solution and increase the formulation viscosity application of a product or a solution to the skin, under occlusion,
through an entanglement-like mechanism [1]. The addition of salt and the visual grading of the irritant response. Physical and bio-
solution, or brine, to alkyl sulphate- and alkyl ether sulphate-based physical skin testing methods are also used (e.g. chromameters to
formulations produces the familiar salt curve measured using sim- measure redness and laser Doppler flowmetry to measure blood
ple bench-top viscometers. At very high salt levels, the viscosity flow), although they do not typically improve the overall quality of
drops again as the micelles become parallel rodlike micelles that the results obtained by visual grading [39].
slip more easily over each other [1]. It is usually best to remain on Mildness can also be linked with the absence of skin sensitiza-
the ascending part of the salt curve. This way the product viscosity tion, also known as allergic contact dermatitis (ACD). ACD is
is easier to adjust and control. In some cases, product viscosity most commonly associated with nickel in jewellery, fragrances
needs to be brought back down. A number of agents are used to and preservatives, and not directly with surfactants. Allergic
do this, including ethanol, propylene glycol, polypropylene glycol reactions are usually tested by skin patch tests, usually on the
and sodium xylene sulfonate. skin of the back [40]. Individuals with a history of ACD are re-
The addition of salt not only increases the viscosity of alkyl exposed to the suspected allergens under controlled conditions.
sulphate and alkyl ether sulphate solutions at most shear rates, Patch tests help identify possible allergens, but they not allow for
it also encourages solutions to become non-Newtonian shear- the assessment of a new product’s potential for causing ACD. In
thinning fluids. Here, products have relatively higher viscosities this instance, a human repeated insult patch test (HRIPT) may
at low shear rates. As discussed above, this is desirable for pro- be necessary [41].
duct aesthetics and for suspending materials. It is believed that Mildness to the eyes is also very important for shampoo prod-
the viscosity drop at high shear rates is caused by the alignment ucts. For many years, the Draize eye test was the industry standard
of the wormlike micelles that begin to slip over each other more method [42]. However, with the banning of animal testing for cos-
easily under faster shear. This effect is reversible, and with metics in many markets, several in vitro alternatives have been
decreasing shear rate, the wormlike micelles entangle again and developed, for example the red blood cell test [43]. Human clinical
the viscosity increases. tests have also been developed to support ‘no tears’-like claims.

20 © 2017 Society of Cosmetic Scientists and the Soci
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etologie

International Journal of Cosmetic Science, 40, 16–30
A review of shampoo surfactant technology P.A. Cornwell

