University of Science and Technology of Hanoi

Department of Fundamental and Applied Sciences

PROPERTIES AND APPLICATIONS RELATED

TO SURFACTANTS
Dr. Nguyen Duc Anh
Department of Fundamental and Applied Sciences (FAS)
nguyen-duc.anh@usth.edu.vn
0904888819

September 2019
 Reduction of
Solubility
surface tension

Dispersion and
Wettability
Aggregation

Foaming and
Emulsions
Defoaming

Synthesis and
Detergency
Nanotechnology
Where can you find Emulsions ?

Pesticide Asphalt Skin cream

Metal cutting oils Margarine Ice cream

Stability of emulsions may be engineered to vary from seconds to years depending on application
Emulsion
Suspension of liquid droplets (dispersed phase) of certain size within a second immiscible
liquid (continuous phase).

Emulsion composition

Interfacial layer (emulsifying agent): Essential to stabilizing the emulsion

Internal phase (Dispersed medium): The phase that is added tends to

become the internal phase

External phase (Continuous medium): The predominant solubility of the

emulsifier tends to determine the external phase (Bancroft’s rule)

Generally, the phase of the greatest volume tends to become the external phase
 Emulsion
Emulsion classification
- Based on dispersed phase
+ Oil in Water (O/W): Oil droplets dispersed in water
+ Water in Oil (W/O): Water droplets dispersed in oil
Emulsion
Emulsion classification
O/W vs W/O
Emulsion

- Based on size of liquid droplets

(1) macroemulsions, the most well-known type, opaque

emulsions with particles >400 nm (0.4 μm), easily
visible under a microscope
(2) microemulsions, transparent dispersions with
particles <100 nm (0.1 μm) in size
(3) Nanoemulsions (miniemulsions), a type that is blue-
white, with particle sizes between those of the first
two types (100–400 nm [0.1–0.4 μm]).
Emulsion

Differences of emulsion types

 Emulsions are non-stable?

• Emulsions are thermodynamically unstable

• This means that their natural tendency is to
revert to a state of least energy i.e.
separated into two layers

• The process of emulsification is to

produce droplets but also to maintain
them in this state over a reasonable
shelf life
 Emulsion breaking phenomena
Emulsions are non-stable?

Factors that contribute to emulsion

instability

 Forces of attraction between

droplets

 Gravity

 Random movement of droplets

 Creaming / Sedimentation

• No change in droplet size

• Reversible
• Driven by density difference
• Usually results from gravitational forces

Creaming Sedimentation
 Flocculation
Flocculation refers to the process by which fine particulates are caused to clump together into a floc

• No change in droplet size

• Reversible
• Improve in the presence of flocculants
 Coalescence and Ostwald Ripening

Coalescence A process in which 2 drops of discontinuous phase combine together to form a bigger one

• Fat or ice crystals present

• Viscosity of continuous phase is
decreased
• Emulsion is agitated
• Interfacial viscosity is decreased

• In the presence of promoters

- Non-polar oils
- Lower polar co-solvent

Ostwald Ripening The process by which components of the discontinuous phase diffuse from smaller to larger droplets
through the continuous phase.
 Forces between colloidal particles

• Interaction (attractive/repulsive) forces

• Two main interacting forces in affecting colloid systems:
(1) van der Waals attractive forces
(2) electrostatic repulsive forces.

• Attractive forces tend to destabilize colloids whereas repulsive forces generally impart stability.

Van der Waals forces

• Originates from the dipole-dipole interactions.

• The force between two droplets arising from van der Waals interactions
is always attractive for like droplets.
_ + _ +
• The attractive force increases more and more rapidly as the droplets
approach F

Electrostatic repulsive forces

The force between two droplets arising from intrinsic bearing charges from surfactants

5
 Electrical Double Layer & Zeta Potential

Oppositely charged ions (counterions) are

Slipping plane
preferentially attracted towards the surface, and ions
of the same charge (coions) tend to be repelled away. Stern layer

The combination of the charged surface & the Diffuse layer

unequal distribution of coions & counterions
near the surface is called the electrical double
layer.
The formation of a double layer is very important
for the stability of the colloid.

The double layer is sensitive to electrolytes and also Particle with negative Surface potential
temperature. Stern potential
surface charge
Zeta potential
This means that the stability of the colloid may be mV
manipulated by adding electrolytes or changing the
temperature.

0
Distance from particle surface
Electrical Double Layer & Zeta Potential

DLVO theory — named after four scientists:

Derjaguin, Landau, Verwey and Overbeek +
Repulsion potential
When two charged surfaces approach so that their
electrical double-layers begin to overlap, a
Secondary minimum
repulsive force is induced which tends to oppose Primary minimum
further approach. Total potential

Energy
DLVO theory suggests that electrical double-layer
repulsion will stabilize emulsion, when the
electrolyte concentration phase is less than a Attraction potential
certain value. (van der Waals)
DLVO theory relates the stability of emulsified
droplets to two independent potentials that come
_ Increasing interdroplet distance
into action when two droplets approach each other.
Electrical Double Layer & Zeta Potential

Zeta potential is the electrical potential at the 60

hydrodynamic plane of shear Stable

Zeta potential (mV)

40
Particles interact according to the magnitude of
the zeta potential, not their surface charge 20
Zeta potential tells us the effectiveness of the Isoelectric point
surface charge 0 Unstable
For electrostatically stabilized dispersions, the
-20
higher the value of zeta potential, the more
stable the dispersion is likely to be
-40
Stability dividing line is generally considered Stable
-60
to be ±30mV 2 4 6 8 10 12
Particles with zeta potential more positive than +30 pH
mV or more negative than -30 mV are formed a stable
dispersion.
1
6
 Improving emulsion stability

Emulsion stability – ability to resist changes in its physicochemical properties with time

• Charge stabilisation • Steric stabilisation

• Interfacial film strengthening • Continuous phase viscosity
• with powders • Droplet size
• Co-emulsifiers / polar waxes
• with polymers
• Liquid crystals
• with non-ionic emulsifiers
 Ionic (Electrostatic) Stabilization

+
The introduction of charged groups on the surface of
the emulsion droplets increases the repulsive forces. Addition of salt changes
salt added the distance distribution
Ionic emulsifiers will form an electrically charge
double layer in the aqueous solution surrounding No salt present of the repulsive potential
each oil droplet.

