Advances in Colloid and Interface Science 283 (2020) 102234

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Advances in Colloid and Interface Science

journal homepage: www.elsevier.com/locate/cis

Historical Perspective

Fundamentals and applications of particle stabilized emulsions

in cosmetic formulations
Deepika Venkataramani, Ana Tsulaia, Samiul Amin ⁎
School of Chemical Engineering, Manhattan College, Riverdale, NY 10471, United States of America

a r t i c l e i n f o a b s t r a c t

Article history: The cosmetic industry is one of the fastest growing industrial sectors that is constantly evolving by absorbing new
5 August 2020 technologies and incorporating innovative yet sustainable products. Cosmetic products are comprised of diverse
Available online 6 August 2020 formulations such as skin care, color cosmetics, hair care, makeup, body care products. Traditionally, cosmetic
emulsions are stabilized using surfactants or polymers. Due to its adverse effects on environment, cytotoxicity
Keywords:
effects, numerous health hazards, there is a strong drive to shift towards sustainable and surfactant free
Particle stabilized cosmetic emulsions
Cosmetic formulations
emulsions. With increasing consumer demand for a safer and more biodegradable products, formulating
Janus particles in cosmetic formulations “surfactant- free” emulsions by replacing conventional stabilizers with particles has gained popularity. In
Surfactant stabilized cosmetic emulsions this review, various important aspects and applications of particle stabilized emulsions in cosmetic formu-
lations will be discussed. Importantly, novel ideas on surface modification of particles and use of Janus par-
ticles in cosmetic formulations will be discussed.
© 2020 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
2. Particle stabilized emulsions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2.1. Stabilization mechanism: similarities and differences between surfactant and particle stabilized emulsions . . . . . . . . . . . . . . . . . 2
2.2. Particles in cosmetic formulations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.3. Key features of particle stabilized cosmetic formulations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
3. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5

1. Introduction Cosmetic emulsions are composed of water/ hydrophilic base material,

Emulsions are colloidal dispersions of a liquid in another immiscible
liquid stabilized using a surfactant and/or solid particles. Emulsions are
of great importance due to their widespread occurrence in industries
such as pharmaceutical, cosmetics, food, agricultural, and energy. In
the cosmetic industry, emulsions represent one of the most common
media characterized by two-phase systems that are highly versatile
and find widespread use in color cosmetics, skin care, and personal
care [1].
Cosmetic formulations can be broadly classified into skin care cos-
metics, color cosmetics, body-care, haircare, and personal care products.
⁎ Corresponding author.
E-mail address: samin01@manhattan.edu (S. Amin).
oleaginous (oil)/ hydrophobic base material, surfactants/ amphiphilic
substances, and materials that add or improve the functional value,
fragrance, sensory feelings and quality control (for example shelf-
life, viscosity) [2]. In cosmetic emulsions, amphiphilic substances
or otherwise known as surfactants are primarily used to emulsify,
solubilize, disperse the oil or aqueous phase, increase stability, and
enhance adsorption (help the emulsion penetration into skin and
hair). A unique feature of cosmetic formulations is that they are com-
posed of a mixed surfactant system instead a single surfactant
thereby creating a synergistic effect [3]. Some of the most commonly
used surfactants in cosmetic emulsions include tween 80, span 80,
sodium laureth sulfate (SLES), sodium lauryl sulfate (SLS), sodium
dodecyl sulfate (SDS), cocamidopropyl betaine (CAPB), polyethyl-
ene glycol ethers and several others [4]. Though the presence of

https://doi.org/10.1016/j.cis.2020.102234
0001-8686/© 2020 Elsevier B.V. All rights reserved.
2 D. Venkataramani et al. / Advances in Colloid and Interface Science 283 (2020) 102234
surfactants in cosmetic products is quite common, recent studies
have indicated that surfactants cause adverse effects such as skin ir-
ritation, hemolysis, and cytotoxicity [4]. In addition to this, surfac-
tants are not biodegradable, biocompatible, and have adverse effect
on the environment. Studies have indicated that surfactants interact
with the hydrolipidic film of the skin thereby leading to greater per-
meability that causes perturbance of the cell membranes, and some-
times cell lysis and protein denaturation [3]. Long term stability and
increased shelf life, parameters such as sensory feeling during prod-
uct application, long lasting effects of the products appearance, and
texture play a vital role in cosmetic formulations. In response to
consumer's demand for a safer and more biodegradable products,
formulating “surfactant- free” emulsions by replacing the conven-
tional stabilizers with particles has gained popularity.
Particle stabilized emulsion also known as Pickering emulsions have
gained popularity particularly in the cosmetic industry as they are
known to aid stable and highly versatile emulsions. Studies have indi-
cated that in addition to improving emulsion stability, particles enhance
sensory feeling during product application, product appearance and
texture as the surface of the particles can be easily modified [5].
