FACULTY OF ENGINEERING

MATERIALS SCIENCE AND ENGINEERING DEPARTMENT

MLZ441

Nanomaterials and Nanotechnology Lecture

Project Report

07.01.2013

“Nanoemulsions in Cosmetics”

Sinan Özgün

16220064562

Supervisor: Prof. Dr. Ender SUVACI

Sinan Özgün Submitted on;
Anadolu University, MatS&E Dept. Jan. 7th, 2013

NANOEMULSIONS IN COSMETICS

Report Prepared by : Sinan Özgün

Supervisor : Prof. Dr. Ender SUVACI

Abstract:

This report is prepared to fulfill the partial requirement for “MLZ441 Nanomaterials
and Nanotechnology Lecture”. The main subject is the applications of nanoemulsion systems
in cosmetics. Nanoemulsion systems is investigated in terms of their properties, preparation
methods, application areas and considerations related to health and environment; furthermore,
preliminary information about the emulsion systems in general is covered to provide a
background.

Contents:
1. Introduction..…………………………………….…………………………………………2
2. Emulsion Systems and Nanoemulsions…..……………………………………………….2
2.1. Properties of Nanoemulsions…………………………….................................…4
2.2. Preparation Methods for Nanoemulsions…...……………………………….…5
2.2.1. Ingredients...…………………………………………………………....5
2.2.2. Phase Inversion Method ………………………………………...….…6
2.2.3. Sonication Method …………………………………………………….6
2.2.4. High Pressure Homogenization ……………………………………....6
2.2.5. Microfluidization ……………………………………………………...7
2.2.6. Production With High-Amplitude Ultrasound……………………... 7
2.3. Application Areas for Nanoemulsions…………………………...……………..7
3. Nanoemulsions in Cosmetics……………………………………………………...……....8
3.1. Some Patented Nanoemulsion Applications and Commercial Products…….9
3.2. Risk of Health Hazard and Impact on Environment…………….………...…10
4. Conclusions………………………………………………………………………………..10

List of Figures
References
Appendix 1: Estimated worldwide public funding for nanotechnology R&D in 2004
Attachment: Poster “Nanoemulsions in Cosmetics”

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1. Introduction

Today almost all the major cosmetics manufacturers use nanomaterials in their
products. For instance, the world’s largest cosmetics company, L’Oréal is devoting about
$600 million, of its $17 billion revenues to nanotechnology, ranks 6th in US in the number of
nanotech related patents and already has nanotechnology-related products in the market.[1]

Figure 1. Ranking of top 10 beauty companies in terms of number of nano-related patents.

(Taken from: J Pharm Bioallied Sci. 4(3): 186–193, Jul-Sep 2012)

Funding for nanotechnology research and development in Europe and worldwide is

provided in Appendix 1.[2]

A promising application of nanomaterials in cosmetics is the utilization of

nanoemulsions (NE) in skin care products, which became increasingly important due to the
potential of the nanoemulsion systems for the controlled delivery and optimized dispersion of
active ingredients into the desired layers of skin.

2. Emulsion Systems and Nanoemulsions

An emulsion is a system in which one fluid is dispersed in another with which it is

immiscible.[3] Due to the differences in attractive interactions between the molecules of the
two liquid phases, an interfacial tension exists between the two liquids where they are in
contact. In the absence of any surfactants or other impurities the system will always revert to
its lowest energy configuration at thermodynamic equilibrium. Even after, if the lyotropic
phase is sheared to produce nonequilibrium structures these ephemeral structures will
coalesce and eventually disappear. To make a long-lived emulsion of droplets that can persist
over weeks or years without coalescing, it is necessary to add a surfactant, which is usually
soluble in the continuous liquid phase but not highly soluble in the dispersed phase. This

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specification of solubility is not a rule without exceptions, but it is generally true. A system of
classification of the tendency of surfactants to disperse in polar or non-polar liquids is referred
to as the hydrophile–lipophile balance (HLB), and a numerical HLB scheme exists for
classifying surfactants in terms of their relative solubility in aqueous and oily liquid phases.[4]

Figure 2. (a) Two immiscible liquids, such as oil and water, will phase separate into a layer of the less dense
liquid on top of a layer of the more dense liquid below with a flat interface to minimize the interfacial and
gravitational energies. (b) A surfactant, generally soluble in the continuous phase, preferentially adsorbs on the
oil–water interface and exchanges with monomers and micelles in solution. In this example, the surfactant is
soluble in the water phase, so a direct emulsion is anticipated. (c) Shear is applied to the system, causing the oil
to break up into droplets that are coated with surfactant and are inhibited from coalescing due to the interfacial
repulsion. As the emulsion is sheared, larger oil droplets are stretched, undergo a capillary instability, and
rupture into smaller droplets. (d) After the shear has been stopped, the emulsion can persist for many years, and
a fraction of the shear energy applied is stored in the greater surface area of the droplets.

