3-2015

English Edition
International Journal for Applied Science
• Personal Care • Detergents • Specialties

A. Thiemann, N. Grandke, S. Gröne, M. Salmina-Petersen, J. Jänichen

Wetting Agents – Their Concentration-Dependent

Effects on the Energy Demand in the
Formation of Stable Emulsions
 Cosmet ic s
Wet t in g ag en tS

A. Thiemann, N. Grandke, S. Gröne, M. Salmina-Petersen, J. Jänichen*

Wetting Agents – Their Concentration-Dependent

Effects on the Energy Demand in the Formation of
Stable Emulsions

■■ Introduction
Mixing immiscible oil and water leads to
a bi-phase system which tries to adopt
the smallest possible interface between
the two phases. This behaviour is owed to
differences in the attracting molecular
forces within the isolated phases which
as a consequence create a high surface
tension. The production of an emulsion
is connected with a multiple extension
of the interface between the aque-
ous and the lipid phase. Consequently,
these systems are thermodynamically
unstable. Energy in form of mechanical
work, specifically shear force, has to be
applied to the system in order to build
these large interfaces in form of drop-
lets and vesicles. As the surface tension
between two immiscible phases is also
a function of the temperature, addi-
tionally such emulsification processes
are usually performed at elevated tem-
peratures.

Abstract

W
etting agents are amphi-
philic surface active ma-
terials which, like emulsi-
fiers, reduce the interfacial tension
between an immiscible water and
oil phase. However, unlike larger
emulsifier molecules, they do not
have the capacity to form stable
emulsions. On the contrary, wet-
ting agents tend to disrupt orga-
nized structures formed by emulsi-
fiers at the interface between the
polar aqueous and the non-polar
lipid phase, thereby lowering the
viscosity and finally the stability of
the emulsion. Consequently, the
properties of wetting agents do
not seem to make them attractive
raw materials for emulsions on the
formulator’s ingredient list. In the
present study, however, we take
a closer look at possible positive
effects of wetting agents in such
systems.
We therefore analyzed the con-
centration-dependent influence
of three commercially available
wetting agents on the efficacy
of different types of oil in water
emulsifiers. Our results confirm,
that high concentrations of wetting
agents resulted in a destabilization
of emulsions. Lower concentrations
however, helped to produce stable
emulsions with fine and homoge-
neous droplets of the dispersed
phase independent on the type of
emulsifier that was investigated.
Moreover, in the production of
stable emulsions low concentra-
tions of wetting agents allowed for
a saving of thermal and kinetic en-
ergy during the emulsification pro-
cess and enabled the realization
of difficult to achieve applications,
e.g. self-emulsifying formulations.
Further, the implemented low con-
centrations of wetting agents ben-
eficial to the emulsions, revealed
no measurable negative impact on
the sensory profile of the finished
cosmetic formulations.
In summary, wetting agents pos-
sess significant co-emulsifier prop-
erties, beside their already well
described antimicrobial activities,
which e.g. allow for the significant
reduction of preservatives or even
their total elimination from the in-
gredient list.