Energy
The thickness of the electrical double layer is
affected by ionic strength. As long as ionic strength is
low, electrical repulsion is > van de Waals attraction Attraction potential is not
 the droplets remain suspended.
affected
With ionic emulsifiers, low [salt] enhances
stability, while high [salt] concentration
increase flocculation and/or coalescence.
Increasing interdroplet distance
_

1
9
Emulsion Stabilization
Steric Stabilization

 Hydrocolloids such as xanthan gum, arabic gum, CMC, guar gum, etc., significantly
increase emulsion stability (function as stabilizers).

 The macromolecules act by either increasing the viscosity or partitioning into the o/w
interface as a physical barrier to coalescence

2
9
 Emulsion Stabilization
Steric Stabilization
• Interfacial film strengthening
• Reduces the probability of coalescence when
droplets collide

Interfacial film strengthening

• with powders • with polymers • with non-ionic emulsifiers

Tighter
packing at
interface

Pickering emulsion with powders PVAc stabilized emulsions

Powder particle size must be very small Interface strengthening is depended
Polymer sits at emulsion interface
Powder must have an affinity for both the on the number of molecules that are
Polar groups orient into the water phase
oil and water phase packed into the interface
 Improving emulsion stability

• Continuous phase viscosity • Co-emulsifiers / polar waxes

• Thickening the water phase restricts • e.g. Cetyl alcohol
movement of oil droplets + Co-emulsifiers have weaker surface activity than
• Thickeners with yield points are most primary emulsifiers
effective + Adds body and helps prevent coalescence

• Droplet size distribution

Increasing uniformity

Increasing stability

• Temperature
• Increase of temperature promote movement of
droplets and normally enhances flocculation and
coalescence
Micro/Nanoemulsion
Why Microemulsion?
S.
Property Emulsion Microemulsion
No
1. Appearance Cloudy Transparent (or translucent)
2. Optical Isotropy Anisotropic Isotropic
3. Interfacial tension High Ultra low

Dynamic (interface is continuously

4. Microstructure Static
and spontaneously fluctuating)

5. Droplet size > 500 nm 20-200 nm

Thermodynamically
Thermodynamically stable, long
6. Stability unstable (kinetically
shelf-life
stable)
7. Phases Biphasic Mono-phasic
Require a large input of relatively lower cost for commercial
8. Preparation
energy, higher cost production
Low viscosity with Newtonian
9. Viscosity Higher viscosity
behavior
Components of Micro-emulsion - Formulation

1. Oil Phase
• The oil component influences curvature by its
ability to penetrate
Oil phase
Aqueous • Swell the tail group region of the surfactant monolayer
phase
2. Surfactant
Surfactant
+ Low HLB High HLB (>12) HLB> 20
cosurfactant

• w/o micro emulsion • o/w micro • Oftern required co-

surfactant
• Alcohols
emulsion

• Surfactants should lower the surface tension to a very small value to aid in dispersion
Micro emulsion
• Surfactants must provide flexible film that can readily form around the small droplets

• Surfactants should have appropriate curvature to form a correct curvature on interfacial

region
Components of Micro-emulsion - Formulation

Oil phase 3. Cosurfactant

Aqueous
phase • single-chain surfactants alone are unable to reduce the o/w interfacial tension
sufficiently

Surfactant
+
• Cosurfactants allows the interfacial film sufficient flexibility
cosurfactant

• Helps to take up different curvatures required to form microemulsion

• Short to medium chain length alcohols (C3-C8) are commonly added

to reduce it further
Micro emulsion

16
W/O micro-emulsions
• During preparation firstly Reverse
micelles forms, to minimise S. free
energy
• They are dynamic i.e. micelles frequently
collide via random Brownian motion
O/W micro-emulsions
• The charged head group of the
microemulsion droplets is the driving force
for producing O/W micro-emulsion
• This also increases Temperature stability
• can be used as carriers for a wide
number of organic compounds
26
Bi-continous micro-emulsions

• Water and oil both are continuous phases; Amount also comparable
• It is like sponge
• Encountered in microemulsions, in mesophases, and even in relatively dilute surfactant solutions
• Indicated by the average mean curvature zero
• May also exist as hexagonal liquid crystal structure

Malik M.A. et al, Arabian Journal of Chemistry (2012) 5, 397–417 28

Preparation of Microemulsions/nanoemulsion

1. High pressure homogenization

• High pressure homogenization technique was initially used for the production of solid lipid
nanodispersions.

• This technique makes use of high pressure homogenizer/piston homogenizer to produce nanoscale
emulsions of extremely low particle size (up to 1nm).

• There are two methods in high pressure homogenization, i.e. hot homogenization and cold
homogenization.

• Higher stirring rates did not significantly change the particle size, but slightly improved the
polydispersity index.

32
 Preparation of Microemulsions/nanoemulsion

1. High pressure homogenization

• This technique makes use

of high-pressure
homogenizer/piston
homogenizer to produce
NEs of extremely low
particle size (up to 1nm)

33
Preparation of Microemulsions/nanoemulsion

2. Micro fluidization is a patented mixing technology, which makes use of a device called micro fluidizer.

• This device uses a high-pressure positive displacement pump (500-20000 psi per square inch),
which forces the product through the interaction chamber, which consists of small channels called
“micro-channels”.

• The product flows through the micro-channels which resulting in very fine particles of sub-Micron
range.

• The product flows through the micro channels on to an impingement area resulting in very fine
particles of submicron range. The two solutions (aq. Phase and oily phase) are combined together
and processed to obtain a stable nanoemulsion.

34
Preparation of Microemulsions/nanoemulsion
Micro fluidization
• The two solutions (aqueous phase and oily phase) are combination together and processed in an inline
homogenizer to yield a coarse emulsion.
• The coarse emulsion is into a micro fluidizer where it is further processed to obtain a stable nanoemulsion.
• The coarse emulsion is passed through the interaction chamber of the micro fluidizer repeatedly until desired
particle size is obtained.
• The bulk emulsion is then filtered through a filter under nitrogen to remove large droplets resulting in a uniform
nanoemulsion .

35
Preparation of Microemulsions/nanoemulsion
3. Phase inversion temperature technique:
The method employs temperature-dependent solubility of nonionic surfactants, such as
polyethoxylated surfactants, to modify their affinities for water and oil as a function of the
temperature.