In addition to direct irritation or sensitization responses, sham- polyglucoside can, therefore, potentially be drying to the skin. It
poo mildness can also be defined as a lack of skin barrier disruption is interesting to note that, in this study, isethionates seem to deli-
and the lack of induced skin dryness, both of which predispose the ver a unique combination of low zein dissolution scores and low
skin to irritation from the surfactants themselves, or to other chem- lipid bilayer disruption effects. In the same study, Ananthapad-
icals. Surfactants can affect the integrity of the lipid barrier in the manabhan et al. also investigate the effects of increasing the pro-
stratum corneum (SC), and, thus, increase skin permeability [44]. portion of cocamidopropyl betaine in a sodium lauryl ether
Topically applied surfactant solutions can also swell corneocyte sulphate/cocamidopropyl betaine blend. In good agreement with
proteins, which results in the removal of natural moisturizing fac- many other studies, they show that increasing the levels of
tors and enhances penetration of irritant chemicals into the viable cocamidopropyl betaine reduces zein dissolution scores. However,
epidermis [45]. This is believed to lead to skin dryness and to the study also shows that higher levels of cocamidopropyl betaine
increase the probability of skin irritation. Surfactants can also have increase lipid solubilization. The authors suggest that it is impor-
biological effects on the SC. For example, sodium lauryl ether sul- tant to strike the right balance between protein and lipid damage
phate can inhibit enzymes in the SC that control desquamation, to maximize overall mildness.
leading to scaling, skin dryness and impaired barrier function [46]. Purohit et al. [49] have shown that lipid bilayer disruption in
Pape et al. [43] have investigated the relationship between the the stratum corneum by surfactants can change its mechanical
red blood cell (RBC) test data for a series of surfactants and in vitro properties. Their work suggested that harsher surfactants can alter
eye irritation data. Their study showed that the concentrations of the lipid packing and also remove lipid components, which, in
surfactants and finished products required to cause cell haemolysis turn, can affect the stress relaxation properties of the stratum cor-
(breakage of the cytoplasmic membranes) and denaturation of hae- neum, leading to higher drying stresses.
moglobin were highly correlated with in vivo eye irritation scores.
Furthermore, their data suggested that surfactant irritancy went,
Role of surfactants in polymer deposition
generally, in the order: cationics (severe eye irritation) > anion-
ics + amphoterics (moderate/irritant) > non-ionics (moderate/non- Modern shampoo formulations do not only offer a pleasant rheolog-
irritant). The RBC test continues, to this day, to be routinely used ical fingerprint and good cleansing, foaming and skin mildness ben-
to screen shampoos for mildness to mucosal membranes. Schrader efits, but also they offer hair conditioning benefits such as wet
et al., [47] for example, use the RBC to show that increasing the detangling, ease of wet combing and dry smoothness. These bene-
proportion of amphoteric surfactant (e.g. cocamidopropyl betaine) fits are usually delivered by cationic conditioning polymers and sili-
in a sodium lauryl ether sulphate/amphoteric mixture significantly cones. Surfactants play a key role in delivering these benefits as
reduces potential irritancy. They also show that sulfosuccinates they are deeply involved in the mechanisms through which catio-
can produce very good RBC scores and hence potentially very low nic polymers are able to deposit on the hair, and also aid the
eye irritation. It is for this reason that surfactant blends includ- deposition of other benefit agents, such as silicone emulsions and
ing sulfosuccinates are commonly used in children’s ‘no-tears’ anti-dandruff actives. Changing the surfactant system or electrolyte
formulations. levels will always have a knock-on effect on the effectiveness of the
The tendency of surfactants to interact with model proteins has conditioning polymers in a shampoo system.
also been correlated with their harshness towards human skin. Lips The interactions between cationic polymers and anionic surfac-
et al. [48] hypothesize that the tendency of surfactants to swell and tants have been extensively studied [50, 51]. It is widely under-
denature zein proteins can be used to screen actives for skin mild- stood that these interactions will affect formulation viscosity,
ness. They show that, for a series of model surfactants, skin flex foaming behaviour and polymer deposition. It is generally believed
wash and skin patch tests data correlate very well with zein disso- that there are three stages of interaction between cationic polymers
lution data. Lips et al. have also built a structure–activity relation- and anionic surfactants (Fig. 2).
ship that can predict zein dissolution data. Their data show that Stage 1 represents the situation in the undiluted shampoo where
the effective charge density of the head-group region of a surfac- the anionic surfactant is present at high levels. At this stage, the
tant correlates well with its ability to denature zein protein. Test surfactant is usually able to solubilize the polymer. Shampoos con-
results show that surfactant irritancy and zein dissolution (at 5% taining cationic polymers can often, therefore, be formulated as
active) is in the order; (highly irritant) sodium dodecyl sulphate clear products. Micelles are believed to form along the polymer
and sodium laurate (‘soap’), (moderately irritant) cetyl trimethyl chain, stretching it out and increasing the viscosity of the sham-
ammonium bromide, dodecyl trimethyl ammonium bromide and poo. The association of excess surfactant effectively reverses the
sodium lauryl ether sulphate, and (low irritancy) alkyl polyglu- charge on the polymer and would be expected to reduce binding to
coside and sodium dodecyl sulfobetaines. Data also showed that the hair.
blending sodium lauryl ether sulphate with a less irritant ampho- Stage 2 represents the situation when the product has been
teric, cocamidopropyl betaine, at a 1 : 2 ratio is able to reduce the diluted on wet hair during application and foaming up of the prod-
zein solubility, and hence skin irritation versus a 2 : 1 ratio of the uct. Here, the dilution of the product in water causes anionic sur-
same surfactants. This correlates well with RBC test observations. factants to dissociate from the cationic polymer as they partition
The effects of surfactants on skin lipids can also be linked to into the water. The partitioning of surfactants to the air/water and
mildness. Ananthapadmanabhan et al. [23] developed a lipid solu- lipid soil/water interfaces during foaming and the solubilization of
bilization test and a lipid bilayer disruption test to investigate sur- lipid soils will also further pull surfactant from the cationic poly-
factant mildness. Their tests showed that lipid solubilization and mers. A key point is reached in stage 2 when the positive charge
disruption tests can produce data that is the inverse of protein on the polymer is neutralized, or perfectly balanced, with the nega-
dissolution data. For example, alkyl polyglucoside, a very mild tive charge of the anionic surfactant. Charge neutralization can
non-ionic surfactant, which typically has low zein dissolution result in precipitation of the polymer-surfactant complex. The sur-
scores, produces high levels of lipid bilayer disruption. Alkyl face of the polymer-surfactant complex is hydrophobic and thus

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Figure 2 Effect of dilution on cationic poly-

mer/surfactant interactions (based on Goddard,
1999 [50]).