With increasing consumer demand and trends moving towards sus-
tainability, there is strong drive within the cosmetics and personal care
industry to shift towards using biodegradable substances. Although
there is a widespread interest and experimentation conducted on the
use of particles as additives in cosmetic formulations, there is very lim-
ited research available on the use of particles as stabilizing agent in cos-
metic emulsion. The objective of this article is to review the recent
developments and application of particles as an emulsifier in cosmetic
formulations and identify areas of improvement towards developing
sustainable products. Sustainability can be achieved through use of nat-
urally occurring raw materials such as cellulose, biosurfactants, and par-
ticles where the surface can be modified to enhance stability, solubility,
absorption, rheology, sensory feeling, and long lastingness [3]. In this re-
view, use of various kinds of solid particles in cosmetic formulations,
their morphology and application in cosmetic formulations, and deliv-
ery mechanism will be discussed in detail.
2. Particle stabilized emulsions
2.1. Stabilization mechanism: similarities and differences between surfac-
tant and particle stabilized emulsions
Emulsions are thermodynamically unstable systems due to the
high interfacial tension between two immiscible phases, and the
free energy of the system not being minimized [6]. A stable emulsion
is achieved when the surfactant concentration and emulsification
conditions (mixing time, speed) are optimized [7]. Emulsifiers are
Fig. 1. Illustration of water-in-oil and oil-in-water emulsion stabilized using a) surfactant b) solid particles (Pickering emulsion).
added to stabilize the oil-water interface. Surfactants are the usual
choice for this purpose and are used for both water-in-oil (w/o) and
oil-in-water (o/w) emulsions. The role of a surfactant is to reduce the in-
terfacial tension between the phases thereby minimizing the free en-
ergy of the system and subsequently stabilizing the interface to resist
coalescence [8]. Emulsions stabilized using finely divided particles/
nanoparticles are called solid stabilized emulsions (also known as Pick-
ering emulsions) [9]. Solid stabilized emulsions have gained importance
in the last two decades due to their applicability in many industries
(such as cosmetics, food, agriculture, pharmaceutical), their enhanced
emulsion stability, and their ability to produce droplets ranging from a
few microns to several millimeters [10].
Pickering established through extensive experimental study that
solid particles function very similar to surfactant molecules in stabiliz-
ing oil-water interface [9]. Fig. 1 illustrates oil-water interface of an
emulsion stabilized using either surfactant or solid particles. Solid parti-
cles such as pre-treated silica (available in the market as Aerosil) has
been widely used in the pharmaceutical and cosmetic industries as a sta-
bilizer for producing stable and large droplet emulsions [11]. Pickering
observed that solid particles that are preferentially wetted by the oil
phase have a contact angle >90° and act as an emulsifying agent
for w/o emulsions [8,12]. Whereas, particles preferably wetted by
the water phase and have a contact angle <90°, produced o/w emul-
sions. Ramsden and Pickering first quantified that emulsion stabili-
zation by solid particles occurs because of their strong adsorption
at the oil-water interface [9]. The contact angle, coalescence kinetics,
free energy of adsorption of particles, and particle interaction energy
contribute to the stability of the emulsions [12,13]. Stable emulsions
are prepared when the particles are neither too hydrophilic nor hy-
drophobic and if there is complete surface coverage. The particle
shape, size, and concentration greatly affect the emulsion stability
and droplet size [13,14].
Studies have indicated that mixed emulsifier (particle-surfactant
mixture) system enabled novel formulations where emulsions
displayed high thermal resistance at elevated temperatures [15,16].
Masalova and Kharatyan investigated the stability and rheological
properties of w/o emulsions stabilized using a mixture of inorganic
salts, silica particles, and non-ionic surfactant. They observed that
emulsions formed solely using silica particles were stable upto
85 wt% dispersed phase and phase inversion was achieved at higher
internal phase concentration [17]. Factors such as silica particle con-
centration, presence of salt were identified to influence the inversion
point. The influence of particle concentration, surface modification
of silica particles, and concentration of particles to surfactant ratio
on emulsion stability and rheological properties were studied in
emulsions stabilized using either only surfactant or solid-particles
or surfactant-particle mixture. Emulsions containing surfactant-
 D. Venkataramani et al. / Advances in Colloid and Interface Science 283 (2020) 102234
particle mixture and systems containing higher particle to surfactant
ratio were most stable when compared to emulsions stabilized using
either only particles or surfactant [17]. Better stability was observed
in mixed stabilizer system due to enhanced steric hinderance at the
oil-water interface and 3D network of particles formed in the contin-
uous phase.
A study conducted on the rheology of emulsions suggests that sur-
factant stabilized emulsions systems depend on the volume fraction of
the dispersed phase when the elastic modulus of the system is scaled
to γ/R [18]. The scaled modulus was observed to increase drastically at
a volume fraction of around 0.63, which is equal to random close pack-
ing of solid spheres. However, a contrary observation was seen in Pick-
ering emulsions. Elastic storage modulus was determined as function of
interfacial elasticity (not interfacial tension) due to strong adhesion of
particles at the interface [19]. Lee et al. showed that the rheology of gels
was mainly influenced by the volume fraction of particles [20]. Systems
with completely different oil-to-water ratios could have very similar rhe-
ological properties if the particle ratio were the same. In contrast to
surfactant-stabilized emulsions, these systems showed elastic properties
even when the volume fraction of the dispersed phase was below the
random-close-packing limit for spheres. Therefore, Pickering emulsions
are mechanically stable towards creaming at dispersed phase volume
fractions lower than the random-close-packing limit.