It involves 2 steps: An example

• STEP 1 result in the formation of a suitable system. This procedure consists of magnetic stirring
of all the components-the ternary system- prepared in suitable proportions of salt water (salt and
water), non-ionic surfactant and oil, with a rise from room temperature to 85 oC at a rate of 4
oC/minute.

• A progressive cooling from 85 oC to 60 oC at a rate of 4 oC/minute is performed.

• Three temperature cycles (85-60-85-60-85 o c) are applied to reach the inversion process.
• STEP 2 is an irreversible shock induced by dilution with cold water to the mixture maintained at
the previously at a defined temperature.
• This fast cooling dilution process with cold distilled water leads to nano objects. Afterwards, a
slow magnetic stirring is applied to the suspension for 5 minutes.
36
 Preparation of Microemulsions/nanoemulsion

3. Phase inversion temperature technique:

Characterization of micro/nanoemulsion
• Phase Behavior Study
This study is necessary in characterization and optimization of ingredients. This is used in case of NE
formulation prepared by phase inversion temperature method and self-emulsification method.
• Particle Size Analysis
Generally Dynamic Light Scattering(DLS) method are used.
• Surface Charge Measurement
Surface zeta potential of NE droplets should be measured with the help of mini electrode to predict the
surface properties of NEs.
• Viscosity
Viscosity should be measured to ensure the better delivery of the formulation.
• Morphology & structure
Morphology and structure of nanoemulsion can be studied using TEM or FESEM
.38
Characterization of micro/nanoemulsion

Phase diagram of microemulsion

Formation of microemulsion can be predicted using ratio of ingredients

Characterization of micro/nanoemulsion
Electron microscopy

TEM
• Cryo-TEM commonly used
• It also detects spongy phase of bi-continuous micro- emulsion
• Bicontinuous microemulsion phases are seen to have characteristic zig-zag channel like complex structures
• In Water-in-oil/microemulsion systems, small droplets are seen on a continuous background
Characterization of micro/nanoemulsion
Electron microscopy
SEM
• Field emission SEM (FESEM) is used specifically
• Resulting in improved spatial resolution
• Minimized sample charging and damage
• Cryo-FESEM also used for better surface morphology
• Technique can be used differentiate bicontinuous from droplet type micro-emulsions
Characterization of micro/nanoemulsion
Scattering techniques
• Scattering techniques involving X-rays, neutrons and light
• used to obtain quantitative information on size, shape and morphology of microemulsions
• The basic principle of these techniques involves applying an incident beam of radiation to the
sample, and recording the intensity and angle of the scattered beam

• DLS- Dynamic light scattering (DLS), also known as photon correlation spectroscopy, can be
used to analyse microemulsion droplet size via determination of hydrodynamic radius

Acharya D. P. et al, Current Opinion in Colloid & Interface Science 17 (2012) 274–280
Characterization of micro/nanoemulsion
Scattering techniques
• SAXS- Application of SAXS in determining shape and size of microemulsion droplets relies on the difference
in the ability of oil and water phases to scatter x-rays
• This property has been commonly used to estimate the radius of a confined phase in O/W or W/O
microemulsions
• SANS- In small-angle neutron scattering (SANS), neutrons from a reactor source are scattered by the atomic
nuclei of the sample. Different nuclei or even different isotopes of the same element have different abilities
to scatter neutrons, expressed as their characteristic scattering length density (SLD)

Acharya D. P. et al, Current Opinion in Colloid & Interface Science 17 (2012) 274–280
Characterization of micro/nanoemulsion
Spectroscopic techniques

• Chemiluminescence techniques have also been employed to study transitions between polar and non-polar
environments inmicroemulsion systems

• Fluorescence correlation spectroscopy (FCS) is an excellent tool for measuring molecular diffusion and size under
extremely dilute conditions

• Fourier transform Infrared (FTIR) spectroscopy has been used to distinguish between the local environments of water
molecules confined in the core of reverse microemulsions because of its high sensitivity to interactions between
water molecules

• Ultrafast IR spectroscopy techniques have also been employed to study the hydrogen bonding network and dynamics
of water molecules in reverse micelles/microemulsions

• Dielectric spectroscopy is another spectroscopic technique which can provide information about the
morphology of microemulsions and dynamics of different polar groups and aggregates by measuring the variation of
conductivity and dielectric constant

46
Micro/Nanoemulsions - Applications

 Agriculture

 Cleaning products

 Cosmetic

 Pharmaceutic

 Biomedical
Applications of nano-emulsions
 The compositional flexibility of nanoemulsions offers a wide range of applications.

 The incorporation of fluorescent dyes and other molecules into nanoemulsions makes the interesting
probes for exploring properties of living cells and for drug delivery.

 Nanoemulsion vaccine could inactivate and kill the virus and then subsequently induce immunity to the
virus that includes cellular immunity, antibody immunity and mucosal immunity.

 The deformable and liquid nature of the droplets may lead to discoveries of new pathways for cellular
uptake and dispersal. Both oil-soluble and water-soluble drug molecules can be incorporated into the
nanodroplets of direct and inverse nanoemulsions for potential pharmaceutical uses.

 In the printing and data storage industries, one may imagine the resolution of droplets.

46
Applications of nano-emulsions
 In the personal care and food industries, nanoemulsions may provide interesting alternatives as
pleasantly transparent and soft solids that possess plastic-like rheological properties. While being
appealing from an optical and rheological point of view, nanoemulsion also can deliver moisturizers to
the skin quite efficiently and also block ultraviolet light without leaving a white residue.
 The small size of the nano droplets will likely increase transport efficiency of any active drugs or other
molecules inside the droplets across biological membranes, including the skin. Thus, nanoemulsions may
have significant applications in medical patches.
 High-throughput production methodologies make nanoemulsions a realistic commercial-scale alternative
for diverse areas, including lotions and pharmaceuticals.

