10 1111@ics 12439 PDF

DR.
PAUL ALFRED CORNWELL (Orcid ID : 0000-0002-4353-805X)
Article type : Review Article

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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, United States of
America
Correspondence: Dr P.A. Cornwell, 45 Mount Way, Waverton, Cheshire, CH3 7QF, Tel.:
+44 1244 336118; e-mail: paul.cornwell@live.com
A review of shampoo surfactant technology: Consumer benefits, raw materials and

recent developments
Key words
Formulation, Hair+Body care, Claim substantiation in vivo/in vitro, Polymers/Surfactants
Abstract
Surfactants form the core of all shampoo formulations, and contribute to a wide range of
different benefits including cleansing, foaming, rheology control, skin mildness and the
deposition of benefit agents to the hair and scalp. The purpose of this review is to assist the
design of effective, modern, shampoo surfactant technologies. The mechanisms through
which surfactants help deliver their effects are presented, along with the appraisal techniques
through which surfactant options can be tested and screened for product development. The
steps that should be taken to select the most appropriate blend of surfactants are described,
and useful information on the most widely used surfactants is provided. The review
concludes with an examination of recent developments in ‘greener’ surfactants, ‘sulphate-
free’ technologies and structured liquid phases for novel sensory properties and for
suspending benefit agents.
This article has been accepted for publication and undergone full peer review but has not
been through the copyediting, typesetting, pagination and proofreading process, which may
lead to differences between this version and the Version of Record. Please cite this article as
doi: 10.1111/ics.12439
This article is protected by copyright. All rights reserved.
Introduction
Surfactants form the ‘heart’ of most shampoo formulations and perform many different roles
in these systems [1-4]. Their primary function is to remove soils, such as sebum and solid
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particulates, from the hair, but they also are important for foaming, building product
viscosity, suspending actives and the solubilisation of fragrances. Surfactants also play a key
role in the performance of cationic polymer based deposition systems used to deliver actives
onto the hair and scalp. In addition to this, they have to be selected and blended to be as
mild to the skin, hair and eyes as possible.
To anybody first entering the field of shampoo surfactants, the large number of materials that
are available to choose from, and the many claims made about their efficacy can be daunting.
This review provides a broad overview of what is known about shampoo surfactants to help
formulators build the most effective products for their target consumers. The first sections
of this review analyse the five key benefits associated with shampoo surfactants: cleaning,
foaming, rheology control, skin mildness and polymer deposition. For each area the
laboratory screening methods are described that can be used to select the best performing
surfactants. In order to help with the logical choice of surfactants for different benefits,
structure-activity relationships, where they have been defined, are also examined. In the next
section of this review, the steps that need to be taken to select the most appropriate blend of
surfactants for any given shampoo are described. This is followed by detailed descriptions of
widely used primary and secondary surfactants, and by a review of specialised surfactants.
The final sections of this review cover the new developments in ‘greener’ surfactants,
‘sulphate-free’ approaches to shampoo formulation and structured liquid phases for novel
sensory properties.
A detailed explanation of the interfacial and colloid science underlying shampoo surfactant
properties and effects is outside of the scope of this review and can be found in textbooks [5,
6]. A comprehensive description of all the surfactants available to formulators is also
covered elsewhere [7-10].
Cleansing properties of surfactants

As already mentioned, the key benefits associated with shampoo surfactants are: cleaning,
foaming, rheology control, skin mildness and polymer deposition. Of these, the cleaning of
hair is, undoubtedly the most important. Indeed, cleaning of the hair is the main purpose

behind using any shampoo. Most modern shampoos, based on alkyl ether sulphates, clean
the hair very effectively. As a result, formulators often pay little regard to shampoo cleansing
properties. However, consumer demands for new milder and ‘greener’ products mean that
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this area needs to be addressed again for a new set of technologies. The cleansing action of
shampoo surfactants has been reviewed by a number of authors [4, 11-14]. The detergent
effects of surfactants are different for different types of hair soils. In order to describe these
different mechanisms, hair soils are broken down into four groups: (1) sebum (2) skin cell
debris (3) solid air pollutants, and (4) hair product soils.
For the removal of sebum, surfactants are proposed to work through four mechanisms: (a)
roll-up, (b) spontaneous emulsification (c) penetration and (d) solubilisation. Whilst there is
good evidence for each of these mechanisms, it remains unclear which ones are most
important. In reality, it is probably a combination of all the mechanisms that enable sebum
removal. The first mechanism, the roll-up mechanism was first proposed by Adam in 1937
[15, 16]. Here, the driving force causing the oil separation from the solid surface is the
reduction in the interfacial tension at the sebum/water and hair/water interfaces created by the
surfactants. This allows the surface-area of both interfaces to increase and drives sebum
lipids to roll-up into round droplets and detach from the hair surface. Once removed, lipid
soils will tend to stay in solution, as the wet hair, wetted with surfactants, is no longer an
attractive surface for oily materials to adhere to. Whilst attractive in theory, the roll-up
mechanism relies on the soil to be a free-flowing liquid. In reality, sebum is more viscous
and waxy, especially with aging [11]. Lochhead [4] also points out that the roll-up
mechanism is probably best suited to damaged hair that has a more hydrophilic surface.
The second mechanism, spontaneous emulsification, is an extension of the roll-up

mechanism. In this case, it is argued that the reduction in the lipid/water surface tension
makes it possible for the surface area of the interface to expand and for buds of lipid soil to
be formed from larger soil deposits [16]. These buds spontaneously form emulsified lipid
droplets that can be easily removed. The emulsification mechanism is better suited to explain
the emulsification of oils from large areas of lipid soil, which are too big to just roll-up.
However, this mechanism still relies on the soil being mobile and fluid.

The third mechanism, the penetration mechanism of detergency was first proposed by
Lawrence in 1959 [17, 18] after he observed that many soaps and surfactants can penetrate
into insoluble lipid soils and produce liquid-crystalline phases at the soil-water interface.
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Agitation of the system is believed to pull away the loosened material, revealing a fresh layer
of oily soil underneath, and so on.
Finally, the fourth mechanism, the micelle mechanism of soil removal, involves the transfer
of lipid soil molecules from the surface of the soil into micelles adhering to the water/oil
interface. This mechanism relies on the kinetics of micelle adsorption to the hair surface,
lipid transfer into the micelle and, finally, detachment of the filled micelle back into the bulk
solution [19]. The micelle mechanism is the only mechanism that can easily account for the
selective removal of lipid soils, as it allows for the removal of lipid soils at a molecular, not a
bulk, level.
Laboratory tests for shampoo detergency involve the dosing of hair switches with synthetic
sebum. Thompson et al [20] describe useful protocols for the artificial soiling of hair, various
cleaning processes and the analysis of the lipids remaining on the hair by gas
chromatography. Using these protocols, Clarke et al [21] have compared the detergency of
three surfactants, sodium laureth-2 sulphate, ammonium lauryl sulphate and sodium octeth-
1/deceth-1 sulphate. Their work suggests that sodium laureth-2 sulphate is the most effective
at removing sebum after one and ten wash cycles. The study also showed that the ammonium
lauryl sulphate and sodium octeth-1/deceth-1 sulphate selectively removed different sebum
components from the hair. The authors argue that the effectiveness of sodium laureth-2
sulphate is related to its superior detergency, which, in turn is driven by its lower Critical
Micelle Concentration (CMC). The selective removal of different sebum components points
to the micelle mechanism as being important for sebum removal. In a closely related study,
Clarke et al also show that sebum removal is more selective at higher washing temperatures
[22]. No explanation for this effect was offered by the authors.
The relative solubilising power of different surfactants with a given hydrophobic tail usually
follows the order nonionics > cationics > anionics [5]. Nonionic surfactants, such as the
alkyl polyglucosides, with their low CMCs, are well known to be very effective detergents
for skin and sebum lipids. Unfortunately, inclusion of alkyl polyglucosides as the primary

