REPORT ON

PHASE INVERSION TEMPERATURE

Synopsis
Oil-in-water emulsions stabilized with nonionic emulsifiers change to water-in-oil emulsions as
the temperature rises when the hydrophilic and lipophilic properties of the mixed emulsifier are
just balanced. Preparation above the phase inversion temperature followed by rapid cooling
yields emulsions that exhibit very fine droplet size and extreme long-term stability. Cosmetic
emulsions were prepared by this phase inversion temperature (PIT) method using typical raw
materials such as polar oils, e.g. decyl oleate, 2-octyl dodecanol or isopropyl myristate, and
nonionic emulsifiers, e.g. ceteareth-12 or polyoxyethylene eicosyl/docosyl ether combined with
cetostearyl alcohol as a co-emulsifier. The relationship between phase inversion temperature,
droplet size and emulsion stability was investigated. In addition, self-bodying agents such as
cetostearyl alcohol or monoglycerides were added to these thin, fine disperse emulsions to adjust
the consistency. The influence of these ingredients on phase inversion temperature, droplet size,
yield value and emulsion
stability was studied.

Abstract

A quantitative analysis is made of the phase changes during the phase inversion temperature (PIT)
emulsification process of an aqueous hexadecane emulsion stabilized by a tetra-ethylene glycol
dodecyl ether surfactant. The mechanical dispersion part of the process takes place at the PIT, at
which temperature the emulsion contains three phases: (1) water, with only minute fractions of
surfactant and hydrocarbon; (2) an inverse micellar solution, with modest fractions of solubilized
water; and (3) a bicontinuous microemulsion, with large concurrent solubilization of both water
and hydrocarbon. After the mechanical action at the PIT, the emulsion is immediately cooled to
temperatures beneath the PIT range, reducing the number of phases in the emulsion to two, an
oil/water (O/W) microemulsion with moderate surfactant and hydrocarbon content, and an inverse
micellar hydrocarbon solution with a significantly greater surfactant fraction. The emulsion is
characterized by its large fraction of extremely small oil drops, significantly smaller than expected
from the mechanical process. These drops are commonly assumed to emanate from the
hydrocarbon fraction of the original bicontinuous microemulsion, the small size of the oil drops
being a rational consequence of the colloidal dispersion prior to the phase separation. The
quantitative analysis of the phase fractions versus temperature revealed this assumption to be
premature. The original water phase is not the final aqueous phase in the emulsion; this phase is
instead formed from the microemulsion phase by absorbing the original water phase, gradually
modifying its own structure to become water-continuous with the originally large hydrocarbon
fraction reduced to modest levels. In the process, a part of the original microemulsion is separated,
forming the small oil drops.
The nanoemulsions prepared with the PIT method showed a good stability over time. For instance,
a fresh nanoemulsion made with 10 % (w / w) of soya bean oil in the continuous set-up displayed
an average droplet size of 21 nm. A month and a half later, this average size had increased only 5
nm. The average size and polydispersity index of the emulsions obtained using both techniques
were similar. The continuous device allowed the preparation of emulsions more rapidly and in a
more reproducible way than the batch set-up