Emulsions are generally classified with respect to their morphology. Emulsions that
have water as a continuous phase and oil as a dispersed phase are called “direct”, “water-
based”, and “O/W” emulsions; for direct emulsions, the surfactant is generally soluble in the
aqueous phase and provides more stability of water films. By contrast, emulsions that have oil
as a continuous phase are called “inverse”, “oil-based”, or “W/O” emulsions; for inverse
emulsions, the surfactant is generally soluble in the oil phase and increases the stability of oil
films.[4]

The term "Nanoemulsion" refers to a thermodynamically stable and isotropically clear

dispersion of two immiscible liquids, as mentioned in the definition of emulsions in general.
The difference is the size; a nanoemulsion is considered to be a thermodynamically or

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kinetically stable liquid dispersion of an oil phase and a water phase in combination with a
surfactant. The dispersed phase typically comprises small particles or droplets, with a size
range of 5 nm-200 nm, and has very low oil/water interfacial tension.[3]

Three types of Nanoemulsions are most likely to be formed: [3]

• Oil in water Nanoemulsions wherein oil droplets are dispersed in the continuos
aqueous phase
• Water in oil Nanoemulsions wherein water droplets are dispersed in the continuous oil
phase;
• Bi-continuous Nanoemulsions wherein microdomains of oil and water are
interdispersed within the system.
In all three types of Nanoemulsions, the interface is stabilized by an appropriate combination
of surfactants and/or co-surfactants. [3]

2.1. Properties of Nanoemulsions

Nanoemulsions have many interesting properties that are different from those of larger
scale emulsion systems. The most distinguishing properties and advantages are listed below:

1. The dispersed phase have a size range of 5 nm-200 nm, and have a very low oil/water
interfacial tension. Because the droplet size is less than 25% of the wavelength of
visible light, Nanoemulsions are transparent.[3]

Figure 3. Ultraviolet–visible spectroscopy of nanoemulsions

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2. Nanoemulsions do not show the problems of inherent creaming (gravitationally driven

Creaming), flocculation, coalescence, and sedimentation, which are commonly
associated with macroemulsions.[5]

3. Nanoemulsions have a much more higher surface area and free energy than macro
emulsions that maket hem an effective transport system.[6]

4. Nanoemulsions can be formulated in variety of formulations, it is possible to produce

non-toxic and non-irritant formulations, hence they can be easily applied to skin and
mucous membranes and they can be produced as foams, creams, liquids, and sprays.

2.2. Preparation Methods of Nanoemulsions

There are plenty of methods suggested for the preparation of nanoemulsion in the
literature. The fundamental ideas of the all nanoemulsion preparation methods is to reduce the
droplet size below 600 nm (in most recent applications below 200 nm), and to achieve the
stability condition. Formation of nanoemulsions requires high amounts of energy which can
be provided either by mechanical means (extremely high shear forces, emulsification) or
through the chemical potential and phase transformation mechanisms. The most widely used
processing methods are “High Pressure Homogenization” and “Microfluidization”.
Figure 4. Hypothetical Phase
Regions of Microemulsion Systems.
Pseudo-ternary phase diagrams of oil,
water, and co-surfactant/surfactants
mixtures are constructed at fixed
cosurfactant/surfactant weight ratios.
Phase diagrams are obtained by
mixing of the ingredients titrated with
water and stirred well at room
temperature. Formation of
monophasic/biphasic system is
confirmed by visual inspection. In
case turbidity appears followed by a
phase separation, the samples shall be
considered as biphasic. In case
monophasic, clear and transparent
mixtures are visualized after stirring;
the samples shall be marked as points
in the phase diagram. The area
covered by these points is considered
as the Nanoemulsion region of
existence.

Three important conditions should be considered during preparation of nanoemulsion:[3]

• Surfactants must be carefully chosen so that an ultra low interfacial tension (< 10-3
mN/m) can be attained at the oil / water interface which is a prime requirement to
produce Nanoemulsions.

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• Concentration of surfactant must be high enough to provide the number of surfactant

molecules needed to stabilize the microdroplets to be produced by an ultra low
interfacial tension.
• The interface must be flexible or fluid enough to promote the formation of
Nanoemulsions.

Frequently used raw materials and processes are explained in the following sections.