10 SOFW-Journal | 141 | 3-2015

 Co sm etics
W et t i ng ag ents

The thermodynamically unstable sys-
tem tries to reduce the high surface
tension and internal energy by coales-
cence of the droplets. The oil droplets
creep together and form a separated
phase which, depending on the den-
sity, is on the top or the bottom of the
system. Factors promoting coalescence
are creaming or sedimentation, driven
by different densities of water and oil,
and Ostwald ripening, driven by vapor
pressure differences of smaller and
larger droplets. According to Stokes’
law for the frictional force exerted
on spherical objects, the velocity of
creaming or sedimentation, and there-
fore the stability of the interfaces, is
partly influenced by the droplet di-
ameters and emulsion viscosity. There-
fore small and homogeneous droplets
of the dispersed phase together with a
high viscosity are strong indicators for
a stable emulsion.
Stabilizing the formed interfaces, as ev-
ery formulator knows, is the function
of the emulsifier. They belong to the
group of surface active substances, the
surfactants. As all surfactants emulsi-
fiers possess an amphiphilic molecule
structure with a polar, hydrophilic part
and a non-polar, lipophilic part. The
hydrophilic-lipophilic balance value,
or HLB-value, devised by W.C. Griffin
in 1949 is a way to categorize surfac-
tants and to draw conclusions regard-
ing their cosmetic properties (1). On a
scale of 1 to 20, a low HLB-value indi-
cates a low polar molecule proportion,
whereas a high HLB-value indicates a
surfactant whose polar part outweighs
its non-polar part. Oil in water emul-
sifiers (O/W-emulsifiers) according to
Fishman (2) have an HLB between 8
and 18, indicating a tendency towards
a higher molecular weight of the polar,
hydrophilic part.
In the range of skin care products O/W-
emulsions are playing a dominant role.
Consequently, a variety of emulsifiers
are present on the market, promising
stable emulsions of high sensorial qual-
ity for different applications. A factor
that is usually not taken into account
in the evaluation of emulsifiers is the
energy and mechanical work which has
to be introduced into the system in or-
der to overcome the interfacial tension
and to obtain a homogeneous and fine
emulsion. However, the performance of
an emulsifier, regarding its energy de-
mand, is not an insignificant cost fac-
tor which needs to be considered by the
formulator.
At this point, wetting agents with
their high surface activity, as a part
of the emulsifier system can help to
reduce the interfacial tension and sub-
sequently the amount of mechanical
work and heat energy which is needed
during the production process to ob-
tain a fine and homogeneous emul-
sion. Under the term wetting agent,
amphiphilic surfactants are summa-
rized, which possess a significant sur-
face activity but a molecular weight
much lower than the one of classical
O/W-emulsifiers. Wetting agents have
an HLB between 6 and 9, indicating a
slightly higher molecular weight of the
non-polar, hydrophobic part. In con-
trast to typical emulsifier structures
wetting agents do not have any emul-
sifying properties by themself that al-
low to create stable emulsions. At el-
evated concentrations wetting agents
are known to rather disrupt micelle
structures and reduce the viscosity of
emulsions, thereby destroying them
rapidly. The presence of low concen-
trations of wetting agents during the
manufacturing of emulsions, however,
may support the formation of very fine
and homogeneous systems by a more
effective conversion of mechanical
work into micelle formation.
In order to check for this assumption,
three commercially available wetting
agents were evaluated in this study.
Glyceryl Caprylate (trade name: der-

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SOFW-Journal | 141 | 3-2015 11