surfactants in shampoos, can make hair feel stripped and dry. Whilst they are very mild to
the skin, they can also extract lipids and increase skin dryness [23].
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The removal of skin cell debris and solid air pollutants from the hair by detergents is widely
believed to occur through surfactant spreading forces, which force water into the soil/water
interface and also through the formation of stable dispersions which prevent the re-deposition
of soils once they have been removed [13]. It is well known that anionic surfactants increase
the negative potential of the electrical double layers on the soil particles and hair, and so
increase repulsive forces between the surfaces. This tends to stabilize the dispersion during
washing and prevent re-deposition of the soil particles. Cationic surfactants are much less
effective at cleaning solid soils than anionic surfactants as they cause, what is known as, an
inversion of the cleansing action, i.e. a cleansing action less than that of pure water [13].
Hydrodynamic forces are very important in the removal of solid soil particles. These are
most effective at removing larger soil particles. However, as streaming velocities reduce
closer to the hair surface, there comes a point when Van der Waals forces of attraction
between soil particles and the hair surface outweigh the displacement forces from the water.
Soil particles smaller than about 0.1 μm cannot be easily removed from textile materials or
hair by detergents [13, 14]. In textiles, this leads to irreversible greying of fabrics. In hair, it
suggests that soils such as fine sand (90 μm in diameter) may be easy to remove from the
hair, but that ultra-fine airborne particulate pollution from, for example, combustion engines,
(< 2.5 μm, known as PM2.5 ) may be harder to remove. The lack of published work suggests
further work should be done on the effectiveness of shampoos in removing solid soils of
different sizes, and particularly pollution particles.
The mechanisms through which shampoos remove hair product soils are not very well
defined and there don’t seem to be any rules governing surfactant choice. However, it is
understood that, unlike sebum, the conditioning surfactants, polymers and silicones used in
hair products may sometimes not be easily removed by washing with a standard anionic
surfactant based shampoo. Robbins et al [24], for example, show that mono-functional
cationic surfactants are not completely removed by washing with anionic surfactants.
Hannah et al [25] have shown that coacervates formed between poly-quaternium polymers
and anionic surfactants during shampoo use can resist removal from the hair from subsequent
shampoo washes. This can cause build-up problems if shampoo products are not carefully

formulated. Haake et al [26] have shown that the silicones deposited by typical 2-in-1
shampoos are only removed gradually after a number of washes in aqueous solutions of
sodium lauryl ether sulphate. In some cases only 50% of the deposited silicone was removed
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after three washes. It is widely understood that amodimethicones and silicone quats have the
greatest substantivity to the hair (in comparison to non-polar dimethicones) [27]. As a
consequence there is a greater risk of build-up with these ingredients and formulators need to
use them with great care.
Foaming properties of surfactants

Whilst cleaning is the main function of surfactants in a shampoo, it is actually the foaming
properties that more often drive consumer preference. Foams are an important cue for
product quality. This is, of course, ironic, since technically speaking, the foam is not
necessarily linked to the cleansing power of the product. Despite this, consumers demand
that shampoos foam easily and produce lots of creamy foam.
The science behind the creation of foam for personal care products is reviewed by Rieger [2].
The creation of foams from shampoos has also been reviewed by Lochhead [4]. Surfactants
help generate foam because they are able to concentrate at the air/water interface and reduce
surface tension. During hair washing, small air bubbles, each surrounded by liquid, are
formed. These bubbles stretch the surface area of the air/water interface. Without surfactants
present, the strong surface tension of water would quickly pull the bubbles closed. However,
with surfactants present, the bubbles are stabilised and remain for longer. A fully formed
foam consists of the bubble walls (or lamallae) and the triple-bubble junctions (or plateau
borders). The lamellae are stabilised by surfactants concentrated at the air/water interface.
Foams degrade either through drainage of the liquid phase or through puncture of the
lamellae.
The relationship between surfactant structure and foam creation and sustainability is
complex. It is widely understood that most surfactants with low CMCs foam well. However,
non-ionic surfactants (which have low CMCs) generally foam less well as they have
difficulty with lateral packing at the air/water interface. Generally speaking very pure
surfactants, even if they have the ideal structure, do not produce good foams. The best foams
are produced when blends of surfactants are used and when foam boosters are introduced.
Beyond these rather general observations, there don’t seem to be any detailed rules for

predicting which surfactants or surfactant blends, produce the best foam. It is, unfortunately,
a matter of trial and error.
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Foams can be stabilised in a number of different ways. Thickening of the liquid phase can
help the lamellae resist deformation and puncturing. In addition, thickening the liquid phase
can slow drainage and help maintain the foam for longer. Formulators can stabilise foams in
this way, with a wide range of polymeric rheology modifiers and thickeners. Thickening the
liquid phase of a sodium lauryl sulphate or sodium lauryl ether sulphate based shampoo with
sodium chloride will also help with stabilising the foam. Some amphoteric and non-ionic
surfactants can be included in shampoos, as secondary surfactants to boost foam and to
modify the lather from a loose structure to more dense foam. However, it seems that the
inclusion of foam boosters is more of an ‘art’ than a science. Rieger [2] argues that the
mechanisms for foam boosting are essentially unknown. It may, in part be related to how
they influence the bulk viscosity of the shampoo. The most commonly used foam boosters in
shampoos at present are alkanolamides, such as cocamide monoethanolamide, and betaines,
such cocamidopropyl betaine. Fatty alcohols, commonly found as impurities in alkyl
sulphate surfactants, also boost foam [2]. In order to get the best foam, alkanolamides and
betaines are often added to the main anionic surfactant at a ratio of 10 parts anionic to 1 part
foam booster [3]. A typical shampoo would, for example, contain, for the purposes of foam
creation: 10% w/w sodium lauryl ether sulphate and 1% w/w cocamidopropyl betaine. Of
course, as will be discussed below, different ratios can also be used to boost viscosity and
product mildness. In addition to the above approaches, it is well know that low levels (<0.5
% w/w) of high molecular weight, water soluble polyethylene glycol polymers (e.g. PEG-
800) can, at relatively low cost, give shampoos a denser, more creamy foam [28]. Cationic
conditioning polymers, introduced at low levels (0.1-0.3% w/w) to provide hair conditioning
benefits, can also have, as an added bonus, positive effects on shampoo foam quality.
Laboratory tests for shampoo foam performance are very diverse, and are often different
from one laboratory to the next [29]. The Ross Miles test [30] dates back to 1941 and is the
technique most frequently used by detergent manufacturers. It involves dropping a dilute
surfactant solution from a fixed height into a pool of the same dilute solution and measuring
the height of the foam thus generated. The strength of the method is that cross comparison
with literature data is possible, however, the great drawback it bears very little relation to
how shampoos actually foam on consumers hair. The cylinder shake method is the most

frequently used in the cosmetics industry for evaluating foam in shampoos and shower gels
[29]. It involves placing diluted shampoo solution in a graduated cylinder, sealing the
cylinder and then rotating it a number of times to create the foam. The test can be used to
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measure flash foam, foam volume and drainage time. Introduction of artificial sebum can
also be used to investigate how well a shampoo may perform on very soiled hair. Many more
laboratory methods exist to test shampoo foam, and are reviewed by Klein [29]. In Klein’s
opinion the most effective method to date is the blender foam volume/drainage test developed
by Henkel Corporation. In this test, 4 g of a 10% solution of shampoo is added to 146 g of
water (50 ppm hardness) at 29°C. The solution is agitated for 10 s at a medium speed in a
blender. The foam is poured into a 1000 mL graduated cylinder and the volume measured.
After 3.5 minutes the position of the foam water interface is recorded. This gives a measure
of foam drainage. Additionally, the time of agitation may be decreased to 5 s to determine
flash foam.
Automated foam testers have been introduced into the market to assist formulators. The
SITA Foam Tester R2000 (Messtechnik GmbH) offers repeatable and automated monitoring
of foam characteristics of diluted shampoos. Other devices include the FoamScan foam
analyser (Teclis Instruments) and the DFA100 Dynamic Foam Analyzer (Orbit Research
Associates Private Limited).
Surfactant phase behaviour and the role of surfactants in rheology control

