Inverse Gas Chromatography in Analysis of Polymers: James Guillet

INVERSE GAS CHROMATOGRAPHY IN ANALYSIS OF POLYMERS 1
Inverse Gas Chromatography 13.3 Coating the Support: the Pile

Method 24
in Analysis of Polymers 13.4 Determination of Degree of
Crosslinking of Polymer Networks 24
James Guillet Abbreviations and Acronyms 26
University of Toronto, Canada Related Articles 26
References 26
Zeki Y. Al-Saigh
Columbus State University, USA
This article describes the application of inverse gas chro-

matography (IGC) to the study of synthetic and natural
1 Introduction 1 polymers. The word ‘‘inverse’’ is used to indicate that the
2 Conventional Gas Chromatography 2 component of interest is the stationary phase, either as a
3 Inverse Gas Chromatography 3 finely divided powder or coating, dispersed on a suitable
inert support and packed into a chromatographic column.
4 The Glass Transition 5 The time required for a probe molecule to pass through
5 Surface Studies 6 the column gives a measure of the molecular interactions
5.1 Adsorption Isotherms 6 between the probe and the polymer which can be quanti-
5.2 Surface Areas 7 fied with the help of chromatographic theory. Historically,
5.3 Surface Energy of Polymers 8 most thermodynamic studies on polymers were carried
6 Crystallinity 8 out in dilute solution, but IGC provides information on
6.1 Degree of Crystallinity 8 condensed phases under conditions much more similar to
6.2 Rates of Crystallization 10 those under which polymers are actually used.
Using this technique, melting, glass and other solid-
7 Diffusion 10 phase transitions can be studied and quantified. Degrees
7.1 Determination of Diffusion of crystallinity can be determined in an unambiguous pro-
Constants 11 cedure without calibration by other methods. Solubility,
8 Thermodynamic Studies 13 permeability and diffusion constants can be determined
8.1 Activity Coefficients, Heats of for probe molecules. IGC is also used extensively in deter-
Mixing and Heats of Solution 13 mining the permeability of additives such as antioxidants
8.2 Finite Concentration Gas in polymers, as well as thermodynamic quantities such
Chromatography 14 as activity coefficients, heats of solution, Flory – Huggins
8.3 Henry’s Law Constants interaction parameters (c), and solubility parameters. Sur-
(Solubilities) 14 face areas can be measured at any desired temperature
8.4 Solubility Parameters 15 by the determination of the adsorption isotherms of suit-
8.5 Hydrogen Bonding 16 able probes. Measurements on polymer blends can yield
9 Polymer Blends 17 important information on polymer – polymer interactions
9.1 Experimental Studies on Polymer and can be used to predict the compatibility of the compo-
Blends 19 nents over a wide range of temperatures. The use of finite
9.2 Amorphous Plasticizer Blends 19 concentration IGC provides a rapid method of determining
the density of crosslinks in rubber-like polymers.
10 Inverse Gas Chromatography Studies on
Almost any commercial gas chromatograph can be eas-
Natural and Synthetic Fibers 20
ily modified to carry out IGC experiments by procedures
11 Biological Molecules 20 described in this report. The method provides a wealth of
12 Applications 20 information of both fundamental and practical importance
12.1 Amorphous and Semicrystalline in the study of polymeric materials.
Polymer Blends 21
12.2 Comparison with Other Methods 21
13 Experimental 22 1 INTRODUCTION
13.1 Thermodynamic Measurement on
Blends 22 Much of what is now known about the structure and
13.2 Column Preparation 23 chemical interactions of macromolecules comes from
Encyclopedia of Analytical Chemistry, Online © 2006 John Wiley & Sons, Ltd.
This article is © 2006 John Wiley & Sons, Ltd.
This article was published in the Encyclopedia of Analytical Chemistry in 2006 by John Wiley & Sons, Ltd.
DOI: 10.1002/9780470027318.a2016
2 POLYMERS AND RUBBERS
studies in dilute solution where the polymer molecules There are two mechanisms of gas – solid interaction,
are more or less isolated from each other. However, in namely sorption of the solute into the bulk stationary
most practical applications of polymers, the polymer is phase (absorption) or on the surface of the stationary
highly concentrated and usually represents 90% or more phase (adsorption), or a combination of both. For con-
of the bulk phase. Experimental techniques developed for ventional GC, the surface adsorption term is considered to
dilute solution studies are often inapplicable under these be negligible. The net volume required to move the probe
conditions. Furthermore, there is a large and increasingly molecules through the column is VN , the total volume of
important category of polymers that are insoluble in all gas needed minus the ‘‘dead’’ volume in the column,
known solvents and hence cannot be studied at all in found by sending an inert probe such as methane through
dilute solution. the column (Figure 1). VN is equal to .tR tM / ð UT ,
The inverse gas chromatographic procedure (some- where tR is the probe retention time, tM is the marker
times called the molecular probe technique) eliminates retention time and UT is the flow rate of carrier gas at
both of these difficulties. The polymer is studied in the the temperature at which it is measured. The parameter
solid phase under conditions which can be made to used in further calculations is Vg , the specific retention
approximate conditions of use, or processing and fabrica- volume, Equation (1)
tion. Furthermore, although polymers may be insoluble 273.16 VN 760 3
in solvents, virtually all small organic molecules will have Vg D J .1/
T w Po 2
measurable solubilities in solid organic polymers, even
when the latter are crosslinked or highly crystalline. where T (K) is the temperature of the column at which the
Hence the range of interactions which can be probed flow rate is measured, Po is the column outlet pressure,
by the technique is virtually unlimited. w is the number of grams of polymer in the column and
In view of the general availability of gas chromato- J23 is a small correction due to the pressure drop along
graphic equipment, the experimental simplicity, and the the column equal to .2/3/f[.Pi /Po /2 1]/[.Pi /Po /3 1]g
ease with which large amounts of data can be collected, where Pi and Po are the inlet and outlet pressure on the
IGC is becoming the method of choice for the study column.
of thermodynamic interactions of small molecules with Usually the retention volume is obtained using the
polymers in the solid phase. However, the method is not experimental peak maximum to define the retention
limited to equilibrium measurements in the bulk phase. time. In this treatment for conventional GC, only bulk
It can also be used to measure surface areas and adsorp- adsorption is assumed, and band broadening effects and
tion isotherms, glass and other solid-phase transitions the existence of a nonlinear sorption isotherm are not
in polymers, degrees of crystallinity, crosslink density considered.
and diffusion constants for small molecules in polymeric Everett.1/ developed the thermodynamic analysis for a
materials. binary solution of components 1 (probe) and 2 (stationary
phase) in the presence of a gas which is insoluble in the
solution. Assuming that the molar volume of the probe,
V1 , does not vary greatly with pressure, that the gas
2 CONVENTIONAL GAS
phases are only slightly imperfect, that the system is in
CHROMATOGRAPHY
equilibrium, and that the solute is infinitely dilute in both
phases, then the infinite dilution activity coefficient of
Gas chromatography (GC), like any other chromato- component 1 (g1 1 ) at temperature T and total pressure P
graphic technique, is based on the distribution of a probe
molecule between two phases. In gas – solid chromatog- tR
raphy (GSC) the phases are gas and solid; as the injected
tM VN
compound is carried by the gas phase through a col-
umn filled with solid phase, partition occurs via the
sorption – desorption of the solute as it travels past the
solid. Superimposed upon the forward velocity is radial
motion of the probe molecules caused by random dif-
fusion throughout the stationary phase. Separation of Inject Marker Probe
two or more components injected simultaneously is due
to their differing affinities for the stationary phase. In Time
gas – liquid chromatography (GLC) the stationary phase
is a liquid coated onto a solid support. The mathematical Figure 1 Information obtained for a probe interacting with a
treatment is equivalent for GLC and GSC. polymer-coated stationary phase at temperature T.
DOI: 10.1002/9780470027318.a2016
can be written as Equation (2) values differed from those obtained using the packed
column by as much as 20% for poly(isobutylene) (PIB)
nL RT .B11 V1 /p01 and poly(dimethylsiloxane) (PDMS), and even more for
ln g1
1 D ln
KVL p01 RT poly(vinylacetate) (PVAc). In both cases, the difference
.2B13 V11 /P decreased as the temperature increased. Both studies
C .2/ reported that the basic disadvantage of the capillary
RT
method was the difficulty in calculating the amount of
where nL is the number of moles of component 2 polymer present.
occupying volume VL on the column, p01 is the partial Most of the work discussed here concerns data obtained
pressure of 1 in the vapor phase, R is the gas constant, with columns containing a polymer-coated support. The
B11 is the second virial coefficient for the probe, B13 is the amount of polymer can be determined from Soxhlet
mixed virial coefficient of the solute vapor and carrier gas, extraction or by calcination of both coated and uncoated
V11 is the partial molar volume of 1 at infinite dilution, support, giving the weight percent of volatile material, and
P is the total pressure and K is the equilibrium partition hence the weight of polymer. Errors involved in using IGC
coefficient, defined as the ratio of concentration of solute to do thermodynamic calculations have been examined..6/
in the stationary phase, q, to that in the gas phase, c, i.e. The largest source of error is in the determination of
K q/c. the amount of polymer present. It was concluded that
Mixed virial coefficients are difficult to find: if the calcination was preferred over extraction owing to the
carrier gas is used at moderate pressures (a pressure of presence of extractable inorganic materials in common
less than 2 atm or 202.65 KN m 2 ) the last term can be supports.
ignored. Rewriting Equation (2) in terms of the specific For the characterization of new polymers the most
retention volume gives Equation (3) informative IGC data are obtained from a retention
diagram. In this experiment the value of Vg is determined
273.16R p01 .B11 V1 /
ln g1
1 D ln 0
.3/ over a range of temperatures and log Vg is plotted as
Vg p1 M1 RT a function of 1/T. An instrument designed to carry out
where M1 is the molar volume of the probe. Other this process automatically has been described,.7 – 9/ and
thermodynamic quantities can be calculated once the conventional GCs can be readily modified to obtain these
activity coefficient is known, for example the excess free data in a similar manner.
energy of mixing, Equation (4) A typical curve for a semicrystalline polymer such as
polypropylene (PP) is shown in Figure 2. The slope rever-
Gem D RT ln g1
1 .4/ sals are indicative of phase transitions. Such transitions
were noted.10/ as early as 1965 for polyethylene (PE) and
and the excess enthalpy of mixing, Equation (5) PP, but the first comprehensive study of polymer struc-
@ ln g1 Hme ture using IGC was reported in 1969 by Smidsrød and
1
D .5/ Guillet.11/ on poly(N-isopropyl acrylamide). The infor-
@.1/T/ R
mation obtained in such an experiment depends on the
temperature region of study. In the sample retention
diagram shown,.12/ segment AB represents the polymer
3 INVERSE GAS CHROMATOGRAPHY below its glass transition temperature (Tg ). Retention of
the probe in this region arises from condensation and
In an experiment using IGC, the species of interest is the adsorption onto the polymer surface, because the probe
stationary phase which is usually made up of a polymer- is unable to diffuse into the bulk of the polymer within
coated support, or finely ground polymer mixed with the time of passage of the probe peak. The slope of this
an inert support. A GC column can be packed with straight segment is given by .Hv Ha //2.3R, where
such a mixture, or coated on the inside with polymer, Hv is the latent heat of vaporization of the probe and
to give a capillary column. Some studies have been Ha is the enthalpy of adsorption of the probe on the
done using pure polymer in the column.2,3/ and using polymer surface.
capillary columns..4/ In work on the latter, Gray and In a study of PS.13/ Braun and Guillet examined the
Guillet.4/ found that Vg values for polystyrene (PS) change in shape of the retention diagram with respect to
were slightly higher for the open than for the packed the surface-to-volume ratio of the stationary phase. As
column, possibly because of the higher specific surface the amount of polymer on the support decreased, reversal
area available in the open column. In another study, from normal linear behavior became less pronounced
Lichtenthaler et al..5/ found that the capillary system is (Figure 3) and at low loadings (0.36%) the minimum
more sensitive to carrier gas flow rate, and that the Vg was no longer detectable. However, the data collected
DOI: 10.1002/9780470027318.a2016
T /°C
A 110 100 90 80
3.6
Log Vg
Slope × 10–3
F B
D
3.4
G 3.2
T1
3.0
1/Tm 1/Tg
1/T
Figure 2 Retention diagram for a semicrystalline polymer. Tg is

the glass transition temperature. Tm is the melting temperature. 2.4
Log10 Vg
Area A – C represents a nonequilibrium absorption of the

probe into the bulk phase; area C – D represents equilibrium
absorption of the probe molecules in the amorphous polymer
phase; area D – F represents the transition that occurs in 2.0
crystalline polymers – the melting process; area F – G represents
Tg = 98 °C
the equilibrium absorption of the probe molecules in the
amorphous polymer phase.
2.6 2.7 2.8
103/T (K)
Tg 0.07%
Figure 4 () Overall slope and ( ) derivative of (ž) retention
0.36
diagram for n-hexadecane on PS.
4.0
Log10 Vg
0.98
4.9 transition Tg . Theoretically this represents the first
3.0 detectable contribution of bulk sorption to the total reten-
12.5 tion volume, attributed to the diffusion of the probe into
19.7 the bulk polymer which reflects the mobility of small
2.0 20 – 40 carbon atom segments, leading to a large increase
in its free volume. This is the temperature at which
the amorphous polymer changes from the glassy to the
2.2 2.4 2.6 2.8 rubber-like state. These authors also derived model cal-
103/T (K) culations of retention diagrams using a simple bimodal
absorption mechanism which matched the experimental
Figure 3 Effect (experimental) of loading (%) on retention curves (Figure 5).
diagram for n-hexadecane on PS. Tg is taken as the first deviation The next region, corresponding to a change in the
from linearity of the plot. slope of the diagram (B – C in Figure 2), represents a
nonequilibrium absorption of the probe into the bulk
on an automatic molecular probe machine is sufficiently phase. The diffusion rate is slow in this region, hence the
precise that in this lower concentration region, Tg can be molecules injected as a pulse at this temperature would
easily determined from plots of both the first and second not penetrate through the entire bulk of the polymer
derivatives of the experimental plots of log Vg versus 1/T during the time of passage of the solute peak. The solute
(see Figure 4). does not have time to reach an equilibrium partition
The results for PS (Figure 3) showed that the temper- between polymer and carrier gas, hence the Vg value
ature of first deviation from linearity remained constant obtained is flow rate dependent. Bulk contribution to
(96 – 98 ° C). This temperature is interpreted as the glass the retention volume increases up to point C, which is a
DOI: 10.1002/9780470027318.a2016
percentage crystallinity of the sample at any temperature,