2.2.1. Ingredients

Main three components of nanoemulsion systems are as follows:[5]

1. Oil (carrier for active reagents or the reagent itself)

2. Surfactant/Co-Surfactant (Emulsifiers)

3. Aqueous Phase (usually water or alcohols)

Also some additives such as antioxidants and preservatives are used.

Table 1. Components of Nanoemulsion Formulations

2.2.2. Phase inversion method:

In this method fine dispersion is obtained by chemical energy resulting of phase

transitions taking place through emulsification path. The adequate phase transitions are
produced by varying the composition at constant temperature or by varying the temperature at

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constant composition. Phase inversion temperature (PIT) method was introduced by Shinoda
et al. based on the changes of solubility of polyoxyethylene type surfactant with temperature.
This surfactant becomes lipophilic with increase in temperature due to dehydration of
polymer chain. But at low temperature, the surfactant monolayer has a large positive
spontaneous curvature forming oil-swollen micellar solution phase.[7]

2.2.3. Sonication Method:

Sonication method is another best way to prepare nanoemulsion. In this method the
droplet size of conventional emulsion are reduced with the help of sonication mechanism.
This method is not suitable for large batches, only small batches of nanoemulsion can be
prepared by this method.[7]

2.2.4. High Pressure Homogenization:

This method is performed by applying a high pressure over the system having oil
phase, aqueous phase and surfactant or co-surfactant. The pressure is applied with the help of
a special equipment know as homogenizer. There are some problems which are associated
with homogenizer such as poor productivity, component deterioration due to difficult mass
production and generation of much heat. With this method only oil in water (o/w) liquid
nanoemulsion of less than 20% oil phase can be prepared and cream nanoemulsion of high
viscosity or hardness with a mean droplet diameter lower than 200 nm cannot be prepared.
However it is still the most widely used method.[7]

2.2.5. Microfluidization:

Microfluidization is a patented mixing technology, which makes use of a device called

microfluidizer. This device uses a high-pressure positive displacement pump (500-20000 psi),
which forces the product through the interaction chamber,consisting of small channels called
"microchannels." The product flows through the microchannels on to an impingement area
resulting in very fine particles of submicron range. The two solutions (aqueous phase and oily
phase) are combined together and processed in an inline homogenizer to yield a coarse
emulsion. The coarse emulsion is into a microfluidizer where it is further processed to obtain
a stable nanoemulsion. The coarse emulsion is passed through the interaction chamber of the
microfluidizer repeatedly until desired particle size is obtained. The bulk emulsion is then
filtered through a fitler under nitrogen to remove large droplets resulting in a uniform
nanoemulsion.[7]

2.2.6. Production With High-Amplitude Ultrasound:

High-amplitude ultrasound is a viable alternative to high-pressure homogenization.

Intense shear forces necessary for the nanoemulsification are generated by ultrasonic
cavitation, which produces violently and asymmetrically imploding vacuum bubbles and
causes micro-jets that disperse and break up particles down to the nanometer scale. Known for
many decades, this effect has been extensively studied and successfully used in smallscale
production of pharmaceutical nanoemulsions and liposomes. Conventional high-power

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ultrasonic technology inherently forces all processes to run either at a small scale and high
amplitude or a large scale and low amplitude, not allowing for the possibility of implementing
high amplitudes on industrial scale. Thus, despite its potential, the ultrasonic method has
mainly been restricted to laboratory investigations.[7]

2.3. Application Areas for Nanoemulsions

The advantages and properties of nanoemulsions provided many potential application

areas which can be categorized under the following main titles;

•Parenteral Delivery: Parenteral administration (especially via the intravenous route)