 Cosmet ic s
Wet t in g ag en tS
mosoft® GMCY) and Glyceryl Caprate
(trade name: dermosoft® GMC) two
glycerin monoesters, and Caprylyl
Glycol (trade name: dermosoft® oc-
tiol) a medium size glycol. Beside the
wetting ability, their multifunctional
cosmetic properties comprise moistur-
izing, refatting, viscosity regulating,
antimicrobial, and also co-solubilizer
(3) activities.
Glyceryl Caprylate and Glyceryl Caprate
moreover are available from 100 % nat-
ural resources and are compliant with
Ecocert, BDIH, NaTrue and NPA. Fig. 1
illustrates their function-determining
amphiphilic structure.
■■ Test Methods and Results
Concentration-Dependent Effects of a
Wetting Agent on Emulsions
The stability of an emulsion depends
on the emulsifier and on parameters
like droplet size and droplet homoge-
neity of the dispersed phase and also
on the viscosity of the emulsion. These
parameters influence the coalescence
velocity of the oil droplets in an O/W-
emulsion. A reduction of the interfa-
cial tension during the emulsification
process could lead to a more effective
conversion of mechanical work into a
finer and therefore more stable mi-
celle/droplet structure. A high inter-
facial tension reduction, however can
also disrupt the organized structures
of an emulsion. Therefore, the surface-
active properties of wetting agents po-
Fig. 1 Glyceryl Caprylate, Glyceryl Caprate and Caprylyl Glycol. Amphiphilic structure (4) and properties of the three commer-
cially available wetting agents. (HLB values according to Griffin (1))
12 SOFW-Journal | 141 | 3-2015
tentially allow for beneficial as well as
adverse effects on the stability of an
emulsion.
For a better understanding of these
antagonistic forces of wetting agents
in emulsions, we examined the concen-
tration-dependent effects of a wetting
agent on the efficacy of an emulsifier.
For this purpose the emulsifier system
symbio®muls rich (composed of Poly-
glyceryl-3 Stearate, Behenyl Alcohol,
Glyceryl Stearate Citrate, Helianthus
Annuus (Sunflower) Seed Cera (Wax),
Glyceryl Caprate) was selected. Its nat-
urally-derived components comprise a
main emulsifier, a co-emulsifier, two
consistency agents and the wetting
agent Glyceryl Caprate. Together these
components allow for a rich skin feel,
suitable for nurturing creams. In order
to determine the effect of the wetting
agent Glyceryl Caprate, a component
of symbio®muls rich, its concentration
was gradually varied and afterwards
the droplet size distribution and vis-
cosity of the emulsion was measured.
The stability of the emulsions was
tested immediately after production
by centrifugation test (1725 x g) for
30 min and on long term by storage
for 2 week at 50°C, and 6 weeks at 4°C,
21°C and 40°C.
The results in Fig. 2 reveal, that the
droplet size and the droplet size dis-
tribution of the emulsions gradually
decreased with increasing wetting
agent concentrations. This positive
trend peaked at a concentration of
0.3 % Glyceryl Caprate with a highly
significant average droplet size reduc-
tion of 21 % compared to the emul-
sion without Glyceryl Caprate (t-test,
p<0.01). With further increasing con-
centrations of the wetting agent the
droplet size and variance started to
increase again indicating that the dis-
ruptive effects of the wetting agent on
the emulsion predominates. At a con-
centration of 0.75 % Glyceryl Caprate
the emulsion appeared homogeneous
after the emulsification process, but
turned out to be unstable after 30 min
of centrifugation and finally, at a con-
centration of 1 % Glyceryl Caprate the
production of a homogeneous emul-
sion was not possible anymore.
The viscosity of the emulsions was only
varied marginally by the wetting agent.
Interestingly, at first the viscosity of the
emulsion even increased due to Glyc-
eryl Caprate and then decreased only
slightly after further addition of wet-
ting agent. This initial increase, which
was observed for a variety of emulsi-
fiers and wetting agents yet, might be
explained by a denser packaging of the
smaller droplets inside the emulsion.
With increasing concentrations how-
ever, this initial viscosity-enhancing ef-
fect might be overturned by the general
viscosity-reducing effect of the wetting
agents. This general reduction of the
viscosity is caused by the wetting agent
at higher concentrations, interrupting
the arranged structure of the two main
emulsifiers of symbio®muls rich at the
interface between the oil and the water
phase.
 Co sm etics
W et t i ng ag ents