47
 Micro/Nanoemulsions in synthesis of nanoparticles

Microemulsion containing reactant A

 Metallic nanomaterials Collision and coalescence of droplets

 Oxide nanomaterials

 Inorganic compounds Chemical reaction occurs

 Inorganic composites Microemulsion containing reactant B

 Organic ＆ inorganic composites

Add reducing agent
 Polymer nanomaterials (reactant B)

Microemulsion containing reactant A Chemical reaction occurs

Micro/Nanoemulsions in synthesis of nanoparticles procedures
Micro/Nanoemulsions in synthesis of nanoparticles

Synthesis Pd, Au, Au/Pd nanoparticles using

AOT/isooctane microemulsion

Ming-Li Wu, Langmuir, 2001, 17, 3877-3883

Micro/Nanoemulsions in synthesis of nanoparticles procedures
Preparation of Monodisperse GeO2 Nanocubes in a Reverse Micelle System

GeCl4, heptane (or octane), CTAB

Fig. (a) TEM image of a single GeO2 cube. (b) SAED pattern of the particle in a; (c) illustration of the cubelike
shape of the single crystal in a; (d) and (e) SEM images at different magnifications. Scale bar in e is 500 nm.

H. P. Wu. et al., Chem. Mater. 2006, 18, 1817-1820

Micro/Nanoemulsions in synthesis of nanoparticles procedures

Synthesis Rh/SiO2 nanoparticles

polyoxyethylene (15) cetyl ether (C-15), cyclohexane and water.(tetraethylorthosilicate, TEOS)

Fig. TEM photographs of SiO2-coated Rh nanoparticles

prepared with hydrolysis times of (a) 1, (b) 5 and (c) 30 minutes.

T. Tago, Journal of Materials Science, 37, 2002, 977– 982

Micro/Nanoemulsions in synthesis of nanoparticles procedures

Synthesis of spherical polymers

 Advantages of Microemulsion Technique

• Metal particles are reduced directly in microemulsion and can be used as a

catalyst in suspension without further thermal treatment.
• A narrow particle size distribution can be obtained.
• The particle size can be controlled to a great extent.
• Bimetallic particles can be obtained at room temperature.
• No effect of the support on the formation of the particles.

 Disadvantages of Microemulsion Technique

• Amount of catalyst prepared from a single microemulsion.

• Recovery and recycling of the liquid phase.
 University of Science and Technology of Hanoi
Department of Fundamental and Applied Sciences

PROPERTIES AND APPLICATIONS RELATED

TO SURFACTANTS
Dr. Nguyen Duc Anh
Department of Fundamental and Applied Sciences (FAS)
nguyen-duc.anh@usth.edu.vn
0904888819

September 2019
Wetting

Wetting is the ability of a liquid to maintain contact

with a solid surface, resulting from intermolecular
interactions when the two are brought together.
The degree of wetting is determined by a force
balance between adhesive and cohesive forces.

Adhesive forces between a liquid and solid cause

a liquid drop to spread across the surface.

Cohesive forces within the liquid cause the drop

to ball up and avoid contact with the surface.

Three types of wetting have been distinguished

(1) spreading wetting, (2) adhesional wetting, and (3) immersional wetting.
Spreading wetting

Spreading wetting: a liquid in contact with a substrate spreads over

the substrate and displaces another fluid, such as air, from the
surface.

The spreading to occur spontaneously, the surface free energy of the

system must decrease during the spreading process.

Spreading coefficient SL/S measure of the driving force behind

the spreading process.

SL/S = S/A – (S/L + L/A)

SL/S > 0: spreading can occur spontaneously;
SL/S < 0, the liquid will not spread spontaneously
The Contact Angle

The angle θ that the liquid makes when it is at

equilibrium with the other phases in contact with it
is related to the interfacial free energies per unit
area of those phases.

At equilibrium,
 the free energy change of surface equals to 0

S/A + S/L + L/A = 0


 Measurement of the Contact Angle
Contact angles are measured on macroscopic, smooth, nonporous, planar substrates by merely placing a droplet of
the liquid or solution on the substrate and determining the contact angle by any of a number of techniques
Measurement of the Contact Angle

Troubles ?

1. Contamination of the droplet by adsorption of impurities

from the gas phase
2. A solid surface, even when apparently smooth, may have
impurities and defects that vary from place to place on the
surface and from sample to sample.
3. The contact angle may show hysteresis even when the
surface is clean and the substrate is pure.
+ A change in orientation of the surface molecules
+ Low receding angles are penetration of the wetting liquid
into the substrate
+ Removal of an adsorbed surface film from the substrate
by the wetting liquid
 Adhesional wetting

The ability of the liquid to wet the solid will be dependent on its ability to ‘stick’ to the solid. In adhesional wetting,
a liquid not originally in contact with a substrate makes contact with that substrate and adheres to it

liquid droplets
The change in surface free energy:  la
−ΔGW = a(γSA + γLA − γSL),

 sl
Work of adhesion, Wa, the reversible
work required to separate the unit
area of liquid from the substrate Solid Surface
droplets adhering
to solid surface

The reduction of the interfacial tension between substrate and the wetting liquid results in an increased tendency for adhesion to occur
The reduction of either the surface tension of the liquid or the surface tension of the substrate decreases the tendency of adhesion to occur.
Adhesional wetting

The work of self-adhesion of a liquid is known as the work of cohesion, the work required to produce two unit
areas of interface from an original unbroken column of the liquid or the (−ΔGW)/a when the two columns are
joined
Wc = 2γLA

The difference between the work of adhesion of the

liquid for the substrate and its work of cohesion equals
the spreading coefficient SL/S

If Wa > Wc, the spreading coefficient is positive, the liquid spreads spontaneously over the substrate to form a thin film.
If Wa < Wc, the spreading coefficient is negative, the liquid does not spread over the substrate but forms droplets or lenses with
a finite contact angle
If Wa = Wc ??
Immersional wetting

• Immerse a solid substance in a pure liquid or
solution
• area of the solid-air interface decreases
• interfacial contact between solid and liquid is
increased
• Work required to immerse the solid in the
liquid
• Examine the difference ion the solid-air
‘surface tension’ and the solid-liquid
interfacial tension

Wi =
solid particle
 sa
If sa > sl, spontaneous wetting
If sa < sl, work must be done to wet the surface
Water immersed
 sl solid particle
 MODIFICATION OF WETTING BY SURFACTANTS

The addition of a surface-active agent to water, to modify the interfacial tensions of the system, is
therefore often necessary to enable water to wet a solid or liquid surface.