of drugs with limited solubility is a major problem in industry because of the
extremely low amount of drug actually delivered to a targeted site. Nanoemulsion
formulations have distinct advantages over macroemulsion systems when delivered
parenterally because of the fine particle Nanoemulsion is cleared more slowly than the
coarse particle emulsion and, therefore, have a longer residence time in the body. [3]
• Oral and Topical Drug Delivery: Nanoemulsion formulations offer the several
benefits over conventional oral formulation for oral administration including increased
absorption, improved clinical potency and decreased drug toxicity. Therefore,
Nanoemulsion have been reported to be ideal delivery of drugs such as steroids,
hormones, diuretic and antibiotics. Nanoemulsion formulation provides a rapid
penetration of active ingredients through skin due to the large surface area of droplets.
Even sometimes it is found that nanoemulsion penetrate easily through rough skin.
This property of nanoemulsion minimizes the additional utilization of special
penetration enhancer which is responsible for incompatibility of formulation. Topical
administration of drugs can have advantages over other methods for several reasons,
one of which is the avoidance of hepatic first pass metabolism of the drug and related
toxicity effects. Another is the direct delivery and targetability of the drug to affected
area of the skin.[7]
• Ocular and Pulmonary Delivery: For the treatment of eye diseases, drugs are
essentially delivered topically. O/W Nanoemulsions have been investigated for ocular
administration, to dissolve poorly soluble drugs, to increase absorption and to attain
prolong release profile.[3]
• Nanoemulsions in Biotechnology: Enzymatic catalysis in Nanoemulsions has been
used for a variety of reactions, such as synthesis of esters, peptides and sugar acetals
transesterification; various hydrolysis reactions and steroid transformation. The most
widely used class of enzymes in microemulsion-based reactions is of lipases.[3]
• Nanoemulsion as Non-toxic Disinfectant Cleaners: A breakthrough nontoxic
disinfectant cleaner for use in commercial markets that include healthcare, hospitality,
travel, food processing, and military applications has been developed by
EnviroSystems Inc. that kills tuberculosis and a wide spectrum of viruses, bacteria and
fungi in 5-10 min without any of the hazards posed by other categories of
disinfectants. The product needs no warning labels. It does not irritate eyes and can be
absorbed through the skin, inhaled, or swallowed without harmful effects.[7]

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Figure 5. Mechanism of action of nanoemulsion vaccine

3. Nanoemulsions in Cosmetics

NEs have recently become increasingly important as potential vehicles for the
controlled delivery of cosmetics and for the optimized dispersion of active ingredients in
particular skin layers. Due to their lipophilic interior, NEs are more suitable for the transport
of lipophilic compounds than liposomes. Similar to liposomes, they support the skin
penetration of active ingredients and thus increase their concentration in the skin.[5]
Another advantage is the small sized droplet with its high surface area allowing effective
transport of the active to the skin. Furthermore, NEs gain increasing interest due to their own
bioactive effects.[5] Many studies show the appropriateness of SMEs for increased cutaneous
penetration of active ingredients, and reduced transepidermal water loss, which confirms
support in the barrier function of the skin.[8]

Nanoemulsions are feasible in cosmetics as they do not exhibit inherent creaming,

sedimentation, flocculation, or coalescence which are observed with macroemulsions.[5]

NanoGel technology provides a simple process and system to create submicron

emulsions from an easy-to-use, oil-in-water concentrate. The Formula is particularly suited to
minimizing transepidermal water loss, enhanced skin production, and penetration of active
ingredient. These characteristics suggest that it would be particularly useful for sun care
products as well as moisturizing and anti-aging creams-particular areas where nanotechnology
is already being incorporated into a host of products currently on the market. Likewise, it is
also highlighted that it helps to give skin care formulations a good skin feel, an increasingly
important characteristic for formulators. Advantages of nanoemulsions over other dosage
forms are as follows:[7]

•Increase the rate of absorption.

•Eliminates variability in absorption.
•Helps solublize lipophilic drug.

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•Provides aqueous dosage form for water insoluble drugs.

•Increases bioavailability.
•Various routes like tropical, oral and intravenous can be used to deliver the product.
•Rapid and efficient penetration of the drug moiety.
•Helpful in taste masking.
•Provides protection from hydrolysis and oxidation as drug in oil phase in O/W
Nanoemulsion is not exposed to attack by water and air.
•Liquid dosage form increases patient compliance.
•Less amount of energy requirement.
•Nanoemulsion has a transparent and fluidy property which improves the formulation
patient compliance and safe for administration due to the absence of any thickening agent
and colloidal particles.
•Nanoemulsions are thermodynamically stable system and the stability allows
selfemulsification of the system .
•Nanoemulsion formulation required low amount of surfactant compared to
microemulsion. For example about 20- 25 % surfactant is required for the preparation of
microemulsion but 5-10 % surfactant is sufficient in case of nanoemulsion.

3.1. Some Patented Nanoemulsion Applications and Commercial Products

Some examples to patents taken by the major cosmetics producer L’Oreal are given
below:

1. Patent Name: NE based on phosphoric acid fatty acid esters and its uses in cosmetics,
dermatological, pharmaceutical and/or ophthalmological fields. Assignee: L’Oreal (Paris,
FR). US Patent Number: 6,274,150.

2. Patent Name: NE based on ethylene oxide and propylene oxide block copolymers and its
uses in the cosmetics, dermatological and/or ophthalmological fields. Assignee: L’Oreal
(Paris, FR). US Patent Number: 6,464,990.