Several researchers identified that solid particles impart mechanical
rigidity and viscosity to the interfacial film if the solid particles form a
tightly packed network around the droplet [14,21–23]. To this end,
Simon et al. studied the viscoelastic behavior of emulsions stabilized
with particles of different polarity and observed that their rheological
properties were similar [24]. This study also indicated that the viscosity
and stability of the emulsion decreased with increase in the particle
concentration. The stabilization mechanism in Pickering emulsions
was attributed to the strong adhesion of particles at the oil water inter-
face due to steric hindrance or surface rheology effects [25]. Fan and
Striolo implemented particle dynamics simulation to study the influ-
ence of solid nanoparticles on the oil-water interfacial tension measure-
ments and observed that the interfacial tension is a function of particle
coverage and affinity of nanoparticles to the interface [26]. They ob-
served that increase in the primary particle size significantly increased
the nanoparticles desorption energy, leading to larger surface coverage
and interfacial tension reduction. Sullivan and Kilpatrick, Hannisdal,
et al. investigated the effect of silica nanoparticles on model oil emulsion
stability and demonstrated that the stabilization mechanism and ease of
achieving catastrophic phase inversion in solid stabilized emulsions was
achieved using particles with intermediate wettability [13,27–29].
A recent study on the competitive absorption of surfactants and sil-
ica particles at the oil-water interface revealed that silica particles have
no effect on the interfacial tension and contact angle whereas, an antag-
onist effect was observed in the presence of surfactant [30]. Silica parti-
cles were observed to have no effect on the interfacial tension in the
presence of w/o surfactant. Whereas, a contrary observation was seen
in the presence of particles and o/w surfactant. Irrespective of the sur-
factant type, the contact angle profile at the oil-water interface was at-
tributed primarily due to surfactants at high concentrations. Whereas,
at low surfactant concentration, both particles and surfactant determine
the contact angle profile.
2.2. Particles in cosmetic formulations
Pickering emulsions are widely used in color cosmetics such as facial
makeup, nail, skin, and hair care products. Some of the most commonly
used solid stabilizers in cosmetic formulation are polymer latexes, inor-
ganic particles, silicone particles, silica, lysosomes, chitosan, clays,
starches, carbon nanotubes, and several others [2]. Choosing an appro-
priate solid stabilizer is of great importance due their multifaceted char-
acteristics such as emulsion stabilization, film forming, moisturizing and
exfoliating, conditioning and waterproofing properties [2,31].
3
With the recent trend moving towards sustainability, particle stabi-
lized emulsions has gained popularity over traditional emulsifier systems
as they are less toxic, biocompatible, have enhanced skin permeation,
controlled release mechanism, non-allergic, and surface properties can
be tailored to achieve better results. Studies have indicated that surface
modification of particles (using either physical adsorption or chemical
treatment) with polymers or small molecules results in enhanced skin re-
tention and controlled diffusion mechanism [32,33]. Adsorption of ions,
molecules such as La3+, hydroquinoline onto silica particles was found
to promote stable emulsion [32,33]. In-situ modification of particles,
changes in pH of the solution were also identified as a technique for
forming switchable Pickering emulsions and phase inversion [34–36]. A
similar study was conducted by Llamas et al. on the interaction of micro-
molecules and surfactants in the alteration of surface properties for hair
care formulation [37]. In their work, polycations and negatively charged
surfactant were combined to enhance the adsorption onto keratin sub-
strate of hair and therefore optimized film-forming and conditioning per-
formance imparted from the shampoo. Additionally, a combination of
amphoteric starch particles with cationic surfactants in personal care for-
mulations demonstrated cosmetic effects such as smoothness, lightness,
and suppleness. This formulation may be used for the formulation of hair
care products such as shampoos and conditioners, bath gels or facial
make up removers [38].
A recent study conducted on the rheological characterization of
polysaccharide–surfactant matrices demonstrated enhanced effects on
mechanical properties in cosmetic o/w emulsion. This observation was
attributed to the coexistence of surfactant-polymer mixture that causes
steric and electrostatic stabilization [39]. The system was comprised of
polysaccharide scleroglucan, a nonionic surfactant dimethicone copolyol
(DC), cationic surfactant TTAB, and silicone oil as the internal phase. Addi-
tion of higher concentration of nonionic surfactant reduced intermolecu-
lar connection of the weak gel matrix the most by decreasing its linear
viscoelastic moduli and low shear viscosity values. Depending at the con-
centrations of surfactants, droplet sized reduced with increasing surfac-
tant concentration. Addition of polysaccharide to surfactant mixture
demonstrated a synergistic effect on the linear viscoelasticity moduli. Ad-
dition of a small quantity of TTAB resulted in a reduction in the sauter
mean diameter and therefore preventing droplet coalescence and yield-
ing narrow droplet size distribution.