In addition to having a good cleansing and foaming action, a good quality shampoo needs to
have a well-balanced rheological finger-print. This finger-print needs to deliver different
benefits at various stages in the product’s use. If we first consider a more standard shampoo,
then, in-store and in the bathroom, if presented in clear bottles, it needs to flow well as the
bottle is tipped from side to side to cue product quality. In the shower, or at the basin, it
needs to be easy to dispense into the hand, without any stringiness, particularly if it is pump
dispensed. It also needs to have to right appearance and consistency in the hand and needs to
be easy to spread into the hair. If we next consider a more unusual shampoo with structured
surfactant technology, then this might have a different finger-print, with, for example, a
lotion-like feel in the hand, but with a good ease of spread in the hair. In addition to sensory
benefits, shampoos also often need to suspend materials such as pearlisers, silicones, anti-
dandruff agents and encapsulated actives. This creates new demands on the rheological

finger-print of products as they will need to have a high yield point over a wide range of
storage temperatures.
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At the heart of the rheology of a shampoo is the phase behaviour of the surfactants included
in the formulation. In other words, the way the surfactants pack together and form three-
dimensional structures in the product. The subject of surfactant phase behaviour is large and
complex, and outside the scope of this review. However, there are two key insights that will
help formulators select the best surfactants for a particular sort of phase behaviour. Firstly, it
is understood that a key parameter involved in the formation of different surfactant structures
is the geometrical structures of the molecules themselves [31]. The Critical Packing
Parameter (PC) is a conceptual tool used to describe different surfactant structures in
numerical terms. It is calculated using the cross-sectional area of the surfactant head-group
and the tail volume and length. Figure 1 shows that surfactants with a PC of <0.5 prefer to
form micellar structures in water with their alkyl chains facing inwards. The anionic
surfactants most commonly used in shampoos tend to fall into this category, and act as good
detergents. In contrast, surfactants with a PC = 1 can form lamellar phases and liquid
crystals. Of course the PC is an over-simplification, the relative size of the head-group region
can often be altered by changes in pH or by the levels of various counter-ions. Surfactant
packing can also be modified through the use of co-surfactants. However, the PC is still a
good place to start and helps explain many common phenomena, and can help as a basic
guide for surfactant selection.
Surfactant phase behaviour is often driven by surfactant concentration. Many anionic

surfactants tend to go through a similar sequence of phases as their concentration is increased
[1]. At low concentrations, above their CMC, they tend to form low viscosity, isotropic
solutions of micelles. As the concentration is raised the micelles elongate into rods that
eventually stack to form a high viscosity hexagonal phase. As the concentration rises further
they form a lower viscosity, liquid crystalline lamellar phase, then inverse hexagonal phase
and, finally, inverse micelles. This description of concentration effects is, of course, an
oversimplification, many different liquid crystals, or mesophases, have been described in the
literature, and they will vary with the blend of the surfactants used, the concentration, the
temperature and various other factors. However, the sequence of phases shown here tends to
hold for many anionic shampoo surfactants, such as alkyl sulphates and alkyl ether sulphates.
As we will see later, this sequence of phases explains the problems often encountered with

the dilution of concentrated solutions of surfactant used as raw materials. It also means that it
is hard to create ‘concentrated’ shampoo products, as high viscosities at high surfactant
concentrations make pouring and diluting these products difficult.
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Three types of measurements can be used to define the rheological finger-print of a shampoo.
Firstly, the viscosity of the product at different shear rates is usually characterised using a
flow curve [32]. Most shampoos exhibit non-Newtonian flow characteristics and have higher
viscosities at low shear rates. This is usually advantageous, since higher viscosities at low
shear rates (e.g. dispensing the product into the hand) cue product quality. Whereas, low
viscosities at high shear rates (e.g. spreading the product on the hair) make the product easier
to apply. High viscosities at low shear rates may also help suspend materials in the product.
Various methods can be used to calculate the yield point required to suspend materials of
different sizes and relative densities [33, 34]. Flow curves can be measured on a wide range
of viscometers [32], including rotary and cone-and-plate instruments. The second type of
measurement used in the rheological finger-print is the characterisation of the viscoelasticity
of the system, or, how easily the product can regain its viscosity after being exposed to shear
[32]. Most shampoos show pseudo-plastic behaviour and have an elastic element to their
flow properties[35]. This is important, since products that are too elastic may thicken too
quickly after shearing and become stringy, or may suck-back into the bottle when being
dispensed. Product viscoelasticity can be measured on a range of oscillatory viscometers
[32], including cone-and-plate instruments. The third type of measurement in the finger-print
relates to the stringiness of the shampoo when it is dispensed. Stringiness has been
characterised using a thread-drawing apparatus [36].
An added factor in the characterisation of the finger-print is that shampoos can be sensitive to
temperature. A product that flows perfectly at 20oC, may, for example, become thick and
jelly-like in a cold bathroom. Another product that suspends pearl effectively at 20oC, may
be unstable at high summer temperatures. It is important, therefore, to make measurements
over the temperature range that the product may be stored or used at.
The rheological properties of alkyl sulphates and alkyl ether sulphate surfactants are well
known. These surfactants are commonly used for low-cost viscosity build. It has been
shown that aqueous solutions of alkyl sulphates and alkyl ether sulphates, with low levels of
added sodium chloride, have spherical micelles, and flow like Newtonian liquids (i.e. their

viscosity is independent of the shear rate) [1,4]. This behaviour, as discussed already, is
driven by their low PC. The addition of salt to these surfactants reduces the ionic repulsion
between the head groups, which encourages the micelles to transition to worm-like rods [1,
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4]. The salt effectively reduces the size of the head-groups and raises the PC, and changes the
packing behaviour. The worm-like micelles behave like polymers in solution and increase
the formulation viscosity through an entanglement-like mechanism [1]. The addition of salt
solution, or brine, to alkyl sulphate and alkyl ether sulphate based formulations produces the
familiar salt curve measured using simple bench-top viscometers. At very high salt levels the
viscosity drops again as the micelles become parallel rod-like micelles that slip more easily
over each other [1]. It is usually best to remain on the ascending part of the salt curve. This
way the product viscosity is easier to adjust and control. In some cases product viscosity
needs to be brought back down. A number of agents are used to do this including: ethanol,
propylene glycol, polypropylene glycol and sodium xylene sulfonate.
The addition of salt not only increases the viscosity of alkyl sulphate and alkyl ether sulphate
solutions at most shear rates, it also encourages solutions to become non-Newtonian shear-
thinning fluids. Here products have relatively higher viscosities at low shear rates. As
discussed above, this is desirable for product aesthetics and for suspending materials. It is
believed that the viscosity drop at high shear rates is caused by the alignment of the worm-
like micelles that begin to slip over each other more easily under faster shear. This effect is
reversible and, with decreasing shear rate, the worm-like micelles entangle again and the
viscosity increases.
Aqueous solutions of alkyl sulphate and alkyl ether sulphate surfactants, thickened with salt,
are also viscoelastic. They usually behave like Maxwell fluids, with viscous and elastic
properties [35]. Balzer et al show that understanding the balance of viscosity and elasticity
can explain the stringiness of the product as it is dispensed [35].
The addition of low molecular weight, non-ionic or amphoteric surfactants to an alkyl

