The Role of Interfacial Tension Measurement in the Oil Industry

Carole Moules, Camtel Ltd

Abstract
This paper concentrates on the principles and measurement of interfacial tension and its value in
predicting the contamination of oil e.g. by organic polar compounds which are formed by the
interaction of oil, water and oxygen and reduce the functionality of the oil. These contaminants
are attracted to the oil/water interface and as a result significantly lower the interfacial tension.
A pure interface is compared to one modified by surface active additives for the effect on
interfacial tension, various methods for measuring interfacial tension are described and a method
using interfacial tension to determine the polar and dispersed components of a liquid will be
explained.. The ASTM Standard D971 will be discussed and results shown for both transformer
and lubrication oils. The question The Surface Tension Test - Is it Worth resurrecting?1 can be
discussed during Question Time.

Introduction
Many industrial processes involve different phases (liquids and/or solids) which come together at
some stage to form an interface e.g. emulsification, flotation, coating, detergency, lubrication,
dispersion of powders etc. The physical behaviour of these interfaces is quantified by the values
of the interfacial tension of the liquids and where solids are involved the contact angles of these
liquids on the solids, both of which can be measured directly. It is possible to breakdown the
surface tension of a liquid and solid (more commonly called surface energy when referring to a
solid) into disperse and polar components using equations found in many text books. Solid
interfaces however are not the subject of this paper.
Terminology
The terms surface, interface and phases are scattered throughout literature, sometimes
indiscriminately, hence it is important to ensure that the definitions used here are clarified so that
the reader understands which boundary is being described.

Interface general term to cover the boundary between phases (liquid/gas, liquid/liquid,
liquid/solid etc.) but specifically used for liquid/liquid boundary

Surface term normally used for a liquid/gas boundary

Phase gas, liquid and solid

Interfacial Tension in broad terms the tension at a liquid/gas, liquid/liquid, liquid/solid

interface but normally reserved for the liquid/liquid boundary

Surface Tension generally accepted as the tension at the liquid/gas boundary

Interfacial Free Energy excess of free energy at the liquid/solid interface

Surface Free Energy excess of free energy at the gas/solid interface

Tension can be shown by either the Greek symbol or

Liquid/Gas and Liquid/Liquid Interfaces

Within the bulk of a liquid the molecules are completely surrounded by other molecules such
that the forces of attraction are equal in all directions but at the interface there are unsatisfied
forces resulting in an inward attraction. This is what causes small drops to assume a spherical
shape and soap films to contract. The tendency of an interface to contract in order to minimise
the interfacial area leads to a state of tension hence surface tension is the tension along the
surface of a liquid in air. It is the force acting at right angles to a line of unit length in the
surface. Figure1 represents the interface of a pure liquid in air and Figure 2 a pure liquid/liquid.

Figure 1. Pure Liquid/Air Interface

Figure 2. Pure Liquid/Liquid Interface

With the formation of any type of interface work is done and there is an associated free energy
change i.e. the molecules at the interface have an excess of free energy due to being in the
interface. The units (per unit area) of specific excess free energy are the same as those for
interfacial tension but are only numerically equal for pure liquids in equilibrium with their
vapour or when two pure immiscible liquids make contact at a plane interface:
work/area

or

force/distance (length)

where
Free Energy
Tension

= Work/Area (J m-2 ) J = m2 kg s-2 & Area = m2 hence m2 kg s-2 /m2 = kg s-2

= Force/Length (N m-1 ) N = m kg s-2 & Length = m hence m kg s-2 /m = kg s-2

Generally the interfacial tension of two liquids is less than the highest individual surface tension
of one of the liquids because the mutual attraction is moderated by all the molecules involved.
Some authors consider it sufficient to define both interfacial tension and interfacial free energy
as the work required to increase the area of an interface isothermally and reversibly by unit
amount.
It is normal to express interfacial tension in mN/m which is exactly equivalent to the older units
of dyne/cm.
Modified Interfaces
An interface can be modified by the addition of soluble and insoluble materials which results in
either an adsorbed film or a deposited film, see Figure 3.