2.3. Key features of particle stabilized cosmetic formulations
Cosmetic emulsions are formulated differently when compared to
emulsions encountered in other industries as one of their primary roles
is to deliver pleasant sensorial feelings in addition to physicochemical
functions such as cleansing, moisturizing, hydrating, and nourishing at
the skin level. Some of the important factors that are critical in formulat-
ing cosmetic emulsions are: user sensory experience, use and perfor-
mance of several functional materials and stabilizing agents, prevention
of phase separation (stability)/ shelf-life of the product, and biodegrad-
ability of the raw materials, compatibility of the raw material on skin,
pH, temperature, and rheological profile [2,31,40]. Advantages of particle
stabilized cosmetic formulation over surfactant stabilized emulsions are:
increased stability, better skin permeation, better sensory effects, con-
trolled and slow drug release, better rheological profile, ability to form
tunable emulsion, and sustainable.
Stability of an emulsion involves physical stability, chemical stability
and microbiological stability [34]. Physical stability is usually measured
by the absence of phase separation and coarsening which is regulated
by the choice of emulsifier, modifying the rheology of the emulsions,
and producing emulsions with narrow drop size distribution [35,36].
For example, during an application of a moisturizer, an emulsion should
not be either too runny or too viscous but something that can stay stable
in the jar. When applied on the skin, it should have a shear thinning be-
havior leaving a smooth sensorial feeling. Therefore, viscosity of an
emulsion can be tuned accordingly by the addition of colloidal particles
4 D. Venkataramani et al. / Advances in Colloid and Interface Science 283 (2020) 102234
such as cellulose derivatives, or natural gums such as xanthan or
Caesalpinia spinosa gum, or minerals such as clays and pyrogenic silica
[41,42]. A recent study of rheology of particle stabilized emulsions iden-
tified that an increase in contact angle resulted in a decrease in relative
viscosity in o/w Pickering emulsions [43]. Whereas, a contrary observa-
tion was seen in w/o Pickering emulsions.
In cosmetic industry, sensory feeling is one of the most important
parameters that is detrimental for a product's success or failure. In the
consumer market, cosmetic products by default provide more emo-
tional value for the three senses (sight, smell, and touch) [44]. Color,
smell, and touch are the most important senses that strongly influence
the preference of a product over another. After-feel, greasiness, texture,
stickiness, shine, residual coating, smell, appearance are some of the
properties that are evaluated when developing a cosmetic formulation.
In recent years, formulations stabilized with particles were found to fur-
ther add beneficiary sensory properties and improve customer experi-
ence when compared to conventional formulations [44–46]. Pickering
emulsions are known to offer a non-irritant, pleasant sensory, and de-
sired texture such as viscosity and shear thinning that are often perti-
nent to customer experience during product application [44–46].
A study conducted on the sensory evaluation using blind ranking test
indicated that emulsions stabilized using particles had better after feel,
less greasy and sticky, minimal residual coating [44]. Particle stabilized
emulsions showed the best sensory profile in terms of improved sensory
effect, absorbance, spreadability, and transient stability (stability remained
unaffected under varying conditions) when compared to traditional emul-
sifier system [44]. Terescenco et al. investigated textural and sensory prop-
erties of colloidal based emulsions stabilized using either surfactant or
particles or surfactant-particle in topical applications [5]. The study
demonstrated that the sensorial profile of mixed emulsifier system
produced the most in-between results in terms of skin feel, texture,
glossiness, and greasiness. The choice of particles dictated the sen-
sory perception in terms of determining the emulsion orientation
(O/W or W/O) and therefore which phase permeated first onto the
skin [5,47,48]. Conventional emulsifier system resulted into glossy,
greasy, and difficult to spread. Whereas, particle stabilized system
brought improvement in sensorial and textural properties when
combined with surfactant [5]. The addition of SiO2 decreased greas-
iness, while TiO2 eased spreadability and ensured whiteness of the
emulsion. Emulsions formulated with ZnO had small differences as
they were already aqueous and easy to spread; the minor difference
was observed in film whiteness that is directly related to the concen-
tration of particles [5].
Recent studies by Frelichowska et al. suggested that surfactant-free
emulsion has better skin absorption, enhanced permeation and physico-
chemical properties when compared to surfactant stabilized emulsions
[49,50]. Skin permeation of hydrophilic particles was investigated in
both particle and surfactant stabilized w/o emulsions and it was observed
that the permeation rate (absorption on skin) was three times higher and
enhanced (retention in skin was >24 h) in Pickering emulsions due to
strong adhesion of the droplets on skin surface [49]. These studies indi-
cated that particles provides faster diffusion and slow release of drug to
deeper layers (drug penetration vehicle) due to the encapsulation system
(3D structure around droplets), high adhesion energy, and small particle
size [49,50].
