Study on emulsion

mechanism of textile
lubricants
3rd year 2nd Semester Project

This article describes the difference between nano and

microemulsion, reason of unstability of nanoemulsion over
microemulsion using a mathematical model and free
energy diagram,synthesis of oil in water nanoemulsion
using low energy method,optimization of process and their
applications in Textile lubricants]

Arijit Bhattacharyya(UG-III, Roll-001410301026)

Supervised By
Prof. Sudeshna Saha
Department of Chemical Engineering
Jadavpur University
Contents:
Page Number

1.Introduction : 3

2.Terminology : 3-4

3.Nano VS Microemulsion: 4-5

4.Mathematical reason for 5-6

unstability of Nanoemulsion:

5.Synthesis of nanoemulsions: 6-7

6.Optimization of Nanoemulsions: 7-8

7.Applications in textile lubricants: 8

8.References: 8-9

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Study On Emulsion Mechanism of textile lubricants

[This article describes the difference between nano and microemulsion,

reason of unstability of nanoemulsion over microemulsion using a
mathematical model and free energy diagram,synthesis of oil in water
nanoemulsion using low energy method,optimization of process and
their applications in Textile lubricants]

Introduction:

Emulsions and foams are grouped together since they involve two partially miscible fluids
and usually,a surfactant.Both cases comprise a dispersion of one phase in another;if both
phases are liquid ,the system is called an emulsion.Here we carry our discussion regarding
emulsion mechanism and their applications on textile lubricants.In case of emulsios,the
systems are generally unstable with respect to separation of the two fluid phases.

Terminology:

An emulsion may be defined as a mixture of particles of one liquid with some second liquid
.The two common types of emulsion are oil in water(O/W) and water in oil(W/O),where
the term oil is used to denote the water insoluble fluid.

Commercially emulsions are developed to encapsulate liophilic components so that they can
be dispersed into an aqueous medium,so we restrict ourselves to consideration of Oil-in-
water(O/W) type systems in this article.

The two most common types of colloidal dispersions that can be created from these
components are microemulsions and nanoemulsions. There are many structural similarities

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between these two kinds of colloidal dispersion

but definetly they aren’t the same.They differ in stability , size, particle distribution,surface
tension etc.

Nanoemulsion vs Microemulsion:

The term ‘‘microemulsion’’ is generally usually used to refer to thermodynamically stable

isotropic liquids formed by mixing oil, water, and surfactants together.Mixtures of oil (O),
water (W), and surfactant (S) can form a variety of different systems depending on their
composition and the environmental conditions (particularly temperature).They may form
one, two, three or moreseparate phases that are in equilibrium with each other. These
phases may be water-continuous, oil-continuous, or bicontinuous depending on the
concentrations, nature, and arrangements of the molecules present. The structures within
these phases may be spheroid (e.g., micelles or reverse micelles), cylinder-like(such as rod-
micelles or reverse micelles),plane-like (e.g., lamellar structures), or sponge-like (e.g.,
bicontinuous).[6]
On the other hand, A nanoemulsion can be considered to be a conventional emulsion that
contains very small particles. Nanoemulsions may be of the oil-in-water (O/W) or water-in-
oil (W/O) types depending on whether the oil is dispersed as droplets in water, or vice versa.
As mentioned previously, we are primarily concerned with colloidal dispersions suitable for
encapsulating lipophilic components in aqueous environments, and so we focus on oil-in

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water nanoemulsions that consist of small particles comprised of oil and surfactant
molecules dispersed within an aqueous medium.
Nanoemulsion and microemulsion differentiated using their stability and free energy
diagrams as follows:

For a nanoemulsion, the free energy of the colloidal dispersion (droplets in water) is
higher than the free energy of the separate phases (oil and water), which means that
a nanoemulsion is thermodynamically unstable .A nanoemulsion can be made to be
kinetically stable (metastable) by ensuring that there is a sufficiently large energy barrier
between the two states.[4]
For a microemulsion, the free energy of the colloidal dispersion (droplets in water) is lower
than the free energy of the separate phases (oil and water), which means that a
microemulsion is thermodynamically stable .Nevertheless, there may still be an activation
energy separating the two systems whose height determines the rate at which the separate
phases form a microemulsion.