The PIT method

The Phase Inversion Temperature (PIT) method was introduced by Shinoda et al. They used non-
ionic ethoxylated surfactants whose properties at the droplet interface are highly dependent on
temperature. These surfactants are subjected to the dehydration of the polyethyleneoxide chain
with increasing temperature . As a consequence, the surfactants get more lipophilic. Mixtures of
oil, water and surfactant are prepared at their Phase Inversion Temperature (PIT), also referred to
as hydrophilic-lipophilic balance (HLB) temperature, which is the temperature for which the
affinities of the surfactant for water and oil are balanced. Then, the solutions are quickly heated
or cooled in order to obtain water-in-oil (W / O) or oil-in-water (O / W) emulsions respectively
At low temperature, O / W macroemulsions can be formed and are quite stable as the surfactant
has more affinity with the aqueous phase. On increasing the temperature, the O / W emulsion
stability decreases and the macroemulsion finally resolves at the HLB temperature (both O / W
and W / O emulsions are unstable). In this temperature zone, the interfacial tension reaches a
minimum and the system crosses a point of zero spontaneous curvature. At higher temperature,
W / O emulsions become stable. By preparing the emulsion in the region of the PIT and
proceeding with rapid cooling (or heating), the system is subjected to a transitional inversion and
nanoemulsions may be produced (Figure 1.23). HLB temperatures can be measured with
conductimetry, by gradually increasing the temperature until a conductivity jump is produced.
They can also be determined by visual observation of phase separation . The PIT value depends
on the phase volume ratio, the nature of the oil, and the type of surfactant . If the surfactant is
monodistributed, then the PIT is independent of its concentration. Commercial surfactants
usually display a certain polydispersity in the number of ethylene oxide groups. Since the most
ethoxylated surfactants impose their behaviour 36 at the interface , the HLB temperature
increases with decrease in concentration of these commercial surfactants . This effect becomes
less important at high surfactant concentration. .
Generalized by the surfactant affinity difference (SAD) concept, the PIT method can be applied
using other parameters rather than the temperature. Salt concentration or pH value may be
considered as well. These latter techniques have some advantages over their thermal counterpart
since they do not require a temperature-sensitive surfactant and would not result in eventual
thermal degradation. However, these changes can often be applied in one direction only. One of
the main requirements for the formation of O / W nanoemulsions with the smallest droplet size is
to achieve a complete solubilization of the oil phase at the HLB temperature; if there is water in
excess, it acts as a dilution medium for the dispersed oil droplets and viceversa if the preparation
of small droplets of water in oil is desired. Temperature cycling around the PIT might also
improve the size of the nanoemulsion droplets because it increases the concentration of
amphiphiles that get trapped in the interfacial region. Another parameter to take into account for
the successful preparation of fine nanodroplets is the rate of cooling or heating. If the cooling or
heating process is not fast enough, coalescence predominates and polydispersed coarse
emulsions are formed . It was also shown that relatively stable O / W type emulsions are
obtained when the PIT of respective systems are about 20 to 65 °C higher than the storage
temperature. Finally, the stability of the nanoemulsions decreases with the increase in oil
solubility in the continuous phase, as it results in an increase in the oil diffusion rate and
therefore enhances Ostwald ripening.
Nanoemulsions with a droplet size in the range 50-130 nm have been obtained in the system
water / polyoxyethylene lauryl ether (abbreviated as C12E4 for the 12 C in the carbon chain and
an average of 4 mol of ethylene oxide per surfactant molecule) / hexadecane at 20 wt % oil
concentration and at concentration of surfactant higher than 3.5 wt % by the group of Izquierdo
et al. Morales’ team managed to prepare O / W nanoemulsions with droplet sizes as low as 40
nm in the system water / hexaethylene glycol monohexadecyl ether (C16E6) / mineral oil .

How to choose an emulsifier

Oil (O), Water (W) and Surfactant (S)

Tertiary systems W/S/O are very sensitive to variations in temperature because surfactants lose
their affinity for water with an increase in temperature, become insoluble in the aqueous phase
and tend to become dispersed into the oil phase. This change of the hydrophile lipophile
properties of the surfactant due to effects of temperature occurs in a gradual and continuous way.
It becomes clearly visible over the temperature interval in which the affinity of the emulsifier for
the water becomes balanced by its affinity for the oil. A phase inversion takes place over this
temperature interval. The emulsion which at lower temperatures is an oil in water type becomes a
water in oil type when this particular temperature is exceeded.

The phase inversion temperature (PIT) can be considered as a typical parameter of the W/S/O
tertiary system and because it is influenced both by the type of surfactant and by the type of oil
phase used it proves to be useful for interpreting the behavior of emulsions. Phase inversion can
be produced by modifying some physical variables or the composition of a W/O/S system.
Normally the parameters that influence the transition from W/O to O/W in a W/Nonionic S/O are
an increase in salinity, the molecular weight of the hydrophobic part, the branched structure of
the hydrophobic portion, the decrease in temperature, the atomic number of carbons in the
hydrocarbon oil, the EO number, the polarity and the HLB value of the surfactant or, also,
adding a long chain alcohol.

T
he path of a typical phase inversion temperature curve varying with the water/oil fraction is
illustrated in the graph foregoing.
On the same scale, are the curves of the O/W clouding temperature (a), the W/O clouding
temperature (b), the O/W limpidity temperature (c) and the W/O limpidity temperature (d). The
oil/(oil + water) ratio is expressed as a weight.