For water to wet a substrate spontaneously, the

spreading coefficient must be positive

The addition of a surface-active agent to the water, by

reducing the surface tension of the water γLA and
perhaps also the interfacial tension between the water
and the substrate γSL, may cause the spreading
coefficient to have a positive value and make spreading
or immersion spontaneous
Why ?

https://www.youtube.com/watch?v=KGBGqG7mGdc
SOLUBILIZATION IN THE PRESENCE OF SURFACTANTS
 Solubilization
Solubilization may be defined as the spontaneous dissolving of a substance (solid, liquid, or gas) by
reversible interaction with the micelles of a surfactant in a solvent to form a thermodynamically stable
isotropic solution with reduced thermodynamic activity of the solubilized material.

Solubilization is in term of
micellization and emulsification

The ingredience that enhances

solubilization of insoluble
materials is called solubilizers
Why we need solubilizers

Solubilization into aqueous media is of major practical importance in such areas as the formulation of
products containing water-insoluble ingredients

Purposes:
- Replace the use of organic solvents or cosolvents in
detergency, removal of oily soil; emulsion polymerization
…
 SOLUBILIZATION IN AQUEOUS MEDIA

Locus of Solubilization
The exact location in the micelle at which solubilization occurs (i.e., the locus of solubilization) varies with the
nature of the material solubilized and is of importance in that it reflects the type of interaction occurring between
surfactant and solubilizate.

Solubilization at a number of different sites in the

micelle
(1) on the surface of the micelle, at the micelle–
solvent interface;
(2) between the hydrophilic head groups (e.g., in
polyoxyethylene [POE] materials);
(3) in the so-called palisade layer of the micelle
between the hydrophilic groups and the first few
carbon atoms of the hydrophobic groups that
comprise the outer core of the micellar interior;
(4) more deeply in the palisade layer
(5) in the inner core of the micelle
Factors Determining the Extent of Solubilization

The solubilization capacity or solubilizing power: The number of moles of solubilizate per mole of micellized
surfactant
SW is the molar solubility of the solubilizate in the aqueous
system
(SW − SCMC) SCMC its molar solubility at the CMC
Solubilization capacity =
(Csurf − CMC) Csurf the molar concentration of the surfactant

• Solubilization capacity is greater for polar

solubilizates than for nonpolar one
• Solubilization capacity decreases with increase
in the molar volume of the solubilizate.
• The promotion of micellization increases
solubilization capacity
Factors Determining the Extent of Solubilization
1. Structure of the Surfactant
• For hydrocarbon and long chain compounds, any
factor that causes an increase in either the diameter
of the micelle or its aggregation number can be
expected to produce an increase in the solubilization
capacity
• Nonionic surfactants, because of their lower critical
micelle concentrations, are better solubilizing agents
than ionics in very dilute solutions.
• The order of solubilizing power: nonionics > cationics
> anionics for surfactants with the same hydrophobic
chain length
• For polar molecules: Almost no generalization of
solubilization power since the solubilization can
occur on both outer and inner parts of micelles.
2. Structure of the Solubilizate
• Crystalline solids generally show less solubility in
micelles than do liquids of similar structure
• Generally, the extent of solubilization appears to
decrease with increase in the chain length and to
increase with unsaturation or cyclization
• Branched-chain compounds appear to have
approximately the same solubility as their normal
chain isomers.
• For polar solubilizates, the situation is complicated
by the possibility of variation in the depth of
penetration into the micelle as the structure of the
solubilizate is changed.
 Factors Determining the Extent of Solubilization
3. Effect of Electrolyte
• The addition of small amounts of neutral electrolyte to
solutions of ionic surfactants appears to increase the
extent of solubilization of hydrocarbons that are
solubilized in the inner core of the micelle and to
decrease that of polar compounds that are solubilized
in the outer portion of the palisade layer
• The effect of electrolyte addition on the solubilization
of polar materials is not clear.
4. Effect of Monomeric Organic Additives
• The presence of solubilized hydrocarbon in the
surfactant micelles generally increases the solubility of
compounds in these micelles.
• The solubilization small polar material as long-chain
alcohols, amines, mercaptans, and fatty acids into the
micelles of a surfactant appears to increase their
solubilization of hydrocarbons
•
5. Effect of Polymeric Organic Additives
• Solubilized macromolecular compounds, such as
polymers, tend to adsorb surfactant molecules, then
reduce CMC and improve solubilization capacity of
both polar and non-polar compounds
Factors Determining the Extent of Solubilization

6. Effect of Temperature 7. Hydrotropy

• For ionic surfactants, an increase in temperature • Some strong interaction surfactants tend to form
generally results in an increase in the extent of solid insoluble crystals or liquid crystal formation
solubilization for both polar and nonpolar then reduce the solubility of solutes. The reduction
solubilizates of liquid crystal formation by adding of certain
• For nonionic surfactants: nonsurfactant organic additives is hydrotropy.
+ Solubilization of non-polar compounds normally • The non-surfactants additives are called
increase with temperature. hydrotropes.
+ For polar compounds: Solubilization firstly increases • Hydrotropes contains hydrophilic and short, cyclic
until cloud points then decreases. or branch hydrophobic groups.
• Use of hydrotrope with short hydrophobic group
promote the formation of spherical micellar
structure rather than liquid crystal formation.
• Typical hydrotropes include sodium benzene-,
toluene-, xylene-, cumene-, and p-
cymenesulfonates, 1-hydroxy-2-naphthoate,
2-hydroxy-1-naphthalenesulfonate, and sodium 2-
ethylhexyl sulfate
DISPERSION AND AGGREGATION OF SUSPENSIONS
Dispersion systems

Mayonaise Paints
Suspensions

A suspension: is a disperse system in which one substance (the disperse phase) is distributed in particulate form
throughout another (the continuous phase) (i.e. at least 2 phases).

According to the particle size of the

dispersed phase, suspensions are
divided into:

Coarse suspension: which is a

dispersion of particles with a mean
diameter greater than 0.5 µm.
 Colloidal suspension: a dispersion
of particles with a mean diameter
less than 0.5 µm.
Suspensions applications

Most common in pharmacy ??