Other parameters that aid to stability of Pickering emulsions are
particle size of the solid stabilizer and the ability of form narrow
drop size distribution. Stability of an emulsion increases as particle
size decreases [14]. These parameters are important not only for
the stability of the emulsion, but also for the texture and skin feel of
the cosmetic formulation. In comparison to the size of dispersed drop-
lets, particles must be small enough to be kept at the interface and
thus allow formation of a smooth film around the droplets [51]. If the
particles are too big then they are more susceptible to phase separation
and will coalesce. Therefore, it is essential to maintain larger ratio
between the droplet size and particles to form a stable emulsion.
Wettability of particles can be tailored by modifying its surface with
small molecules such as surfactants, oil molecules, acids or polymers,
that can either be adsorbed physically or anchored chemically [52].
Modification of surface configuration of particles with switchable sur-
factants form stable emulsions [53]. This type of switchable emulsions
are called as SWOP posse the ability to invert W/O emulsions when me-
chanical energy is applied such as rubbing onto the skin. Hence, they
find great application in cosmetic industry, especially for sun protection
products [54,55]. In recent years, tailoring the surface properties of solid
particles has gained importance due to its widespread functionality and
use. In a study conducted by Zhu et al., the surface of negatively charged
silica particle was chemically modified in-situ with cationic surfactant
twice causing destabilization-restabilization mechanism [36]. The
strong electrostatic interaction between the oppositely charged ions re-
sulted in switchable emulsions. Surface modification of solid particles
has gained widespread interest and numerous applications in cosmetic
and personal care industry. Several commercially available products
such as shampoos, hair conditioners, foams, moisturizer, foundation,
sunscreen and another cosmetic product are developed by using the
synergistic action of particles and surfactants. Particles such as silica,
TiO2 are treated with surfactants such as SDS, CTAB, AOT to generate
and stabilize colloidal suspensions [56]. A synergistic effect in terms of
foamability, foam stability was observed at various surfactant concen-
tration. Phase inversion, emulsion stabilization-destabilization, and re-
stabilization and vice-versa can be easily achieved by surface modifica-
tion of solid particle using either surfactants, solid particles, acids, or any
other surface-active agents. The two ways for improving the versatility
and tunability of particles are: surface modification by coating the par-
ticles homogenously or by modifying the particle surface to function
as Janus particles [8,12,34,56–58].
Janus particles are substances that are surface active and have amphi-
philic properties (i.e. one half of the hemisphere is hydrophobic in nature
and the other one hydrophilic) [28]. Due to this amphiphilic structure,
Janus particles mimics the behavior of surfactants by forming stable clus-
ters or micelle like structure with defined size that can reduce the interfa-
cial tension between two different phases [59]. Recent studies have
indicated that though Janus particles are structurally homologous to sur-
factants, there are however differences in terms of emulsion stability, cat-
alytic activity, and stimuli-responsiveness. Janus particle stabilized
emulsions are known to be thermodynamically stable due to the substan-
tially large adsorption energy associated with attachment of particles at
the interface. The factors that determine the emulsion type in a surfactant
stabilized emulsion are shape, amphiphilicity, packing parameter, HLB
ratio, and concentration of the immiscible phases. Whereas, in a Janus
particle stabilized emulsion, the Janus structure parameter (JSP)(ratio of
hydrophilic domain to total particle volume) and water affinity of the
two regions of Janus particle plays a critical role in determining the emul-
sion type [60]. A recent study by Yan et al. identified that when the water
affinity of the two regions are strong, configuration of the Janus particle or
in other terms JSP factor determines the emulsion type [60]. A particle
with a JSP threshold of 0.48 was identified to cause phase inversion sug-
gesting that particles with larger hydrophobic domain stabilize w/o emul-
sion whereas, particle with larger hydrophilic domain stabilize o/w
emulsion. Studies indicate that synthesis of pH – responsive, stimuli-
responsive Janus particles are capable of stabilizing different types of
emulsions (O/W and W/O) as well invert the phase of the emulsions in re-
sponse to change in pH of the solution [33]. The advantage of using Janus
particles over particles of intermediate wettability is that they can be up
to three times or more surface active which leads to greater emulsion sta-
bility [12,30]. The ability to tailor functionalities of Janus particles and the
ease in synthesizing at both small-scale and large-scale capacity provides
wide range of applications and opportunities to explore within the cos-
metic industry.
In the last few decades, cosmeceuticals has emerged as one of the
fastest growing market in the personal care and cosmetic industry.
Cosmeceuticals involves the use of biologically active ingredients in
 D. Venkataramani et al. / Advances in Colloid and Interface Science 283 (2020) 102234
cosmetic products with therapeutic benefits [61–64]. Cosmeceuticals
products are synthesized to produce formulations that have measurable
therapeutic benefits on skin, body, hair such as antiwrinkle creams,
photoaging creams, creams for dark spots, hyperpigmentation, sun
care products [45,46,61,62,65–69]. Nanoparticles that are most widely
used in cosmeceuticals include solid lipid nanoparticles, gold nanoparti-
cles, inorganic nanoparticles, carbon nanotubes (CNT's), nanospheres
and several others. Studies have indicated that the nanocarriers used
in cosmeceuticals have high stability, show cytotoxicity effects, biode-
gradable, and deliver active ingredients into deep layers of the skin in
a targeted and controlled release mechanism. Chemically modified
CNT's is one of the most commonly used ingredients in hair care formu-
lations such as hair coloring agents, conditioners [62].