can be attracted to the hydrophobic surface of the hair. It is the wet hair. A spectrophotometer can be used to quantitate the tur-
precipitation of the polymer-surfactant complex that enables the bidity of samples if necessary.
entrapment and deposition of the polymer on the hair and scalp, Another approach for product development is to measure the
and the deposition of any associated benefit agents, such as sili- levels of deposition of benefit agents, such as silicones on the hair
cones and anti-dandruff agents [52, 53]. The wet conditioning and using techniques such as atomic absorption [54] and X-ray fluores-
wet detangling benefits of cationic polymers are largely associated cence [26]. The wet conditioning benefits of the polymers and sili-
with the lubricating effects of the polymer-surfactant complexes on cones can also be measured directly using wet combing and wet
the hair. It is believed that the polymer-surfactant complexes form detangling tests [55].
lubricating gel-like films on the hair surface. Cationic polymers that
do not precipitate during the washing stages are usually less effec-
Surfactant selection
tive conditioning agents.
As the hair is rinsed further with water, stage 3 is reached The previous sections have reviewed the five key actions of sham-
where anionic surfactant is present at low levels relative to the poo surfactants: cleaning, foaming, rheology control, skin mildness
cationic polymer. In this situation, surfactant molecules bind to the and polymer deposition. Armed with this understanding, the next
polymer chain and only partially neutralize the charge. Cationic step, when designing a shampoo formulation, is to select the most
polymers in this situation would be solubilized again. They will also appropriate blend of surfactants.
be positively charged and able to bind to the negatively charged Shampoos formulations normally need both primary and sec-
surface of the hair. Polymer deposited at this stage will also provide ondary surfactants. Primary surfactants, as their names suggests,
some lubricating effects in the wet and dry. usually exist at the highest concentrations in products and provide
Many different cationic polymers exist for the use in shampoos. most of their fundamental properties. The role of the secondary
By far the most popular are polyquaternium-10 and guar hydrox- surfactants is then, usually, to boost the effects of the primary sur-
ypropyl trimonium chloride. Both are available in a wide range of factants in the directions required for a specific product. For exam-
molecular weights and charge densities, and both can be formu- ple, many secondary surfactants boost foam or make the shampoo
lated to precipitate on shampoo dilution. The precipitation of catio- milder to the scalp and eyes.
nic polymers on shampoo dilution, and the deposition of suspended The key decision for a formulator is to decide whether to pick
benefit agents, is affected by the levels of primary and secondary widely used, low-cost materials as the primary and secondary sur-
surfactants. Precipitation is also affected by salt levels in the pro- factants. Or, to select more specialized surfactants that can deliver
duct, and by the presence of high molecular weight, water-soluble unique benefits, for example ‘no tears’ for baby shampoos, deep-
PEGs. Addition of low levels (<0.1% w/w) of PEGs can significantly cleansing for ‘detox’ shampoos or alternative surfactants for ‘sul-
improve the efficiency of polymer precipitation and active deposi- phate-free’ shampoos. The primary surfactants that are most widely
tion (supplier data). used are exclusively anionic surfactants and include sodium lauryl
When developing a shampoo it is often necessary to measure ether sulphate, sodium lauryl sulphate, ammonium lauryl ether
polymer precipitation and the associated deposition of benefit sulphate and ammonium lauryl sulphate. Secondary surfactants
agents on the hair. Although it is possible to use sophisticated tech- that are most widely used include mainly amphoteric and non-
niques to directly measure polymer deposition, one of the simplest ionic surfactants. Amphoterics used most widely include cocamido-
ways to investigate polymer precipitation is to dilute the shampoo propyl betaine and coco-betaine. Non-ionics include cocamide
product in water. A clear shampoo product should go cloudy as it monoethanolamide and cocamide monoisopropanolamide. When
is diluted if the system is performing properly. As a rule of thumb, selecting surfactants, it is important to consider any technical con-
shampoos should precipitate at roughly a 1-in-5 to 1-in-10 dilu- straints, such as the target cost, the product pH required for the
tion, believed to be the sort of dilution a shampoo experiences on preservation system and processing issues.

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thing, as it is understood that fatty alcohols are important as foam