sulphate or alkyl ether sulphate based shampoo can also thicken the product. These
secondary surfactants are sometimes termed hydrophobic thickeners because their alkyl
chains form the largest proportion of their mass [37]. They include cocamide MEA and
cocamidopropyl betaine. These hydrophobic thickeners generally act to create more worm-
like micelles and encourage more non-Newtonian flow behaviour. In practice, they also act

to push the salt curve to the left. This means they can increase the product viscosity at low
salt levels, making the product easier to thicken with brine.
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High molecular weight, polymeric non-ionic surfactants can also be added to an alkyl
sulphate or alkyl ether sulphate based shampoo to increase viscosity. These are known as
hydrophilic thickeners because their highly extended, ethoxylated head-groups form the
largest proportion of their mass [37]. They include PEG-120 methyl glucose dioleate and
PEG-7 glyceryl cocoate. These thickeners can increase the micelle size or bridge
neighbouring micelles, and encourage more Newtonian-like flow [37].
Surfactant mildness
Mildness to the skin and eyes is another key benefit that shampoos need to deliver to
consumers. Unfortunately, there is no one scientific definition of mildness. It is, instead,
defined by the absence of a series of negatives [38]. Mildness is most commonly associated
with the absence of skin irritation, i.e. redness, heat, swelling and pain. Medically, skin
irritation is described as irritant contact dermatitis (ICD). ICD is classified as an immediate
biological response to irritation from a chemical, such as a surfactant, or abrasion of the skin.
The in vivo skin patch test is the gold standard for screening products for an irritant response
[39]. It usually involves the application of a product or a solution to the skin, under
occlusion, and the visual grading of the irritant response. Physical and biophysical skin
testing methods are also used (e.g. chromameters to measure redness and laser Doppler
flowmetry to measure blood-flow), although they do not typically improve the overall quality
of the results obtained by visual grading [39].
Mildness can also be linked with the absence of skin sensitization, also known as allergic
contact dermatitis (ACD). ACD is most commonly associated with nickel in jewellery,
fragrances and preservatives, and not directly with surfactants. Allergic reactions are usually
tested by skin patch tests, usually on the skin of the back [40]. Individuals with a history of
ACD are re-exposed to the suspected allergens under controlled conditions. Patch tests help
identify possible allergens, but they not allow for the assessment of a new product’s potential
for causing ACD. In this instance, a human repeated insult patch test (HRIPT) may be
necessary [41].

Mildness to the eyes is also very important for shampoo products. For many years the
Draize eye test was the industry standard method [42]. However, with the banning of animal
testing for cosmetics in many markets, several in vitro alternatives have been developed, for
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example, the red blood cell test [43]. Human clinical tests have also been developed to
support ‘no tears’-like claims.
In addition to direct irritation or sensitisation responses, shampoo mildness can also be

defined as a lack of skin barrier disruption and the lack of induced skin dryness, both of
which predispose the skin to irritation from the surfactants themselves, or to other chemicals.
Surfactants can affect the integrity of the lipid barrier in the stratum corneum (SC), and, thus,
increase skin permeability [44]. Topically applied surfactant solutions can also swell
corneocyte proteins, which results in the removal of natural moisturising factors and
enhances penetration of irritant chemicals into the viable epidermis[45]. This is believed to
lead to skin dryness and to increase the probability of skin irritation. Surfactants can also
have biological effects on the SC. For example, sodium lauryl ether sulphate can inhibit
enzymes in the SC that control desquamation, leading to scaling, skin dryness and impaired
barrier function [46].
Pape et al have investigated the relationship between the red blood cell (RBC) test data for a
series of surfactants and in vitro eye irritation data [43]. Their study showed that the
concentrations of surfactants and finished products required to cause cell hemolysis
(breakage of the cytoplasmic membranes) and denaturation of haemoglobin were highly
correlated to in vivo eye irritation scores. Furthermore, their data suggested that surfactant
irritancy went, generally, in the order: cationics (severe eye irritation) > anionics +
amphoterics (moderate/irritant) > non-ionics (moderate/nonirritant). The RBC test continues,
to this day, to be routinely used to screen shampoos for mildness to mucosal membranes.
Schrader et al, for example, use the RBC to show that increasing the proportion of
amphoteric surfactant (e.g. cocoamidopropyl betaine) in a sodium lauryl ether
sulphate/amphoteric mixture significantly reduces potential irritancy [47]. They also show
that sulfosuccinates can produce very good RBC scores, and hence, potentially very low eye
irritation. It is for this reason that surfactant blends including sulfosuccinates are commonly
used in childrens’ ‘no-tears’ formulations.

The tendency of surfactants to interact with model proteins has also been correlated with their
harshness towards human skin. Lips et al hypothesise that the tendency of surfactants to
swell and denature zein proteins can be used to screen actives for skin mildness [48]. They
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show that, for a series of model surfactants, skin flex wash and skin patch tests data correlate
very well with zein dissolution data. Lips et al have also built a structure-activity relationship
that can predict zein dissolution data. Their data show that the effective charge density of
the head-group region of a surfactant correlates well with its ability to denature zein protein.
Test results show that surfactant irritancy and zein dissolution (at 5% active) is in the order;
(highly irritant) sodium dodecyl sulphate and sodium laurate (‘soap’), (moderately irritant)
cetyl trimethyl ammonium bromide, dodecyl trimethyl ammonium bromide and sodium
lauryl ether sulphate, (low irritancy) alkyl polyglucoside and sodium dodecyl sulfobetaines.
Data also showed that blending sodium lauryl ether sulphate with a less irritant amphoteric,
cocoamidopropyl betaine, at a 1:2 ratio is able to reduce the zein solubility, an hence skin
irritation, versus a 2:1 ratio of the same surfactants. This correlates well with RBC test
observations.
The effects of surfactants on skin lipids can also be linked to mildness.

Ananthapadmanabhan et al developed a lipid solubilisation test and a lipid bilayer disruption
test to investigate surfactant mildness [49]. Their tests showed that lipid solubilisation and
disruption tests can produce data that is the inverse of protein dissolution data. For example,
alkyl polyglucoside, a very mild non-ionic surfactant, which typically has low zein
dissolution scores, produces high levels of lipid bilayer disruption. Alkyl polyglucoside can,
therefore, potentially be drying to the skin. It is interesting to note that, in this study,
isethionates seem to deliver a unique combination of low zein dissolution scores and low
lipid bilayer disruption effects. In the same study, Ananthapadmanabhan et al also
investigate the effects of increasing the proportion of cocoamidopropyl betaine in a sodium
lauryl ether sulphate/cocoamidopropyl betaine blend. In good agreement with many other
studies, they show that increasing the levels of cocoamidopropyl betaine reduces zein
dissolution scores. However, the study also shows that higher levels of cocoamidopropyl
betaine increase lipid solubilisation. The authors suggest that it is important to strike the
right balance between protein and lipid damage to maximise overall mildness.