3. Conclusion
With increasing consumer demand and trends moving towards sus-
tainability, there is strong drive within the cosmetics industry to shift
towards using biodegradable and “surfactant-free” formulations. For
this purpose, researchers have been investigating various particles whose
surface properties can be easily modified, environmentally friendly, versa-
tile, cost effective, and offer rigorous stabilization with characteristic
surface-active properties and amphiphilicity. The two ways for improving
the versatility and tunability of particles are: surface modification by coat-
ing the particles homogenously or by using Janus particles and tailoring
the functionalities of these particles. Surface modification and tailoring
the properties of solid particles and Janus particles would provide consid-
erable advantage in terms of emulsion stability, sustainability, versatility as
well as wide range of technological applications in several cosmetic formu-
lations. Though there are several studies on the use of solid particles and
Janus particles, there is very limited research conducted on the use of
these particles in cosmetic industry. Hence, further investigation in the
use and application of these particulate system in cosmetic formulations
would prove to be significant both from the manufacturer's and consumer
perspective.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
References
[1] Knowlton JL. Emulsion theory. In: Butler H, editor. Poucher’s perfumes. Springer
Netherlands, Dordrecht: Cosmetics and Soaps; 2000. p. 601–23.
[2] Hayase M. Introduction to cosmetic materials, cosmetic science and technology;
2017; 149–54.
[3] Varvaresou A, Iakovou K. Biosurfactants in cosmetics and biopharmaceuticals. Lett
Appl Microbiol 2015;61(3):214–23.
[4] Naves LB, Almeida L, Marques MJ, Soares G, Ramakrishna S. Emulsions stabilization
for topical application. Biomater Med Appl 2017;1:1.
[5] Terescenco D, Hucher N, Picard C, Savary G. Sensory perception of textural proper-
ties of cosmetic pickering emulsions. Int J Cosmet Sci 2020;42(2):198–207.
[6] Becher P. Encyclopedia of emulsion technology. Washington, DC: Oxford University
Press; 1983.
[7] Drelich A, Gomez F, Clausse D, Pezron I. Evolution of water-in-oil emulsions stabi-
lized with solid particles: influence of added emulsifier. Colloids Surf A Physicochem
Eng Asp 2010;365(1):171–7.
[8] Binks BP. Particles as surfactants—similarities and differences. Curr Opin Colloid
Interface Sci 2002;7(1):21–41.
[9] Pickering SU. CXCVI.—Emulsions, journal of the chemical society. Transactions 1907;
91(0):2001–21.
[10] Levine S, Bowen BD, Partridge SJ. Stabilization of emulsions by fine particles I.
Partitioning of particles between continuous phase and oil/water interface. Colloids
Surf 1989;38(2):325–43.
[11] Leal-Calderon F, Schmitt V. Solid-stabilized emulsions. Curr Opin Colloid Interface
Sci 2008;13(4):217–27.
5
[12] Binks BP, Fletcher PDI. Particles adsorbed at the oil−water interface: a theoretical
comparison between spheres of uniform wettability and “Janus” particles. Langmuir
2001;17(16):4708–10.
[13] Binks BP, Lumsdon SO. Influence of particle wettability on the type and stability of
surfactant-free emulsions. Langmuir 2000;16(23):8622–31.
[14] Tambe DE, Sharma MM. Factors controlling the stability of colloid-stabilized emul-
sions: I. An experimental investigation. J Colloid Interface Sci 1993;157(1):244–53.
[15] Sharma T, Kumar GS, Chon BH, Sangwai JS. Thermal stability of oil-in-water picker-
ing emulsion in the presence of nanoparticle, surfactant, and polymer. J Ind Eng
Chem 2015;22:324–34.
[16] Taherpour A, Hashemi A. A novel formulation of the pickering emulsion stabilized
with silica nanoparticles and its thermal resistance at high temperatures. J Dispers
Sci Technol 2018;39(12):1710–20.
[17] Masalova I, Kharatyan E. Effect of silica particles on stability of highly concentrated
water-in-oil emulsions with non-ionic surfactant. Colloid J 2013;75(1):95–102.
[18] Mason TG, Bibette J, Weitz DA. Elasticity of compressed emulsions. Phys Rev Lett
1995;75(10):2051–4.
[19] Arditty S, Schmitt V, Giermanska-Kahn J, Leal-Calderon F. Materials based on solid-
stabilized emulsions. J Colloid Interface Sci 2004;275(2):659–64.
[20] Lee MN, Chan HK, Mohraz A. Characteristics of pickering emulsion gels formed by
droplet bridging. Langmuir 2012;28(6):3085–91.