In summary the beneficial effect of
the wetting agent followed a func-
tion with an optimal concentration
level. Low concentrations of wetting
agents in the production of emul-
sions supported the formation of
stable systems with very fine and ho-
mogeneous droplets and even slight-
ly higher viscosities (Fig. 2), whereas
at elevated concentrations, the high
surface activity of the wetting agent
resulted in a destabilization of the
emulsion. We assume that this con-
centration-dependent progression
also applies to other emulsifiers and
wetting agents. This hypothesis was
tested amongst others in the follow-
ing experiments.
Temperature-Dependent Effects of
Wetting Agents
The temperature during the emulsi-
fication process plays a critical role in
the formation of fine dispersed, small
droplets and therefore in the stability
of emulsions. Consequently, emulsifica-
tion processes are conducted usually at
70-80°C.
To determine if wetting agents allow for
a reduction of the applied thermal ener-
gy in the emulsification process, emul-
sions with and without wetting agents
were produced within a hot-process
(78°C) and a cold-process (40°C). Ex-
periments were conducted with a nat-
urally-derived emulsifier, symbio®muls
GC (INCI: Glyceryl Stearate Citrate, Ce-
tearyl Alcohol, Glyceryl Caprylate), and
a petrochemically-derived, polyethox-
ylated benchmark emulsifier, PEG-100
Stearate. Symbio®muls GC is a highly
versatile emulsifier system containing
a strong wetting agent, Glyceryl Cap-
rylate. The blend allows the formation
of stable and fine O/W-emulsions with
high sensorial quality and which, due
to the presence of a wetting agent, are
easy to preserve. The analyzed wetting
agents comprised Glyceryl Caprylate,
Glyceryl Caprate and Caprylyl Glycol.
O/W-emulsions with either one of the
two emulsifiers and one or neither of
the wetting agents were produced, mi-
croscopic images were taken and the
stabilities of the emulsions were tested
by centrifugation and long-time stor-
age at different temperatures (see
above).
The results in Fig. 3 show, that the wet-
ting agent positively influenced the
droplet size distribution of the final
emulsion. In the case of symbio®muls
GC (without Glyceryl Caprylate), initially
lacking its wetting agent Glyceryl Cap-
rylate, the subsequent addition of the
different wetting agents resulted in two
of three cases in a more stable, and in ev-
ery case a more macroscopically homo-
geneous emulsion after a cold-process
(40°C) emulsification. This result there-
fore indicates that the implementation
of wetting agents can save thermal en-
ergy during the emulsification process.
It further confirms our previous assump-
tion that the concentration-dependent
beneficial effect of Glyceryl Caprate also
applies to other emulsifiers and wetting
agents, though, depending on the com-
bination, with slight differences in the
performance.

Kinetic Energy-Dependent Effects of

Wetting Agents
We already demonstrated that low con-
centrations of wetting agents lower the
Fig. 2 Concentration-dependent influence of a wetting agent (Glyceryl Caprate) thermal energy required to form homog-
on the emulsification process (78°C). The emulsifier was symbio®muls rich (in enous emulsions. In order to see whether
this experiment initially lacking Glyceryl Caprate (yellow box plot)). Shown are wetting agents also allow for a reduction
boxplots of the droplet sizes of the respective emulsions, depicting the full range of the kinetic energy needed for a suc-
of variation in form of quartiles (25 %) and the median of the values. Further cessful emulsification, we conducted ex-
given are the variances of the droplet sizes, the viscosities of the emulsions and periments on the self-emulsifying prop-
an information if the emulsions were stable after centrifugation and/or storage. erties of a naturally-derived emulsifier.
The emulsion containing 1 % Glyceryl Caprate was the only emulsion separated
Formulations with self-emulsifying prop-
already after emulsification.
erties are e.g. desired in applications like