Widely used primary Surfactants
boosters and stabilizers [2]. Trace amounts of 1,4-dioxane, a poten-
Alkyl and alkyl ether sulphates form, by far, the most popular tial carcinogen, can be found in alkyl ether sulphates [58]. The EU
group of anionic surfactants used as primary surfactants in sham- Scientific Committee on Consumer Safety propose that cosmetic prod-
poos. The alkyl and alkyl ether sulphates most widely used include ucts sold in the EU should contain less than 10 ppm 1,4-dioxane as a
sodium lauryl ether sulphate, sodium lauryl sulphate, ammonium trace impurity [59]. Regular checks on 1,4-dioxane levels are neces-
lauryl ether sulphate and ammonium lauryl sulphate. These are sary.
cost-effective materials that, if formulated effectively, deliver effec-
tive cleansing, foaming, rheology control and polymer deposition.
Widely used secondary surfactants
The alkyl sulphates have a hydrophobic alkyl chain tail and a
sulphate head-group. The sulphate head group in this group of sur- Cocamidopropyl betaine and coco-betaine are the most commonly
factants is attached with a sulphate ester bond. Extremes of temper- used amphoteric secondary surfactants in shampoo products.
ature and pH can break this ester bond and give rise to chemical Cocamidopropyl betaine is by far the most widely used. Cocamido-
instability [56]. When using sulphates, the pH of formulations is propyl betaine is normally obtained as a 30% aqueous solution
normally kept between 5.5 and 8.0 to guarantee good stability. [60]. At higher levels, it forms non-flowable, gel-like phases. Most
However, formulations can be made, with care, at lower pHs. commercial cocamidopropyl betaine contains approximately 7%
The alkyl chain lengths of sulphate surfactants tend to range sodium chloride, 2–3% glycerol and <1% glycolic acid [60]. The
between 8 and 18 carbons. The average chain length tends to be significant levels of salt will usually help with viscosity building in
12 carbons (hence the lauryl). The fatty alcohols used to make alkyl ether sulphate and cocamidopropyl betaine mixtures. The
these surfactants are usually sourced from coconut and/or palm residual glycerol in some commercial grades of cocamidopropyl
kernel oil. Petrochemical sourced lauryl-range alcohols are also betaine is due to these grades being made direct from triglyceride
used [57]. The chain length of 12 carbon atoms gives a good com- oils, rather than from fatty acids, which give glycerol-free grades.
promise between detergency and water solubility. Increasing the Increasing the levels of cocamidopropyl betaine in an alkyl ether
chain length decreases the CMC and increases the micelle size, and sulphate and cocamidopropyl betaine blend will increase mildness
is associated with improved solubilizing power. However, going too to the skin and eyes. This is related to the low inherent irritancy
far can reduce surfactant solubility, resulting in cloudy products. of cocamidopropyl betaine relative to sulphate surfactants. Increas-
The distribution of chain lengths will vary between suppliers and ing the levels of cocamidopropyl betaine will also increase the vis-
with different grades and batches of materials. It is now understood cosity of the system. This is, in part, due to the high levels of
that having a varied range of chain lengths is actually a good sodium chloride in commercial cocamidopropyl betaine. Increasing
thing and helps foam creation and viscosity building. It is interest- levels of cocamidopropyl betaine will also reduce bubble size and
ing to note that ultra-pure sodium dodecyl sulphate foams rela- make the foam thicker. However, very high levels of cocamido-
tively poorly. propyl betaine will depress the overall foam levels in anionic sur-
The degree of ethoxylation in alkyl ether sulphates usually varies factant systems. Cocamidopropyl betaine does not have as strong
between 1 and 5 units. Introduction of oxyethylene groups is foaming properties as alkyl ether sulphates. Most shampoos use a
known to reduce the CMC of sulphate surfactants. The biggest drop 10 : 1 ratio of alkyl ether sulphate to cocamidopropyl betaine,
in CMC occurs after the addition of just one oxyethylene group. although higher levels of cocamidopropyl betaine are sometimes
Much smaller decreases are seen after the addition of 2–4 more used to give more luxurious foam or to build viscosity in low sur-
[5]. Introduction of oxyethylene groups is also associated with factant level formulations. As cocamidopropyl betaine is an
improved skin mildness. It has been shown that with 10 oxyethy- amphoteric, it is sensitive to pH and the viscosity building effects
lene units almost no skin irritation is observed [5]. However, intro- are pH dependant.
duction of oxyethylene groups increases surfactant solubility, and Alkanolamides such as cocamide monoethanolamide and coca-
this can prevent viscosity build. In the end, as always, a balance mide monoisopropanolamide are also widely used secondary surfac-
needs to be found, and many commercial shampoos use alkyl ether tants in shampoos and are classed as non-ionics. Both are waxy
sulphates with an average of 1–3 oxyethylene units. It should not solids that need heating before incorporation. As a result, both can
be forgotten, however, that a range of oxyethylene group lengths be bought as liquids in commercial blends with other surfactants.
can be found in commercial grades of alkyl ether sulphates and Alkanolamides act very much like the betaines, to reduce the ionic
that a significant proportion of the material could be just alkyl sul- repulsion between the head groups of alkyl sulphate and alkyl
phate (with no oxyethylene groups). ether sulphate surfactants. This encourages micelles to transition to
Sodium lauryl ether sulphate is usually supplied as a concentrated wormlike rods [1]. As a result, alkanolamides are very effective at
aqueous solution containing 70% w/w active. This allows for more increasing product viscosity and improving foam stability [1]. Like
cost-effective transportation and avoids the need for additional the betaines, alkanolamides are used at a 1 : 10 or 1 : 5 ratio with
preservatives. At this level, the surfactant exists as a lamellar G phase alkyl ether sulphates [3]. Cocamide monoethanolamide and coca-
and the mixture is a free-flowing liquid [1]. However, as the mixture mide monoisopropanolamide can contain trace levels of nitrosami-
is diluted with water to finished product levels (5–15% w/w), it goes nes and have the potential to form nitrosamines in finished
through a highly viscous gel phase, known as the M1 phase [1]. It is products. Nitrosamines are potential human carcinogens. Formula-
for this reason that 70% w/w sodium lauryl ether sulphate should be tors working with alkanolamides should avoid raw materials con-
gradually added to water under shear. Adding water to 70% w/w taining nitrosating agents such as nitrogen oxides, ionic nitrites
sodium lauryl ether sulphate can create lumps of viscous gel phase and some preservatives. Cocamide monoethanolamide and coca-
that are difficult to disperse, even under shear [1]. mide monoisopropanolamide have no limits on inclusion levels
Low levels (1–3%) of unreacted alcohols commonly remain in under European regulations, but, in order to control potential
commercial grades of sulphate surfactants. This may not be a bad nitrosamine formulation, must have <0.5% secondary amine as