Mathematical reason for unstability of Nanoemulsion:

We Consider a system that exists in equilibrium between a colloidal dispersion

(nanoemulsion or microemulsion) and the separate phases (oil and an aqueous surfactant
solution). To a first approximation, the free energy change associated with forming a
colloidal dispersion from the separate phases consists of an interfacial free energy term
(∆Gi) and a configuration entropy term (-T∆Sconfig):
∆Gformation =∆Gi-T∆Sconfig
At constant temperature, pressure and interfacial chemical potential, the interfacial
free energy term is equal to the increase in contact area between the oil and aqueous
phases (∆A) multiplied by the interfacial tension (ᵞ) at the oil–water interface:
∆Gi=ᵞ∆A

The interfacial free energy term is always positive because the increase in contact area and
interfacial tension are positive. Hence, this term always opposes the formation of colloidal
dispersions. The configuration entropy term depends on the number of different ways that
the oil phase can be arranged within the system. The configuration entropy term is always

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negative because the number of arrangements accessible to the oil phase in an emulsified
state is much greater than in a non-emulsified state, and therefore it always favors the
formation of colloidal dispersions.[4]
Initially, we calculated the interfacial(∆Gi), configuration (-T∆Sconfig):), and total free energies
for the formation of a colloidal dispersion assuming that the interfacial tension was always
the same as that measured at a planar oil–water interface.The interfacial free energy
contribution becomes increasingly positive (unfavorable to the formation of a colloidal
dispersion) with decreasing particle size due to the increase in interfacial area, whereas the
configuration free energy becomes increasingly negative (favorable) with decreasing particle
size due to the increase in the number of different ways the droplets can be organized.
Nevertheless, the overall free energy change becomes increasingly positive with decreasing
particle size, since the interfacial free energy term dominates the configuration entropy
term. These calculations suggest that the formation of a nanoemulsion becomes
increasingly thermodynamically unfavourable as the particle size decreases for systems
where the interfacial tension is similar to that at a planar interface.

Synthesis of nanoemulsions:

So the above calculation suggests that to prepare Nanoemulsion we should go for some
external technique to overcome this unfavourable energy barrier.This can be done in two
ways-
i) Low Energy Method

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 ii) High Energy Method
In this article we will discuss the nanoemulsion formation using low energy method only. [1]

Low energy method involves very low quantity of energy during the formation
nanoemulsions.There are two proposed techniques for low energy method-
i) the first one describes emulsification as spontaneous phenomenon[1] which uses
the rapid diffusion of water-soluble solvent, solubilized first in the organic phase,
moving towards the aqueous one when the two phases are mixed.
ii) Secondly, the so called Phase Inversion Temperature(PIT)[3] method, in which the
specific properties of surfactants are used to modify their partitioning coefficient as
a function of temperature, and leads to formation of oil in water emulsions.

Spontaneous phenomenon is simply results of the initial non-equillibrium states of the two
bulk liquids when they are brought into contact without stirring. So this kind of
emulsification increases the entropy and decreases the gibbs free energy.This mechanism
can be predicted by diffusion pathway. The source of energy of spontaneous emulsification
reportedly stemmed mainly from interfacial turbulences, closely related to the surface
tension gradient induced by the diffusion of solutes between two phases. Likewise, the
interfaces are subject to capillary waves from thermal origins, gradually amplified as the
surface tension decreases . This model, however, is based on the following assumptions,
(i)that non-equilibrium phases are brought into contact, and eventually some species
should diffuse into the opposite phase, (ii) that for ‘semi infinite’ phases, the theory is
limited to time, for which some proportions of both contacted phases retain their initial
composition, (iii) that the diffusion coefficients of all components are equal in a phase,
which is precisely the condition for representing the diffusion paths as straight lines, and
finally (iv) that the interface presents a local equilibrium. Thus, spontaneous emulsification
only depends on the diffusion path with regards to the equilibrium phase diagram.