Figure 3. Modified Interfaces

Surface active materials have molecules containing polar heads (hydrophilic) and non-polar tails
(hydrophobic) which orientate at the interface as a monolayer. This is the more favoured
situation compared with complete solution in one or other of the phases. The effect is to expand
the interface which in turn must be balanced by the tendency for the interface to contract under
normal interfacial tension forces. The result is a lowering of interfacial tension according to the
following: = 0 -
where

(1)

0 = initial interfacial tension before addition of surfactant

= final interfacial tension
= expanding (interfacial) pressure

Ideal conditions for spontaneous emulsification and miscibility of liquids exist when > 0 .
Surfactant solutions reach equilibrium (static interfacial tension) when all the surfactant
molecules are aligned and orientated at the interface. Once the monolayer is saturated excess
molecules aggregate to form micelles.
At this critical micelle concentration (CMC) the
interfacial tension remains constant and cannot be further reduced by the addition of more of the
surfactant, Figure 4. The CMC occurs at the point when the minimum interfacial tension for a
particular surfactant or surfactant mix is reached, the value of which determines its potential use
as a wetting agent for a particular application. Knowledge of the CMC can act as a measure to
prevent unnecessary additional amounts of expensive ingredients from being used in a
formulation.

Figure 4. Surface Tension vs. Surfactant Concentration

An interfacial measurement that detects change over a time by definition is dynamic. At the
constant area of interface between two so-called immiscible pure liquids some of each phase will
dissolve into the other until saturation is reached thus lowering interfacial tension, e.g.
water/hexane falls from ~ 49 to 47 mN/m in 1 hour. This phenomenon should not be mistaken as
the dynamic tension which is a measure of the tension as new interface is created. By definition
the dynamic surface tension relates to the liquid/gas interface and the dynamic interfacial tension
to the liquid/liquid interface.
The rate at which new interfaces are formed can be controlled and changed to study the
efficiency of individual surfactants and mixtures of surfactants to reach the surface to lower
interfacial tension. For pure liquids the measurement of interfacial tension is independent of the
rate at which the interface is created.

Measurement Techniques
The following section describes the most used methods for measuring static surface and
interfacial tension which can be found in standard text books.
Du Noy Ring for Liquid/Gas & Liquid/Liquid Interfaces
The universally accepted technique for measuring interfacial tension is by the Du Noy ring
which is a precise geometry made of Pt-Ir. International standards for both the liquid/gas and
liquid/liquid interface, from a range of industries e.g. electrical insulation & electronics, water &
environmental, rubber and surfactants, are based on this technique. The methods for cleaning the
ring are described in these standards but it should be noted that new health and safety rules may
preclude their use. Depending on the test material, water or a legal solvent should be used to
remove the test liquid from the surface followed by an acetone rinse and a final clean water rinse
before flaming to red heat.
The measurement simply requires the ring to be wetted by the liquid and then pulled through the
interface while measuring the force exerted on the ring. The ring must sit square and parallel to
the interface as failure to do so will result in errors in the measurements. The maximum force of
the vertical constituent is directly proportional to the surface tension. The measuring sensor of
the Camtel range of Tensiometers is an electronic balance so the weight is monitored and
converted to force i.e. 1cm = 9.81mN. Calibration is done using traceable weights.