Purohit et al [50] have shown that lipid bilayer disruption in the stratum corneum by
surfactants can change its mechanical properties. Their work suggested that harsher
surfactants can alter the lipid packing and also remove lipid components, which, in turn, can
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affect the stress relaxation properties of the stratum corneum, leading to higher drying
stresses.
Role of surfactants in polymer deposition

Modern shampoo formulations do not only offer a pleasant rheological finger-print and good
cleansing, foaming and skin mildness benefits, they also offer hair conditioning benefits such
as wet detangling, ease of wet combing and dry smoothness. These benefits are usually
delivered by cationic conditioning polymers and silicones. Surfactants play a key role in
delivering these benefits as they are deeply involved in the mechanisms through which
cationic polymers are able to deposit on the hair, and also aid the deposition of other benefit
agents, such as silicone emulsions and anti-dandruff actives. Changing the surfactant system
or electrolyte levels will always have a knock-on effect on the effectiveness of the
conditioning polymers in a shampoo system.
The interactions between cationic polymers and anionic surfactants have been extensively
studied [51,52]. It is widely understood that these interactions will affect formulation
viscosity, foaming behaviour and polymer deposition. It is generally believed that there are
three stages of interaction between cationic polymers and anionic surfactants (Figure 2).
Stage 1 represents the situation in the undiluted shampoo where the anionic surfactant is
present at high levels. At this stage the surfactant is usually able to solubilise the polymer.
Shampoos containing cationic polymers can often, therefore, be formulated as clear products.
Micelles are believed to form along the polymer chain, stretching it out and increasing the
viscosity of the shampoo. The association of excess surfactant effectively reverses the
charge on the polymer and would be expected to reduce binding to the hair.
Stage 2 represents the situation when the product has been diluted on wet hair during
application and foaming-up of the product. Here the dilution of the product in water causes
anionic surfactants to dissociate from the cationic polymer as they partition into the water.
The partitioning of surfactants to the air/water and lipid soil/water interfaces during foaming
and the solubilisation of lipid soils, will also further pull surfactant from the cationic

polymers. A key point is reached in stage 2 when the positive charge on the polymer is
neutralised, or perfectly balanced, with the negative charge of the anionic surfactant. Charge
neutralisation can result in precipitation of the polymer-surfactant complex. The surface of
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the polymer-surfactant complex is hydrophobic, and thus can be attracted to the hydrophobic
surface of the hair. It is the precipitation of the polymer-surfactant complex that enables the
entrapment and deposition of the polymer on the hair and scalp, and the deposition of any
associated benefit agents, such as silicones and anti-dandruff agents [53,54]. The wet
conditioning and wet detangling benefits of cationic polymers are largely associated with the
lubricating effects of the polymer-surfactant complexes on the hair. It is believed that the
polymer-surfactant complexes form lubricating gel-like films on the hair surface. Cationic
polymers that do not precipitate during the washing stages are usually less effective
conditioning agents.
As the hair is rinsed further with water, stage 3 is reached where anionic surfactant is present
at low levels relative to the cationic polymer. In this situation surfactant molecules bind to
the polymer chain and only partially neutralise the charge. Cationic polymers in this situation
would be solubilised again. They will also be positively charged and able to bind to the
negatively charged surface of the hair. Polymer deposited at this stage will also provide
some lubricating effects in the wet and dry.
Many different cationic polymers exist for the use in shampoos. By far the most popular are
polyquaternium-10 and guar hydroxypropyl trimonium chloride. Both are available in a wide
range of molecular weights and charge densities, and both can be formulated to precipitate on
shampoo dilution. The precipitation of cationic polymers on shampoo dilution, and the
deposition of suspended benefit agents, is affected by the levels of primary and secondary
surfactants. Precipitation is also affected by salt levels in the product, and by the presence of
high molecular weight, water soluble PEGs. Addition of low levels (<0.1% w/w) of PEGs
can significantly improve the efficiency of polymer precipitation and active deposition
(supplier data).

When developing a shampoo it is often necessary to measure polymer precipitation and the
associated deposition of benefit agents on the hair. Whilst it is possible to use sophisticated
techniques to directly measure polymer deposition, one of the simplest ways to investigate
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polymer precipitation is to dilute the shampoo product in water. A clear shampoo product
should go cloudy as it is diluted if the system is performing properly. As a rule-of-thumb,
shampoos should precipitate at roughly a 1 in 5 to 1 in 10 dilution, believed to be the sort of
dilution a shampoo experiences on wet hair. A spectrophotometer can be used to quantitate
the turbidity of samples if necessary.
Another approach for product development is to measure the levels of deposition of benefit
agents, such as silicones on the hair using techniques such as atomic absorption [55] and x-
ray fluorescence [26]. The wet conditioning benefits of the polymers and silicones can also
be measured directly using wet combing and wet detangling tests [56].
Surfactant selection
The previous sections have reviewed the five key actions of shampoo surfactants; cleaning,
foaming, rheology control, skin mildness and polymer deposition. Armed with this
understanding, the next step, when designing a shampoo formulation, is to select the most
appropriate blend of surfactants.
Shampoos formulations normally need both primary and secondary surfactants. Primary
surfactants, as their names suggests, usually exist at the highest concentrations in products
and provide most of their fundamental properties. The role of the secondary surfactants is
then, usually, to boost the effects of the primary surfactants in the directions required for a
specific product. For example, many secondary surfactants boost foam or make the shampoo
milder to the scalp and eyes.
The key decision for a formulator is to decide whether to pick widely used, low cost materials
as the primary and secondary surfactants. Or, to select more specialised surfactants that can
deliver unique benefits, e.g. ‘no-tears’ for baby shampoos, deep-cleansing for ‘detox’
shampoos or alternative surfactants for ‘sulphate-free’ shampoos. The primary surfactants
that are most widely used are exclusively anionic surfactants and include sodium lauryl ether
sulphate, sodium lauryl sulphate, ammonium lauryl ether sulphate and ammonium lauryl
sulphate. Secondary surfactants that are most widely used include mainly amphoteric and

non-ionic surfactants. Amphoterics used most widely include cocamidopropyl betaine and
coco-betaine. Non-ionics include cocamide monoethanolamide and cocamide
monoisopropanolamide. When selecting surfactants it is important to consider any technical
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constraints, such as the target cost, the product pH required for the preservation system and
processing issues.
Widely used primary Surfactants
Alkyl and alkyl ether sulphates form, by far, the most popular group of anionic surfactants
used as primary surfactants in shampoos. The alkyl and alkyl ether sulphates most widely
used include: sodium lauryl ether sulphate, sodium lauryl sulphate, ammonium lauryl ether
sulphate and ammonium lauryl sulphate. These are cost-effective materials that, if
formulated effectively, deliver effective cleansing, foaming, rheology control and polymer
deposition.
The alkyl sulphates have a hydrophobic alkyl chain tail, and a sulphate head-group. The
sulphate head group in this group of surfactants is attached with a sulphate ester bond.
Extremes of temperature and pH can break this ester bond and give rise to chemical
instability [57]. When using sulphates, the pH of formulations is normally kept between 5.5
and 8.0 to guarantee good stability. However, formulations can be made, with care, at lower
pH’s.
The alkyl chain lengths of sulphate surfactants tend to range between 8 to 18 carbons. The
average chain length tends to be 12 carbons (hence the lauryl). The fatty alcohols used to
make these surfactants are usually sourced from coconut and/or palm kernel oil.
Petrochemical sourced lauryl-range alcohols are also used [58]. The chain length of 12
carbon atoms gives a good compromise between detergency and water solubility. Increasing
the chain length decreases the CMC and increases the micelle size, and is associated with
improved solubilising power. However, going too far can reduce surfactant solubility,
resulting in cloudy products. The distribution of chain lengths will vary between suppliers
and with different grades and batches of materials. It is now understood that having a varied
range of chain lengths is actually a good thing and helps foam creation and viscosity
building. It is interesting to note that ultra-pure sodium dodecyl sulphate foams relatively
poorly.