The phase inversion temperature (PIT) method is particularly interesting since it is an

organic, solvent-free and low-energy method. Since the process is relatively simple and low-
energy consuming, it allows easy industrial scale-up. an oil-in-water (o/w)emulsion is

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subjected to a phase inversion, giving rise to awater-in-oil (w/o) one, when the temperature
rises.
Optimization of Nanoemulsions:

The properties of nano-emulsions, as non-equilibrium systems, depend not only on

composition variables but preparation variables such as emulsifying path, agitation or
emulsification time. These variables can have a significant influence on the nano-emulsion
final properties. Direct application of nanoemulsions requires optimization studies for
achieving the best properties for specific applications. The most frequent aim for
optimization is to exploit the advantages of nano-emulsions with respect to conventional
emulsions (i.e. macroemulsion): small size and low polydispersity. Therefore, in general,
optimization is directed to obtain minimum droplet size and/or minimum polydispersity.
Another aim in nano-emulsion optimization is to improve the stability because, as stated
above, stability is the main problem to overcome to find practical applications for nano-
emulsions. Optimization is also directed to obtain an optimum in the function for which the
nano-emulsions are used (e.g. drug delivery). The properties to be optimized, for example
droplet size and polydispersity, will depend, of course, on composition variables, and could
depend on preparation variables, so optimization can be carried out with respect to these
two types of variables. Concerning optimization methods, sometimes the characteristics of
emulsification path allow predicting optimum properties of nanoemulsions, so optimizations
are carried out by studying the phase behavior of the systems. In other occasions,
optimization is experimentally carried out by selective variation of one variable. Finally,
given the high number of variables that can influence the final properties of nano-
emulsions, optimization is carried out by experimental designs which allow reducing the
number of experiments needed. Review of papers about optimization is presently classified
according to these three types of methods.[2]
Applications in textile lubricants:

Oil in water emulsion(O/W) has been used in industrial rolling mills for many decades and
plays an important role in their film forming and tribiological behaviour. Among textile
lubricants, Lissoflix coning oils protect yarns during throwing processes by reducing friction
coefficient and lowering static electricity’s impact on yarn . Due to its emulsifiable
techonology, Lissoflix is easily removeable through conventional washing processes.

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Another textile lubricant Paratex is based on water soluble waxes , prepared via oil in
water emulsion mechanism .[5]

References:

[1] Design and production of nanoparticles formulated from nano-emulsion

templates—A review
Nicolas Anton , Jean-Pierre Benoit , Patrick Saulnier

[2] Nano-emulsions: New applications and optimization of their preparation

J.M. Gutiérrez , C. González a, A. Maestro a, I. Solè a, C.M. Pey a, J. Nolla b

[3] Nano-emulsion formation by emulsion phase inversion

Patrick Fernandez, Val´erie Andr´e, Jens Rieger, Angelika K¨uhnlea,

[4] Nanoemulsions versus microemulsions: terminology, differences, and similarities

David Julian McClements

[5] www.lubricants.total.com

[6] A textbook of Physical Chemistry by P.C.Rakshit

[7] Solans C, Esquena J, Forgiarini AM, Usón N, Morales D, Izquierdo P,

Azemar N, Garcia-Celma MJ. Nano-emulsions: formation, properties and
applications. Surfactant Science Series 2003;109:525–54. First review on
nano-emulsions obtained by low energy methods.

[8] P. Walstra, Principles of emulsion formation, Chem. Engng. Sci. 48 (1993) 333.

[9] T. Tadros, R. Izquierdo, J. Esquena and C. Solans, Adv. Colloid Interface Sci.,
2004, 108–109, 303–318.

[10] K. Shinoda, Solution behavior of surfactants: the importance of surfactant phase

and the continuous change in hlb of surfactant, Prog. Colloid Polym. Sci. 68 (1983)
1–7.

[11] K. P. Velikov and E. Pelan, Soft Matter, 2008, 4, 1964–1980.

[12] Tadros T, Izquierdo P, Esquena J, Solans C. Formation and stability of nanoemulsions.
Advances in Colloid and Interface Science 2004;108–109:303–18.
[13] M. Fanun, Microemulsions: Properties and Applications, CRC Press, Boca Raton, FL,
2008.
[14] I. Solè, A. Maestro, C.M. Pey, C. González, C. Solans, J.M. Gutiérrez, Nanoemulsions

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preparation by low energy methods in an ionic surfactant system, Colloids Surf. A 288 (2006)
138–143.
[15] K. Shinoda, S. Friberg, Microemulsions colloidal aspects, Adv. Colloid Interface Sci.
4 (1975) 281–300.

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