Against solid dosage forms:

• If patient has a difficulty of swallowing solid dosage
forms (a need for oral liquid dosage form).
• Faster rate of dissolution and oral absorption than solid
dosage forms, yet slower than solutions.
• Bulky insoluble powders as kaolin or chalk are better
formulated as suspensions so that they are easier to
take.
Against solutions:
• Drugs that have very low solubility are usefully
formulated as suspensions.
• Drugs that have an unpleasant taste in their soluble forms (e.g., chloramphenicol (soluble) vs. chloramphenicol palmitate
(insoluble )).
• Prolongation of effect (e.g. I.M and S.C. suspensions).
• Stability and instability issues:
Insoluble forms of drugs may prolong the action of a drug by preventing rapid degradation of the drug in the presence of water
Suspensions applications

Important in paints production ?

Quality paints rely on decent pigment dispersion in the
manufacturing process. Without proper dispersion of
pigments, the paint will not hold up and maintain the
expected colour standards. Pigments are insoluble particles
that impart colour to paint and other materials. Proper
pigment and additive selection are vital to ensure the
finished paint or coating effectively displays the required
colour.

Dispersed pigments have a strong tendency to return to their initial agglomerated state. Pigments must be properly
wetted, de-agglomerated/dispersed and uniformly distributed and stabilized in order to achieve maximum color
intensity, gloss, and hiding power. Stabilization of a pigment dispersion requires time and energy.
Suspensions stability and affected factors

Suspensions stability Suspension behaviours

One aspect of physical stability in suspensions is concerned with keeping 1. Sedimentation.

the particles uniformly distributed throughout the dispersion. + Brownian movements

2. Thermodynamic instability.
While it is seldom possible to prevent settling completely over a prolonged
+ Flocculation and aggregation
period of time, it is necessary to consider the factors which influence the
3. Wetting.
velocity of sedimentation.

Particle size of any suspension is critical.

Larger particles will settle faster at the bottom of the container.

The particle size can be reduced by using mortar and pastel, but very fine
particles will easily form hard cake at the bottom of the container.
Suspensions stability and affected factors

Sedimentation Theory of suspension: Sedimentation

Sedimentation is the process of allowing particles in The velocity of sedimentation is expressed by Stoke’s
suspension in water to settle out of the suspension under law.
the effect of gravity. The particles that settle out from the
suspension become sediment.

r = the radius of the particle in cm.

σ = the density of the dispersed phase (particles).
 = the density of the dispersed medium.
g = the acceleration due to gravity
n = the viscosity of the dispersion medium in poise.
Suspensions stability and affected factors
Sedimentation
For particles having a diameter of about 2- 5 m Brownian
movement counteracts sedimentation to a measurable extent
at room temperature by keeping the dispersed material in
random motion.
Ideal/Optimal suspensions
Ideally, the particles in a suspension should not
sediment at any time during the storage period.
The particles which settle to the bottom of the
container must not form a hard cake.
Should be easily re-dispersed by gentle shaking and
should have the desired flow (Easy to pour yet not
watery).
Must remain sufficiently homogeneous for at least
the period of time necessary.
Suspensions stability and affected factors

Flocculation and aggregation

Flocculation refers to the process by which fine particulates are caused to clump together into a floc

• The natural tendency of particles towards aggregation will

determine the properties of a suspension. Whether or not a
suspension is flocculated or deflocculated depends on the
relative magnitude of repulsive/attractive forces between
particles.
• Deflocculated suspension: the dispersed solid particles remain
separate and settle slowly. However, the sediment that
eventually forms is hard to re-disperse and is described as a
'cake' or clay.
• Flocculated suspension, individual particles aggregate into
clumps or floccules in suspension. Because these flocs are larger
than individual particles, sedimentation is more rapid, but the
sediment is loose and easily re-dispersible. Excess flocculation
may prevent 'pourability' due to its effect on rheological
properties.
Suspensions stability and affected factors
Wetting
Diffusible solids (dispersible solids): These are insoluble
solids that are light and easily wetted by water.
+ They mix readily with water, and stay dispersed long
enough for measurement.
+ After settling they redisperse easily.
+ Examples: magnesium trisilicate, light magnesium
carbonate, bismuth carbonate and light kaolin.
Indiffusible solids: Most insoluble solids are not easily
wetted, and some particles may form large porous clumps
in the liquid, whereas others may remain on the surface.
+ These solids will not remain evenly distributed in the
vehicle long enough measurement.
+ They may not re-disperse easily.
+ Examples: aspirin, phenobarbital, calamine containing
zinc oxide, sulfadinidine and chalk, hydrocortisone…
 Role of the Surfactant in the Dispersion Process

Wetting of the Powder – Wetting agents

 It is difficult to disperse solid particles in a liquid vehicle

due to the layer of adsorbed air on the surface.

 Thus, the particles, even high density, float on the

surface of the liquid until the layer of air is displaced
completely.

 The use of wetting agent allows to remove this air from

the surface and to easy penetration of the vehicle into
the pores.

 Powders, which are not easily wetted by water and accordingly show a large contact angle, such as sulfur, charcoal
and magnesium stearate are called hydrophobic.

 Powders which are readily wetted by water are called hydrophilic e.g. zinc oxide, talc.

 The wettability of a powder may be ascertained easily by observing the contact angle and spreading coefficient.
Suspending agents

• Suspending agents increase the viscosity of the vehicle so-called thickening agents, thereby slowing
down sedimentation. Most agents can form thixotropic gels which are semisolid on standing, but flow
readily after shaking.

Natural gums (acacia, tragacanth, Xanthan gum ),

Sugars (glucose, fructose) Co-solvents
Some solvents which themselves have high viscosity are
Cellulose derivatives (sodium CMC, methyl
used as co-solvents to enhance the viscosity of dispersion
cellulose, MCC), medium: For example glycerol, propylene glycol, sorbitol.
Alginates & Gelatin  Glycerin viscosity is too high to pour easily and to
Clays (bentonite, veegum), spread on the skin.
 Carbomers,  It shows the undesirable property of stickiness.
Colloidal silicon dioxide (Aerosil)
 It is too hygroscopic to use in undiluted form.
 Suspending agents
• Should have a high viscosity at negligible shear, i.e., during
storage.
• Should have a low viscosity at high shearing rate, i.e., it
should be free flowing during agitation, pouring, and
spreading.
 A suspending agent which is thixotropic as well as pseudo-
plastic are useful since it forms a gel on standing and
becomes fluid when disturbed.
 Apart from above, suspending agents should also be inert,
non-toxic and compatible with other excipients used in
suspensions.
 They should be readily dissolved or dispersed in water
without need of special technique.
 They should not influence the absorption or dissolution
rate of the insoluble.
 Flocculating agents

Flocculating agents are added to enhance particle “re-dispersability”.