The degree of ethoxylation in alkyl ether sulphates usually varies between 1 and 5 units.
Introduction of oxyethylene groups is known to reduce the CMC of sulphate surfactants. The
biggest drop in CMC occurs after the addition of just one oxyethylene group. Much smaller
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decreases are seen after the addition of 2-4 more [5]. Introduction of oxyethylene groups is
also associated with improved skin mildness. It has been shown that with 10 oxyethylene
units almost no skin irritation is observed [5]. However, introduction of oxyethylene groups
increases surfactant solubility, and this can prevent viscosity build. In the end, as always, a
balance needs to be found, and many commercial shampoos use alkyl ether sulphates with an
average of 1-3 oxyethylene units. It shouldn’t be forgotten, however, that a range of
oxyethylene group lengths can be found in commercial grades of alkyl ether sulphates, and
that a significant proportion of the material could be just alkyl sulphate (with no oxyethylene
groups).
Sodium lauryl ether sulphate is usually supplied as a concentrated aqueous solution

containing 70% w/w active. This allows for more cost effective transportation and avoids the
need for additional preservatives. At this level the surfactant exists as a lamellar G phase and
the mixture is a free flowing liquid [1]. However, as the mixture is diluted with water to
finished product levels (5 -15% w/w) it goes through a highly viscous gel phase, known as
the M1 phase [1]. It is for this reason that 70% w/w sodium lauryl ether sulphate should be
gradually added to water under shear. Adding water to 70% w/w sodium lauryl ether
sulphate can create lumps of viscous gel phase that are difficult to disperse, even under shear
[1].
Low levels (1-3%) of unreacted alcohols commonly remain in commercial grades of sulphate
surfactants. This may not be a bad thing, as it is understood that fatty alcohols are important
as foam boosters and stabilisers [2]. Trace amounts of 1,4-dioxane, a potential carcinogen,
can be found in alkyl ether sulphates [59]. The EU Scientific Committee on Consumer
Safety propose that cosmetic products sold in the EU should contain less than 10 ppm 1,4-
dioxane as a trace impurity [60]. Regular checks on 1,4-dioxane levels are necessary.

Widely used secondary surfactants
Cocamidopropyl betaine and coco-betaine are the most commonly used amphoteric
secondary surfactants in shampoo products. Cocamidopropyl betaine is by far the most
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widely used. Cocamidopropyl betaine is normally obtained as a 30% aqueous solution [61].
At higher levels it forms non-flowable, gel-like phases. Most commercial cocamidopropyl
betaine contains approximately 7% sodium chloride, 2-3% glycerol and <1% glycolic acid
[61]. The significant levels of salt will usually help with viscosity building in alkyl ether
sulphate and cocamidopropyl betaine mixtures. The residual glycerol in some commercial
grades of cocamidopropyl betaine is due to these grades being made direct from triglyceride
oils, rather than from fatty acids which give glycerol-free grades. Increasing the levels of
cocamidopropyl betaine in an alkyl ether sulphate and cocamidopropyl betaine blend will
increase mildness to the skin and eyes. This is related to the low inherent irritancy of
cocamidopropyl betaine relative to sulphate surfactants. Increasing the levels of
cocamidopropyl betaine will also increase the viscosity of the system. This is, in part, due to
the high levels of sodium chloride in commercial cocamidopropyl betaine. Increasing levels
of cocamidopropyl betaine will also reduce bubble size and make the foam thicker.
However, very high levels of cocamidopropyl betaine will depress the overall foam levels in
anionic surfactant systems. Cocamidopropyl betaine doesn’t have as strong foaming
properties as alkyl ether sulphates. Most shampoos use a 10:1 ratio of alkyl ether sulphate to
cocamidopropyl betaine, although higher levels of cocamidopropyl betaine are sometimes
used to give more luxurious foam or to build viscosity in low surfactant level formulations.
As cocamidopropyl betaine is an amphoteric it is sensitive to pH and the viscosity building
effects are pH dependant.
Alkanolamides such as cocamide monoethanolamide and cocamide monoisopropanolamide

are also widely used secondary surfactants in shampoos, and are classed as non-ionics. Both
are waxy solids that need heating before incorporation. As a result both can be bought as
liquids in commercial blends with other surfactants. Alkanolamides act, very much like the
betaines, to reduce the ionic repulsion between the head groups of alkyl sulphate and alkyl
ether sulphate surfactants. This encourages micelles to transition to worm-like rods [1]. As a
result, alkanolamides are very effective at increasing product viscosity and improving foam
stability [1]. Like the betaines, alkanolamides are used at a 1:10 or 1:5 ratio with alkyl ether
sulphates [3]. Cocamide monoethanolamide and cocamide monoisopropanolamide can
contain trace levels of nitrosamines and have the potential to form nitrosamines in finished

products. Nitrosamines are potential human carcinogens. Formulators working with
alkanolamides should avoid raw materials containing nitrosating agents such as nitrogen
oxides, ionic nitrites and some preservatives. Cocamide monoethanolamide and cocamide
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monoisopropanolamide have no limits on inclusion levels under European regulations, but, in
order to control potential nitrosamine formulation, must have < 0.5% secondary amine as
impurities in the final product [62]. The maximum nitrosamine content in the finished
product is 50 µg Kg-1 [62].
Specialised surfactants
Alkyl and alkyl ether sulphates are the most widely used anionic primary surfactants in
shampoos. However, more specialised anionic primary surfactants are available for
particular applications. Figure 3 shows the head-group structures of a range of specialised
surfactants that can be used in shampoos.
Alkyl glyceride sulphates provide improved mildness, but with the foaming power of alkyl
ether sulphates. Cocomonoglyceride sulphate, for example, foams well but gives better skin
compatibility than alkyl ether sulphates and other anionics [9]. Unfortunately this class of
surfactants is not suitable for ‘sulphate-free’ formulas.
For both milder and ‘sulphate-free’ products, carboxylates can be considered as alternative
primary anionic surfactants. Ether carboxylates (e.g. laureth-5 carboxylic acid), for example,
provide good water solubility in comparison with traditional carboxylates (‘soaps’) and are
less sensitive to hard water [9]. These surfactants provide good skin mildness and good foam
properties [9]. Glucose carboxylates (e.g. sodium lauryl glucose carboxylate) provide the
mildness associated with non-ionic glucose based surfactants (e.g. alkyl polyglucosides), but
with better foam properties [9]. Other carboxylates include the acyl glutamates (e.g. sodium
lauroyl glutamate) and acyl sarcosinates (e.g. sodium lauroyl sarcosinate). Both also provide
good skin mildness [9]. Adding sodium cocoyl glutamate to an acyl ether sulphate and
cocoamidopropyl betaine system, has been shown to reduce inhibition of stratum corneum
tryptic enzyme by sodium lauryl ether sulphate and to prevent surfactant induced skin
dryness [46].

Sulphonates can be considered as alternative primary anionic surfactants for ‘SLES-free’
products. They have a more chemically stable C-S bond between the SO3- head-group and
the alkyl chain in comparison to the ester bond in sulphate surfactants. There are many sub-
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classes of sulphonates including; taurates, sulphoacetates, sulphosuccinates and isothionates.
Taurates (e.g. sodium methyl cocoyl taurate) are effective as primary anionic surfactants for
shampoos. They have good flash foam, and are chemically stable over a wide pH range.
Sulphoacetates (e.g. sodium lauryl sulfoacetate) and sulphosuccinates (e.g. disodium lauryl
sulfosuccinate) can be used for milder and ‘SLES-free’ shampoos. Unlike the taurates, the
acyl tail group on sulphoacetates and sulphosuccinates is attached to the head-group through
an ester linkage, making them less chemically stable. Sulphosuccinates are very mild to the
skin and eyes, and are widely used in baby shampoos. However, they are not easily salt
thickened, adding cost to formulations. Isethionates (e.g. sodium lauroyl isethionate and
sodium lauroyl methyl isethionate) have been traditionally used to make synthetic detergent
soap bars and body washes and are mild to the skin. Recently, they have drawn a lot of
interest as suitable replacements for sulphates in ‘sulphate-free’ shampoos. They work well
as primary surfactants and produce good foam. Isethionates are typically best formulated
between pH 6.0 – 8.0 to prevent hydrolysis of the ester bond that attaches the head group to
the acyl chain. Sodium lauroyl methyl isethionate has better water solubility and a wider
range of pH stability than sodium lauroyl isethionate and can be salt thickened.
In addition to various specialised anionic surfactants, a wide range of non-ionic surfactants