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A review of shampoo surfactant technology P.A. Cornwell

(I) Sulphates - alkyl glyceride sulphates (e.g. sodium cocomonoglyceride

sulphate)
O

R C O CH2 CH CH2 O S O- Na+

O OH O

(II) Carboxylates - ether carboxylates (e.g. laureth-5-carboxylic acid)

R O (CH2CH2O)5 CH2 C O- Na+

O
(III) Carboxylates - glucose carboxylates (e.g. sodium lauryl glucose
carboxylate)
CH2 OH
O
R O H H
H OH
H O CH2 C O- Na+
OH H O

(IV) Carboxylates - acyl glutamates (e.g. sodium lauroyl glutamate)

O- Na+
O
C
R C NH CH CH2 CH2 C O- Na+
O O

(V) Carboxylates - acyl sarcosinates (e.g. sodium lauroyl sarcosinate)

CH3
R C N CH2 C O- Na+
O O
(VI) Sulphonates - taurates (e.g. sodium methyl cocoyl taurate)
O
CH3 Figure 3 Head-group structures of a range of
specialized surfactants that can be used in
R C N CH2 CH2 S O- Na+ shampoos. The structures illustrated relate to
the example materials. Slight differences in

O O head-group structure may occur within chemi-

cal groups.

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(VII) Sulphonates - sulphoacetates (e.g. sodium lauryl sulfoacetate)

R O C CH2 S O- Na+
O O
(VIII) Sulphonates - sulphosuccinates (e.g. disodium lauryl sulfosuccinate)

O- Na+
O
O S
R O C CH2 CH C O- Na+
O O

(IX) Sulphonates - isethionates (e.g. sodium lauroyl methyl isethionate)

CH3
O

R O C CH CH2 S O- Na+
O O
(X) Non-ionics - alkyl polyglucosides (e.g. lauryl glucoside)

CH2 OH
O
R O H H
H OH
H OH
OH H
(XI) Non-ionics – acyl glucamides (e.g. cocoyl methyl glucamide)

HO HO
CH3
HO
R C N CH2 CH CH CH CH CH
HO HO
Figure 3 Continued. O

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A review of shampoo surfactant technology P.A. Cornwell

Table I Biorenewable Carbon Index (BCI) for a

Example Raw selection of commonly used shampoo surfactants
Surfactant Type Material Supplier BCI References

Sodium lauryl sulphate Anionic STEPANOL Stepan 100% Supplier data

WA-EXTRA
Sodium lauryl ether sulphate Anionic STEOL CS-130 Stepan 86% Supplier data
(1 EO)
Sodium lauryl ether sulphate Anionic STEOL CS-225 Stepan 75% Supplier data
(2 EO)
Sodium lauryl ether sulphate Anionic RHODAPEX Solvay 100% [64]
ESB_70 NAT
Cocamidopropyl betaine Amphoteric AMPHOSOL CA Stepan 63% Supplier data
Cocamide monoethanolamide Nonionic NINOL CMP Stepan 86% Supplier data
Cocamide monoisopropanolamide Nonionic NINOL M10 Stepan 80% Supplier data
Lauryl glucoside Nonionic PLANTACARE BASF 100% [62]
1200 UP
Cocoyl methyl glucamide Nonionic GLUCOTAIN CARE Clariant 95% Supplier data