• In contrast to deflocculated particles, flocculated

suspensions can always be re-suspended with
gentle agitation.
• The best approach is to achieve a controlled
flocculation of the particles, where they appear as
floccules or like tufts of wool with a loose fibrous
structure.
• Controlled flocculation of particles is obtained by
adding flocculating agents, which are (1)-
electrolytes (2)- surfactants (3)- polymers
Flocculating agents

Electrolytes acts as flocculating agents by reducing

the electrical barrier between the particles, thus,

decrease the zeta potential, this leads to decrease

in repulsion potential and makes the particle come

together to form loosely arranged structure

 Flocculating agents

• Both ionic and non ionic surfactants could be used

to control flocculation, e.g. Tween 80, Sodium lauryl
sulfate.

• Optimum concentrations of surfactants bring down

the surface free energy by reducing the surface
tension between liquid medium and solid particles.

• The particles possessing less surface free energy are

attracted towards each other by van der-waals forces
and forms loose agglomerates.
Flocculating agents

 Polymers like Starch, alginates, cellulose

derivatives, carbomers, tragacanth are
long chain, high molecular weight
compounds containing active groups
spaced along their length.
 These agents act as flocculating agents
because part of the chain is adsorbed on
the particle surface with the remaining
parts projecting out in the dispersion
medium.
 Bridging between these portions leads to
the formation of floccules.
 Polymers exhibit pseudo-plastic flow in
solution promoting the physical stability
of suspension.
Preparation of Suspensions

• Reduce insoluble powder to desired size

• Add powder and wetting agent to solution
• Prepare solution of suspending agent
• Add other ingredients - electrolytes, color, flavor
• Homogenize medium
• Package
FOAMS
Applications: Governed by Bubble Size and Stability

FIRE FIGHTING FROTH

FLOTATION

SHAVING CREAM,
SHAMPOO

DETERGENTS STRAWBERRY &

CREAM
Foams
Agglomeration of gas bubbles separated from each other by thin liquid films.

A. Types of foams:
Based on the state of aggregation of the two phases.
(1) Gases dispersed in liquids-Foams, gas emulsion
(2) Liquids dispersed in gases-Fog, mist, aerosol
(3) Gases dispersed in solids-Solid foams
(4) Solids dispersed in gases-Smoke, fume
Structure of Foams

(i) For three bubbles (ii) Four bubbles

1200 Plateau’s border

Septum Or
Gibb’s triangle

A two dimensional foam consists of more or less

Septa to meet at 1200 for mechanical stability
uniform hexagonal type of network.
In three dimensional foams
- Three septums to meet at 1200
- Four septums to meet at the tetrahedral angle of
109028’
Foamability parameters

Foaming efficiency
Measure of (ease of) production of foam

Foaming effectiveness
Measure of stability of the foam produced

Ross-Miles Method:
200 ml solution in a pipette (2.9 mm ID) allowed to fill 90cm
onto 50 ml of same solution in a cylindrical vessel at 600C.

Stability determined by measuring the film height after certain

intervals of time.
https://www.youtube.com/watch?v=UryTtDYqvz8
 Foam Stability

In a foam, liquid from the lamellae region drains because of following factors.
(i) Liquid pressure at B < liquid pressure at A

Laplace equation:

Max curvature in the plateau border: Greater pressure across the interface in these regions
drainage of the liquid from the lamellae into the Plateau borders

(ii) Hydrostatic pressure

When lamella thickness reaches a critical thickness (50-100Å), the film collapses.
Film Elasticity

The ability to resist excessive LOCALIZED thinning of the lamellae.

Film elasticity is a necessary condition for the production of foams. It is not a sufficient condition for formation of a
stable foam.

Theories of Film Elasticity

Local increase in surface tension with extension of the film.

1 1
2
2 >  1 Restoring force = 2-1

Gibbs effect: the change in surface tension with change in concentration of the surface-active solute; Explains
it on the basis of equilibrium value of .

Marangoni effect: the change in surface tension with time; Explains the increase in the restoring force on the
basis of the instantaneous value of .
 Factors Determining the Foam Stability

1. Drainage of liquid in the lamellae

Drainage by gravity (thick lamellae)
Bulk viscosity is a major factor.
It can be increased by,
(a) adding thickeners
(b) orienting surface molecules
Drainage by Surface tension (thin lamellae)

Greater the difference between R1 & R2(bubble size) and the greater the surface tension , greater
the pressure difference causing drainage.
Factors Determining the Foam Stability
2. Diffusion of gas through the Lamellae

The rate of diffusion q, of a gas, between two bubbles of radii R1 and R2 is given by,
q = - J A P
J = permeability of diffusion path
A = effective area through which diffusion occurs
P = difference in gas pressure of the two bubbles
 P =  (1/RA + 1/RB), and P  2  / R

Larger bubbles tend to grow. As curvature  , drainage 

Transfer of gas between bubbles takes place through aqueous pores between the surfactant molecules in the surface
films of the lamellae.

Closer packing should reduce gas diffusion. Resistance to gas diffusion , when -CH2-  or molecular mass of the polar
head .
Factors Determining the Foam Stability

3. Thickness of the Electrical Double Layer

A film of liquid composed of two charged monolayers may resist
- - - - - - - - - - - -
further thinning by: + +++ + ++ ++ + + +++
(a) repulsion between the approaching charged surfaces - - - - - - - - - - - -
(b) high osmotic pressure (due to counter ion concentration)

4. Surface viscosity

High surface and bulk viscosity can

(a) Reduce the drainage rate.
(b) Provide cushion against mechanical, thermal
or chemical shocks.
(c) Slow down self healing by surface transport mechanism.
Relationship of Surfactant Structure to Foaming
Efficiency of foamers

+ The lower the CMC surfactants, the more efficient the surfactant as a foamer

+ Ionic surfactants more effective than nonionics in aqueous media.(due to larger surface area/molecule and the
absence of highly charged surface in the nonionics.)

Effectiveness of foamers

(i) Its effectiveness in reducing the surface tension. The lower the surface tension of the aqueous solution, the
greater appears to be the volume of foam of the same average bubble size produced by a given amount of
work under the same foaming conditions.