Figure 5. Schematic of the Du Noy Ring Method

When the interface is liquid/liquid the ring should ideally be zeroed in the light phase. The ring
is then cleaned and heavy phase poured into the sample vessel. The ring is positioned under the
surface of the heavy phase to completely wet it and while in this position the light phase is
carefully pipetted onto the surface of the heavy phase. The interface should be allowed to reach

equilibrium (there is always a slight solubility of one phase in the other) before pulling the ring
through the light phase.
The equation to calculate interfacial tension assumes that the contact angle of the liquid on the
ring is zero hence cos = 1 (the condition which exists when the force vectors, as the ring is
pulled out of the liquid, are vertical), see Figure 5.
The wetted length, L = 4R, is obtained from the circumference of the inner + outer (2*mean)
radii of the ring: = F/L cos

(2)

Unfortunately with this method, due to the volume of the liquid hanging from the ring as it is
pulled above the surface, a correction needs to be applied: = (Fmax Fv )/L cos

(3)

where Fv = gV (L - A)
V = volume of liquid at F = Fmax
Work by Harkins & Jordan2 (table of empirical values) and Zuidema & Waters3 (algorithm based
on 2 ) allows a correction to be made for the additional volume of liquid raised above the
interface:(4)

1.452 * Raw.ST
1.679
Fv = 0.725 +
+ 0.04534
2
(R / r)
( 2R) * ( )
where
R is mean ring radius & r is mean wire radius
is heavy phase density & is light phase density

The time to reach maximum pull on the ring depends on the speed with which the ring is pulled
through the interface but is typically 20-60 seconds. If surface tension changes as a function of
time then a single measurement with the ring will not show the ageing effect hence it is
necessary to lower the ring into the liquid before the lamella breaks to relieve the force and then
repeat the measurement. This sequence must be conducted many times to acquire a series of data
points over the specified time period. Obviously every time the ring is moved it creates an
artificial dynamic movement of molecules within the interface which can mask naturally
occurring time dependent behaviour. It is therefore better to use the Du Noy ring technique for
pure liquids and the Wilhelmy plate or pendant drop methods for solutions containing surfactants
or impurities.
Note that measurements of interfacial tension are affected by temperature and hence literature
values for pure liquids will always make reference to the temperature e.g. water is 72.8 mN/m at
20o C, see Figure 6.
SS uu rr ff aa ccee T
Tee nn ss ii oo nn oo ff P
P uu rr ee W
W aa tt ee rr vvss.. T
Tee m
m ppee rr aa tt uu rr ee

S u r f a ce te n s i o n , m N / m

88 00

77 00

66 00

55 00
-- 22 00

00

22 00

44 00

66 00

88 00

11 00 00

TT ee m
m pp ee rr aa tt uu rr ee ,, dd ee gg rr ee ee ss C
C

Figure 6. Effect of Temperature on Surface Tension of Water

11 22 00

Wilhelmy Plate - for Liquid/Gas & Liquid/Liquid Interfaces

An alternative geometry for measuring interfacial tension is the Wilhelmy plate, which is made
ideally from micro-roughened platinum but can be pre-wetted paper or glass with a hydrophylic
coating. In this technique the plate is suspended at the interface and maintained in this position
by a force which balances the weight of the plate and the meniscus force of the liquid acting on
the lower edge of the plate. Again this force is proportional to the interfacial tension as
described by Equation 2 where the wetted length is the circumference of the plate, Figure 7.
The contact angle of the liquid with the high surface energy Pt plate is assumed to be zero
hence no corrections for additional forces are required. With the platinum plate it is easy to see
if liquid jumps up the plate as it is immersed into the liquid, a sign of total wetting or contact
angle equal to zero.
One major difference between the ring and plate is the way in which the measurement is carried
out i.e. the ring moves through the interface whereas the plate is static at the interface. Therefore
there is no artificial disturbance of the interface and no increase in the time to reach equilibrium
when using the plate method. Any time dependent effects are true effects hence the plate is the
recommended geometry for studying time dependent characteristics.
When using a plate to determine interfacial tension between two liquids it is necessary to zero
the balance with the plate completely under the surface of the light phase. The plate should then
be cleaned and re-positioned at the surface of the heavy phase and air before adding sufficient
light phase to completely cover the plate otherwise the measurement will include a contribution
from the light phase/air interface.
Both ring and plate geometries can be used with the force balance type of tensiometer.