impurities in the final product [61]. The maximum nitrosamine taurates, the acyl tail group on sulphoacetates and sulphosucci-
content in the finished product is 50 lg kg 1 [61]. nates is attached to the head group through an ester linkage, mak-
ing them less chemically stable. Sulphosuccinates are very mild to
the skin and eyes and are widely used in baby shampoos. However,
Specialized surfactants
they are not easily salt thickened, adding cost to formulations.
Alkyl and alkyl ether sulphates are the most widely used anionic Isethionates (e.g. sodium lauroyl isethionate and sodium lauroyl
primary surfactants in shampoos. However, more specialized anio- methyl isethionate) have been traditionally used to make synthetic
nic primary surfactants are available for particular applications. detergent soap bars and body washes and are mild to the skin.
Figure 3 shows the head-group structures of a range of specialized Recently, they have drawn a lot of interest as suitable replacements
surfactants that can be used in shampoos. for sulphates in ‘sulphate-free’ shampoos. They work well as pri-
Alkyl glyceride sulphates provide improved mildness, but with mary surfactants and produce good foam. Isethionates are typically
the foaming power of alkyl ether sulphates. Cocomonoglyceride sul- best formulated between pH 6.0 and 8.0 to prevent hydrolysis of
phate, for example, foams well but gives better skin compatibility the ester bond that attaches the head group to the acyl chain.
than alkyl ether sulphates and other anionics [9]. Unfortunately, Sodium lauroyl methyl isethionate has better water solubility and a
this class of surfactants is not suitable for ‘sulphate-free’ formulas. wider range of pH stability than sodium lauroyl isethionate and
For both milder and ‘sulphate-free’ products, carboxylates can be can be salt thickened.
considered as alternative primary anionic surfactants. Ether car- In addition to various specialized anionic surfactants, a wide
boxylates (e.g. laureth-5 carboxylic acid), for example, provide good range of non-ionic surfactants can be incorporated in shampoos to
water solubility in comparison with traditional carboxylates give mildness, ‘sulphate-free’ claims and added ‘natural’ creden-
(‘soaps’) and are less sensitive to hard water [9]. These surfactants tials. In most instances, they are incorporated as secondary surfac-
provide good skin mildness and good foam properties [9]. Glucose tants. Useful classes of non-ionics for shampoos include alkyl
carboxylates (e.g. sodium lauryl glucose carboxylate) provide the polyglucosides and acyl glucamides. Alkyl polyglucosides (e.g. coco-
mildness associated with non-ionic glucose-based surfactants (e.g. glucoside and lauryl glucoside) are usually incorporated to boost
alkyl polyglucosides), but with better foam properties [9]. Other mildness and the formulation’s ‘natural’ credentials (they are pro-
carboxylates include the acyl glutamates (e.g. sodium lauroyl gluta- duced from 100% plant derived feed-stocks) [62]. Alkyl polygluco-
mate) and acyl sarcosinates (e.g. sodium lauroyl sarcosinate). Both sides are also very good oil solubilizers and can be used in deep-
also provide good skin mildness [9]. Adding sodium cocoyl gluta- cleansing (or ‘detox’) shampoos. The foaming properties of alkyl
mate to an acyl ether sulphate and cocamidopropyl betaine system polyglucosides are reasonable, but not as strong as the alkyl sul-
has been shown to reduce inhibition of stratum corneum tryptic phates or alkyl ether sulphates. Alkyl polyglucosides can have
enzyme by sodium lauryl ether sulphate and to prevent surfactant- impaired chemical stability below pH 5 [9]. Acyl glucamides (e.g.
induced skin dryness [46]. cocoyl methyl glucamide) are also derived largely from natural,
Sulphonates can be considered as alternative primary anionic renewable sources. They are mild and are claimed to foam better
surfactants for ‘SLES-free’ products. They have a more chemically than alkyl polyglucosides when inserted into alkyl ether sulphate-
stable C–S bond between the SO3 head-group and the alkyl chain based formulas.
in comparison with the ester bond in sulphate surfactants. There
are many sub-classes of sulphonates, including taurates, sulphoac-
Sustainable sourcing
etates, sulphosuccinates and isothionates. Taurates (e.g. sodium
methyl cocoyl taurate) are effective as primary anionic surfactants Consumer concerns about the impact of cosmetic products on the
for shampoos. They have good flash foam and are chemically stable environment have risen sharply in recent years. As a result, manu-
over a wide pH range. Sulphoacetates (e.g. sodium lauryl sulfoac- facturers have started to pay much closer attention to the environ-
etate) and sulphosuccinates (e.g. disodium lauryl sulfosuccinate) mental footprint that their products make, in terms of greenhouse
can be used for milder and ‘SLES-free’ shampoos. Unlike the gas emissions, water usage, waste and the sustainable sourcing of