L /1000
reflected by the difference in specific volume (caused by
5.0 bulk sorption) between a totally amorphous and partially
crystalline product. This percentage crystallinity is given
L /100
by Equation (7)
Log10 Vg
4.0
Vg.experimental/
%Crystallinity D 1 ð 100 .7/
L /10 Vg.extrapolated/
3.0
Since the use of GC data to obtain thermodynamic
L quantities is based on the bulk absorption model, it is only
2.0 in the latter region that experimental data can be used
to obtain activity coefficients, and so on..13/ To ensure
2.2 2.6 3.0 3.4 that the Vg values do represent pure bulk absorption they
3 must be independent of the carrier gas flow rate. Once
10 /T (°C)
this is confirmed, the presence of bulk sorption only is
Figure 5 Model calculations of the shape of the retention verified by measuring Vg for the same probe at several
diagram for a glassy polymer (such as PS) as a function of the percentage loadings of polymer. If Vg changes, it should
thickness of the polymer layer (L). be extrapolated to infinite percentage loading. This step
is essential before doing any thermodynamic calculations.
function of the film thickness. This maximum temperature
is reached when the increase in bulk sorption caused by
the increase in the probe diffusion constant, D, is balanced
4 THE GLASS TRANSITION
by the decrease in retention caused by increased volatility
of the probe. In this nonequilibrium region it is possible to
obtain information about the probe diffusion coefficient, Numerous studies have been carried out concerning the
D, and its dependence on temperature. For noncrystalline effect of experimental variables on the glass transition.
polymers, normal liquid-like behavior is achieved at Llorente et al..15/ studied poly(cyclohexyl methacrylate)
C. Section C – D represents equilibrium absorption of using good and bad solvents as probes; both showed
the probe molecules in the amorphous polymer phase. a transition in the retention diagram, but only the
Contributions to Vg come from surface adsorption, nonsolvents gave Tg in quantitative agreement with
bulk absorption and condensation on the surface. The values from differential scanning calorimetry (DSC)
surfaces available to the probe are the polymer – gas and measurements.
polymer – support interface, and any additional surfaces Studies have been reported on the glass transitions of
between crystalline and amorphous regions in the bulk PVAc,.16/ PP, poly(1-butene), and ethylene – propylene
polymer. The slope here is given by Equation (6) copolymers,.17/ as well as polymer blends including
X PS – butadiene,.18/ polyacrylonitrile,.2,19/ poly(ethylene
Hv bi Hai Hm terephthalate) (PET).20/ and poly(e-caprolactam),.21/
i blends of poly(methyl methacrylate) (PMMA) and
.6/
2.3R poly(vinyl chloride) (PVC),.22/ block copolymers of
The bi values are weighting factors for each surface styrene and tetrahydrofuran.23/ and graft polymers of
and Ha are the enthalpies of adsorption; these can be methyl methacrylate and stearyl methacrylate..24/ In gen-
found experimentally.14/ and are related to the surface-to- eral, compatible systems are detectable if the mixture
polymer ratio for the polymer film (Hm is the enthalpy demonstrates only a single glass transition.
of mixing of the polymer and probe.) Braun and Guillet.25/ investigated the failure of some
The following section of the curve (D– F) represents the probes to detect Tg . They found that the solubility of a
next transition that occurs in crystalline polymers – the probe in the polymer was not enough to characterize the
melting process. Since the crystalline phase is usually polymer – probe interaction near Tg . Interactions of the
impermeable, this section of the plot can give information probe with both the bulk and the surface of the stationary
about the size, shape and distribution of crystalline phase must be considered. To maximize reversal in the
regions. The final, linear section of the plot represents the ln Vg versus 1/T plot, the bulk contribution should be as
wholly amorphous polymer. Extrapolation of this line to large as possible and the surface term as small as possible,
lower temperatures and comparison of these values with hence the bulk to surface ratio, not the solubility of probe
the true experimental values gives information about the in polymer, is the critical parameter.
DOI: 10.1002/9780470027318.a2016
5 SURFACE STUDIES
5.1 Adsorption Isotherms

For the case of bulk absorption, when the retention
Detector response, h
volume is independent of probe sample size, the equi-
librium concentrations of the probe in the polymer and
gas phase are linearly related for low concentrations of
the sample..26/ When surface adsorption is present, the
isotherm relating these two concentrations is often curved
owing to surface heterogeneity and saturation of avail-
able sites. In addition, the experimental concentrations
used may not be low enough to ensure a linear isotherm;
under these conditions the shape of the isotherm can be
used to investigate the adsorbate – adsorbant interaction.
There are two approaches using GC to obtain adsorp-
tion isotherms. The ‘‘frontal’’ technique takes into 0 20 40 60 80 100
account kinetic factors and gas phase volume changes
due to vapor adsorption. Here.27/ the sample is con- Retention volume (mL)
tinuously fed into the column. For substances with a
Figure 6 Chromatographic peak shapes for larger injections of
Langmuir isotherm (adsorption) the result is a single decane (0.03, 0.06, 0.15, 0.3, 0.5, 0.7, 1.0 µL) on a column packed
sharp step, produced at the first exit of the substance. with PMMA beads.
From the time needed for breakthrough, the amount of
substance retained can be determined. Usually, the ‘‘elu- weight of sorbant corresponding to the partial pressure p
tion’’ technique.28/ is used, where a pulse of material is is, Equation (10)
injected and the shape of the isotherm is found from a
single unsymmetrical peak. Using the gas phase concen- mcal Sads
aD .10/
tration of eluted probe vapor, c, the retention volume mScal
may be calculated,.29/ Equation (8)
where m is the mass of sorbant and Sads is the chart area
Z
1 c bounded by the diffuse profile of the chromatogram. If
aD Vc dc .8/ different areas (Sads ) corresponding to different values of
m 0
h are measured, the isotherm relating a and p may be
where a is the amount of probe vapor adsorbed on mass m found, using the above two equations.
of adsorbant. If the only peak broadening effect present is Several polymers were investigated by Gray and
nonlinearity of the isotherm, then one side of the elution Guillet.26/ using nC10 as the probe. For PMMA beads,
peak should be vertical and Vc can be determined from and PS- and PVAc-coated glass beads, the isotherms
the other, diffuse side, as in Figure 6. represented multilayer adsorption (type II in Brunauer’s
Figure 6 shows the change in peak size with varying classification.31/ ); here the heat of adsorption is equal to
amounts of n-decane (nC10 ) traveling through a column or less than the heat of liquification of the adsorbate. As
filled with PMMA-coated support..26/ As the concentra- the amount of adsorbate on the surface was increased,
tion of nC10 increases, the front profiles become more the partial vapor pressure approached (as a limit) the
diffuse but fall on a common curve while the rear profiles vapor pressure of pure adsorbate at T. Apparently, for
remain almost vertical, fulfilling the experimental require- nC10 interaction with glassy polymers, the shape of the
ments needed to use the elution technique in finding the isotherm at high coverages is governed primarily by
adsorption isotherm. The amount of nC10 adsorbed on surface saturation. Using the frontal curve in Figure 6
the column can be described.30/ as a function of its partial one can construct.26/ adsorption isotherms, as shown in
pressure, p, Equation (9) Figure 7 at various temperatures.
mcal qRT For nC10 on poly(styrene-co-divinylbenzene) beads,
pD h .9/ and on PS-coated glass beads, the peak retention times
Scal VP
increased with decreasing sample size. The rear profiles
where h is the peak height, Scal the calibration peak area did not fall on a common curve, implying nonequilibrium
on the recorder chart, mcal the number of moles of nC10 , conditions and that some kinetic process (probably
q the recorder chart speed and VP the carrier gas flow rate penetration of the probe into bulk polymer) was the
at temperature T. The amount of nC10 sorbed per unit cause of the peak broadening. Bulk sorption below Tg
DOI: 10.1002/9780470027318.a2016
VR equal to Ka AL . The surface partition coefficient can

35.3 °C
mol)
therefore be found by using a support of known surface

area; conversely, by comparison of retention volumes
–6
3 for the same polymer – probe system the surface area of

31.7°
Decane adsorbed (10
the stationary phase can be found. The surface partition

coefficient can be rewritten as Equation (12)
2 40.6°
Ha
ln Ka D ln Ka,0 .12/
RT
46.1°
1 where Ha is the enthalpy of adsorption. If the specific
50.3°
retention volume, Vg , is used, the expression for the
surface area is, Equation (13)

0 100 200 300 400 500 Ha
ln AL D ln Vg C ln wL ln Ka,0 C .13/
Partial pressure of decane (Pa) RT
Another expression for surface area involves the
Figure 7 Adsorption isotherms at indicated temperatures for
n-decane on PMMA blends.
surface area of the uncoated stationary phase and
the known amounts of polymer and inert support,
Equation (14)
is known, but it is slower and more complex than for

above Tg ..32/ This explanation was substantiated by a 100
comparison study of nC10 with PE (where bulk sorption AL D wL Sps 1 .14/
c
is rapid) and with glass beads (no bulk sorption). For the
latter case, at low concentrations of probe the rear slopes where c is percentage loading of polymer on the support
were almost superimposable, hence the factor causing and Sps is the accessible surface area, i.e. that covered
peak broadening was absent; it therefore seems probable by the polymer, as seen by the probe. From studies on
that peak tailing was due to limited bulk sorption. PS.13/ it was found that for greater than 1% loading,
film thicknesses of 103 Å and larger were obtained; for
loadings of 19%, the film thickness was 17 000 Å. Below
5.2 Surface Areas
0.02% loading, it appeared that there was not sufficient
Usually it is assumed that bulk and surface processes material to give monolayer coverage; hence, even above
make independent contributions to the retention volume Tg , surface contributions would have to be taken into
(VR ),.33/ Equation (11) account when dealing with very thin films.
In a study on PS by Galin and Rupprecht.34/ it was
VR D Kb wL C Ka AL .11/ found that the value of accessible surface area available
to the probe decreased with its molecular weight; this
where Kb and Ka are the bulk and surface partition was thought to be related to the relative dimensions of
coefficients, respectively, wL is the mass and AL is the the probe molecules and the smallest pore size in the
surface area of the stationary phase. If wL is varied, a plot support. Branched PS.34/ and cellulose fibers.35/ have also
of VR /wL against 1/wL will give an intercept of Kb and been studied using this technique.
a slope of Ka /AL . To ensure that equilibrium data are A third method of finding surface areas is the
being used, the retention volumes must be extrapolated to Brunauer – Emmett – Teller (BET) approach, which uses
infinite dilution of probe, zero flow rate of carrier gas, then the experimental isotherm. A two-parameter BET equa-
infinite percentage loading of the column. Knowing AL as tion is Equation (15)
a function of VL , Ka can be found. This approach assumes

negligible contribution from other adsorption processes. p1 /p01 1 c 1 p1
In addition, small sample sizes are used so that VR , Kb D C .15/
v.1 p1 /p01 / vm c vm c p01
and Ka can be assumed to be independent of sample
concentration. The surface contribution is expected to where p01 is the saturated vapor pressure of the solute, v
be important if the vapor has low solubility (therefore the volume of the solute on the surface, vm the volume of
low bulk concentration) in the polymer, or if there are the solute on the surface supposing monolayer coverage,
strong dipole – dipole or hydrogen bonding interactions and c is a constant. Using values for v and p1 /p01 from
between the probe and the polymer. Below Tg the bulk experimental data, the left side of Equation (15) is plotted
contribution is often assumed to be negligible, leaving against p1 /p01 to give a straight line from whose slope and
DOI: 10.1002/9780470027318.a2016
intercept vm can be calculated. Knowing the surface area where C is a constant depending on A. Equation (19)
covered by the probe molecule, the surface area in the relates the energy of adhesion to the free energy of
column may be found. Results using this approach.26/ adsorption:
were found to be in good agreement with geometric q
surface areas of PMMA beads and of polymers coated on RT ln Vg0 C C D 2Na gds gdi .19/
glass beads.
An early example of the use of this technique was where gds and gdi are the dispersive components of the solid
carried out by Tremaine and Gray.36/ who calculated surface and the interactive solute phase, respectively. N is
an adsorption isotherm from the variation of the peak Avogadro’s number and a is the area of the adsorbed
maximum retention volume with sample size on cellulose. molecules (solutes). In IGC experiments, a series of
Surface areas, enthalpies and entropies of adsorption interactive solutes such as alkanes can be injected into
were found. the chromatographic column in order to determine the
In another work.37/ by these authors the retention dispersive surface energy, gds . A plot of Ga1 or RT ln Vg0
volumes were fitted directly to a modified BET equation versus the number of carbons in the alkane series is linear
to find the monolayer capacity without deriving the and the slope of the straight lines will account for the
adsorption isotherm. Surface area results agreed to incremental contribution of Ga1 .
within 5% of the values calculated using the adsorption The molar enthalpy of adsorption can also be calculated
isotherm. The GC method is particularly advantageous from Ga1 data directly, Equation (20)
using materials like cellulose where the dry and wet
d Ga1
polymer have very different properties. By saturating H1a D T2 .20/
the carrier gas with water vapor (or any other vapor of dT T
interest), measurements can be obtained under conditions Combining Equations (19) and (20), the dispersive
in which the material is used. surface energy is, Equation (21)
2
5.3 Surface Energy of Polymers 1 GCH
a
2
gds D .21/
4gCH2 NaCH2
To quantify the interaction of solute in the gaseous form
with the polymer layer, the surface energy, gs , may where gCH2 is the surface energy of a hydrocarbon
be obtained. The surface energy describes interaction consisting only of n-alkanes, and aCH2 is the area of
caused by dispersive forces or a combination of dispersive one CH2 group. Equation (21) usually tests the IGC
forces with H-bonding or with dipole – dipole forces. method for obtaining the dispersive surface energy of
Fowkes.38/ first reported this method of characterization polymers.
and determined the surface energy of several components.
Generally, the contribution of all forces can be expressed
as the energy of adhesion, Equation (16) 6 CRYSTALLINITY
ga D gd C gsp .16/
The crystallinity of a polymer can be studied using X-ray,
where gd is the contribution of dispersive forces and gsp is infrared (IR), calorimetry, density, and other techniques,
the contribution of specific interaction forces such as H- but these methods require knowledge of the properties of
bonding, dipole – dipole, acid base, and so on. From the a 100% crystalline polymer and involve the assumption
gas chromatographic measurements, Vg0 is determined that the variation of the chosen property is linear with
by using Equation (17). Vg0 relates to the equilibrium the degree of crystallinity. The gas chromatographic
constant K between the adsorbed solute and the polymer technique only assumes nonpenetration of the probe into
surface: the crystal phase below Tm .
Vg0 D Ks A .17/ 6.1 Degree of Crystallinity