Figure 7. The Wilhelmy Plate Technique

Pendant or Hanging Drop for Liquid/Gas and Liquid/Liquid Interfaces
Drop Shape analysis of a hanging or inverted bubble is a text book method for determining
interfacial tension based on the following assumptions:

The drop is symmetric about a central vertical axis i.e. the drop can be viewed from any
angle.

The drop is not in motion i.e. interfacial tension and gravity are the only forces affecting
the shape and viscosity and inertia play no part in determining the shape

Interfacial tension is obtained by fitting the shape of the drop to the Young-Laplace equation. For
any curved surface with principle radii of curvature (r1 & r2 and r1 = r2 for a spherical drop) the
balancing pressure as a consequence of interfacial tension which is greater on the concave side,
is:1 1
P = +
r1 r2

(5)

In a column of fluid of density and height h, P = gh where g is acceleration due to gravity.

The equatorial diameter of the drop and other related geometrical parameters are measured and
the experimental shape is fitted to theoretical profiles derived from Bashforth and Adams tables
and other workers such as Andreas and Padday, see Figure 8.
A video system is used to capture the drop and embedded algorithms in the software compute the
interfacial tension. Like the Wilhelmy plate technique it is possible to monitor the change of
drop shape over time (time dependent interfacial tension) when surface active agents are present.

Figure 8. Pendant drop Profile

Calibration with this type of instrument is simple requiring only optical magnification accuracy
which is easy to a trace to national standards.
The volume (or more correctly the weight) of a pendant drop which can be supported on a round
tip is described by Tates Law as:W = 2 r

(6)

where W = weight of drop and r = radius of wetted tip

It is based on the theory that the interfacial tension of a liquid acting vertically around the rim of
a tube holds the drop up against gravity although Tate did not state that the drop weight is
proportional to the interfacial tension.
Drop Weight/Drop Volume Method
There is an ASTM Standard Test for measuring the Interfacial Tension of Electrical Insulating
Oils, D2285-99, by the Drop Weight technique4 . A relatively simple apparatus is described
which uses a piston which has a scale, graduated in mN/m, attached to it to force water into oil
contained in a glass beaker. Calibration of a parameter R2 is performed by expelling from a
blunt ended needle ten drops of water in a saturated atmosphere into air and noting the change in

scale readings before and after. The needle tip size and dial scale must be selected to ensure an
R2 value of around 9 scale divisions. This is used in the following equation: S
= R1 (D d )
R2

(7)

where R1 = scale divisions per drop of water in oil

R2 = scale divisions per drop of water in air
D = density of water and d = density of oil
S = surface tension of water
75% of a drop (found by expelling a trial drop) is expelled and allowed to age suspended from
the needle for 30s and then the volume of the drop is increased slowly to allow it to fall after a
further 45-60s. The volume of water in terms of scale divisions gives the interfacial tension
assuming an average oil density. A correction curve for different oil densities can be made from
running tests with different oils and applying the factor.
The method is described as rapid and for field use, giving a semi-quantitative answer subject to
significant error.
In a book by Adam5 the drop volume/weight method is described and much detail is given
regarding the shortfalls of the technique e.g. only part of a drop falls and is smaller than Tates
crude formula by on average 40%. Harkins and Brown6 did much work with different tip sizes
and found that the weight of a drop is a function of the radius of the tip and the square root of the
capillary constant. For greater description of the problems associated with this technique please
refer to the literature. For now accept that this technique requires laborious standardisation with
liquids whose surface tension has been found by a more accurate method using carefully
regulated conditions and tubes with sharp tips (not blunt ends) and time to form a drop of around
10 minutes.