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A review of shampoo surfactant technology P.A. Cornwell

raw materials. This global trend has started to make an impact on bars [67], it may not be long before many shampoo surfactants are
the surfactant technologies used in shampoos [63, 64]. made from biotechnology sourced materials.
In response to consumer demands for natural products, brands
are now starting to claim that their products contain ‘natural’,
Sulphate-free shampoos
‘naturally derived’ or ‘organic’ ingredients. At present, these claims
do not have any legal definition, but they can be supported with Over the past 10–15 years, consumer concerns about alkyl sul-
various certification standards (e.g. Ecocert, NATRUE and COSMOS phate and alkyl ether sulphate products have grown significantly.
standards) [63]. Consumers worry about possible skin and eye irritation, and the
It is possible to quantify how ‘natural’ a surfactant is by look- potential drying effects these surfactants are having on their skin.
ing at its composition and the materials used to make it. There Added to this are safety concerns about 1,4-dioxane present as
are two methods currently being used. The first method, called the trace ingredients in alkyl ether sulphates. Although these concerns
biorenewable carbon index [65], calculates the percentage of car- may not be supported by any strong technical evidence, and are
bon atoms that come from renewable plant or animal sources ver- mainly misinformation spread on the Internet, they have increased
sus non-renewable petrochemical sources. An advantage of this the demand for ‘sulphate-free’ shampoos. As a result, the numbers
method is that the value is not distorted by atoms in a material of ‘sulphate-free’ products have continued to grow and grow. Even
with high atomic masses, such as the sulphur commonly used in mass brands are now embracing this trend, and patents are emerg-
anionic surfactants. It also fits well with the standard test method ing for sulphate-free formulas [68].
used for determining the bio-based content of materials [66]. This The challenges in moving away from alkyl sulphates and alkyl
method involves carbon dating samples to determine the relative ether sulphates are many-fold. Firstly, replacement surfactants are
proportions of natural and petroleum based carbons. The second invariably more expensive than standard sulphate ones. Secondly,
method, called simply the percentage renewable by molecular the levels of surfactants in ‘sulphate-free’ products often need to be
weight, simply takes the relative proportion of the molecular higher to achieve equivalent foam, adding further to costs. Thirdly,
weight of the surfactant that comes from renewable sources. This sulphate surfactants thicken with sodium chloride and with
second method is quite tricky to do in practice as each atom in betaines, whilst many alternative surfactants do not. Addition of
the surfactant has to be defined as coming either from a renew- polymeric thickeners adds to formulation costs, and can negatively
able or non-renewable source. This means that chemical reactions affect the deposition of cationic polymers and silicones, compromis-
used in the synthesis of the material need to be precisely under- ing performance. Finally, it is difficult to achieve equivalent product
stood, and difficult judgements often have to be made as to where performance in ‘sulphate-free’ systems. This can be for many rea-
each atom has actually come from in the process. The percentage sons. For example, cationic polymer deposition is well known to be
renewable by molecular weight is also difficult as there is no sensitive to the types of anionic surfactant used and the propor-
instrumental test that can validate your calculations. Table I sum- tions of co-surfactants and salt. Moving away from well-established
marizes the ‘biorenewable carbon index’ for the most commonly standard sulphate surfactant blends requires large amounts of
used shampoo surfactants. Clearly, materials such as lauryl glu- deposition testing. In addition, alternative surfactants may create
coside provide consumers with a very ‘natural’ choice of ingredi- unwanted, structured phases (anisotropic microstructures) that can
ent. compromise foaming and silicone deposition, and which can make
Table I also shows that different grades of the same material can products harder to rinse away. Finally, alternative surfactants may
be made more ‘natural’. The ethoxylate groups in sodium lauryl be less chemically stable at the low pHs needed for more popular
ether sulphate, for example, can be made using bio-ethylene synthe- preservatives (e.g. sodium benzoate). Moving away from sulphates
sized by sugar cane fermentation, rather than from petrochemicals, means going right back to basics and considering the key functions
taking the biorenewable carbon index up from approx. 75% to 100% of the surfactants in the shampoo: cleansing, foaming, rheology
[64]. control, mildness and polymer deposition.
Clearly, the biorenewable carbon index and percentage renew-
able value are very simplistic measures of the environmental
Structured liquid surfactants
impact of cosmetic ingredients. Just because an ingredient is plant-
based does not mean that it is produced sustainably. Many sham- Structured liquid surfactants systems comprise surfactants in liquid
poo surfactants use palm oil as a feedstock, and the development of crystalline phase. These are currently receiving a lot of attention as
new palm oil plantations is associated with rainforest destruction they can give a very unique rheological profile to shampoo products.
around the world. The Roundtable on Sustainable Palm Oil (RSPO) If formulated correctly, they can give a shampoo a lotionlike feel
helps suppliers source sustainable palm oil [67], and many are when it is dispensed, and then good foaming and conditioning prop-
moving towards using mass-balance-certified palm oil or segregated erties on the hair. Structured liquid systems can also give excellent
sustainable palm oil. Many raw material suppliers now offer grades oil and silicone suspension properties, and interesting product visual
of common shampoo surfactants that have been made with guar- effects (e.g. marblelike colour effects, and multilayered colour effects).
anteed sustainable palm oil (e.g. Cocamidopropyl betaine made Typically structured liquid surfactants are formed at high levels
with RSPO-certified sustainable palm kernel oil). of surfactant concentrations and electrolyte. For example, it is well
The ultimate step in improving the environmental sustainability known that sodium lauryl ether sulphate moves from a micellar
of surfactants may by to source palm oil-like materials from phase to lamellar phase as the concentration is increased. However,
biotechnology. Biotechnology has the potential to make palm oil- with some careful blending of ingredients, it is possible to create
like materials in much higher yields per acre than traditional palm structured liquid surfactant systems at lower active levels. Surfac-
oils, and with starting materials that are already available in tem- tants with high PCs (PC ~ 1) will tend to form lamellar structures
perate climates. Fatty acids derived from the algal fermentation of (e.g. phospholipids in cell membranes). Lamellar packing can also
sugars are already being used to make the detergents in some soap be encouraged using surfactants with carefully branched alkyl