where Ks is the surface partition coefficient and A is Measurements of polymer crystallinity can be readily
the total surface area of the polymer powder in the made using the molecular probe apparatus described in
chromatographic column. Thermodynamically, the molar section 13. The polymer can be coated from solution onto
free energy of adsorption, Ga1 , of solute on the polymer a suitable support such as Chromosorb W. However, with
layer can be related to Vg0 by Equation (18) many polymers the thermal history of the coating process
may alter the crystallinity of the sample. In this case,
Ga1 D RT ln Vg0 C C .18/ cryogenic grinding of the polymer, followed by screening
DOI: 10.1002/9780470027318.a2016
to remove particles larger than about 0.1 mm, will give

particles which can be blended mechanically with the 80
support prior to packing the chromatography column.
Percent crystallinity
Figure 8 shows the IGC retention diagram for linear
PE using decane as a probe, acquired using an automated 60
molecular probe instrument. The column was heated at a
rate of 0.50 ° C min 1 through the melting transition while
very small samples of decane (<1.5 ð 10 6 mol) vapor 40
and nitrogen were injected into the helium carrier gas
at intervals of approximately 2.5 min. The 1-m column
contained 0.16 g of polymer coated on 60/80 mesh glass 20
beads..39/
Above the crystalline melting point, the 32 data points
are exactly linear with a standard deviation for the 0
100 110 120 130
slope of less than 0.2%. This gives some confidence
in a linear extrapolation to lower temperatures to give Temperature (°C)
log Vg0 , where Vg0 is the expected value of the retention
volume of the completely amorphous polymer at each Figure 9 Percentage crystallinity versus temperature for linear
PE using DSC and the molecular probe techniques: (ž) DSC
temperature in question. Thus the percent crystallinity at data, annealed at 1.25 ° C min 1 , heated at 1.25 ° C min 1 ; ( )
any temperature below Tm is given by Equation (22) molecular probe data, annealed at 1.0 ° C min 1 , heated at
! 0.5 ° C min 1 .
Vg
%Crystallinity D 100 1 .22/
Vg0 cycle as the sample used in the GC. The latent heat of
crystallization of perfectly crystallized PE was assumed
where Vg0 is the value for the 100% amorphous polymer to be 68.5 cal g 1 . The small differences in the two curves
obtained by extrapolation. could be due to PE being a thin layer coated on glass when
Figure 9.39/ shows a plot of percentage crystallinity studied by DSC and being the bulk phase when studied
against temperature, comparing GC results with DSC by GC. Retention times were found to decrease as the
results. The latter were obtained by integrating the heat polymer was cooled from melt to below Tm , a reflection
of fusion curve for a sample put through the same thermal of the decrease in the amount of amorphous material.
Although the heating rate in the DSC experiments was
more than twice that used in the IGC run, the close
2.4 agreement between two entirely different experiments is
remarkable, and is a strong confirmation of the validity of
the assumptions involved in the use of both procedures.
A further improvement in crystallinity measurements
2.2 by IGC is known as curvilinear extrapolation. In a study
on semicrystalline PP, Braun and Guillet.40/ found that the
linear extrapolation gave a crystallinity of 36% at 50 ° C,
(tR)
2.0 while using curvilinear extrapolation the curve leveled off

10
near 66%, which was near the value of 64% obtained from
Log
density measurements. Besides giving a more accurate

1.8
extension of the curved part of the retention diagram,
the applicability of this approach is less dependent on the
temperature range chosen than the linear method.
Experiments can also be done using mixed support
1.6 with ground-up polymer; this latter method is preferred
over using the solution-coated support, as the coating
procedure changes the thermal history and thus the
1.4 crystallinity of the sample. In a study on PE powder
22 24 26 28 Hudec.41/ found that a correction was necessary to
4
1/T × 10 account for contributions to Vg from adsorption on the
support used; when performing the experiments using
Figure 8 Retention diagram for decane on high-density PE. support alone, it was found that the retention times for
DOI: 10.1002/9780470027318.a2016
the probes were inversely dependent on temperature and poly(ethylene glycol) adipate.44/ Lipatov and Nesterov
represented 10% of the net retention time for the PE- found that the degree of crystallinity of the polymer
coated support using the same probes. Tetradecane was decreased with the film thickness. This was explained by
most effective as a probe for particles of less than 0.07-mm hypothesizing the formation of an adsorption polymer
diameter. Braun and Guillet.42/ also found in their study layer at the solid interface. The proximity of this layer
on PE that for alkane probes C8 – C12 particles of diameter to the interface would result in smaller packing density,
less than 0.1 mm were most effective. Equation (22) can diminishing the mobility of the polymer molecules. This
be approximated by Equation (23) effect was found to be independent of the nature of the
support.
tc
%Crystallinity D 100 1 .23/ In some systems there will be a surface contribution to
ta the retention volume below Tm , leading to a low apparent
where ta is the retention time expected for the totally crystallinity. Courval and Gray.33/ studied the interactions
amorphous sample from the extrapolation and tc is the of hydrogen-bonding probes on low-molecular-weight
retention time obtained from the melting or cooling curve. poly(ethylene oxide) (PEO). They found it necessary to
extrapolate the retention volumes to infinite percentage
loading of polymer, where surface sorption would be
6.2 Rates of Crystallization
negligible.
In an analogous experiment, rates of crystallization for Crystallinity measurements have been made on a
a polymer sample can be determined by melting the variety of polymers, including PP,.32/ PEO,.32/ and linear
polymer coating and measuring its percent crystallinity and branched PE,.42/ and copolymers of PE with vinyl
as a function of time at constant temperatures below acetate (VAc) and carbon monoxide (CO)..42/
Tm . Typical plots on high-density PE are shown in In later work, Al-Saigh and Chen.45/ proposed that
Figure 10..39/ below Tm a second adsorption term due to solute
The plots of percentage crystallinity against log time adsorption on the surface of small crystallites needs to be
show some curvature, possibly indicating a complex considered. Since the crystalline regions in semicrystalline
kinetic scheme; the nucleation and growth process may polymers can be very small, their surface area may be
also change with time and the amount of crystallinity. significantly larger than either that of the support or the
The fact that the sample is a thin polymer film coated on coated polymer.
glass could cause this behavior, as the surface-to-volume
ratio has been shown.43/ to affect polymer crystallization
rates. It is possible that the glass surface can initiate or 7 DIFFUSION
stabilize nucleation on sites at a temperature where no
crystallinity is detectable.
A number of early studies helped to define the scope The ability of a small molecule to diffuse through a solid
of the IGC crystallinity procedures. In work done on polymer phase is of great importance when considering
polymers for industrial applications. The diffusion of trace
contaminants into a bulk polymer, and the rate at which
stabilizers migrate from containers to the food inside,
0 are two such applications where diffusion constants for
Percent crystallization
small molecules at infinite dilution in the polymer system

127.5 °C
20 are needed. These conditions are reproduced closely in
126.8 °C IGC experiments, making it the preferred method for
40
obtaining diffusion constants under actual use conditions.
60 126.2 °C In theory, a sample injection that can be represented
as a delta function should give a chromatogram which
125.5 °C
80 can also be described as a delta function. In fact, at best,
the eluted peak will be broadened to give a Gaussian.
100 Often the peak is skewed as well. Various factors
combine to produce these effects, including instrumental
5 10 50 100 500 imperfections such as dead volume in the detector, and
Time elapsed (min) these can be minimized by proper design.
Nonequilibrium conditions in the column and the
Figure 10 Percentage isothermal crystallization at the indi- existence of a nonlinear adsorption isotherm will result
cated temperatures as a function of time for high-density PE. in skewed peaks. Other peak broadening factors are
DOI: 10.1002/9780470027318.a2016
diffusion of the solute through the stationary phase by the stationary phase, i.e. glass beads of average
perpendicular (axial) to the direction of flow, and eddy radius r (for support consisting of spherical beads).
diffusion, which is a result of the flow of moving gas Figure 11 shows experimental data of H versus u for
around the particles of the column packing. Van Deemter a number of probes in low-density PE and natural
et al..46/ related some of these effects to the plate height rubber.47/ at various temperatures. In later work, mea-
of the column, H, Equation (24) surements were made on the diffusion of antioxidants
B and other solvents in molten PE. The values of D and
H DAC C Cu .24/ Ea , the activation energy for diffusion, are shown in
u
Table 1..48/
where u is the linear velocity of the carrier gas in the Giddings.49/ worked out an expression for C under
column and A is a constant which accounts for broadening nonequilibrium conditions for a thin film distributed
due to instrumental factors. B/u describes the diffusional evenly over a solid surface, and found that the constant
spreading of the vapor as it flows through the column in Equation (26) changed from 8/p2 to 2/3. In addition,
where, Equation (25) he divided C into two terms where Cg represents the gas
phase mass transfer and Cs the stationary phase mass
B D 2wDg .25/
transfer. The expression for C (Equation 26) accounts
Dg is the diffusion coefficient of the vapor in the gas phase only for Cs , but for a highly loaded system (>0.9%) Cg is
and w is the eddy diffusion constant (<1). only 3 – 5% of C; for a system of 0.2% loading Cg would
C is a constant related to the finite amount of time be 15% of C and hence would have to be subtracted
needed for the gas and stationary phases to reach from C before accurate diffusion coefficients could be
equilibrium. Using a simple model, C can be expressed calculated..50/
by Equation (26)
8 d2f k
CD .26/
p D1 .1 C k/2
2
5.0
1
where df is the thickness of the stationary phase, D1 is
the diffusion coefficient of the vapor in the stationary
phase and k the partition coefficient (the experimental
retention time minus the retention time for an inert 4.0
marker, i.e. methane).
7.1 Determination of Diffusion Constants

3.0 3
To find diffusion coefficients for solutes in the polymer
H (cm)
phase, H values are calculated from the chromatographic 2

peak shapes using Equation (27)
2 2.0 4
l d
HD .27/
5.54 tr
where l is the column length and d the measured peak
6
width at half-height. By choosing experimental conditions 1.0
carefully (minimizing dead volume and experimental 5
7
response time) one factor can be made to predominate,
namely diffusion in the stationary phase. 8
At high flow rate, B/u will approach zero, so a plot of H 0.0
against u (Equation 24) should produce a linear section 10 20 30
with slope C..45/ The stationary phase thickness can be Linear flow rate u (cm s–1)
found using Equation (28)
Figure 11 Van Deemter curves for various columns: (1) ben-
w 3v zene/low-density PE at 27 ° C; (2) benzene/natural rubber at
df D .28/
r r 27 ° C; (3) benzene/low-density PE at 25 ° C; (4) benzene/natural
rubber at 25 ° C; (5) nonane/low-density PE at 50 ° C; (6) decane/
where w is the weight and r the density of the poly- natural rubber at 40 ° C; (7) dodecane/natural rubber at 85 ° C;
mer on the column, and v is the volume occupied (8) hexadecane/PE at 200 ° C.
DOI: 10.1002/9780470027318.a2016
Table 1 Diffusion coefficients and activation energies for form a stable even coating on the support and rates of
selected solutes in low-density PE diffusion through polymers are slower than through other
stationary phases, so the contribution to peak spreading
Solute Temperature Diffusion Activation
(° C) coefficient energy, Ea from diffusion is more important.
D` ð 108 (kcal mol 1 ) In traditional analytical GC, the peak broadening is
(cm2 s 1 ) directly related to the resolving power of the columns and
as such has received extensive theoretical attention..52 – 55/
n-Dodecane 121.8 9.15 8.9 š 1.3
125.0 10.5
There are two major factors that contribute to peak
132.0 12.0 broadening: diffusion of the injected solute in the carrier
Tetralin 115.0 9.44 10.2 š 0.5 gas and diffusion of the solute in the stationary phase.
125.0 13.9 The first factor is known as the gas-phase mutual diffusion
132.0 16.1 coefficient, Dg , and the second factor is related to the
140.0 21.3
liquid-phase mutual diffusion coefficient, DL .
cis-Decalin 121.8 9.12 9.0 š 1.0
125.0 10.6 In IGC experiments, where a polymer is a stationary
132.0 12.3 phase, DL is the polymer – solute diffusion coefficient. A
trans-Decalin 121.8 10.6 9.2 š 0.7 large body of data is accumulated using PIB coated on
125.0 11.9 Chromosorb W as the stationary phase and linear alkanes
132.0 13.5
starting from methane to undecane as solutes..56/ Munk
140.0 18.1
BHA 136.8 7.38 10.0 š 0.2 et al..52/ varied the temperature, flow rate of the carrier
143.3 9.20 gas, and column loading systematically. They were able
158.9 13.8 to design a method of evaluating the peak broadening
169.2 18.3 data from which both diffusion coefficients, Dg and DL ,
BHT 136.8 4.70 9.4 š 0.2 were obtained as follows, Equation (30)
143.3 5.83
158.9 8.51 !
2gD1 g JgL gg
169.2 11.1 H DAC C Rf .1 Rf /u0 C 0 .30/
u0 DL Dg
BHA D Butylated hydroxyaniline, BHT D butylated hydroxytoluene.
where H is the average height equivalent to one
Giddings revised Equation (26) to Equation (29) theoretical plate which is the ratio of the length of the
column to the number of theoretical plates (N), u0 is the
2 d21 k carrier gas flow rate measured at column outlet, J is the
CD .29/
3 D1 .1 C k/2 pressure correction factor defined in Equation (1), Rf is
Knowing C, df and k, the diffusion coefficient D1 can the retardation factor, g, gL and gg are the tortuosities
be calculated. According to this model a decrease in D1 of the structural factor (L and g refer to the liquid and
should result in greater peak spread but no change in the gas phase, respectively), A is a constant factor that is
independent of the flow rate, and Dg and DL are the
peak maximum.
The temperature dependence of D can be determined diffusion coefficients of the solute in the gas and liquid
by monitoring peak shape changes with T. Gray and phase, respectively. Thus the average height equivalent
to one theoretical plate of the column depends on
Guillet.47/ found that for tetradecane in PE melt, D1
the solute-related parameters Dg and DL and on the
increased only ten-fold between 125 and 170 ° C and hence
column-dependent parameters A, g, gg , and gL . The latter
there was little change in peak shape or maximum. For the
parameters are the same for all solutes, but they vary
same probe in PS melt,.51/ calculated D1 values dropped
from column to column. If a set of columns is prepared in
sharply as T approached Tg . The peak distortion as T
a similar way, one would expect the column parameters
approaches Tg is related to the temperature dependence
to have similar values. Therefore, for a set of columns
of D1 . At 130 ° C no peak is detectable, and the solute
differing only in column loading, one would expect that
is eluted with the carrier gas. This total absence of
the parameters A, g, gg , and gL that depend only on the
peak is not uncommon, and occurs because the thick
column packing will be similar for all columns. In this case
polymer layer gives poor column performance (peak
gL will be strongly dependent on the polymer loading. The
spreading is large compared to retention volume). Work
Rf value can be calculated as follows, Equation (31)
has also been done on the effect of diffusion on the
shape of chromatographic peaks in the region of the glass Rf D .V0 Vd /.Vr Vd / .31/
transition..51/
There are advantages to finding diffusion coefficients of where V0 is the empty volume of the chromatographic
solutes in polymers using IGC. Polymers, being viscous, column equal to the retention time of the marker, Vr
DOI: 10.1002/9780470027318.a2016
is the retention time of the solute, and Vd is the dead the weight fraction activity coefficient, partial molar
volume in the column measured as the retention time of heats of mixing (H11 ) can be calculated (Equa-
e
the marker. tion 5), equivalent to Hmix . DiPaola-Baranyi et al..58/
In order to calculate both diffusion coefficients, it is tabulated these for alkane and butanol probes at
necessary to correct Equation (30) for gas compressibility, infinite dilution in PS, poly(ethylene – carbon monox-
Equation (32) ide), PE, poly(ethylene – vinyl acetate) (P(E-VAc)),
! PVC, poly(1-butene), poly(methylacrylate) and poly(N-
.H A/u0 0 gL f gg J isopropyl acrylamide). Equation (34) does not include
D 2gDg C C 0 Rf .1 Rf /u20
f DL Dg f the correction for gas phase nonideality, but using an
.32/ inert carrier gas and low column pressures, the tem-
where f in most circumstances is within a few percent perature coefficient of the correction should be small.
of unity and is a correction for gas compressibility. It is Polymer – solvent systems showed small activity coef-
defined as follows, Equation (33) ficients .a1 /w1 /1 and excess heats of mixing (H11 ).
" # Nonsolvent systems had much larger activities and heats
Pi 2 J2 of mixing.
f D C1 .33/ Heats of solution can be calculated using Equation (35)
Po 2