Determination of the Disperse and Polar Components of a Liquid

In order to determine the disperse and polar components of the surface energy of a solid it is
necessary to use mathematical models which require the total surface tension (Liquid/Air
interface) of the test liquids and their disperse and polar components to be known. For the
purpose of this document it is assumed the reader is aware of surface energy models such as
Owens/Wendt and Wu and also that the contact angles of the test fluid on the solid are known.
When the test liquid values are unknown then by using the theory of Fowkes regarding the
interactions between two fluids it is possible to calculate both the disperse and polar components.
Background to the Theory of Fowkes
The surface tension of a liquid is a direct measurement of the intermolecular forces and when
only dispersion forces are involved then:
total = disperse

(6)

where = surface tension

However this is not always the case and when polar forces are present the equation becomes
total = disperse + polar

(7)

When two immiscible liquids such as oil and water are in contact each individual liquid is
subjected not only to forces from within its bulk but also from the second liquid which lowers
the tension. The magnitude of the oil/water interfacial tension is a function of the dispersion
forces of the oil and water molecules and Fowkes showed that the geometric mean of the
contributions to these forces describes the force of interaction:

 ow = o + w 2 ( o w )

(8)

where o = oil, w = water, ow = oil/water interface, d = dispersion contribution

In general for any two immiscible fluids, 1 and 2, the equation is:
12 = 1 + 2 2[ (1d 2d ) +

p
1

2p )]

(9)

where p = polar contribution

Experimental Method
It is necessary to use a known test liquid with no polar component e.g. n-hexane and measure the
interfacial tension between this liquid and the unknown sample. The surface tension and
disperse component of n-hexane which in this case are equal, can be found in the literature and in
the Database of the Camtel software. It is also necessary to know or use your instrument to
measure the surface tension of the unknown liquid.
Example Assume the 2 liquids used are n-hexane and water measured at 20C.
For n-hexane, total = 18.4 mN/m = disperse and polar = 0
For water, total = 72.8 mN/m = disperse + polar
Interfacial tension between n-hexane and water = 51.0 mN/m
Therefore the disperse component of water can be found by re-arranging Equation (9):
1 0 + w ow
=
*

o
2

d
w

1 18.4 + 72.8 51
=
*

18.4
2

(10)
2

d
w

= 21.85 mN/m

ASTM Standard: D 971-99a for Electrical Insulating Oils 7

The Du Noy ring method described in the Standard clearly states that the interfacial tension
between a mineral oil and water is obtained under strict non-equilibrium conditions whereby the
measurement is completed within 60 seconds after the formation of the oil/water interface. The
force used to calculate the non-equilibrium tension is the force required to break the liquid
lamella from the ring rather than the maximum force. A correction factor by Zuidema & Waters3
based on Harkins & Jordans2 work is applied.
It should be noted that the work of the latter is the basis for measuring the absolute or
theoretically correct value of interfacial tension. The force used must be the maximum pull on
the ring which theoretically is proven to be proportional to interfacial tension and is the point
where the contact angle of the liquid attached to the ring is zero and not the break point as the
liquid detaches itself from the ring which is a lower value, see Figure 5.
The apparatus described and shown schematically in the Standard is a manual device which
relies on the dexterity of the operator to lower the platform on which the sample vessel sits and
turn a dial with the other hand to maintain the torsion arm in the zero position. The break point
is clearly an obvious event which unskilled operators can be trained to note.
However a variety of means to measure force (torsion wire, load cell or other means to linearly
determine tension) and raise or lower the platform (mechanical screw, electronic drive or other
means to precisely change vertical position) are allowed. Simply by using a computer controlled
system the ring can be pulled through the interface at a steady and repeatable user selected speed
time after time while force is constantly monitored thus removing differences in operator
techniques. It is also possible to pick out the maximum force thus eliminating any need to
deviate from theoretical accuracy.