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International Journal of Cosmetic Science, 40, 16–30
A review of shampoo surfactant technology P.A. Cornwell

chains that straighten the packing arrangements, or by blending A more recent patent from Hawkins et al. (Stepan, priority date
anionic surfactants that have large head groups and small tails 2012) [73] describes a structured surfactant system that is transpar-
with non-ionics or amphoterics that have small head groups and ent, and comprised of a blend of surfactants that produce multilamel-
large tails, again, ‘straightening’ the packing arrangements. lar vesicles in the absence of any electrolytes. Some blends were
Patents from Puvvada et al. (Unilever, priority date 1999) [69] based on glyceryl caprylate/caprate and lauramine oxide, or glyceryl
and Frantz et al. (Rhodia, now Solvay, priority date 2001) [70] are caprylate/caprate and sodium lauryl ether sulphate. These blends
examples of many patents that describe the use of sodium trideceth were claimed to be effective at suspending beads and oil droplets.
sulphate as the primary anionic in structured surfactant systems.
The branching of the alkyl chain in this surfactant increases the
Conclusions
cross-sectional size of the tail group and encourages lamellar pack-
ing. Puvvada et al. combine the sodium trideceth sulphate with sec- Shampoo surfactant technology is changing rapidly at present, as
ondary surfactants such as cocamidopropyl betaine and isostearic the result of consumer needs for more environmentally sustain-
acid for personal wash applications. Frantz et al. combine it with able products, for ‘sulphate-free’ products and for products with
sodium lauroamphoacetate and cocamide monoethanolamide. The much more interesting rheological profiles. This review has cov-
blend of sodium trideceth sulphate, sodium lauroamphoacetate and ered all of the key uses of surfactants in shampoos, cleaning,
cocamide monoethanolamide is available as a pre-blended concen- foaming, rheology control, mildness and polymer deposition, and
trate for use in shampoos and personal wash formulations. has shown how surfactants deliver these benefits and how each
Tsaur et al. (Unilever, priority date 2006) [71] describe the use of these can be measured. It has also described the steps that
of fatty acyl isothionates, such as those used in mild soap bars, to need to be taken to select the most appropriate blend of surfac-
create structured surfactant systems for use in liquid personal wash tants for any given shampoo and has pulled together useful infor-
applications. The authors describe the combination of isothionates mation on the most widely used surfactants. It is hoped that the
with a specific combination of liquid crystal modifiers (e.g. fatty knowledge shared here can help develop the shampoos of the
acids, fatty alcohols) and co-surfactants (e.g. alkanolamide, alky- future.
lamineoxide). Structured surfactant systems can also be made using
sodium lauroyl methyl isethionate. Concentrates are commercially
Acknowledgements
available containing sodium lauroyl methyl isethionate, sodium
lauroamphoacetate and cocamide monoisopropanolamide that can Many thanks to Dr Nick Ainger (Unilever R&D, UK) for his advice
instantly produce structured surfactant formulations. on sections of this review. Thanks as well to Dr Tony Gough
Another way of achieving structured systems is to combine anion- (Innospec Ltd, UK) and Prof Robert Y. Lochhead (The University of
ics with cationic surfactants. Bendejacq (Rhodia, now Solvay, prior- Southern Mississippi, USA) for reviewing the manuscript. No finan-
ity date 2009) [72] describes the formation of structured shampoo cial support was sought, or was received, for the creation of this
systems using cetrimonium chloride as a co-surfactant. It is claimed review.
that the formulations successfully suspended silicones and oils.

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