Some commercially available but not mass produced examples include Nanogel by
Kemira[3] and Alginate-based "pearls" containing antiaging ingredients by Capsum (more
information can be obtained from Capsum’s webpage: http://www.capsum.eu)

3.2. Risk of Health Hazard and Impact on Environment

The main consideration of health hazard that may be possessed by the nanoemulsion
systems is the use of surfactants which may be toxic. Before using a nanoemulsion based
cosmetics or pharmaceutical product it is advisable to check the list of GRAS (generally
recognized as safe) substances published by the U.S. Food and Drug Administration.[9]
Several alternatives are developed to eliminate the negative effects of surfactants. The most
attractive alternatives are polymeric emulsifiers such as copolymers of acrylic acid or
hydroxypropylcellulose, on the one hand, and surfactant free systems featuring solid particles

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such as alumina, silica or titanium dioxide packed in the interface, on the other hand. This can
lead to a stable interfacial film with a good protection against coalescence.[8]

In environmental discussions the most problematic side of the nanoemulsions is their

high energy consuming production methods. Currently the only solution to this backdraw
relies on the advancements in ultrasonic technology.[7]

4. Conclusions

Nanoemulsions have recently attracked attention as potential systems for the

controlled delivery of cosmetics and dispersion of active ingredients in particular skin layers.
Also they possess great potential for pharmaceuticals and other application areas ranging from
military to packaged food industry. Major cosmetics companies have started investments and
some products are already available in the market. Although recent studies prove their
superiority over conventional products, further investigation of the nanoemulsion systems is
needed especially in terms of surfactant free systems. Production methods should also be
enhanced to reduce the energy consumption and increase the product output to be able to meet
with the market requirements.

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List of Figures & Tables:

Figure 1: J Pharm Bioallied Sci. 4(3): 186–193, Jul-Sep, (2012).

Figure 2: Mason T.G., Wilking J.N., Meleson K., Chang C.B., Graves S.M., Nanoemulsions:
Formation Structure, and Physical Properties, Journal of Physics: Condensed Matter, 18, 635-
666, (2006).
Figure 3: Mason T.G., Wilking J.N., Meleson K., Chang C.B., Graves S.M., Nanoemulsions:
Formation Structure, and Physical Properties, Journal of Physics: Condensed Matter, 18, 635-
666, (2006).
Figure 4: Devarajan V., Ravichandran V., Nanoemulsions: As Modified Drug Delivery Tool,
International Journal of Comprehensive Pharmacy, 2, 4, (2011).
Figure 5: Kumari Ch.T.L., Sowjanya G.N., Bandhavi P., Nanoemulsions An Emerging
Trend: A Review, IJPRD, 4(06), 137-152, (2012).
Table 1: Shah P., Bhalodia D., Shelat P., Nanoemulsions: A Pharmaceutical Review, Sys.
Rev. Pharm. 1, 1, 24-32, (2010).

References:

[1] Nano, Nano, On The Wall... L’Oréal and others are betting big on products with
microparticles. Business Week, 12 December 2005.
[2] Some Figures about Nanotechnology R&D in Europe and Beyond, Unit G4 Nanosciences
and Nanotechnologies European Commission, Research DG, (2005).
[3] Devarajan V., Ravichandran V., Nanoemulsions: As Modified Drug Delivery Tool,
International Journal of Comprehensive Pharmacy, 2, 4, (2011).
[4] Mason T.G., Wilking J.N., Meleson K., Chang C.B., Graves S.M., Nanoemulsions:
Formation Structure, and Physical Properties, Journal of Physics: Condensed Matter, 18, 635-
666, (2006).
[5] Sharma S., Sarangdevot K., Nanoemulsions for Cosmetics, IJARPB , 1(3), 408-415,
(2012).
[6] Shah P., Bhalodia D., Shelat P., Nanoemulsions: A Pharmaceutical Review, Sys. Rev.
Pharm. 1, 1, 24-32, (2010).
[7] Kumari Ch.T.L., Sowjanya G.N., Bandhavi P., Nanoemulsions An Emerging Trend: A
Review, IJPRD, 4(06), 137-152, (2012) .
[8] Nielloud F., Current Galenical Research Challenges In Human Dermatology: Application
for The Development of Products for Sensitive and Atopic Skin, Virbac Symposium, (2003).
[9] Generally Recognized as Safe Substances, U.S. Food and Drug Administration:
http://www.fda.gov/Food/FoodIngredientsPackaging/GenerallyRecognizedasSafeGRAS/GRA
SSubstancesSCOGSDatabase/default.htm

Appendix I : Estimated worldwide public funding for nanotechnology R&D in 2004

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