[21] Aveyard R, Binks BP, Clint JH. Emulsions stabilised solely by colloidal particles. Adv
Colloid Interface Sci 2003;100–102:503–46.
[22] Binks BP, Kirkland M. Interfacial structure of solid-stabilised emulsions studied by
scanning electron microscopy. Phys Chem Chem Phys 2002;4(15):3727–33.
[23] Tambe DE, Sharma MM. Factors controlling the stability of colloid-stabilized emul-
sions: II. A model for the rheological properties of colloid-laden interfaces. J Colloid
Interface Sci 1994;162(1):1–10.
[24] Simon S, Theiler S, Knudsen A, Øye G, Sjöblom J. Rheological properties of particle-
stabilized emulsions. J Dispers Sci Technol 2010;31(5):632–40.
[25] Vignati E, Piazza R, Lockhart TP. Pickering emulsions: interfacial tension, colloidal
layer morphology, and trapped-particle motion. Langmuir 2003;19(17):6650–6.
[26] Fan H, Striolo A. Nanoparticle effects on the water-oil interfacial tension. Phys Rev E
2012;86(5):051610.
[27] Sullivan A, Kilpatrick P. The effects of inorganic solid particles on water and crude oil
emulsion stability. Ind Eng Chem Res 2002;41.
[28] Hannisdal A, Ese M-H, Hemmingsen PV, Sjöblom J. Particle-stabilized emulsions:
effect of heavy crude oil components pre-adsorbed onto stabilizing solids. Col-
loids Surf A Physicochem Eng Asp 2006;276(1):45–58.
[29] Binks BP, Lumsdon SO. Catastrophic phase inversion of water-in-oil emulsions stabi-
lized by hydrophobic silica. Langmuir 2000;16(6):2539–47.
[30] Pichot R, Spyropoulos F, Norton IT. Competitive adsorption of surfactants and hydro-
philic silica particles at the oil–water interface: interfacial tension and contact angle
studies. J Colloid Interface Sci 2012;377(1):396–405.
[31] Hosoi J, Koyama J, Ozawa T. New aspects of cosmetics and cosmetic science. Cosmet
Sci Technol 2017:87–100.
[32] Haase MF, Grigoriev D, Moehwald H, Tiersch B, Shchukin DG. Encapsulation of am-
photeric substances in a pH-sensitive pickering emulsion. J Phys Chem C 2010;114
(41):17304–10.
[33] Frith WJ, Pichot R, Kirkland M, Wolf B. Formation, stability, and rheology of particle
stabilized emulsions: influence of multivalent cations. Ind Eng Chem Res 2008;47
(17):6434–44.
[34] Cui ZG, Cui CF, Zhu Y, Binks BP. Multiple phase inversion of emulsions stabilized by
in situ surface activation of CaCO3 nanoparticles via adsorption of fatty acids. Lang-
muir 2012;28(1):314–20.
[35] Cui ZG, Yang LL, Cui YZ, Binks BP. Effects of surfactant structure on the phase inver-
sion of emulsions stabilized by mixtures of silica nanoparticles and cationic surfac-
tant. Langmuir 2010;26(7):4717–24.
[36] Zhu Y, Jiang J, Liu K, Cui Z, Binks BP. Switchable pickering emulsions stabilized by sil-
ica nanoparticles hydrophobized in situ with a conventional cationic surfactant.
Langmuir 2015;31(11):3301–7.
[37] Llamas S, Guzmán E, Ortega F, Baghdadli N, Cazeneuve C, Rubio RG, et al. Adsorption
of polyelectrolytes and polyelectrolytes-surfactant mixtures at surfaces: a physico-
chemical approach to a cosmetic challenge. Adv Colloid Interface Sci 2015;222:
461–87.
[38] Veronique Douin LC, Decoster Sandrine. Cosmetic compositions comprising an am-
photeric starch and a cationic conditioner, and uses thereof. United States: L'Oreal
SA; 2000.
[39] Bais D, Trevisan A, Lapasin R, Partal P, Gallegos C. Rheological characterization of
polysaccharide–surfactant matrices for cosmetic O/W emulsions. J Colloid Interface
Sci 2005;290(2):546–56.
[40] Huber P. Sensory measurement—evaluation and testing of cosmetic products.
Cosmet Sci Technol 2017:617–33.
[41] Burey P, Bhandari B, Howes T, Gidley M. Hydrocolloid gel particles: formation, char-
acterization, and application. Crit Rev Food Sci Nutr 2008;48:361–77.
[42] Rigano L, Deola M, Zaccariotto F, Colleoni T, Lionetti N. A new gelling agent and rhe-
ology modifier in cosmetics: Caesalpinia spinosa gum. Cosmetics 2019;6:34.
[43] Pal R. A simple model for the viscosity of pickering emulsions. Fluids 2017;3(2).
[44] Ali A, Yilmaz E, Sjöö M. A novel technology for personal care emulsions. SOFW J
2015;141.