Differences in the method using manual or semi-automatic digital control compared to a fully
automated PC controlled tensiometer are listed below.
The Camtel CIT-100 Interfacial
Tensiometer was used to provide the data. Fig. 9 shows the difference in non-equilibrium
surface tension for water measured automatically at two different stage speeds, 66.9 mN/m at
0.2mm/s and 62.9 mN/m at 0.1mm/s. It indicates that the slower the withdrawal of the ring the
longer the lamella stretches before breaking and hence the lower the non-equilibrium interfacial
tension. The true surface tension, ~72 mN/m, is obtained at both speeds and is therefore
independent of speed.
The literature value for the interfacial tension of water/n-hexane interface is 51 mN/m. The
maximum force value is displayed in Fig.9 at 50.4 mN/m whereas the non-equilibrium value is
45.4 mN/m. The spike in the data at around 20s is because the procedure was deliberately set to
show the values from the start of the stage moving the sample to the ring. It allows the user to
see the contact point of ring and liquid (the spike) which triggers a position reading to ensure the
ring is immersed to the selected depth before being pulled out through the interface. This option
is normally de-selected but was left on in this case as an example.
Finally a typical clean and dirty electrical insulating oil are also shown in Fig.9 using timescales
for raising and lowering the stage of the CIT-100 which allow the test to be carried out according
to times stated in the Standard. Again the true and non-equilibrium values are very different,
41.6 mN/m and 32.7 mN/m for the clean oil respectively and 9.17 mN/m and 8.14 mN/m for the
dirty oil.

Comparison of Actual Interfacial Tension to Break Point Tension

& cf. of Water at 2 different speeds
80

Non-Eq =66.9

Non-Eq =62.9

60

Interfacial Tension (mN/m)

Water @ 0.2mm/s
Water @ 0.1mm/s
Water-Hexane @ 0.1mm/s
Water-Clean Oil @ 0.1mm/Sl
Water-Dirty Oil @ 0.1mm/S

True IT = 72.8

True IT = 50.4
True IT = 41.6

Non-Eq =45.4

40

Non-Eq =32.7
20
True IT = 9.17

Non-Eq =8.14

0
0

20

40

60

80

100

120

Time (s)

Figure 9. Comparison of Maximum Force to Break Force Interfacial Tension using a PC

controlled Tensiometer

The clear advantage of the CIT-100 over a manual instrument is that it removes operator
error e.g. the ring is pulled through the interface at a constant speed, manual control will
have a degree of stop/start to the movement as the operator turns the mechanism to raise
and lower the stage which can affect when the lamella breaks and hence the nonequilibrium value reported.

In the CIT-100 the force (weight registered on the balance) is constantly monitored and
displayed so it is possible to see clearly the maximum force required to obtain the
absolute tension. This is not possible with the design shown in the Standard.

In the CIT-100 the decrease in weight after maximum force and before the lamella breaks
can be seen clearly i.e. as the force drops so the contact angle of liquid attached to the

ring becomes non-zero. The calculation of surface tension assumes contact angel is zero,
see Section 1, Equation 1, hence values obtained with the CIT-100 are absolute. The
Standard calculation of Non-equilibrium surface tension makes no mention that cos
should = 1. As the height of the lamella increases so the contact angle continues to
change and force drop. Manual control and sample properties can affect the lamella
height and break point.

In the CIT-100 water from a bath can be circulated to maintain temperature at 25 C

In the CIT-100 a stored database contains the test fluids with associated density values
and these are automatically used to compute the Zuidema correction.

Comparison of an Electrical Insulating Oil and an Engine (lubricating) Oil

Interfacial tension measurements against pure water were made on the Camtel CIT-100 to
compare a clean and dirty synthetic electrical insulating oil with two clean and dirty engine oils,
one a natural base oil and the other a synthetic base.
Figure 10 shows a clean, dirty and 50:50 mix of the clean and dirty synthetic insulating oil from
one of the UK Electricity boards. As predicted the clean oil has the highest interfacial tension at
around 32 mN/m and the dirty oil the lowest, 15 mN/m with the mix falling somewhere in
between at 20 mN/m. The results agree with the general rule that when interfacial tension falls
between 15-20 mN/m deposits which are hydrophilic in nature may be forming and the oil
should be changed.