(ii) On the magnitude of its intermolecular cohesive forces. Requirement of an interfacial film with sufficient
cohesion to impart elasticity and mechanical strength to the liquid lamellae enclosing the gas in the foam.

+ Longer hydrophobic chains  better cohesion force; shorter chains  high crystallinity surfactants layer and
reduce elasticity.
 Foam Stabilizers

• Additives that decrease the rate of attainment of surface tension equilibrium (e.g. by lowering the CMC)
• Additives that produce a closer-packed, more coherent film of high surface viscosity

Examples: long chain, often water insoluble, polar compounds with straight chain hydrocarbon groups of about the
same length as that of the surfactant.
(i) Lauryl alcohol with sodium dodecyl sulfate
(ii) Lauryl acid with potassium laurate
(iii) N,N-bis(hydroxyethyl) lauramide with dodecyl benzene sulphonate
Antifoaming Agents
Foam Breakers- destroy existing foam by:
(i) Reducing the surface tension locally (e.g. ethyl ether γ =17 mN/m)
(ii) Promoting drainage of the liquid from foam (tributyl phosphate reduces surface viscosity)

Foam Inhibitors- prevent the formation of foam by eliminating surface elasticity

(i) By swamping the surface with non foaming rapidly diffusing, non cohesive, and only moderately surface active
molecules (ethylene oxide-propylene oxide block copolymer)
(ii) By replacing the elastic surface film with a brittle, close-packed surface film. (calcium stearate or palmitate with
the foam of sodium dodecyl benzene-sulphonate or sodium lauryl sulfate.
DETERGENCY OF SURFACTANTS
Detergency
• Detergency means removal of dirt from surface

• Detergency requires the largest use of surfactants

• The dirt also-called soil (liquid soil, solid soil); the surface that
soil needed to be removed is substrates; the solution used to
remove soil is bath.

• Mechanism of detergency operation is still non-clear since

cleaning process is a very complex process;

• No surfactants by self can clean a surface;

• Detergency– this term, when applied to a surfactants, means

the special property it has of enhancing the cleaning power of
a liquid.
Detergency

Detergency – a combination of
effects involving adsorption at
interface, alteration of interfacial
tension, solubilization, emulsification,
and the formation and dissipation of
surface charges;
Detergency – involving mechanical
action, biochemical action, and fabric
softening.
The cleaning process
1. Three elements in cleaning process
(1) The substrate (the surface that is to be
cleaned)
 Hard surface – glass , metals, and etc
 Soft surface – fabric , fiber

(2) The soil (the material that is to be removed

from the substrate in the cleaning process)
 Liquid soils – oil or fat
 Solid soils – black carbon, dust, and etc

(3) The bath or cleaning solution.

 The cleaning process
2. Force between substrates and soils
(1) Mechanical force – soft & porous substrates,
+ particle diameter
- r of the particles , then force
- r < 100nm, then difficult to wash off Soil
(2) Electrostatic force – surface potential -----
wool/water= - 48mV ++++
cotton/water= - 38mV
----------------
silk/water= - 1mV
cation bridge - polyvalency ions
(3) Chemical force – polar soils proteins , fats , oxides etc
Hydrogen bond and electrovalent bond
(4) Van Der Waals force
The cleaning process

Two partial cleaning processes:

 removal of the soil from the substrates
 suspension of the soil in the bath and
prevention of its redeposition

Removal of the soil from the substrates

It not cover the removal of soil by mechanical work, or chemical reagents (e.g. bleaches, reducing agents)
or enzymes

The cleaning process involves:

1. Adsorption at the interfaces 4. Solubilization

2. Alteration of surface tension 5. Emulsification
3. Micellization 6. Formation and dissipation of surface charges
 (1) Removal of liquid soil – roll-up mechanism

The work of adhesion of the liquid soil for the substrate

The contact angle

Cos ,   roll-up or cleaning process
Cos ,   spreading or more adhesive process
(1) Removal of liquid soil – roll-up mechanism

Without surfactants (Initial state) With surfactant  reduction of SB and OB
 We need cos decrease to increase .
>0  Surfactants should adsorb on SB interface more than
 < 90o
OB interface
 If SB < SO  cos < 0   > 90o ; the contact area of
S and O decrease  roll up.
Two kinds of roll-up

 Complete removal

•  = 180°
Complete removal of oil droplets from
Spontaneously roll-up
substrate
e.g. anionics: only S/B,O/B

• 90o <  < 180°

The soil will not be displaced spontaneously but can

be removed by hydraulic currents in the bath
e.g. nonionics: S/B, O/B, S/O

 Incomplete removal Rupture and incomplete removal of large

oil droplets from substrate
SO < SB , Cos  > 0;  < 90°
https://www.youtube.com/watch?v=yOYYIhCiKOQ&t=1s
Removal of solid soil
Mechanism
(a) Liquefiable soil – roll-up
The solid soil that can be liquefacted then remove by roll-up process. It is similar to removal of liquid soil
with increase of temperature.

b) Particulate soil: The solid soil that can not be liquefacted.

1. Wetting of the substrate and the soil particles by the bath
 Spreading coefficient
particles SB/P=PV- PB- BV > 0
substrates SB/S=SV- SB- BV > 0
2. Adsorption of Surfactant and Other Bath Components at the Substrate–Liquid and Particle–Liquid
Interfaces.
 Work of adhesion of particles and substrate: WSP= SB+ PB- SP > 0
 The presence of surfactant reduce SB PB and decrease work of adhesion.
 Non-ionic surfactants are not suitable since their adsorption does not significantly
increase its electrical potential at the Stern layer
Suspension of the soil in the bath and prevention of re-deposition
(1) Solid particulate soil: formation of electrical and steric barrier
(2) Liquid oily soil
(a) Solubilization – C > CMC
 Ionic surfactants C < CMC (only adsorption)
 Nonionic surfactants C > CMC (adsorption and solubilization)
(b) Macro-emulsification

Dry cleaning – hydrocarbon or chlorinated hydrocarbon

(1) Thickness of electrical double layer is very thin (very low dielectric constant)
– low electrical barrier
(2) Surfactants are probably adsorbed with polar head oriented toward the
substrate and soil – high steric barrier