where Pi and Po are inlet and outlet pressures on the Hs Vg0 1
D @ ln .35/
column. A plot of [.H A/u0 /f ] versus [Rf .1 Rf /u20 J] R @ T
should yield a straight line with a slope of gg /Dg .
Plots constructed in this manner using uncoated columns In a study on ethylene – vinylacetate copolymers,.59/
yielded negligible slopes within the experimental error. Dincer and Bonner divided Hs into contributions from
Considering gg is negligible, then plots of [.H A/u0 /f ] dispersion, dipole and induced dipole interactions and
versus [Rf .1 Rf /u20 J/f ] using coated columns should be from specific interactions such as hydrogen bonding and
linear and should yield 2gDg as the intercept and gL /DL charge-transfer complexes, Equation (36)
as the slope.
Hs D f .a, µ/ C X .36/
where f .a, µ/ is a function of the probe’s polarizability

8 THERMODYNAMIC STUDIES (a) and dipole moment (µ). A plot was made of
Hs against a for alkanes and aromatics. These
8.1 Activity Coefficients, Heats of Mixing and Heats of points were fitted to quadratic equations, and the
Solution difference between the fitted and experimental values
In conventional GC the infinite dilution activity coeffi- was interpreted as the contribution due to permanent
cient is expressed in terms of, among other variables, dipole and special interactions. This was taken to be
the molecular weight of the stationary phase, M2 . This quantitatively equivalent to the enthalpy of hydrogen
approach has been used to find M2 , but in IGC the bonding..60/ Plots were also done of Hs against µ; the
quantity of interest is g1 1 . When the stationary phase is form of f .a, µ/ was deduced from the two plots.
a polymer, M2 becomes difficult to quantify, especially The free energy of mixing, Gm , can be expressed
in the case of a polydisperse sample. In addition, g1 1 is using volume fractions, Equation (37)
defined with respect to the mole fraction of component 1
in a binary solution of small molecules. In IGC the two Gm D kT[N1 ln f1 C N2 ln f2 C cf1 f2 .N1 C rN2 /]
components are very different, both in molecular size and .37/
concentrations present. These problems are rationalized Mixing is unfavorable for Gm 0, therefore,
by the use of the weight fraction infinite dilution activity Equation (38)
coefficient. Patterson et al..57/ defined the infinite dilution 2
activity coefficient with respect to the weight fraction of 1 1
ccritical 1C p .38/
component 1 (w1 ), giving, Equation (34) 2 r
1
a1 273.16R p01 .B11 V1 / For large molecular weights r is much larger than 1,
ln D ln .34/ giving ccritical as approximately 0.5. Since c is a free energy
w1 p01 Vg M1 RT
parameter, it can be separated into an enthalpic (cH ) and
In this manner the activity coefficient of the probe an entropic (cS ) component, Equation (39)
in the polymer can be found using experimental
data and pure component properties alone. Using c D c H C cS .39/
DOI: 10.1002/9780470027318.a2016
cH can be calculated from pure component properties 8.2 Finite Concentration Gas Chromatography
using the Hildebrand– Scatchard regular solution theory
for nonpolar substances,.61/ Equation (40) Work has also been done at finite concentration using
GC. It involves the use of a carrier gas with a significant
V1 concentration of probe molecule in the vapor phase. A
cH D .d1 d2 /2 .40/
RT series of articles by Condor and Purnell explain the theory
where the d values are solubility parameters, Equa- and experimental set-up for these studies..77 – 80/ Several
tion (41) elution techniques can be used; all start from Equation (1)
and one technique is described below.

Evap 1/2 Brockmeier et al..73/ studied PS, amorphous PE and
dD .41/ atactic PP at both infinite and finite dilution. The latter
V
experiments were carried out using the technique of
The quantity on the right is known as the cohesive elution-on-a-plateau. The column is equilibrated with a
energy density and is an indication of the strength of stream of solute gas at steady concentration c. A sample
intermolecular forces in the pure component. concentration infinitesimally greater or less than c is
Experimental studies.62 – 64/ have shown cS to be of the injected, yielding a Gaussian peak. The first quantity of
order of 0.35 and it is sometimes left as a constant. interest is the distribution isotherm which (at pressure P)
c can be related to the weight fraction activity is given by Equation (45)
coefficient. For f2 ! 1, Equation (42)
Z y0
1 j Vg
a1 v1 V1 q.P/ D y dc .45/
ln D ln C 1 C c .42/ w2 0 1
w1 v2 .M2 /n v2
where y0 is the mole fraction of solute in the gas phase
where v1 and v2 are the specific volumes of the probe and
at pressure P0 in a zone of concentration c, and j
polymer, respectively.
is a compressibility correction which approaches J32 as
In polymers .M2 /n , the number average molecular
values were always positive and decreased with increas-
weight is usually large enough so that the second term
ing temperature in a complicated manner. There was a
in the last parentheses is very small. Substituting for
slight composition dependence, with c023 becoming lower
ln.a1 /w1 /1 gives Equation (43)
for the PS-rich copolymers. Patterson and Robard.81/

273.16Rv2 p01 .B11 V1 / reviewed the theory and its application to mixed sta-
c D ln 0
1 .43/ tionary phases. Other studies have been carried out
p1 Vg V1 RT
by Olabisi,.82/ Galin and Rupprecht,.83/ and others..84,85/
Using Equation (43), c can be determined directly from An apparatus for performing these studies is shown in
measurements of Vg under appropriate conditions. Figure 15.
Most experimental work uses the original Flory –
Huggins and/or the modified approach using core volumes
and segments, giving c and/or cŁ . c is sometimes taken 8.3 Henry’s Law Constants (Solubilities)
to have a temperature dependence of the form of Henry’s Law describes a two-component system where
Equation (44) one of the components (1) is in very low concentration
b relative to the other (2). Under this condition the
cDaC .44/ solubility of 1 in 2 (i.e. X1 ) can be related to the partial
T
pressure of 1 in the vapor (p1 ) by Equation (46)
From the original Flory – Huggins definition, a plot of c
versus 1/T should give a straight line. In fact, this inverse p1
H1 D .46/
trend is only true for part of the plot. The c – T curve is X1
more parabolic in shape and care should be used in doing
where H1 is Henry’s law constant. Liu and Prausnitz.86/
any extrapolation of c data.
expressed this in terms of the fugacity of component 1,
According to Flory – Huggins theory, c should show
Equation (47)
a composition dependence but studies.65/ on PS and
high-density PE with benzene and decane showed no
f1
such dependence. There is an extensive literature on H1 D lim .47/
x!0 X1
this subject including studies on PIB,.66 – 68/ PDMS,.69 – 72/
PS, amorphous PE and PP,.73/ cis-polyisoprene,.74/ linear Assuming ideal behavior of the gas in the column, and
and branched PE,.75/ poly(methyl sulfoxide),.70/ and that f1 is proportional to the weight fraction of solute in
poly(ethylene glycol)..76/ the polymer phase, then under equilibrium conditions,
DOI: 10.1002/9780470027318.a2016
Equation (48)
RT
H1 D .48/ 10
Vg M 1
[(δ12/RT ) –(χ/ V 1)] × 102

Infinite dilution weight fraction Henry’s constants
have been found for n-alkane solutes in long-chain 9
alkanes.87,88/ (C28 H58 – C36 H74 ), for volatile solutes
in PVAc,.89/ for liquid low-density PE at high pres-
sures.90/ and for PE.86,91/ and P(E-VAc).86/ at ambient 8
pressures.
7
8.4 Solubility Parameters
Solubility parameters provide another way of quantifying