can be incorporated in shampoos to give mildness, ‘sulphate-free’ claims and added ‘natural’
credentials. In most instances they are incorporated as secondary surfactants. Useful classes
of non-ionics for shampoos include alkyl polyglucosides and acyl glucamides. Alkyl
polyglucosides (e.g. coco-glucoside and lauryl glucoside) are usually incorporated to boost
mildness and the formulation’s ‘natural’ credentials (they are produced from 100% plant
derived feed-stocks) [63]. Alkyl polyglucosides are also very good oil solubilisers and can be
used in deep-cleansing (or ‘detox’) shampoos. The foaming properties of alkyl
polyglucosides are reasonable, but not as strong as the alkyl sulphates or alkyl ether
sulphates. Alkyl polyglucosides can have impaired chemical stability below pH 5 [9]. Acyl
glucamides (e.g. cocoyl methyl glucamide) are also derived largely from natural, renewable
sources. They are mild and are claimed to foam better than alkyl polyglucosides when
inserted into alkyl ether sulphate based formulas.

Sustainable sourcing
Consumer concerns about the impact of cosmetic products on the environment have risen
sharply in recent years. As a result manufacturers have started to pay much closer attention
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to the environmental footprint that their products make, in terms of greenhouse gas
emissions, water usage, waste and the sustainable sourcing of raw materials. This global
trend has started to make an impact on the surfactant technologies used in shampoos [64, 65].
In response to consumer demands for natural products, brands are now starting to claim that
their products contain ‘natural’, ‘naturally derived’ or ‘organic’ ingredients. At present,
these claims do not have any legal definition, but they can be supported with various
certification standards (e.g. Ecocert, NATRUE and COSMOS standards) [64].
It is possible to quantify how ‘natural’ a surfactant is by looking at its composition and the
materials used to make it. There are two methods currently being used. The first method,
called the biorenewable carbon index [66], calculates the percentage of carbon atoms that
come from renewable plant or animal sources versus non-renewable petrochemical sources.
An advantage of this method is that the value is not distorted by atoms in a material with high
atomic masses, such as the sulphur commonly used in anionic surfactants. It also fits well
with the standard test method used for determining the bio-based content of materials [67].
This method involves carbon dating samples to determine the relative proportions of natural
and petroleum based carbons. The second method, called simply the percentage renewable
by molecular weight, simply takes the relative proportion of the molecular weight of the
surfactant that comes from renewable sources. This second method is quite tricky to do in
practice as each atom in the surfactant has to be defined as coming either from a renewable or
non-renewable source. This means that chemical reactions used in the synthesis of the
material need to be precisely understood, and difficult judgements often have to be made as
to where each atom has actually come from in the process. The percentage renewable by
molecular weight is also difficult as there is no instrumental test that can validate your
calculations. Table I summarises the ‘biorenewable carbon index’ for the most commonly
used shampoo surfactants. Clearly, materials such as lauryl glucoside provide consumers
with a very ‘natural’ choice of ingredient.

Table I also shows that different grades of the same material can be made more ‘natural’.
The ethoxylate groups in sodium lauryl ether sulphate, for example, can be made using bio-
ethylene synthesised by sugar cane fermentation, rather than from petro-chemicals, taking the
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biorenewable carbon index up from approx. 75% to 100% [65].
Clearly, the biorenewable carbon index and percentage renewable value are very simplistic
measures of the environmental impact of cosmetic ingredients. Just because an ingredient is
plant-based doesn’t mean that it is produced sustainably. Many shampoo surfactants use
palm oil as a feedstock, and the development of new palm oil plantations is associated with
rain-forest destruction around the world. The Roundtable on Sustainable Palm Oil (RSPO)
helps suppliers source sustainable palm oil [68], and many are moving towards using mass-
balance-certified palm oil or segregated sustainable palm oil. Many raw material suppliers
now offer grades of common shampoo surfactants that have been made with guaranteed
sustainable palm oil (e.g. Cocamidopropyl betaine made with RSPO certified sustainable
palm kernel oil)
The ultimate step in improving the environmental sustainability of surfactants may by to

source palm oil-like materials from biotechnology. Biotechnology has the potential to make
palm oil-like materials in much higher yields per acre than traditional palm oils, and with
starting materials that are already available in temperate climates. Fatty acids derived from
the algal fermentation of sugars are already being used to make the detergents in some soap
bars [68], it may not be long before many shampoo surfactants are made from biotechnology
sourced materials.
Sulphate-free shampoos
Over the past 10-15 years consumer concerns about alkyl sulphate and alkyl ether sulphate
products has grown significantly. Consumers worry about possible skin and eye irritation,
and the potential drying effects these surfactants are having on their skin. Added to this are
safety concerns about 1,4-dioxane present as trace ingredients in alkyl ether sulphates.
Whilst these concerns may not be supported by any strong technical evidence, and are mainly
misinformation spread on the internet, they have increased the demand for ‘sulphate-free’
shampoos. As a result, the numbers of ‘sulphate-free’ products have continued to grow and

grow. Even mass-brands are now embracing this trend and patents are emerging for sulphate
free formulas [69].
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The challenges in moving away from alkyl sulphates and alkyl ether sulphates are many-fold.
Firstly, replacement surfactants are invariably more expensive than standard sulphate ones.
Secondly, the levels of surfactants in ‘sulphate-free’ products often need to be higher to
achieve equivalent foam, adding further to costs. Thirdly, sulphate surfactants thicken with
sodium chloride and with betaines, whilst many alternative surfactants do not. Addition of
polymeric thickeners adds to formulation costs, and can negatively affect the deposition of
cationic polymers and silicones, compromising performance. Finally, it is difficult to achieve
equivalent product performance in ‘sulphate-free’ systems. This can be for many reasons.
For example, cationic polymer deposition is well known to be sensitive to the types of
anionic surfactant used and the proportions of co-surfactants and salt. Moving away from
well established standard sulphate surfactant blends requires large amounts of deposition
testing. In addition, alternative surfactants may create unwanted, structured phases
(anisotropic microstructures) that can compromise foaming and silicone deposition, and
which can make products harder to rinse away. Finally, alternative surfactants may be less
chemically stable at the low pH’s needed for more popular preservatives (e.g. sodium
benzoate). Moving away from sulphates means going right back to basics and considering
the key functions of the surfactants in the shampoo; cleansing, foaming, rheology control,
mildness and polymer deposition.
Structured liquid surfactants