SOFW-Journal | 141 | 3-2015 13

 Cosmet ic s
Wet t i n g ag en ts

bath oils or facial cleansing oils (makeup

remover).
Self-emulsifiying oils are able to sponta-
neously emulsify in water at room tem-
perature and low agitation. The emulsi-
fication is often achieved with the aid
of suitable surfactants like Polyglyceryl-3
Palmitate (dermofeel® PP) as the main
O/W-emulsifier in combination with the
wetting agent Glyceryl Caprylate. The lat-
ter prevents the separation of polar com-
pounds and is able to interact between
the polar O/W-emulsifier dermofeel® PP
and the non-polar oil providing clear ho-
mogeneous self-emulsifying oils.
In this experiment, dermofeel® PP alone,
or in combination with Glyceryl Capry-
late (3:5 mixture of Glyceryl Caprylate/
dermofeel® PP) was added in a total
Fig. 3 Emulsification experiments at 40°C (cold process) or 78°C (hot process)
concentration range between 2-16 % to
with two emulsifiers (symbio®muls GC without Glyceryl Caprylate and PEG-100
sunflower oil. The resulting oil-emulsifi- Stearate either with or without 0.25 % Caprylyl Glycol, Glyceryl Caprylate or
er-blend was then added to water (1:4 Glyceryl Caprate respectively. Shown are the microscopic images of the respective
mixture of oil phase/water) and was in- emulsions together with an information about their macroscopic appearance
verted for five times. Pictures were taken (homogeneous or inhomogeneous) and stability after centrifugation and storage
immediately after self-emulsification at different temperatures (see text).
and also after 20 min at room tempera-
ture. Because dermofeel® PP without
Glyceryl Caprylate was hard to solubilize,
oil phases were heated to 35°C before
the addition of water.
The results in Fig. 4 reveal that while
7 % dermofeel® PP was necessary to
spontaneously produce a homogeneous
emulsion (0 min) the presence of Glyc-
eryl Caprylate resulted in the formation
of a homogeneous emulsion already
at a concentration of 6 % dermofeel®
PP/Glyceryl Caprylate. Thus, in order to
achieve similar results the partial re-
placement of emulsifier with Glyceryl
Caprylate allows the formulator to use
smaller total amounts of surfactants.
However, with more extensive mechani-
cal work (e.g. homogenizer), 6 % of der-
mofeel® PP was sufficient in creating
an initially homogeneous emulsion (not
shown). Based on this observation it was
concluded, that the wetting agent seems
to lower the kinetic energy necessary for
a successful emulsification.
After 20 minutes, at a concentration of
Fig. 4 Images of emulsions directly after (0 min) or 20 minutes after (20 min) the
10 % dermofeel® PP and lower, emul-
self-emulsification process with varying concentrations of emulsifier (dermofeel®
sions without Glyceryl Caprylate sepa- PP, upper boxes) or emulsifier-wetting agent blend (dermofeel® PP/Glyceryl
rated into two phases. Only a high con- Caprylate (5:3), lower boxes) (for details refer to text). Grey boxes show unstable,
centration of 16 % dermofeel® PP was macroscopically inhomogeneous emulsions (separated), and green boxes show
able to stabilize the emulsion for 20 stable homogeneous emulsions at the moment of observation (not separated).
minutes at room temperature. In con-

14 SOFW-Journal | 141 | 3-2015

 Co sm etics
W et t i ng ag ents

trast, emulsions with Glyceryl Caprylate The triangle test confirmed the test`s tinguishable from each other (p=0.44). A
were stable at a total surfactant con- null hypothesis (H0), that the sensory graphical representation of the compar-
centration of 8 % and higher. Glyceryl profile of the two emulsions was indis- ative sensory profile is shown in Fig. 5.
Caprylate therefore clearly improved the
stability of the emulsions formed in this
experiment.

Comparative Sensory Profile

So far, we demonstrated that wetting
agents at low concentration successfully
increased the stability of emulsions and
allow the formulator to either lower the
total amount of surfactant or the ther-
mal or kinetic energy necessary during
the emulsification process.
To determine the potential influence
of a wetting agent at its effective use
concentrations on the sensorial profile
of a cosmetic formulation, emulsions
with and without 0.5 % Glyceryl Cap-
rate were compared in a sensory tri-
angle test with a panel of 10 experi-
enced subjects. In this test the subjects
were confronted with three emulsions
based on symbio®muls rich, of which
two were identical and one was dif-
ferent (either with or without Glyceryl
Caprate) (Formulation 1). The subjects Fig. 5 Sensory profile (paired comparison with triangle test) of a basic rich emulsion
were asked to point out the emulsion (see Formulation 1) with (blue line) and without (orange line) Glyceryl Caprate.
they think was different.