6
the thermodynamic information obtained from an IGC
experiment. Previous methods for finding d2 values have
involved swelling or viscosity measurements, graphical 5
methods and the group-additive method outlined by 6 7 8 9 10
Small..92/ The IGC approach uses pure component δ1
properties and experimental data only, and gives d1 2
values for solutes at infinite dilution in the solid polymer Figure 12 Infinite dilution solubility parameters for poly(buta-
phase. diene – acrylonitrile) at 75 ° C. () Polar probes; ( ) nonpolar
DiPaola-Baranyi and Guillet.93/ related the solubil- probes. d02 .slope/ D 10.00 š 0.29.
ity parameter for probe (d1 ) and polymer (d2 ) to
several thermodynamic variables. From regular solu- Infinite dilution solubility parameters have been found
tion theory, assuming zero volume change on mixing, by this method for PS and PMMA,.93/ PVAc,.96/ cis-
Equation (49) polyisoprene, amorphous PP and an ethylene – propylene
1
copolymer (40% w/w ethylene),.64/ and also for poly-
H 1 D V1 .d1 d2 /2 .49/ chloroprene and poly(butadiene – acrylonitrile), 34% w/w
acrylonitrile, cis-1,4 polybutadiene and P(E-VAc) (40%
At constant pressure this can be rewritten as Equa- w/w VAc)..94/ Infinite dilution solubility parameters
tion (50) determined in this way for a number of polymers are
1 shown in Table 2.
G1 D V1 .d1 d2 /2 .50/ Experimental d02 values obtained by IGC are usually at
temperatures greater than 25 ° C, which is the temperature
or, combining regular solution theory with the Flory – that literature values are quoted for. To extrapolate the
Huggins theory, as Equation (51) experimental c results down to 25 ° C, Equation (44) is
V1
cD .d1 d2 /2 cs .51/ Table 2 Infinite dilution solubility parameters
RT
Working with hydrocarbon probes in PMMA and Polymer Temperature d1
2 Ref.
PS, plots were made of (d21 /RT A/V1 ) against d1 for (° C)
A D H11 , G1 1 , c, respectively. The plot using c showed PS 193 7.6 š 0.2 93
the least scatter of points and gave best values of d1 2 , and PMMA 100 8.5 š 0.3 93
this was the method chosen for data analysis. PVAc 135 8.5 š 0.4 96
In such a plot the slope would be C2d1 Ethylene – propylene 73 7.18 š 0.11 97
2 /RT and
rubber
the intercept would be d12 2 /RT cs /V1 . A typical Polyisoprene 30 7.96 š 0.10 97
example is shown in Figure 12..94/ Errors quoted for the PP 30 7.67 š 0.16 97
slope or intercept values are the standard deviation for Polychloroprene 75 8.83 š 0.22 94
slope/intercept in a least-squares plot. By definition.95/ Poly(butadiene – 75 10.00 š 0.29 94
the error in the intercept P wouldbe greater than that in acrylonitrile)
2 1/2 P(E-VAc) 75 8.26 š 0.17 94
the slope by a factor of [ N d1 /N] , where N is the cis-1,4-Polybutadiene 75 7.90 š 0.14 94
number of data points.
DOI: 10.1002/9780470027318.a2016
sometimes used. polar usually being alcohols or ketones. The net result is
b an experiment where a smaller fraction of the interactions
cDaC .44/ are specific or polar. For d1
2 calculations the division of
T
d may not be as applicable as for the more qualitative
The validity of this procedure can be tested by industrial applications.
measuring c values for a range of temperatures and
constructing a c versus 1/T plot. If the temperature range
8.5 Hydrogen Bonding
of interest is in the downward curved section of the plot,
Equation (44) can be used with care. When Tg of the DiPaola-Baranyi et al..76/ used IGC to investigate the
polymer is 50 ° C or more below room temperature, an thermodynamics of hydrogen bonding from heats of
extrapolation is not necessary and the easiest method is mixing. In a binary solution of small molecules, contribu-
to perform an experiment at 25 ° C. tions to hydrogen bonding arise from self-association in
Note that the experimental d1 2 values represent infinite the pure solute or solvent, and from hydrogen bonding
dilution solubility parameters, where other values quoted between the two components. The correction for self-
arise from finite concentration solution studies. d12 values association is found by measuring the heat of mixing
usually fall well within the literature range for a polymer, (H11 ) for the compound in question at infinite dilution
but the exact relationship between d and d1 is still not in a nonpolar solvent, such as hexane. When the solvent
certain. in question is a polymer, amorphous PE or PP could
For industrial application d is sometimes divided into be used.
components representing different contributions to the Alternatively, heats of solution (Hs ) can be used in
net interaction. Hansen.97/ proposed that the energy of these studies, since, Equation (54)
vaporization could be divided, Equation (52)
vap vap
H11 D Hvap C Hs .54/
Evap D Ed C Evap
p C Eh .52/
vap
Hvap is a function of the solute and experimental
where Ed is from polar (dipole – dipole and dipole – temperature and not the polymer, so differences in Hs
vap
induced dipole) forces and Eh is from hydrogen bond- for a given solute at fixed temperature will reflect changes
ing or charge-transfer complexes (specific interactions). in H11 .
This equation leads to Equation (53) In studying the hydrogen bonding between a small
molecule (solute and polymer solvent) using Hs ,
d2 D d2d C d2p C d2h .53/
two corrections are needed: one accounts for the
The nonpolar part, dd , can be approximated using nonhydrogen-bonding interactions (dipole – dipole, dis-
Small’s method and this is subtracted from an exper- persion) that the probe is capable of, and is estimated by
imental d to leave the polar and hydrogen bonding subtracting Hsmodel for a model, nonhydrogen-bonding
probe
contributions..62,98/ There is some question about how probe in the polymer from Hs . The other correction
well this division represents the forces experienced by a accounts for the nonhydrogen-bonding interactions that
probe in the polymer phase. Olabisi.82/ concluded that the polymer is capable of, and is estimated by measuring
the contribution of various forces could not be equally Hs values in the polymer and then in a reference poly-
divided, and that a different unknown proportion is mer (such as low-density PE). The net estimate of the
involved for each polymer – probe interaction. enthalpy change arising from hydrogen bonding between
Lipson and Guillet.94/ calculated d1 2 values for polybu-
the probe and polymer is, Equation (55)
tadiene, P(E-VAc), polychloroprene and poly(buta-
diene – acrylonitrile) using polar, then nonpolar, then a Hf D .Hsprobe Hsmodel /polymer
combination of probes, and found no difference within .Hsprobe Hsmodel /reference polymer .55/
experimental error. A factor affecting nonpolar inter-
actions such as a, the polarizability, is also a factor The experimental data needed would be Hs for the
in dipole-induced dipole interactions. Dipole moments probe in the polymer, then in the reference polymer, and
(used in calculating energies of dipole – dipole interac- Hs for the model in the polymer, then in the reference
tions) will also be a partial indication of a molecule’s polymer.
ability to hydrogen bond. The division of d into nonpo- Some results from this procedure.76/ are given in
lar/polar/specific interactions is controversial. In addition, Table 3 for stationary phases P(E-VAc) and PVC using
the magnitude of the energy contribution arising out of probes chosen for their hydrogen-bonding ability. Aver-
these interactions is questionable, since IGC experiments age bond energies were found to correlate well with
often involve a majority of hydrocarbon probes, the most literature values.
DOI: 10.1002/9780470027318.a2016
Table 3 Estimates of hydrogen-bonding contribution to the or excess cohesive density of the polymer – solute system.
heat of solutiona at 135 ° C B12 is related to the parameter c12 , as in Equation (58)
Hydrogen Model Hf (kcal mol 1 ) B12 c12
donor D .58/
PVAc P(E-VAc) RT V1
Chloroform Carbon 1.3 š 0.2 1.0 š 0.3 Subscripts 1, 2, and 3 refer to the solute, polymer 2
tetrachloride and polymer 3, respectively. While the sign of the combi-
Butyl alcohol Butyl chloride 1.1 š 0.3 0.3 š 0.4 natorial entropy always favors mixing, it is clear that its
Cyclohexanol Cyclohexyl 2.3 š 0.3 1.0 š 0.2
chloride
magnitude is greatly diminished as molar volumes become
Phenol Chlorobenzene – 1.7 š 0.3 very large. Since Sm is small, exothermic heat of mixing
is a requirement for miscibility in high-molecular-weight
a Ref. 76. polymer blends. (As a result of the exothermicity prin-
ciple, a number of miscible polymer blends have been
identified.).101,102/ Utilizing the specific retention volume,
9 POLYMER BLENDS Vg0 , the polymer – polymer interaction coefficient c23 can
be derived. When a polymer pair is used as a stationary
In polymer blends, the key term in the miscibility of a (liquid) phase in a chromatographic column, subscripts 2
polymer – polymer pair is the free energy of mixing, Gm , and 3 will be used to represent polymers 2 and 3, respec-
Equation (56) tively. Subscript 1 refers to the test solute. The interaction
between the two polymers is expressed in terms of the
Gm D Hm TSm .56/ free energy of mixing Hmix which has the same form as
Equation (5), only the subscripts change to 2 and 3. The
where Sm is the combinatorial entropy of mixing and first two (entropic) terms in this equation are negligible
Hm is the molar heat of mixing. Flory.99/ attributed for polymer blends. Thus, for the polymer blend to be
the combinatorial entropy of mixing to the mixing of the miscible (Gmix being negative), c23 must be negative.
segments on a lattice of fixed volume. Because entropy When considering the IGC of polymer blends, the free
depends on volume, an additional contribution to the energy of mixing must be written for a three-component
entropy of mixing may be necessary in Equation (56). system. It is usually expressed as in Equation (59)
Sanchez and Lacombe.100/ developed a theory to allow
for this effect by considering that all mixtures obey the Gmix D RT[n1 ln f1 C n2 ln f2 C n3 ln f3 C n1 f2 c12
equation-of-state when appropriate reducing parameters, C n1 f3 c13 C n2 f3 c23 ] .59/
such as pressure and temperature, are used for volume.
Other equation-of-state theories of mixtures yield a Equation (59) is generally satisfactory for nonpolar
combinatorial entropy of mixing similar to that of Flory. mixtures. The interaction coefficients c are largely
However, the combinatorial entropy becomes very small independent of the blend composition. The derivatives of
as the molecular weight of the polymer becomes high. the Gmix are, Equation (60)
Therefore, in the case of high-molecular-weight polymers,
only the value of Hm determines the miscibility of the dGmix V1 V1
D RT ln f1 C 1 f2 f3
polymer pairs. Flory and Huggins first introduced the dn1 nD1,p,T V2 V3
volume fraction term fi in their theory which described
V1
polymer solutions with a reasonable success..100/ The free C f2 c12 C f3 c13 f2 f3 c23 .60/
V2
energy of mixing as described by the Flory – Huggins
theory is, Equation (57) In Equation (60), v2 should be replaced by (w2 v2 C
w3 v3 ) where w2 and w3 are the weight fractions and v2
Gmix D RT.n1 ln f1 C n2 ln f2 C n1 f2 c12 / .57/ and v3 are the corresponding specific volumes of the
where ni is the number of moles of the ith component, two polymers in the blend. Thus, one can easily derive
Equation (61):
RT has its usual meaning, and c12 is a parameter which
is inversely proportional to absolute temperature. c12 is 273.15R.w2 v2 C w3 v3 / B11 V1 0
the same parameter introduced in Equation (37) where ln 0 0
1 P1
Vg V1 P 1 RT
it is an enthalpic contact parameter. The two logarithmic
terms represent the (combinatory) entropy of mixing. A V1 V1 V1
D f2 c12 C f3 c13 f2 f3 c23
second parameter that can be used as an indicator for M2 v2 M 3 V3 V2
mixing is B12 as a binary interaction energy parameter .61/
DOI: 10.1002/9780470027318.a2016
Usually the parameter c023 is introduced as in Equa- For a complex blend involving a semicrystalline diluent,
tion (62) it is possible to obtain the polymer – polymer interaction
coefficient c23 and the interaction energy parameter B23
V1 experimentally in a different way than explained earlier.
c023 D c23 .62/
V2 This technique involves measuring the melting point
The relation for c12 is given by Equation (63) depression of a polymer mixture (blend) containing a
semicrystalline polymer to quantify the heat of mixing of
273.15Rv2 V1 B11 V1 0 the polymer pair.
c12 D ln 1C P1 .63/
Vg0 V1 P10 M2 v2 RT When crystals of the semicrystalline polymer are in
equilibrium with the amorphous part of the semicrys-
Comparison of Equations (61) and (63) suggests that talline polymer and the amorphous counter-polymer, the
to obtain c23 for blends, c12 and c13 should also be melting point of the semicrystalline polymer is lower
known. Thus, three columns are usually prepared, two than when the equilibrium is with the amorphous part
from homopolymers and a third from a blend. The three of the semicrystalline polymer only. This is known as a
columns should be studied under identical conditions for melting point depression, resulting in mixing amorphous
column temperature, carrier gas flow rate, inlet pressure, polymer with a semicrystalline polymer. In most cases,
and the same solutes should be used. This keeps all the amount the melting point is depressed depends on
auxiliary parameters (P10 , T, M2 , M3 , V1 , v2 , v3 , and B11 ) the weight fraction of the diluent polymer. The melting
identical for the three experiments, and a combination of point depression can be used as an indicator for polymer
Equation (61) (taken twice for two homopolymers) and blend miscibility. Most of the work performed thus far
Equation (63) for the blend will yield Equation (64) using melting point depression is based on calorimetry,
0 0 0
and there have only been a few studies using IGC..45/
Vg,blend Vg,2 Vg,3 The thermodynamic analysis of polymer – polymer mix-
ln f2 ln f3 ln
W2 v2 C W3 v3 v2 v3 tures using melting point depression can be based on
c23 D .64/
f2 f3 Flory – Huggins theory..99,106/ Information can only be
obtained at a temperature close to the pure semicrys-
Here, the second subscript of Vg0 identifies the nature of talline polymer melting point. However, a number of
the column. From Equation (64), c023 may be calculated factors influence the measured melting point (perfec-
even for solutes for which the parameters P10 , B11 , and V1 tion, size, and environment of crystals) which must be
are not known or are known with insufficient accuracy. accounted for.
c23 can also be related to B23 , Equation (65) Equation (67) is an expression of the extent of the
c023 depression of the melting point of the semicrystalline
B23 D RT .65/ polymer after mixing,
V1

B23 determines the miscibility of the blend with a negative 1 1 H2u r2 ln f2
0
D R
value being necessary for mixing. Munk et al..103/ intro- Tm Tm V2u M2

