iGC SEA
Measuring Surface Energy for Viscous Fluids
Using Inverse Gas Chromatography
Armando R. Garcia
Surface Measurement Systems Ltd.
The measurement of surface energies of solids is a well proven technique using Inverse Gas
Chromatography (IGC). There is a great deal of interest however in extending this valuable technique to
liquids. This paper explores this possibility and provides data on techniques and results.
Introduction
IGC has been shown to be a valuable research
tool for the measurement of surface energies of
solids [1,2,3]. A wide range of materials have
been analyzed with IGC, yielding repeatable
values of surface energies, where other methods
have been less reliable and more complex to
perform. However, IGC is not limited to solid
surfaces. A substantial amount of work on liquid
systems has been reported in the literature [4,5].
This technical note explores different methods by
which viscous liquids may be analyzed using iGC-
SEA to measure surface energetics, in a manner
that is reproducible and straight forward
Method
All analyses were carried out using the SMS-iGC
SEA instrument and the SMS-iGC v1.3 analysis
suite of macros. All columns were initially
conditioned at the experiment temperatures
listed below, for 2 hours and 0% relative humidity
(RH) and experiments were carried out with
injections of 0.03 P/P0 to 0.06 P/P0 elutant vapour
Technical
Note 803
concentrations. A flame ionisation detector was
used to determine the chromatogram and
resulting retention times.
The analysis of the dispersive component of the
surface energy was performed by measuring the
net retention volume VN (measured retention
volume – dead volume) for a series of alkane
elutants (undecane, decane, nonane, octane and
heptane). The dead volume was determined by
injecting methane, a probe molecule that does
not interact significantly with low energy
materials. A minimum of four alkanes were used
in all experiments.
By plotting RTln(VN) versus a(γLD)1/2 , where a is
the molecular area of the probe molecule and γLD
is the dispersive component of the surface energy
of the liquid elutant (surface tension), a straight
line is produced. The slope equals to 2NA(γSD)1/2
from which γSD, the dispersive component of the
solid surface energy, can easily be deduced [6].
Three column preparation methods have been
explored. One method uses a support material,
such as glass wool to hold the liquid in place and
to provide a surface upon which the liquid can
spread as a thin film. Another method which has
been explored is the simple coating of the viscous
liquid on the inside wall of the IGC SEA column.
For this method to work, the film deposited on
P-SCI-319 v1.0 12NOV2013
the inside wall must be thin and therefore the
liquid should be amenable to spreading on the
glass. A non-silanised glass column is preferred
for this procedure. Finally, the third method
explored is one where the liquid is dispersed on
glass beads. Excess liquid is allowed to drain from
the beads prior to loading the beads into the
column.
Data has been taken using the above three
methods with two resin materials, A and B, and
also with a very viscous pitch sample C.
As can be seen in Table 1, the initial experiment
on day 1, results in a value of 35.85 mJ/m2. As
time progresses, the value increases significantly
until it reaches 49.95 mJ/m2 on the sixth day.
Upon close inspection of the column, the sample
appears to have formed regions where it has
pooled and is no longer dispersed on the glass
wool. This method therefore is not a good one,
as the data is not reliable.
Column Internal Coating

Results In the second method, samples are coated on the

Glass Wool Support
The results obtained with silanised glass wool as
the sample support, initially appear to give
reasonable data. Data on a 500 mg sample of
resin dispersed on glass wool is shown in Table 1.
However, as time passes and additional
experiments are performed, the dispersive
surface energy values appear to increase. This
effect may be explained as a bulk effect during
the experiment, where solvent is absorbed into
the bulk of the fluid and is retained for a longer
amount of time than it would be, if the
interaction were simply with the surface of the
fluid. In doing so, the solvent molecules spend
time dissolved in the sample rather than simply
interacting with the surface. This occurs because
the fluid forms droplets within the glass wool
once it begins to coalesce. These droplets
provide an area for the solvent to be adsorbed
into the bulk of the sample. This lengthening of
the retention time is incorrectly interpreted as an
increase in γSD by the analysis software.
walls of the column. This is done by wetting a
sterile swab made of foam, and inserting it into
the column to wet the inside walls. Fairly good
results are obtained with this method, but usually
the sample has to be kept at a low temperature
to reduce the possibility of the sample flowing to
the bottom. The low temperatures (from 5 to 10
°C) maintain a film on the walls of the column for
a reasonable amount of time, rather than
allowing the sample to form droplets. This
requires the use of non-silanised columns in order
to create a film on the surface of the glass.
Eventually however, the sample will flow and
begin to form droplets, unless the temperature is
below the sample freezing point. The data shown
below is for the second sample B.
Table 2: Dispersive component of the surface
energy for Sample B coated onto column
Experiment Time Column Dispersive Surface
(Days after sampling) Temperature (°C) Energy (mJ/m2
1 10 34.45
2 10 37.05
3 10 35.53

