nverse gas chromatography

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Analytical Gas Chromatography A (top) compared with Inverse Gas Chromatography B

(bottom). While in gas chromatography a sample containing multiple species is separated
into its components on a stationary phase, Inverse gas chromatography uses injection of a
single species to probe the characteristics of a stationary phase sample.

Inverse gas chromatography is a physical characterization technique that is

used in the analysis of the surfaces of solids. Traditional GC is an analytical
technique.
Inverse gas chromatography or IGC is a highly sensitive and versatile gas phase
technique developed over 40 years ago to study the surface and bulk properties
of particulate and fibrous materials. In IGC the roles of the stationary (solid) and
mobile (gas or vapor) phases are inverted from traditional analytical gas
chromatography (GC). In GC, a standard column is used to separate and
characterize several gases and/or vapors. In IGC, a single gas or vapor (probe
molecule) is injected into a column packed with the solid sample under
investigation. Instead of an analytical technique, IGC is considered a materials
characterization technique.
During an IGC experiment a pulse or constant concentration of a known gas or
vapor (probe molecule) is injected down the column at a fixed carrier gas flow
rate. The retention time of the probe molecule is then measured by traditional GC
detectors (i.e. flame ionization detector or thermal conductivity detector).

Measuring how the retention time changes as a function of probe molecule

chemistry, probe molecule size, probe molecule concentration, column
temperature, or carrier gas flow rate can elucidate a wide range of physicochemical properties of the solid under investigation. Several in depth reviews of
IGC have been published previously.[1][2]
IGC experiments are typically carried out at infinite dilution where only small
amounts of probe molecule are injected. This region is also called Henry's
lawregion or linear region of the sorption isotherm. At infinite dilution probe-probe
interactions are assumed negligible and any retention is only due to probe-solid
interactions. The resulting retention volume, VRo, is given by the following
equation:
where j is the JamesMartin pressure drop correction, m is the sample
mass, F is the carrier gas flow rate at standard temperature and pressure, tR is
the gross retention time for the injected probe, to is the retention time for a
non-interaction probe (i.e. dead-time), and T is the absolute temperature.
Contents
[hide]

1Surface energy determination

o

1.1Applications

1.2Polymers and coatings

1.3Pharmaceuticals

1.4Fibers

1.5Nanomaterials

1.6Metakaolins

1.7Other

2See also

3References

Surface energy determination[edit]

The main application of IGC is to measure the surface energy of solids (fibers,
particulates, and films). Surface energy is defined as the amount of energy

required to create a unit area of a solid surface; analogous to surface tension

of a liquid. Also, the surface energy can be defined as the excess energy at
the surface of a material compared to the bulk. The surface energy () is
directly related to the thermodynamic work of adhesion (Wadh) between two
materials as given by the following equation:
where 1 and 2 represent the two components in the composite or blend.
When determining if two materials will adhere it is common to compare the
work of adhesion with the work of cohesion, Wcoh = 2. If the work of
adhesion is greater than the work of cohesion, then the two materials are
thermodynamically favored to adhere.
Surface energies are commonly measured by contact angle methods.
However, these methods are ideally designed for flat, uniform surfaces.
For contact anglemeasurements on powders, they are typically
compressed or adhered to a substrate which can effectively change the
surface characteristics of the powder. Alternatively, the Washburn method
can be used, but this has been shown to be affected by column packing,
particle size, and pore geometry.[3] IGC is a gas phase technique, thus is
not subject to the above limitations of the liquid phase techniques.
To measure the solid surface energy by IGC a series of injections using
different probe molecules is performed at defined column conditions. It is
possible to ascertain both the dispersive component of the surface
energy and acid-base properties via IGC. For the dispersive surface
energy, the retention volumes for a series of n-alkane vapors (i.e. decane,
nonane, octane, heptanes, etc.) are measured. The Dorris and Gray.[4] or
Schultz [5] methods can then be used to calculate the dispersive surface
energy. Retention volumes for polar probes (i.e. toluene, ethyl
acetate, acetone, ethanol, acetonitrile, chloroform, dichloromethane, etc.)
can then be used to determine the acid-base characteristics of the solid
using either the Gutmann,[6] or Good-van Oss theory.[7]
Other parameters accessible by IGC include: heats of sorption [1],
adsorption isotherms,[8] energetic heterogeneity profiles,[9][10] diffusion
coefficients,[11] glass transition temperatures [1],[12] Hildebrand [13][14] and
Hansen [15] solubility parameters, and crosslink densities.[16]
Applications[edit]

IGC experiments have applications over a wide range of industries. Both

surface and bulk properties obtained from IGC can yield vital information
for materials ranging from pharmaceuticals to carbon nanotubes. Although
surface energy experiments are most common, there are a wide range of
experimental parameters that can be controlled in IGC, thus allowing the

determination of a variety of sample parameters. The below sections

highlight how IGC experiments are utilized in several industries.
Polymers and coatings[edit]

IGC has been used extensively for the characterization of polymer films,
beads, and powders. For instance, IGC was used to study surface
properties and interactions amongst components in paint formulations.
[17]
Also, IGC has been used to investigate the degree of crosslinking
for ethylene propylene rubberusing the FloryRehner equation [17].
Additionally, IGC is a sensitive technique for the detection and
determination of first and second order phase transitions like melting
and glass transition temperatures of polymers.[18] Although other
techniques like dynamic scanning calorimetry are capable of measuring
these transition temperatures, IGC has the capability of glass
transition temperatures as a function of relative humidity.[19]
Pharmaceuticals[edit]

The increasing sophistication of pharmaceutical materials has

necessitated the use for more sensitive, thermodynamic based techniques
for materials characterization. For these reasons, IGC, has seen increased
use throughout the pharmaceutical industry. Applications include
polymorph characterization,[20]effect of processing steps like milling,[21] and
drug-carrier interactions for dry powder formulations.[22] In other studies,
IGC was used to relate surface energyand acid-base values
with triboelectric charging [23] and differentiate
the crystalline and amorphous phases [23].
Fibers[edit]

Surface energy values obtained by IGC have been used extensively on

fibrous materials including textiles,[24] natural fibers,[25] glass fibers,
[26]
and carbon fibers.[27] Most of these and other related studies
investigating the surface energy of fibers are focusing on the use of these
fibers in composites. Ultimately, the changes in surface energy can be
related to composite performance via the works of adhesion and cohesion
discussed previously.
Nanomaterials[edit]

Similar to fibers, nanomaterials like carbon nanotubes, nanoclays, and

nanosilicas are being used as composite reinforcement agents. Therefore,
the surface energy and surface treatment of these materials has been
actively studied by IGC. For instance, IGC has been used to study the
surface activity of nanosilica, nanohematite, and nanogeoethite.[28] Further,
IGC was used to characterize the surface of as received and modified
carbon nanotubes.[29]

Metakaolins[edit]

IGC was used to characterize the adsorption surface properties of

calcined kaolin (metakaolin) and the grinding effect on this material.[30]
Other[edit]

Other applications for IGC include paper-toner adhesion,[31] wood

composites,[32] porous materials [3], and food materials.[33]

See also[edit]