[45] Abbasi BH, Fazal H, Ahmad N, Ali M, Giglioli-Guivarch N, Hano C. Nanomaterials for
cosmeceuticals: nanomaterials-induced advancement in cosmetics, challenges, and
opportunities. Nanocosmetics 2020:79–108.
6 D. Venkataramani et al. / Advances in Colloid and Interface Science 283 (2020) 102234
[46] Nafisi S, Maibach HI. Nanotechnology in cosmetics. Cosmet Sci Technol 2017:
337–69.
[47] Pasquali R, Taurozzi M, Sacco N, Bregni C. Birefringent emulsions stabilized with
Steareth-2 and Steareth-21. Lat Am J Pharm 2008;27.
[48] Rossano M, Hucher N, Picard C, Colletta D, Le Foll F, Grisel M. Effects of aging on
structure and stability of TiO2 nanoparticle-containing oil-in-water emulsions. Int
J Pharm 2014;461(1–2):89–96.
[49] Frelichowska J, Bolzinger M-A, Valour J-P, Mouaziz H, Pelletier J, Chevalier Y. Picker-
ing w/o emulsions: drug release and topical delivery. Int J Pharm 2009;368(1):7–15.
[50] Frelichowska J, Bolzinger M-A, Pelletier J, Valour J-P, Chevalier Y. Topical delivery of
lipophilic drugs from o/w pickering emulsions. Int J Pharm 2009;371(1):56–63.
[51] Menon VB, Wasan DT. Characterization of oil—water interfaces containing finely
divided solids with applications to the coalescence of water-in-oil emulsions: a
review. Colloids Surf 1988;29(1):7–27.
[52] Xiao M, Xu A, Zhang T, Hong L. Tailoring the wettability of colloidal particles for pick-
ering emulsions via surface modification and roughness. Front Chem 2018;6(225).
[53] Jiang J, Zhu Y, Cui Z, Binks BP. Switchable pickering emulsions stabilized by silica
nanoparticles hydrophobized in situ with a switchable surfactant. Angew Chem
Int Ed 2013;52(47):12373–6.
[54] Korać R, Krajišnik D, Milić J. Sensory and instrumental characterization of fast
inverting oil-in-water emulsions for cosmetic application. Int J Cosmet Sci 2016;38
(3):246–56.
[55] Korać R, Krajišnik D, Savić S, Pantelić I, Jovančić P, Cekić N, et al. A new class of emul-
sion systems – fast inverted o/w emulsions: formulation approach, physical stability
and colloidal structure. Colloids Surf A Physicochem Eng Asp 2014;461:267–78.
[56] Cao H, Zhang X, Ding B, Wang L, Lu N. Synergistic action of TiO2 particles and surfac-
tants on the foamability and stabilization of aqueous foams. RSC Adv 2017;7(71):
44972–8.
[57] Perro A, Reculusa S, Ravaine S, Bourgeat-Lami E, Duguet E. Design and synthesis of
Janus micro- and nanoparticles. J Mater Chem 2005;15(35–36):3745–60.
[58] Paunov VN, Cayre OJ. Supraparticles and “Janus” particles fabricated by replication of
particle monolayers at liquid surfaces using a gel trapping technique. Adv Mater
2004;16(9–10):788–91.
[59] Walther A, Müller AHE. Janus particles: synthesis, self-assembly, physical properties,
and applications. Chem Rev 2013;113(7):5194–261.
[60] Lan Y, Choi J, Li H, Jia Y, Huang R, Stebe KJ, et al. Janus particles with varying config-
urations for emulsion stabilization. Ind Eng Chem Res 2019;58(46):20961–8.
[61] Gubitosa J, Rizzi V, Fini P, Cosma P. Nanomaterials in sun-care products.
Nanocosmetics 2020:349–73.
[62] Kaul S, Gulati N, Verma D, Mukherjee S, Nagaich U. Role of nanotechnology in
cosmeceuticals: a review of recent advances. J Pharm 2018;2018:3420204.
[63] Nguyen TA, Rajendran S. Current commercial nanocosmetic products.
Nanocosmetics 2020:445–53.
[64] Pandey V, Shukla R, Garg A, Kori ML, Rai G. Nanoemulsion in cosmetic: from labora-
tory to market. Nanocosmetics 2020:327–47.
[65] Morganti P. Nanocosmetics: an introduction. Nanocosmetics 2020:3–16.
[66] Mu L, Sprando RL. Application of nanotechnology in cosmetics. Pharm Res 2010;27
(8):1746–9.
[67] Mukta S, Adam F. Cosmeceuticals in day-to-day clinical practice. J Drugs Dermatol
2010;9(5 Suppl ODAC Conf Pt 1):s62–6.
[68] Nohynek GJ, Lademann J, Ribaud C, Roberts MS. Grey Goo on the skin? Nanotechnol-
ogy, cosmetic and sunscreen safety. Crit Rev Toxicol 2007;37(3):251–77.
[69] Yukuyama MN, Araújo GLBD, Bou-Chacra NA. Nanomaterials for hair care applica-
tions. Nanocosmetics 2020:205–25.