Structured liquid surfactants systems comprise surfactants in liquid crystalline phase. These
are currently receiving a lot of attention as they can give a very unique rheological profile to
shampoo products. If formulated correctly, they can give a shampoo a lotion-like feel when
it is dispensed, and then good foaming and conditioning properties on the hair. Structured
liquid systems can also give excellent oil and silicone suspension properties, and interesting
product visual effects (e.g. marble-like colour effects, and multi-layered colour effects).
Typically structured liquid surfactants are formed at high levels of surfactant concentrations
and electrolyte. For example, it is well known that sodium lauryl ether sulphate moves from
a micellar phase to lamellar phase as the concentration is increased. However, with some
careful blending of ingredients, it is possible to create structured liquid surfactant systems at

lower active levels. Surfactants with high PC’s (PC~1) will tend to form lamellar structures
(e.g. phospholipids in cell membranes). Lamellar packing can also be encouraged by using
surfactants with carefully branched alkyl chains that straighten the packing arrangements, or
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by blending anionic surfactants that have large head groups and small tails with non-ionics or
amphoterics that have small head groups and large tails, again, ‘straightening’ the packing
arrangements.
Patents from Puvvada et al (Unilever, priority date 1999) [70] and Frantz et al (Rhodia, now
Solvay, priority date 2001) [71] are examples of many patents that describe the use of sodium
tricedeth sulphate as the primary anionic in structured surfactant systems. The branching of
the alkyl chain in this surfactant increases the cross-sectional size of the tail group and
encourages lamellar packing. Puvvada et al combine the sodium tricedeth sulphate with
secondary surfactants such as cocoamidopropyl betaine and isostearic acid for personal wash
applications. Frantz et al combine it with sodium lauroamphoacetate and cocamide
monoethanolamide. The blend of sodium tricedeth sulphate, sodium lauroamphoacetate and
cocamide monoethanolamide is available as a pre-blended concentrate for use in shampoos
and personal wash formulations.
Tsaur et al (Unilever, priority date 2006) [72] describe the use of fatty acyl isothionates, such
as those used in mild soap bars, to create structured surfactant systems for use in liquid
personal wash applications. The authors describe the combination of isothionates with a
specific combination of liquid crystal modifiers (e.g., fatty acids, fatty alcohols) and co-
surfactants (e.g., alkanolamide, alkylamineoxide). Structured surfactant systems can also be
made using sodium lauroyl methyl isethionate. Concentrates are commercially available
containing sodium lauroyl methyl isethionate, sodium lauroamphoacetate and cocamide
monoisopropanolamide that can instantly produce structured surfactant formulations.
Another way of achieving structured systems is to combine anionics with cationic surfactants.
Bendejacq (Rhodia, now Solvay, priority date 2009) [73] describes the formation of
structured shampoo systems using cetrimonium chloride as a co-surfactant. It is claimed that
the formulations successfully suspended silicones and oils.

A more recent patent from Hawkins et al (Stepan, priority date 2012) [74] describes a
structured surfactant system that is transparent, and comprised of a blend of surfactants that
produce multilamellar vesicles in the absence of any electrolytes. Some blends were based
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on glyceryl caprylate/caprate and lauramine oxide, or glyceryl caprylate/caprate and sodium
lauryl ether sulphate. These blends were claimed to be effective at suspending beads and oil
droplets.
Conclusions
Shampoo surfactant technology is changing rapidly at present, as the result of consumer

needs for more environmentally sustainable products, for ‘sulphate-free’ products and for
products with much more interesting rheological profiles. This review has covered all of the
key uses of surfactants in shampoos; cleaning, foaming, rheology control, mildness and
polymer deposition, and has shown how surfactants deliver these benefits and how each of
these can be measured. It has also described the steps that need to be taken to select the most
appropriate blend of surfactants for any given shampoo and has pulled together useful
information on the most widely used surfactants. It is hoped that the knowledge shared here
can help develop the shampoos of the future.
Acknowledgements
Many thanks to Dr Nick Ainger (Unilever R&D, UK) for his advice on sections of this
review. Thanks as well to Dr Tony Gough (Innospec Ltd, UK) and Prof Robert Y. Lochhead
(The University of Southern Mississippi, USA) for reviewing the manuscript. No financial
support was sought, or was received, for the creation of this review.

Figures and Tables
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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Figure 2. Effect of dilution on cationic polymer/surfactant interactions (based on Goddard,
1999 [51])
Accepted Article

Figure 3. Head-group structures of a range of specialised surfactants that can be used in
shampoos. The structures illustrated relate to the example materials. Slight differences in
head-group structure may occur within chemical groups.
Accepted Article
(I) Sulphates - alkyl glyceride sulphates (e.g. sodium cocomonoglyceride sulphate)
(II) Carboxylates - ether carboxylates (e.g. laureth-5-carboxylic acid)
(III) Carboxylates - glucose carboxylates (e.g. sodium lauryl glucose carboxylate)

(IV) Carboxylates - acyl glutamates (e.g. sodium lauroyl glutamate)
Accepted Article
(V) Carboxylates - acyl sarcosinates (e.g. sodium lauroyl sarcosinate)
(VI) Sulphonates - taurates (e.g. sodium methyl cocoyl taurate)
(VII) Sulphonates - sulphoacetates (e.g. sodium lauryl sulfoacetate)

(VIII) Sulphonates - sulphosuccinates (e.g. disodium lauryl sulfosuccinate)
Accepted Article
(IX) Sulphonates - isethionates (e.g. sodium lauroyl methyl isethionate)
(X) Non-ionics - alkyl polyglucosides (e.g. lauryl glucoside)
(XI) Non-ionics – acyl glucamides (e.g. cocoyl methyl glucamide)

Table I. Biorenewable Carbon Index (BCI) for a selection of commonly used shampoo
surfactants.
Accepted Article
Surfactant Type Example Raw Supplier BCI References
Material
Sodium lauryl sulphate Anionic STEPANOL Stepan 100% Supplier
WA-EXTRA data
Sodium lauryl ether Anionic STEOL CS-130 Stepan 86% Supplier
sulphate (1 EO) data
Sodium lauryl ether Anionic STEOL CS-225 Stepan 75% Supplier
sulphate (2 EO) data
Sodium lauryl ether Anionic RHODAPEX Solvay 100% [65]
sulphate ESB_70 NAT
Cocamidopropyl Amphoteric AMPHOSOL Stepan 63% Supplier
betaine CA data
Cocamide Nonionic NINOL CMP Stepan 86% Supplier
monoethanolamide data
Cocamide Nonionic NINOL M10 Stepan 80% Supplier
monoisopropanolamide data
Lauryl glucoside Nonionic PLANTACARE BASF 100% [63]
1200 UP
Cocoyl methyl Nonionic GLUCOTAIN Clariant 95% Supplier
glucamide CARE data

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Accepted Article

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DR.

PAUL ALFRED CORNWELL (Orcid ID : 0000-0002-4353-805X)

Article type : Review Article

A review of shampoo surfactant technology: Consumer benefits, raw materials and

Formulation, Hair+Body care, Claim substantiation in vivo/in vitro, Polymers/Surfactants

Cleansing properties of surfactants

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The second mechanism, spontaneous emulsification, is an extension of the roll-up

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Foaming properties of surfactants

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Surfactant phase behaviour and the role of surfactants in rheology control

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Surfactant phase behaviour is often driven by surfactant concentration. Many anionic

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The addition of low molecular weight, non-ionic or amphoteric surfactants to an alkyl

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In addition to direct irritation or sensitisation responses, shampoo mildness can also be

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The effects of surfactants on skin lipids can also be linked to mildness.

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Role of surfactants in polymer deposition

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Widely used primary Surfactants

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Sodium lauryl ether sulphate is usually supplied as a concentrated aqueous solution

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Alkanolamides such as cocamide monoethanolamide and cocamide monoisopropanolamide

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In addition to various specialised anionic surfactants, a wide range of non-ionic surfactants

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The ultimate step in improving the environmental sustainability of surfactants may by to

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Structured liquid surfactants

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Shampoo surfactant technology is changing rapidly at present, as the result of consumer

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

(III) Carboxylates - glucose carboxylates (e.g. sodium lauryl glucose carboxylate)

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

(VI) Sulphonates - taurates (e.g. sodium methyl cocoyl taurate)

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

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

(X) Non-ionics - alkyl polyglucosides (e.g. lauryl glucoside)

(XI) Non-ionics – acyl glucamides (e.g. cocoyl methyl glucamide)

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6. Florence, A.T. and Attwood, D. Physicochemical Principles of Pharmacy In

7. Ash, M. The condensed encyclopedia of surfactants: Chemical Publishing Company,