Table 1: Dispersive component of the surface
energy for Sample A on glass wool
Experiment Time Column
(Days after sampling) Temperature (°C)
1 30
2 30
5 30
6 30
4 10 42.73
Dispersive Surface
Energy (mJ/m2 The data above shows that the initial experiment
35.85 on Day 1 yields a value of 34.45 mJ/m2, not very
43.06 different from the initial value of Sample A above.
46.97
This value increases with time, though not as
dramatically as with the previous method. On the
49.95
fourth day the value has increased to 42.73
mJ/m2. Clearly, this method is also unreliable at
longer time intervals but good for short
experimental times.
Coated Glass Beads
Samples are prepared by mixing a small amount
of liquid with enough beads to fill a glass column.
This may be done in a shallow container such as a
weighing boat. The beads are stirred in the liquid
in order to completely wet their surface. The
excess liquid may be decanted, or the beads may
be placed on a sieve to allow excess fluid to drain.
The beads are then loaded into the column. The
objective is to have only a thin coating of liquid
on the beads. The column should be plugged at
both ends with glass wool to prevent the beads
from falling out. The column is then ready for
experiments.
The column should not be handled by hand more
than necessary in order to avoid sample heating,
which will speed up the pooling of liquid between
the beads. Instead, use gloves or tongs to keep
the column at room temperature. Enough glass
wool should be used at both ends of the column
so that if the fluid does accumulate at the bottom
of the column, it will not enter the system. This is
very important to prevent contamination of the
IGC SEA lines. It is advisable to let the column
stand upright for a few hours outside the
instrument. This is to make sure that the film on
the beads is thin enough that it will not flow to
the bottom in a length of time comparable to the
experiments being performed. This method
yielded the most reliable results at room
temperature.
Table 3: Dispersive component of the surface
energy for Sample B on glass beads
Experiment Time Column Dispersive Surface
(Days after sampling) Temperature (°C) Energy (mJ/m2
1 30 37.10
1 30 38.07
2 30 37.34
2 30 37.77
The data in Table 3 for Sample B show that on
Day 1, the value obtained is 37.10 mJ/m2. Notice
that this value at a temperature of 30 C is slightly
higher than the value obtained earlier for Sample
B using the internal coating method at 10 °C
(Table 2, line 1). The average of the above
measurements in Table 3 is 37.57 mJ/m2. The
average deviation is 0.35 mJ/m2. This is a very
reasonable deviation for a small set of
experiments. These data were obtained on the
same column, run consecutively.
Table 4: Dispersive component of the surface
energy for Sample A on glass beads
Experiment Time Column Dispersive Surface
(Days after sampling) Temperature (°C) Energy (mJ/m2
1 30 35.38
2 30 35.37
2 30 34.97
3 30 36.69
3 30 37.40
Resin sample A was also analysed using the glass
bead method at 30 °C. This data is shown above
in Table 4. The average of these measurements is
35.96 mJ/m2, and the standard deviation is 0.866
mJ/m2.
These results show a clear difference between
the two samples A and B. As a check of the
procedure, a column of clean beads was analyzed
for surface energy. The result of those
experiments, six in all, was an average of 31.72
mJ/m2, with a standard deviation of 0.57 mJ/m2.
This shows that the data obtained above is really
a result of the interaction between the probe
molecules and the resins, not the beads.
If the columns are stored in an upright position
over an extended period of time, the liquid will
eventually flow to the bottom, therefore if the
columns will be used again, they should not be
stored vertically, but horizontally.
Pitch Sample C on Beads
Experiments were also performed on a Pitch
sample C, coated on glass beads. This sample
does not flow readily at room temperature and
requires heating to 100 °C in order to be able to
coat the beads. A small amount of pitch was
heated in a shallow container in a lab oven and
 iGC SEA
Technical
Note 803

glass beads were then introduced into the

container. Once the beads were coated with
pitch, following manual stirring, the excess pitch
was decanted. The beads were allowed to cool
and then loaded into the column following the
above procedure.
Data were taken for the pitch sample at 30 C as
shown in Table 5. There is little sample flow at
this temperature. One measurement was done at
20 °C. Given enough time however, this sample
too will flow and form regions where the film
pools into droplets. There is a large difference
between the early data, taken soon after sample
preparation, and the later data taken days after
preparation.
Table 5: Dispersive component of the surface
energy for a Pitch sample C on glass beads
Experiment Time Column Dispersive
(Days after Temperature Surface Energy
sampling) (°C) (mJ/m2
1
Conclusions
In conclusion, of the methods studied, the most
promising method is the sample coated on glass
beads. It appears to yield the most reproducible
data over the longest period of time. Coating the
sample on the inside of the glass columns is also
promising but requires that the sample be kept at
low temperature, and the data is not as
reproducible as the glass bead method. With
either method, analysis should always be
performed on a freshly prepared sample to
minimize sample flow. With careful sample
preparation and attention to detail, it should be
possible to obtain good quality data on liquids,
thus extending the capabilities of an already
versatile instrument

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30

30
61.16

61.32
References
1 30 62.70
[1]Thielmann, F., J. Chrom. A 1037 (2004), 115
3 30 76.55 [2]van Astem, A. et al, J. Chrom. A 888 (2000), 175.
[3]Pawlisch, C., Macris, A. and Laurence, R., Macromolecules 20 (1987),
3 30 74.39 1564.
[4]Goss, K.U., J. Coll. Interf. Sci. 190 (1997), 241.
3 30 76.44 [5]Davis, T.C. et al, Anal. Chem. 38 (1966), 241.
[6]Thielmann, F. and Butler, B., SMS Application Note 202.
3 30 72.51

1 20 55.63

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