Interfacial Tension of Synthetic Insulating Oils

35

30

25

New Oil.00I

Surf. Ten. mN/m

50% New Oil - 50% Aged Oil.00I

20

Aged Oil.00I

15

10

0
0

10

20

30

40

50

Time Secs

60

70

80

90

100

Figure 10. Comparison of Clean and Dirty Insulating Oils

Figure 11 shows a similar plot for engine oils where an oil with a natural base is compared to a
synthetic base. Here the data is totally different compared to the insulating oil as there is no
large drop in value between a clean oil and a visually blackened dirty oil. In fact the interfacial
tension values of the clean oils were much lower than a dirty insulating oil with the natural base
at 7.4 mN/m and the synthetic base at 8 mN/m. For the dirty oils the interfacial tension actually
rose slightly to 8.4 mN/m and 9.7 mN/m respectively.
From the marketing claims on the cans of oil which offer protection and cleaning of the engine
etc. it is apparent that modern engine oils are far from simple natural or synthetic products.
Polymer molecules are added to disperse contaminating particles in order to keep viscosity low,
quantities of base are added to soak up corrosion from acid and the oils contain as much as 20%
added surfactant. From the results of the interfacial tests on clean oils they are already saturated

with agents which migrate to the oil/water interface and substantially lower the interfacial
tension.
Interfacial Tension of Clean and Dirty Engine Oils
10

Interfacial Tension

6
Synth-C
Synth-D
Nat-C
Nat-D
4

0
0

10

20

30

40

50

60

Time (s)

Figure 11. Comparison of Clean and Dirty, Natural & Synthetic Based Engine Oils
To complete the picture of interfacial tension tests a more natural oil/water test was run using a
supermarket brand of sunflower oil. In Figure 12 the engine oils can be seen on the same plot as
the sunflower oil which has a much higher value of interfacial tension of 26 mN/m as expected.
Interfacial Tension of Clean and Dirty Engine Oils
30

Interfacial Tension

25

20

Synth-C
Synth-D
Nat-C
Nat-D
SunOil

15

10

0
0

50

100

150

200

250

300

350

400

Time (s)

Figure 12. Comparison of Data from Figure 11 with Sunflower Oil

Finally oil/air surface tension tests were made to compare the engine oils against each other and
against the values obtained for interfacial tension. With much higher surface tension values of
around 30 mN/m for natural and synthetic, clean and dirty engine oils the additives which
improve functionality clearly only migrate to the oil/water (highly polarised) interface.

Conclusion
Electrical insulating oils obey the findings which show that data from interfacial tests can predict
the onset of impurities in oils. Modern day engine oils do not follow the same pattern.

Insulating oils are fairly simple in make-up whereas engine oils contain vast amounts of
additives to improve functionality. These additives can be shown to dramatically lower the
interfacial tension but not the surface tension of a clean oil hence the additives must be
hydrophilic in nature. Impurities which are formed and contaminate oils are also known to be
hydrophilic but with such large amounts of hydrophilic surfactants added in production the
interface is already saturated and no further reduction in interfacial tension is seen i.e. critical
micelle concentration has been reached.
There is a suggestion from the few tests run for the purpose of this paper that interfacial tension
slightly increases with contamination in engine oils.
Camtel would be more than happy to measure further oils to add to the knowledge base.

References
1

Fitch J, Practicing Oil Analysis, Issue No. 200209

Harkins W. D., Jordan F. J. Colloid Int. Sci. 52 (1930) 1751

Zuidema H & Waters G, Ind. Eng. Chem. 13 (1941) 312

ASTM Designation: D2285-99 Standard Test Method for Interfacial Tension of Electrical
Insulating Oils of Petroleum Origin Against Water by the Drop Weight Method

Harkins W. D., Brown, J.A.C.S. (1919), 499

ASTM Designation: D971-99a Standard Test Method for Interfacial Tension of Oil
Against Water by the Ring Method

Adam N.K., The Physics and Chemistry of Surfaces, 3rd Edition, Oxford University Press
1941