Basic Rich Emulsion

A B
Phase Ingredient INCI (PCPC) Supplier
 %  %
dest. water Aqua (Water) ad 100 ad 100
Glycerol 99.5 % Glycerin 4.0 4.0
A
dermofeel® PA-3 Sodium Phytate, Aqua (Water), Alcohol Dr. Straetmans 0.1 0.1
Verstatil® PC Phenoxyethanol, Caprylyl Glycol Dr. Straetmans 1.0 1.0
A1 Keltrol CG-RD Xanthan Gum CP Kelco 0.2 0.2
Polyglyceryl-3 Stearate, Behenyl Alcohol,
Glyceryl Stearate Citrate, Helianthus
symbio®muls rich
Annuus (Sunflower) Seed Cera (Wax), Dr. Straetmans 6.7 6.7
(without Glyceryl Caprate)
Ascorbyl Palmitate, Tocopherol, Helianthus
Annuus (Sunflower) Seed oil
B dermosoft® GMC Glyceryl Caprate Dr. Straetmans 0 0.3
dermofeel® MCT Tricaprylin Dr. Straetmans 0.7 0.7
Sunflower Oil Helianthus Annuus (Sunflower) Seed Oil Gustav Heess 8.0 8.0
Tegosoft DC Decyl Cocoate Evonik Industries 5.0 5.0
dermofeel® Toco 70 Tocopherol, Helianthus Annuus (Sunflower)
Dr. Straetmans 0.2 0.2
non-GMO Seed Oil
100.00 100.00
Formulation 1 Formulation of a nurturing O/W-emulsion without (A) and with (B) Glyceryl Caprate, used in the sensory
triangle test. (Recipe No.: L071-9.1/3-1214)

SOFW-Journal | 141 | 3-2015 15

 Cosmet ic s
Wet t i n g ag en ts
It shows the principal consensus between
the sensory profile of the emulsion with
and without Glyceryl Caprate.
■■ Conclusion
Multifunctional wetting agents, like
Glyceryl Caprylate (dermosoft® GMCY),
Glyceryl Caprate (dermosoft® GMC) and
Caprylyl Glycol (dermosoft® octiol) are
real cosmetic all-rounders. They can be
used in many kind of cosmetic applica-
tions like emulsions, solubilisations, and
surfactants. In our experiments we could
confirm our assumption that low con-
centrations of wetting agents contribute
to a stabilization of emulsions by pro-
moting the formation of homogenous
and fine droplet size emulsions through
the reduction of the interfacial tension.
This beneficial effect of the wetting
agents is concentration dependent and
shows individual optima for the specific
systems. Moreover wetting agents can
help to reduce the amount of mechani-
16 SOFW-Journal | 141 | 3-2015
cal work and the amount of heat energy Thiemann A. et al. Wetting agents: Friends
(3) 
which needs to be introduced into the or Enemies of Solubilizers. SOFW, p. 46, 140
emulsification process to obtain a fine (11-2014).
and homogeneous stable emulsion. These
positive effects make wetting agents a (4) B
 olton et al. PubChem3D: a new resource for
perfect choice for hard to realize for- scientists. J Cheminform. 3(1):32 (2011).
mulations, e.g. self-emulsifying formu-
lations. In addition, the antimicrobial
properties of wetting agents add further *Authors´ address:
valuable function to cosmetic products. Dr. Straetmans GmbH
Merkurring 90
Acknowledgment 22143 Hamburg
We thank Prof. Dr. Stefan Hoth from the Germany
Biocenter Klein Flottbek (University of www.dr-straetmans.de
Hamburg) for the provision of the con-
Dr. Alexander Thiemann
focal microscope and Benjamin Möller (alexander.thiemann@dr-straetmans.de)
for the technical support. Nadja Grandke
(nadja.grandke@dr-straetmans.de)
References Sabrina Gröne
(sabrina.groene@dr-straetmans.de)
(1) G
 riffin W. C. Classification of surface active Manuela Salmina-Petersen
agents by HLB. J. Soc. Cosmet. Chem. Vol. 1 (manuela.salmina-petersen@dr-straetmans.de)
(1949). Dr. Jan Jänichen
(jan.jaenichen@dr-straetmans.de)
(2) F ishman H.M. A look at HLB. Happi, April, p.
28, 128 (1991). n