duced this thermodynamic parameter for the evaluation r2 r3 B23
of the miscibility of blends. B23 may also be evaluated C v3 C f23 .67/
M2 M3 RTm
directly from the experimental retention volumes and
0
weight fractions wi by combining Equations (64) and where Tm and Tm are the melting points of polymer 2
Equation (65) (semicrystalline) in the mixture and pure semicrystalline
polymer, respectively. The quantity H2u /V2u is the
0
RT Vg,blend heat of fusion of the semicrystalline polymer per unit
B23 D ln
V1 f 2 f 3 W2 v2 C W3 v3 volume. The quantities f2 , f3 , r2 , r3 , M2 , and M3 are the
0 0
! volume fractions, densities, and molecular weight of the
Vg,2 Vg,3 semicrystalline (2) and diluent polymer (3), respectively,
f2 ln f3 ln .66/
v2 v3 B23 is the polymer – polymer interaction energy related
to the Flory – Huggins interaction parameter c023 as in
Munk et al..103/ showed that B23 values evaluated from Equation (68)
experiments depended on the chemical nature of the c23
0
solute, in contradiction to theory. To correct for this effect, B23 D RTm .68/
V3
a phenomenological relation suggested by Pouchley
et al..104/ and developed by Al-Saigh and Munk.105/ was where V3 is the molar volume of component 3 (the
introduced. amorphous diluent polymer).
DOI: 10.1002/9780470027318.a2016
The first two terms in Equation (67) are the entropic c23 parameters were obtained in the range of 0.10 to
contribution and the third term is the enthalpic contribu- 0.30. However, isopropyl alcohol, a poor solvent for both
tion. If the molecular weights of the semicrystalline and polymers, yielded values as high as 1.47, while chloroform
the diluent polymers are high, then the entropic contri- yielded 0.65. However, when higher molecular weight PS
bution represents less than 1 ° C which would play only was used, the blends were incompatible. The highest
a minor role in the melting point depression. Therefore, average value for c23 was 0.42 when 30% of PS was used,
the values of the first two terms can be neglected, giving and the lowest average value was 0.23 when 35% PS
Equation (69) was used. DiPaola Baranyi et al..109,110/ and Al-Saigh and
Munk.105/ applied IGC to a variety of polymer blends.
1 1 V2u B23 2 A blend of poly(methyl acrylate) – poly(epichlorohydrin)
D f .69/
Tm Tm0 H2u Tm 3 yielded measured values of c23 that varied between 0.09
and 0.49 with an experimental error of about 0.01 (see
Rearrangement yields Equation (70)
section 5).
0 Values within each family of solutes were clustered
Tm Tm V2u B23 2
D f .70/ together. Thus, the dependence of the interaction param-
0
Tm Tm H2u Tm 3
eters on the chemical nature of solutes was real. The
which can be rewritten in the form of Equation (71) literature on the IGC of polymer blends is now extensive
and beyond the scope of the present report. Much of this
0 0 V2u
Tm D Tm Tm D Tm B23 f23 .71/ work is summarized in a recent review by Al-Saigh..111/
H2u
Tm in Equation (71) is determined experimentally from 9.2 Amorphous Plasticizer Blends
IGC, and is used for calculating the polymer – polymer
interaction energy B23 for semicrystalline – amorphous There are few studies that use IGC to characterize blends
diluent blends. containing amorphous plasticizers. Su et al..112/ applied
IGC to a blend of PVC plasticized by DnOP over a tem-
perature range of 100 – 130 ° C. The interaction parameters
9.1 Experimental Studies on Polymer Blends
were strongly negative, indicating high compatibility.
Most of the work performed in this area has focused on However, the interaction parameters became less neg-
polymer – polymer interaction parameters. This stemmed ative and finally positive at 0.55 vol fraction of DnOP,
from the fact that knowledge of compatibility is most suggesting a lower compatibility limit. The composition
significant when studying polymer blends. Most mea- dependence of c23 reflects a nonrandom solution of the
surements of c23 are reported in the temperature range solute in the stationary phase and/or nonrandom mix-
in which the two polymers are in a molten state; ing of PVC/DnOP, particularly for DnOP in the limited
the solid state is avoided even though the possibility compatibility range.
exists that the polymer pair can be compatible in a Corrective measures have recently been introduced to
solid or semisolid state. Deshpande et al..107/ studied a eliminate several instrumental and procedural artifacts.
blend of PDMS/n-tetracosane and di-n-octyl phthalate It was shown that polymer – solute and polymer – polymer
(DnOP)/n-tetracosane. Although these blends consist of interaction parameters contain other solute-dependent
low-molecular-weight polymers, their results indicated contributions to the free energy of mixing that are
that IGC is useful in characterizing a mixture of low- not properly accounted for by the polymer solution
molecular-weight polymer, and applicable to a ternary thermodynamic theories.105/ and that the variation of
stationary phase. They calculated c23 by using the Pri- polymer – polymer interaction coefficient from solute to
gogine – Flory theory and showed that the interaction solute is partly due to experimental error and artifacts.
parameters depended on the chemical nature of the A series of critical and corrective procedures that yielded
solute. a considerable reduction in experimental error was
Olabisi,.82/ applied IGC to a blend of several blends developed by Card et al..113/
of poly(e-caprolactone) and PVC at 120 ° C. These exper- In order to improve IGC data, new treatments to the
iments involved mainly low-molecular-weight oligomers polymer solution theories were developed. The reader is
ranging from 2000 to 40 000 g mol 1 . referred to original work by Munk et al.,.103/ Prolongo
Su and Patterson.108/ studied a blend of PS (Mn D 600) and co-workers,.114,115/ Shi and Schreiber,.116/ Farooque
with poly(vinylmethyl ether) (Mw D 10 000). This mixture and Deshpande,.117/ and El Hibri and Munk..118/
was found to be compatible. They avoided the difficulties In another attempt to minimize the chemical depen-
associated with the high glass transition temperature of PS dence on the interaction parameters, Tan and Vancso.119/
by selecting a PS oligomer. Polymer – polymer coefficient proposed an alternative route for experimentalists to
DOI: 10.1002/9780470027318.a2016
study the microstructure of polymeric mixtures using the include studies on food that can easily coat a column, such
IGC method. They applied the concept of the cluster as soybean,.132,133/ dehydrated foods like potato starch,
integrals to the nonrandom partitioning of solutes in a egg albumin and wheat gluten,.134/ food packaging,.135/
polymeric blend. Their application yielded an equation pasta and others..132,136 – 139/ King.133/ has determined the
that relates the structure factor of a blend, the nonran- solubility parameters of soybean oil d2 as well as the
dom distribution of solutes in a compatible blend, and oil – solute interaction parameters of 22 solutes which
the experimental quantity obtained from the IGC exper- indicated complete miscibility of the solutes with the oil
iment. This equation delineates the polymer interaction under conditions of infinite dilution. He compared d2
parameters in terms of the structure factor of the blend. at 59, 79, and 123 ° C with the interaction parameters,
and over this temperature range the d2 decreased from
7.9 to 6.9 cal1/2 cm 3/2 with decreasing temperature, a
10 INVERSE GAS CHROMATOGRAPHY trend consistent with the loss of cohesive energy density
STUDIES ON NATURAL AND in the liquid soybean oil. Abraham and Whiting.132/
SYNTHETIC FIBERS characterized soybean oil in terms of polarity and
polarizability. The solubility of a variety of solutes in
IGC is particularly useful in the study of surface soybean oil was factored into components that show the
interactions of fibers. In these experiments it is only compound – soybean oil interactions that favor solubility.
necessary to pack the fibers directly in the open column. Dispersion forces dominate and provide the largest
Care should be taken that the fibers are uniformly solute – oil interaction in all cases, while ethanol is the
dispersed in the column and not packed in such a way least soluble solute in soybean oil because it is small
as to prevent access by the carrier gas to the polymer and lacks dispersive forces in spite of the acidity of the
surface. Column temperatures should not exceed the hydrogen bond.
melting point of the fibers and the data are analyzed by Dry food has also been studied using IGC..140/ Using
the surface energy techniques described in sections 5.1, IGC, one could predict the equilibrium moisture content
5.2 and 5.3. of potato starch, egg albumin and wheat gluten in the
The IGC method is used to characterize carbon.120/ entire range of water activity (0.0 – 0.8). The isosteric heat
and cellulose fibers,.121/ high-solid melamine – alkyd of sorption increases with decreasing moisture content,
formulations,.122/ epoxy resins,.123 – 125/ wood,.126/ suggesting a physical sorption on highly active polar sites.
 .127/
Kevlar , and PE fibers,.128,129/ and eucalypti Kraft The heat of sorption of potato starch is greater than that
.130/ for proteins.
pulp fibers. The surface properties of these fibers
were the prime interest in these studies which include Food packaging is another application of IGC, particu-
the effects of surface extractives and lignin on the surface larly the study of aroma escaping through thermosealable
energy,.130/ comparison of surface chemical properties polymers used to packaged food..135/ Researchers deter-
of chlorine-dioxide-bleached pulps with peroxides and mined ‘‘scalping’’ of aroma components in polymers via
ozone-bleached pulps and to study the influence of a latex IGC solubility experiments. Thermosealable polyesters
binder,.131/ the thermodynamic surface properties,.129/ the appear to be the best choice to minimize aroma loss by
properties of the skin layer of ultrahigh modulus PE sorption in the packaging inner layer. Sorption of aroma
fibers,.128/ mapping of the surface energy levels of Kevlar components was shown to be selective; limonene was
fibers,.127/ solvent – epoxy interaction parameters,.123 – 125/ preferentially sorbed in linear low-density PE. This selec-
solubility parameters of glass fibers,.124/ the nature of tivity may lead to an imbalance in the flavor and may
interactions within pigmented melamine – alkyd coating be more important than the prevention of overall loss of
assemblies,.122/ and the dispersive component of the aroma.
free energy and acid– base properties of cellulose fiber
surfaces..121/ Several of these studies correlated their
IGC results with those obtained by other methods such 12 APPLICATIONS
as X-ray photoelectron spectroscopy (XPS), electrical
conductance, electron microscopy, thermal analysis, and Applications of IGC to polymer systems focus on
surface wetting studies. the determination of partition and activity coefficients
(infinite dilution.82,92,108,141 – 143/ and finite concentra-
tion.18,24,25,57,58,68,69,74,75,107,112,144 – 152/ ), polymer – solvent
11 BIOLOGICAL MOLECULES or polymer – polymer interaction parameters,.153 – 155/ en-
thalpy of mixing,.44,58,142,156/ solubility parameters,.156 – 161/
There are only a few applications of IGC to food glass-transition and melting temperatures,.8,93,156,162 – 167/
compared with applications to polymeric systems. These crystallinity of polymer phase,.33,40,156,163,168 – 170/ solute
DOI: 10.1002/9780470027318.a2016
diffusion coefficients,.47,52,55,171 – 176/ crosslinking stu- that IGC is superior in speed, selectiveness in the range
dies,.177 – 180/ liquid crystals,.8/ interfacial studies,.181,182/ of experimental conditions, versatility and accuracy. Tait
methodology,.103,114,116,183 – 188/ hydrogen-bonding stu- and Abushihada.208/ among other groups compared IGC
dies,.132/ acidity studies,.189/ food,.131,136 – 138/ plastici- results to those obtained by vapor sorption techniques to
zers,.190/ surfactants,.191/ epoxy-resin curing,.192/ paints measure polymer – solvent interaction parameters. They
and coatings,.193/ microstructure studies,.194/ and the concluded that the IGC method is capable of obtaining
characterization of conducting polymers..195 – 197/ In data in the region (concentration and temperature) above
addition, there are several excellent reviews on which vapor pressure measurements became difficult, and
IGC..111,151,181,185,198 – 207/ IGC generally required less experimental time. Al-Saigh
and Munk.105/ concluded that IGC is sufficiently accurate
12.1 Amorphous and Semicrystalline Polymer Blends to be of great value in measuring interaction parameters
at infinite solvent dilution, and that solvent dependency of
There has been much work done on one-component the measured polymer – polymer interaction parameter is
stationary phases, mostly amorphous, using IGC. Such a result of weakness in the thermodynamic theories used,
data are useful for polymers because they measure and not a fault of the technique itself.
the interactions in the regions of concentration which Al-Saigh and Chen.45/ conducted experiments in a
are the most interesting in polymer science. Patterson temperature range below the melting temperature of
et al..57/ resolved the difficulty of applying the usual the semicrystalline diluent. As expected, a depression
thermodynamic equation of GC to polymeric stationary of the melting point of the crystalline component had
phases by introducing activity coefficients based on occurred. They used the melting point depression to
weight fraction. They arrived at a relationship linking measure the miscibility by calculating B23 , and applied
IGC parameters with Flory – Huggins parameters. Many it to a blend of poly(ethyl methacrylate) (PEMA)
workers cautioned that anomalous behavior frequently and semicrystalline poly(vinylidene fluoride) (PVF2 ).
observed in IGC in the temperature region associated Thermodynamic quantities were in excellent agreement
with transitions often alters the resolution of the column with those obtained by calorimetry on the same blend. For
and makes interpretation of the retention time difficult example, the B23 parameter for PVF2 /PEMA using DSC
owing to changes in peak shape. Polymers at glass was 3.18 cal mL 1 ,.209/ compared with 3.15 cal mL 1
transition and melting points, however, offer a wealth using IGC.
of information about the structures and interactions in Studies show that IGC agrees well with the DSC in
polymer stationary phases if the retention mechanism is detecting the immiscibility of poly(isobutyl methacry-
studied quantitatively. Braun and Guillet.13/ reanalyzed late)/styrene – acrylic acid copolymer blends..210/ IGC
the retention curves in the glass retention region. They gave positive values of the polymer – polymer interac-
assumed that if the bulk sorption is the only retention tion parameters, while DSC showed two separate glass
mechanism, specific retention volumes (Vg ) should be transition temperatures. Both methods also agreed well
independent of the mass of the stationary phase and on the miscibility of poly(styrene-co-acrylic acid) with a
carrier gas flow rate. They concluded that bulk sorption series of polycarbonates, showing negative values for c23
and surface absorption mechanisms are operative within and a single glass transition temperature. Although PS is
polymer stationary phases near Tg . They corrected the immiscible with poly(isobutyl methacrylate) owing to the
surface absorption to eliminate the dependence of the absence of specific interactions, it has been shown that
apparent thermodynamic data on the column loading. a blend of a random copolymer (poly(styrene-co-acrylic
Many authors called attention to the effects of surface acid)) and a homopolymer (PMMA) can be miscible in the
absorption and the necessity of performing a careful absence of specific interactions, provided that there is suf-
analysis of the thermodynamic data from IGC. Other ficient repulsion between the two comonomers..210/ Both
authors claimed a reasonable agreement between IGC methods, IGC and DSC, have confirmed the miscibility of
data and data obtained by other procedures. a blend of poly(isobutyl methacrylate) with poly(styrene-
co-acrylic acid) containing 32 mol% acrylic acid and
12.2 Comparison with Other Methods of poly(isobutyl methacrylate-co-acrylic acid) contain-
ing 22 mol% acrylic acid with poly(styrene-co-N,N-
Several IGC researchers have compared their results with dimethylaminoethyl methacrylate) containing 23 mol%
those obtained using other methods. The general consen- of basic comonomer.
sus is that IGC is capable of producing data comparable Djadoun and co-workers have used both IGC and
with other techniques, although there has been disagree- DSC to study the compatibility of a variety of copolymers
ment in individual cases. Nevertheless, where there is a with homopolymer.210 – 212/ and have reported a good
general agreement of results, workers have concluded agreement between the two methods. Some of their
DOI: 10.1002/9780470027318.a2016
blends showed positive interaction coefficients using IGC carrier gas at a nominal flow rate of 10 mL min 1 . Specific
and two glass transition temperatures with DSC. When a retention volumes were confirmed to be independent
blend showed a negative interaction coefficient by IGC, of the carrier flow rate at low flow rates. Barometric
the DSC confirmed the miscibility by showing one single room pressure was measured to š6.67 Pa (0.05 mmHg),
glass transition temperature. and column pressures were measured with a mercury
Guillet et al. used several methods, namely IGC, X- manometer. Carrier gas flow rates were measured from
ray, IR and DSC,.9/ to study the degree of crystallinity of the end of the column with a water-jacketed soap-
poly(b-hydroxybutyrate-co-b-hydroxy) copolymers. The bubble flow meter. Injections of probe vapor at infinite
degree of crystallinity was roughly 60%. The results of dilution (equivalent to 0.01 µL of liquid), mixed with
IGC were quite similar to those of X-ray diffraction methane gas as a marker, were made from a Hewlett-
analysis. They found that DSC and density measurements Packard headspace injector (Model 19395A). Data were
were inappropriate for these copolymers since it is invalid collected, recorded and analyzed using a Hewlett-Packard
to make a prior assumption about the density and the heat Vectra ES-12 personal computer with the associated GC
of fusion of the cocrystalline phase for these copolymers. software package HP 3365 Chemstation. The column
IGC, however, does not depend on assumptions about temperature was continuously measured to 0.1 ° C with
the properties of the 100% crystalline polymer. a thermocouple interfaced to the computer. The column
was equilibrated for several minutes for each temperature
increment of 1 or 2 ° C; the necessary equilibration
time was confirmed by the invariance of the retention
13 EXPERIMENTAL
times with the equilibration times. Equilibration is not
necessary for transition temperature determinations. In
Virtually any gas chromatograph can, with minor modi- this case injections are usually made at intervals during
fications, be used for IGC studies of polymers. Most of a continuous slow heating rate of 0.5 ° C min 1 . However,
the studies published by Guillet et al. were carried out thermal equilibration is usually necessary to obtain good
using commercially available GC instruments equipped activity coefficient data. The retention times tr and tm
with flame detectors, whereas groups such as those of were determined from the positions of the peak maxima
Munk and Al-Saigh prefer to work with larger columns and recorded in the computer.
and thermal conductivity detectors which they claim give
better data on the thermodynamics of polymer blends.
13.1 Thermodynamic Measurement on Blends
The much higher sensitivity of the flame detector allows
studies to be carried out much closer to infinite dilu- Figure 13 shows the design of an automated inverse
tion and thus avoids the need to extrapolate from finite gas chromatograph used for thermodynamic studies of
concentrations of injected probe. blends. With certain modifications, it uses the plumbing
For many studies, manual injection by microsyringe and circuitry for any conventional gas chromatograph. For
is satisfactory, but it is tedious if many data points are thermodynamics studies, a thermal conductivity detector
required. For the determination of retention diagrams is preferred because of the ease of continuous monitoring
early studies were made with automated syringes. A of the flow rate, however, a flame ionization detector can
simpler procedure involves the use of a Hewlett-Packard be modified by adding a three-way valve for diverting
headspace injector (Model 19395A) which injects a small the flow when the flow rate is ready to be measured.
sample of probe vapor mixed with methane as the marker Nitrogen or helium can be used as a carrier gas, although
gas. This gives excellent peaks with the equivalent of less the reader should be aware of the problem of helium
than 0.01 µL of probe. A typical procedure is given below. diffusion through the bubble in the flow meter. The
The polymer was deposited from CHCl3 solution design allows for continuous monitoring of the flow rate,
onto the Chromosorb G support by the pile coating temperature, and inlet and outlet pressures, quantities
method (section 13.3) to a level of 5.33 wt%. A total that must be measured with great precision. The design
of 0.864 g of polymer was packed into a 6.35-mm makes it possible to control these quantities electronically
(OD, outer diameter) ð 1.2-m copper tubing column. by means of controllers or a personal computer, and to
A column containing 0.372 g polymer at 2.99 wt% was adjust these quantities as needed. The software allows
also studied in order to confirm the invariance of researchers to monitor and adjust these quantities as well
specific retention volume with column loading. IGC as to collect and calculate the chromatographic quantities
measurements were performed on a Hewlett-Packard needed for the determination of the thermodynamic
5890 Series II gas chromatograph equipped with a flame parameters.
ionization detector. A precision mass flow controller with Continuous monitoring of carrier gas flow and gas
a range of 0 – 20 mL min 1 was used to control the nitrogen pressure is important to limit the fluctuation in the flow
DOI: 10.1002/9780470027318.a2016
T2
HD
TC TS
NV
UT
S WB
IP T1 TD FL
M
A/D BM
OV
IEEE
R
PC
Figure 13 Inverse gas chromatograph set-up. A/D, analog/digital convertor; BM, bubble meter; FL, flow meter; HD, hood;
IEEE, IEEE 488 board; IP, injection port; M, mouse; NV, needle valve; OV, oven; PC, personal computer; R, two-stage
regulator; S, syringe; T1 , transducer 1; T2 , transducer 2; TC, temperature control; TD, thermal detector; TS, temperature sensor;
UT, ultrathermostat; WB, water bath.
to less than 0.3% in a period of 8 h of operation. The flow accuracy of š0.3 mbar per year. It sends a linear 0 – 5 V DC
rate is varied within a range of 1 – 30 mL min 1 to explore output signal to the data acquisition system. If electronic
its effect on Vg0 values. instruments for pressure measurements are not available,
To maintain electronic communication, precision com- the inlet and outlet pressures should be monitored fre-
munication boards such as an IEEE 488 are interfaced quently using a precision mercury manometer. The outlet
with the apparatus. To measure the flow rate in milliliters pressure is generally atmospheric while the inlet pres-
per minute, an electronic temperature insensitive mass sure is in the range of 900 mmHg in conventional IGC
flow meter is used. The flow meter is calibrated using a experiments.
thermostated soap bubble meter equipped with a glass Temperature control is a critical factor in IGC
hood (Figure 14). Thermostating is important in order experiments. Conventional chromatographs often do not
to eliminate any temperature gradient along the bubble provide sufficient precision in temperature control over
meter. The bubble meter must be fabricated with a cap 8 h of operation to be of value in IGC experiments. It is
as a hood to ensure a complete helium atmosphere inside important to interface a precision electronic thermometer
the meter. If nitrogen is used as carrier gas, such a hood with 0.01 ° C accuracy. Fluctuation of more than 3% in
is not necessary. The thermostating procedure and the temperature measurements may create a considerable
hood design have proved effective in lowering the error error in Vg0 .
in the carrier gas flow measurements. The pressure of In IGC experiments, markers such as methane or air
the gas exiting the thermal conductivity detector is close are used to account for the dead volume in a column.
to atmospheric and passes through a coil immersed in For the thermal conductivity detector, air or nitrogen
a water bath thermostated at room temperature. The are often used as a marker, but for a flame ionization
gas then enters the soap bubble meter. The atmospheric detector, methane is the least noninteractive solute that
pressure is monitored with an electronic barometer that can be used.
transmits readings back to the computer. A barometric
pressure transmitter is available commercially as a sili- 13.2 Column Preparation
con capacitive pressure sensor which offers high accuracy Each sample must be weighed carefully and dissolved
and long-term stability. This type of transmitter offers an in the appropriate solvent (about 100 mL). The polymer
DOI: 10.1002/9780470027318.a2016
13.4 Determination of Degree of Crosslinking of