The system used is water/cyclohexane/nonylphenol 9.6 EO and the concentration of the

surfactant is equal to 5%. At temperatures below the PIT curve the emulsifier shows hydrophile
characteristics and the dispersions that form are the oil in water type. On increasing the
temperature, the emulsifier loses its solubility in water and becomes more lipophilic. Due to this
increase in affinity for the oil there is a phase inversion and above the PIT the oil constitutes the
external phase. Over a wide range of water/oil ratios it is the emulsifier, which on the basis of its
preferential affinity one of the two phases, determines which will be the external phase. At the
extremes a large excess of one of the two components (the water on the left and the oil on the
right) produces a barrier to inversion.
The predominant component being unable to disperse continues to act as the dispersing part,
even if the other factors, not least the HLB value, would favor inversion. In this case the
temperature has little effect on the phase inversion. The effect of increasing the temperature in a
solution of nonionic surfactant is equivalent to shortening the ethylene oxide chain.
For example, an ethoxylated alcohol which has an ethylene oxide percentage equal to 50%
possesses a HLB value=10 (as described before, the HLB of a non ionic emulsifier is empirically
calculated by dividing by 5 the percentage of the whole surfactant which is hydrophilic and
therefore 50/5=10). This type of surfactant shows an affinity for water comparable to that for oil,
therefore, it can be stated that its hydrophilic properties balance its lipophilic ones. Shortening
the oxyethylene chain or lengthening the hydrophobic part produces a loss of balance of the ratio
of the two portions of the surfactant with a consequent increase in affinity for the oil phase and a
reduction of the HLB number.
If on the other hand the ethylene oxide chain is lengthened or the length of the hydrophobic part
shortened, the resulting molecule has better hydrophilic properties and its HLB number
increases. In a water/oil/surfactant system an increase in temperature produces a decrease in
solubility of the surfactant in water. This is due to weakening of the forces of interaction between
the water molecules and the ethylene oxide groups present in the hydrophilic portion of the
surfactant. The consequence is a progressive change of the 1 hydrophile – lipophile properties
which produces an increasing affinity for the oil. In other words, the increase in temperature is
equivalent to a reduction in the HLB number. In fact, an emulsifier with HLB=10 shows a
balance, at room temperature, of the hydrophilic and lipophilic properties. This is proven by the
fact that for W/O/S systems with homologous surfactant, those with an HLB number greater than
10 produce O/W emulsions, while those with HLB lower than 10 tend towards W/O emulsions.
Any emulsifier shows a hydrophile – lipophile balance at the phase inversion temperature (PIT)
so that at lower temperatures O/W are formed and at higher temperatures than the PIT W/O
emulsions form. An emulsifier that is hydrophilic (HLB>10) at room temperature therefore
balances its hydrophilic-lipophilic properties when the temperature is changed to coincide with
the PIT. In this case it behaves like an emulsifier of HLB=10 would at room temperature.
The hydrophilicity or the lipophilicity of a nonionic surfactant is a function of the temperature
and so is the balance between the hydrophilic and the lipophilic character (HLB). The HLB
number, however, is not dependent on the temperature because it is a function of the chemical
structure of the surfactant and not of the state of the system. The HLB changes continuously with
variation in temperature, gradually modifying the colloidal state of the emulsifier. At lower
temperatures, the greater hydrophilicity shown by the surfactant induces the formation of
spherical shaped micelles. These spherical shapes enable water to wedge itself more deeply into
the intermolecular spaces of the hydrophilic portion of the micelle. Increasing the temperature
produces a gradual decrease in the hydrophilicity which can be explained as a partial expulsion
of the water from the internal shell of the micelle. In this way the surfactant tends to aggregate
into more numerous formations and elongated micelles can form which allow a greater
solubilization of the oil in the hydrophobic part of the micelle. As the PIT is approached the
affinities for the oil and water are perfectly balanced.
The arrangement of the surfactant into lamellar structures show that there is no preference for
either of the two phases and both the oil and water find a position in the lamellar spaces. An
increase in temperature above the PIT value produces an increase in affinity for the oil that will
tend to wedge itself in the hydrophobic intermolecular spaces producing the formation of
reversed micelles with an elongated or circular form which exposes the lipophilic part of the
surfactant molecule towards the outside. The formation of elongated micelles enables a greater
solubilization. In fact in the preceding graph, it can be seen that the solubilization areas, that is
the zones embraced by the O/W clear point and the cloud point curves for the O/W part and by
the W/O clear point and haze point curves for the W/O part, tend to come near to the PIT curve
from top and bottom respectively and that there is maximum solubilized content in the vicinity of
the PIT.

Conclusion
Phase Inversion Temperature emulsification is a low-energy technique already widely used in
industry. It is an advantageous method since the only basic equipment required to prepare
nanoemulsions is a heat source. As a consequence, it should be relatively rapid to gather data
about the chosen system.