Polymer Networks
E
A particularly valuable application of IGC is the deter-
mination of crosslink density in rubbers and other
F
crosslinked polymers. Its simplicity and rapidity make
it useful in industrial quality control and similar applica-
tions. It involves the use of finite concentration IGC as
D described in section 8.2.
13.4.1 Theory
B
The full treatment of the elution-on-a-plateau method has
C been given by Conder and Purnell.77 – 80/ and by Price and
Guillet..214/ It involves the equilibration of the polymer
with a stream of inert carrier gas that contains a known
A concentration of solvent vapor. The retention volume,
VN , of a small amount of solvent injected into the stream
is then measured from Equation (72)
Figure 14 Flow meter is calibrated using a thermostated soap VN D .tr tm /F .72/

bubble meter equipped with a glass hood. A D soap solution
reservoir; B D incoming helium gas from the column; C D inlet where tr and tm are the times taken for the solvent and an
valve for fast flushing by helium gas; D D thermostated bubble inert marker to traverse the column and F is the flow rate
meter; E D ground joint; F D inverted U-tube 1/8 in ID. of carrier corrected to standard conditions. Under these
conditions, it may be shown that the partition isotherm
for the solvent between the vapor and solution phases is
solution can then be used to coat the solid support using given by Equation (73)
the pile method. The loading of the polymer sample can
be calculated relative to the weight of the solid support @q jVN
D .1 y/ .73/
(wt%). Chromosorb W with 60/80 mesh is often treated @c vp
with dimethylchlorosilane to deactivate the hydroxyl
groups on the surface. Teflon powder is often used In Equation (73), q and c are the concentrations of
when the solid polymer particles are simply blended with solvent in the liquid and vapor phases, respectively, and
the support. vp is the volume of polymer in the column. y is the
A typical loading in a chromatographic column varies mole fraction of solvent in the vapor stream, corrected by
between about 3 and 10%. the factor j for gas-phase nonideality and compressibility
effects from the pressure gradient along the column.
Integration of Equation (73) and introduction of the
13.3 Coating the Support: the Pile Method weight of polymer in the column, w, allow calculation
of the concentration of solvent in the liquid phase, q,
In this method the polymer is dissolved in a solvent. The expressed as moles per gram of polymer, Equation (74)
support is piled on a watch glass and a small amount of Z c
the solution is applied on the top of the support pile. Care j VN
qD dc .74/
is taken to wet the pile as much as possible without letting w 0 1 y
the solution touch the surface of the dish, either around
The concentration in the vapor stream may be
or under the pile. The solvent is allowed to evaporate and
calculated from the first terms of a virial expansion,
the pile is thoroughly mixed. Then the next portion of the
Equation (75)
solution is applied and the whole procedure is repeated
until all of the solution (including several rinsings of yPA
the solution flask) is consumed. It takes typically 10 – 20 cD .75/
jRT C y2 B11 PA
applications and requires only a few hours. No polymer
is left on the surface of the dish. Then the support is where PA is the total pressure of carrier gas at the column
dried in an oven and quantitatively transferred into the outlet and B11 is the second virial coefficient of the solvent
column. vapor at the column temperature T.
DOI: 10.1002/9780470027318.a2016
From the definition of q given above, the weight frac- as in conventional GC, then to a thermal conductivity
tion of solvent in the solution phase, W1 , is, Equation (76) detector, and finally, via a cold trap, to a soap bubble flow
meter for accurate measurement of the carrier flow rate.
qM1
W1 D .76/ The columns were contained in an oil bath maintained at
1 C qM1 77.0 š 0.02 ° C.
where M1 is the molecular weight of the solvent (probe). After equilibration of the detector at a known concen-
The activity of the solvent in solution may be calculated tration of solvent vapor, the retention times of air (the
from the partial pressure of solvent in the carrier stream, inert marker) and solvent were recorded. An average
P1 , and the saturated vapor pressure of the solvent, of at least three values agreeing within 1% was taken.
P10 . Hence, the activity coefficient 1 may be found, Injections of 0.1 – 0.5 µL were needed to give an adequate
Equation (77) signal.
Since the saturated vapor pressure of the solvent is
a1 P1 required for the calculation of results, solvent purity is of
1 D D 0 W1 .77/
W1 P1 great importance. The n-hexane used was a BDH Assured
grade of certified purity > 99.5%. The polymer used
The weight fraction of solvent in the liquid phase can be
was an Aldrich ethylene – propylene rubber copolymer
calculated from Equation (76) and converted to a volume
of low average molecular weight and an ethylene
fraction by using the densities r, Equation (78)
content of 70%.

W1 /r1 Coating the polymer onto a solid support of 30 – 45 mesh
f1 D .78/ size Chromosorb P was carried out in the usual manner
.W1 /r1 /.W2 /r2 /
employing hot toluene as the solvent. The percentage
The Flory – Huggins interaction parameter is then loading was determined by duplicate calcination to be
calculated from Equation (79) 8.8% after correction for volatiles in the uncoated solid
support.
ln a1 ln f1 [1 .1/r/]f2
cD .79/ Approximately 50 g of the polymer-coated support
f22
was placed in Pyrex glass ampules, and these were
the size ratio being calculated from the ratio of the molar evacuated on a glass-vacuum line to a pressure of
volumes of the polymer and solvent. <10 5 Torr for 2 days to degas the polymers thoroughly.
The ampoules were then sealed and placed in a 60 Co g-
13.4.2 Experimental ray source (Gammacell, Atomic Energy of Canada Ltd.).
The approximate dose rates were estimated from the
The apparatus used is shown schematically in activity and known decay rates of the source supplied by
Figure 15..178/ the manufacturer. After irradiation, the ampoules were
A known partial pressure of the solvent probe n-hexane opened and the packing was loaded into columns.
was introduced into the helium carrier gas by a saturator In this experiment, three columns were prepared
consisting of a flask containing n-hexane near its boiling with the same amounts of polymer, sample A irradiated
point and a condenser through which thermostated water with 140 Mrad, sample B at 200 Mrad, and sample C
was passed. The partial pressure of hexane in the carrier (unirradiated).
gas was controlled by changing the temperature of the A plot of c versus concentration for the uncrosslinked
water in the saturator condenser. polymer showed a linear variation of c with volume
The carrier gas passed over the polymer packing fraction. Linear regression of the results leads to Equa-
contained in one-quarter-inch (6.25-mm) copper columns tion (80) for c:
Detector c D 0.344 C 0.004f1 .80/

A Soap bubble
flow meter For the crosslinked samples, the effective num-
B ber of crosslinks was calculated from the rearranged
Cold trap Flory – Rehner equation, Equation (81)
He
Amplifier ( )
Recorder ln a1 ln f1 [1 .1/r/]f2 cf22
ve D v2 1/3
.81/
Water bath V1 [f2 .f2 /2/]
Saturator
and the value of c determined by Equation (79). If
Figure 15 Schematic diagram of finite concentration GC the Flory – Rehner equation were to hold accurately,
apparatus. ve should be independent of concentration. However,
DOI: 10.1002/9780470027318.a2016
Figure 16 clearly shows that the value of ve increases ABBREVIATIONS AND ACRONYMS
with concentration but rapidly reaches a plateau. The
explanation for this behavior is that ve cannot be BET Brunauer – Emmett – Teller
determined until the network is fully swollen. The DnOP Di-n-octyl Phthalate
values of ve and the molecular weight between crosslinks DSC Differential Scanning Calorimetry
Mc taken from the graphs are shown in Table 4. The GC Gas Chromatography
experimental error of the results is estimated to be 5 – 8%. GLC Gas – Liquid Chromatography
It is clear from these data that in the routine GSC Gas – Solid Chromatography
measurement of crosslink density it is only necessary to IGC Inverse Gas Chromatography
p IR Infrared
measure two retention times, namely Vn0 and Vn , where
Vn0 is the retention time at zero concentration of hexane OD Outer Diameter
p PDMS Poly(dimethylsiloxane)
(probe) in the carrier gas and Vn is the retention time at
a probe concentration above that at which the polymer PE Polyethylene
sample is fully swollen. Since the latter concentration PEMA Poly(ethyl methacrylate)
can be determined experimentally as shown in Figure 16, PEO Poly(ethylene oxide)
the procedure could result in a rapid method for the PET Poly(ethylene terephthalate)
determination of crosslink density in polymer samples by P(E-VAc) Poly(ethylene – vinyl acetate)
IGC. PIB Poly(isobutylene)
Although there is some debate about the theoretical PMMA Poly(methyl methacrylate)
aspects of the Flory – Rehner equation, it is still the PP Polypropylene
basis of the most commonly used experiments to PS Polystyrene
determine crosslink density in polymers. In has been PVAc Poly(vinylacetate)
shown.180/ that the IGC procedure with crosslinked PVC Poly(vinyl chloride)
PDMSs gave results similar to those obtained from PVF2 Poly(vinylidene fluoride)
classical swelling measurements, but consistently about VAc Vinyl Acetate
XPS X-ray Photoelectron Spectroscopy
30% higher in crosslink density. Further research on this
useful technique should lead to an improved theory to
account for these differences.
RELATED ARTICLES
10 Coatings (Volume 2)
Gas Chromatography in Coatings Analysis
Crosslink density
(104 ve /mol g )
Sample A
–1
Industrial Hygiene (Volume 5)

Chromatographic Techniques in Industrial Hygiene
5
Pharmaceuticals and Drugs (Volume 8)
Sample B Gas and Liquid Chromatography, Column Selection for,
in Drug Analysis
Polymers and Rubbers (Volume 8)

0 0.05 0.10 0.15
Polymers and Rubbers: Introduction
Volume fraction of solvent (φ) Polymers and Rubbers (Volume 9)

Gas Chromatography in Analysis of Polymers and
Figure 16 Plot of apparent crosslink density versus concentra- Rubbers
tion for irradiated ethylene – propylene rubber samples.
Gas Chromatography (Volume 12)

Table 4 Degree of crosslinking for ethylene – propylene Liquid Phases for Gas Chromatography
rubber from finite concentration results
Sample Radiation dose (Mrad) 104 ve Mc REFERENCES

A 140 4.5 2500
B 200 8.3 1205 1. D.H. Everett, ‘Effect of Gas Imperfection on GLC
Measurements: a Refined Method for Determining
DOI: 10.1002/9780470027318.a2016
Activity Coefficients and Second Virial Coefficients’, Encompassing Tg : Determination of Tg and c’, Macro-
Trans. Faraday Soc., 61, 1637 – 1645 (1965). molecules, 11, 746 – 751 (1978).
2. J.E. Guillet, M. Galin, ‘Studies of Polyacrylonitrile 17. J.-M. Braun, J.E. Guillet, ‘Glass Transitions of Poly-
Structure by Inverse Chromatography’, J. Polym. Sci., olefins by Inverse Gas Chromatography’, J. Polym. Sci.,
Polym. Lett. Ed., 11, 233 – 237 (1973). Polym. Chem. Ed., 14, 1073 – 1081 (1976).
3. G. Perrault, M. Tremblay, M. Bédard, G. Duchesne, 18. J. Klein, H. Widdecke, ‘The Problem of Solute Reten-
R. Voyzelle, ‘Applications de la Sonde Moleculaire aux tion in Mixed Stationary Phases in Gas – Liquid Chro-
Composites a Teneur Elevee en Solides. I. Determina- matography’, J. Chromatogr., 147, 384 – 387 (1978).
tion des Temperatures de Transition Vitreuse et Etudes 19. R. Hayakawa, T. Nishi, K. Arisawa, Y. Wada, ‘Dielectric
des Phenomenes de Surface’, Eur. Polym. J., 10, 143 – 148 Relaxation in the Paracrystalline Phase in Polyacryloni-
(1974). trile’, J. Polym. Sci., Part A-2: Polym. Phys., 5, 165 – 177
4. D.G. Gray, J.E. Guillet, ‘Open Tubular Columns for (1967).
Studies on Polymer Stationary Phases by Gas Chro- 20. P.L. Hsiung, D.M. Cates, ‘Study of the Glass Transition
matography’, J. Polym. Sci., Polym. Lett. Ed., 12, of Poly(ethylene terephthalate) by Gas Chromatogra-
231 – 235 (1974). phy’, J. Appl. Polym. Sci., 19, 3051 – 3060 (1975).
5. R.N. Lichtenthaler, D.D. Liu, J.M. Prausnitz, ‘Poly- 21. I.A. Schneider, E.-M. Calugaru, ‘The Estimation of
mer – Solvent Interactions from Gas – Liquid Chro- Phase Modifications in Polymers by the Method of
matography with Capillary Columns’, Macromolecules, ‘Molecular Probes’ in Gas Chromatography. V. The
7, 565 – 570 (1974). Study of First and Second-order Transitions in Poly(e-
6. R.J. Laub, J.H. Purnell, P.S. Williams, M.W.P. Harbison, caprolactam)’, Eur. Polym. J., 13, 833 – 835 (1977).
D.E. Martire, ‘Meaningful Error Analysis of Thermody- 22. I.A. Schneider, E.-M. Calugaru, ‘The Estimation of
namic Measurements by Gas – Liquid Chromatography’, Phase Modifications in Polymers by the Method of
J. Chromatogr., 155, 233 – 240 (1978). ‘Molecular Probes’ in Gas Chromatography. III. Glass
7. J.E. Guillet, ‘Molecular Probe Apparatus’, U.S. Patent Transition Behaviour and Compatibility in Mixtures of
3,717,040, Feb. 20, 1973. Poly(methyl methacrylate) with Poly(vinyl chloride)’,
8. M. Romansky, J.E. Guillet, ‘The Use of Inverse Gas Eur. Polym. J., 11, 861 – 863 (1975).
Chromatography to Study Liquid Crystalline Polymers’, 23. K. Ito, H. Sakakura, Y. Yamashita, ‘Characterization of
Polymer, 35, 584 – 589 (1994). Styrene – Tetrahydrofuran Block Copolymers by Inverse
9. W.J. Orts, M. Romansky, J.E. Guillet, ‘Measurement of Gas Chromatography’, J. Polym. Sci., Polym. Lett. Ed.,
Crystallinity of Poly(b-hydroxybutyrate-co-b-hydroxy- 15, 755 – 759 (1977).
valerate) Copolymers by Inverse Gas Chromatography’, 24. K. Ito, N. Usami, Y. Yamashita, ‘Syntheses of Methyl
Macromolecules, 25, 949 – 953 (1992). Methacrylate – Stearyl Methacrylate Graft Copolymers
10. V.R. Alishoev, V.G. Berezkin, Y.V. Mel’nikova, ‘Effect and Characterization by Inverse Gas Chromatography’,
of Phase Transitions in the Stationary Phase on the Macromolecules, 13, 216 – 221 (1980).
Chromatographic Behavior’, Russ. J. Phys. Chem., 39, 25. J.-M. Braun, J.E. Guillet, ‘Inverse Gas Chromatography
105 – 107 (1965). in the Vicinity of Tg : Effects of the Probe Molecule’,
11. O. Smidsrød, J.E. Guillet, ‘Study of Polymer – Solute Macromolecules, 9, 340 – 344 (1976).
Interactions by Gas Chromatography’, Macromolecules, 26. D.G. Gray, J.E. Guillet, ‘A Gas Chromatographic Meth-
2, 272 – 277 (1969). od for the Study of Sorption of Polymers’, Macro-
12. J.E. Guillet, ‘Study of Polymer Structure and Interac- molecules, 5, 316 – 321 (1972).
tions by Inverse Gas Chromatography’, in New Develop- 27. D.H. James, C.S.G. Phillips, ‘The Chromatography of
ments in Gas Chromatography, ed. J.H. Purnell, Wiley, Gases and Vapours. Part III. The Determination of
New York, 187 – 235, 1973. Adsorption Isotherms’, J. Chem. Soc., 1066 – 1070 (1954).
13. J.-M. Braun, J.E. Guillet, ‘Studies of Polystyrene in the 28. E. Glueckauf, ‘Theory of Chromatography’, J. Chem.
Region of the Glass Transition Temperature by Inverse Soc., 1302 – 1329 (1947).
Gas Chromatography’, Macromolecules, 8, 882 – 888 29. D. DeVault, ‘The Theory of Chromatography’, J. Am.
(1975). Chem. Soc., 65, 532 – 540 (1943).
14. J.R. Condor, D.C. Locke, J.H. Purnell, ‘Concurrent 30. A.V. Kiselev, Le. Zung, Yu.S. Nikitin, ‘Adsorption –
Solution and Adsorption Phenomena in Chromatog- Chromatographic Study of Porous Polyacrylates’, Kol-
raphy. I. General Considerations’, J. Phys. Chem., 73, loid Zh., 33, 224 – 229 (1971).
700 – 708 (1969). 31. S. Brunauer, The Absorption of Gases and Vapors,
15. M.A. Llorente, C. Menduina, Q A. Horta, ‘Inverse Gas Princeton University Press, Princeton, NJ, Vol. 1, 1945.
Chromatography of Poly(cyclohexyl methacrylate)’, J. 32. J. Crank, G.S. Park (eds.), Diffusion in Polymers, Aca-
Polym. Sci., Polym. Phys. Ed., 17, 189 – 197 (1979). demic Press, London, 1968.
16. D.D. Deshpande, O.S. Tyagi, ‘Gas Chromatographic 33. G. Courval, D.G. Gray, ‘The Effect of Surface Adsorp-
Behavior of Poly(vinyl acetate) at Temperatures tion on Gas Chromatographic Measurements Near
DOI: 10.1002/9780470027318.a2016
Polymer Melting Transitions’, Macromolecules, 8, 326 – 50. W. Millen, S.J. Hawkes, ‘Determination of Diffusion
331 (1975). Coefficients in Polyethylene by Gas Chromatography’,
34. M. Galin, M.C. Rupprecht, ‘Study by Gas – Liquid Chro- J. Polym. Sci., Polym. Lett. Ed., 15, 463 – 465 (1977).
matography of the Interactions between Linear or 51. D.G. Gray, J.E. Guillet, ‘Gas Chromatography on Poly-
Branched Polystyrenes and Solvents in the Temperature mers at Temperatures Close to the Glass Transition’,
Range 60 – 200 ° C’, Polymer, 19, 506 – 512 (1978). Macromolecules, 7, 244 – 247 (1974).
35. U.-B. Mohlin, D.G. Gray, ‘Gas Chromatography on 52. P. Munk, T.W. Card, P. Hattam, M.J. El-Hibri, Z.Y. Al-
Polymer Surfaces Adsorption on Cellulose’, J. Colloid Saigh, ‘Inverse Gas Chromatography. 4. The Diffu-
Interface Sci., 47, 747 – 754 (1974). sion Phenomena on the Column’, Macromolecules, 20,
36. P.R. Tremaine, D.G. Gray, ‘Adsorption of Non-swelling 1278 – 1285 (1987).
Vapours on the Surface of Cellulose’, J. Chem. Soc., 53. O.E. Schupp, ‘Gas Chromatography’, in Technique of
Faraday I, 71, 2170 – 2185 (1975). Organic Chemistry, eds. E.S. Perry, A. Weissberger,
37. P.R. Tremaine, D.G. Gray, ‘Determination of Bru- Interscience, New York, Chapter III, 1979.
nauer – Emmett – Teller Monolayer Capacities by Gas – 54. J.R. Conder, C.L. Young, Physicochemical Measure-
Solid Chromatography’, Anal. Chem., 48, 380 – 382 ment by Gas Chromatography, Wiley, New York, 1979.
(1976). 55. J.S. Vrentas, C.M. Vrentas, I.H. Romdhane, ‘Analysis
38. F.M. Fowkes, ‘Quantitative Characterization of the of Inverse Gas Chromatography Experiments’, Macro-
Acid – Base Properties of Solvents, Polymers and Inor- molecules, 26, 6670 – 6672 (1993).
ganic Surfaces’, J. Adhes. Sci. Technol., 4, 669 – 691 56. T.W. Card, Z.Y. Al-Saigh, P. Munk, ‘Diffusion in the
(1990). Bubble Flow Meter in IGC Experiments’, J. Chro-
39. D.G. Gray, J.E. Guillet, ‘The Application of the Molec- matogr., 301, 261 – 264 (1984).
ular Probe Technique to a Study of Polymer Crystalliza- 57. D. Patterson, Y.B. Tewari, H.P. Schreiber, J.E. Guillet,
tion Rates’, Macromolecules, 4, 129 – 133 (1971). ‘Application of Gas – Liquid Chromatography to the
40. J.-M. Braun, J.E. Guillet, ‘Determination of Crystallinity Thermodynamics of Polymer Solutions’, Macromole-
by Gas Chromatography: Effect of Curvilinearity of cules, 4, 356 – 359 (1971).
Retention Diagrams’, Macromolecules, 10, 101 – 106 58. G. DiPaola-Baranyi, J.-M. Braun, J.E. Guillet, ‘Partial
(1977). Molar Heats of Mixing of Small Molecules with Polymers
41. P. Hudec, ‘Determination of Crystallinity of Polyethy- by Gas Chromatography’, Macromolecules, 11, 224 – 227
lene Powder by Inverse Gas Chromatography’, Makro- (1978).
mol. Chem., 178, 1187 – 1193 (1977). 59. S. Dinçer, D.C. Bonner, ‘Thermodynamic Analysis of
42. J.-M. Braun, J.E. Guillet, ‘Determination of Crystallinity an Ethylene and Vinyl Acetate Copolymer with Various
of Olefin Copolymers and Polyolefin Powders by Inverse Solvents by Gas Chromatography’, Macromolecules, 11,
Gas Chromatography’, J. Polym. Sci., Polym. Chem. Ed., 107 – 113 (1978).
13, 1119 – 1131 (1975). 60. S. Dinçer, D.C. Bonner, ‘Solubility Criteria for a Ther-
43. R. Buchdahl, R.L. Miller, S. Newman, ‘Crystallization mally Stable Polymer Determined by Gas – Solid Chro-
Kinetics and Mechanical Properties of Polyethylene’, J. matography’, J. Appl. Polym. Sci., 22, 3235 – 3247
Polym. Sci., 36, 215 – 231 (1959). (1978).
44. Y.S. Lipatov, A.E. Nesterov, ‘The Influence of Thick- 61. D. Patterson, ‘Thermodynamics of Non-dilute Polymer
ness of Polymeric Stationary Phase on Its Properties Solutions’, Rubber Chem. Technol., 40, 1 – 35 (1967).
Determined by Gas Chromatography’, Macromolecules, 62. R.F. Blanks, J.M. Prausnitz, ‘Thermodynamics of Poly-
8, 889 – 894 (1975). mer Solubility in Polar and Nonpolar Systems’, Ind. Eng.
45. Z.Y. Al-Saigh, P. Chen, ‘Characterization of Semicrys- Chem. Fundam., 3, 1 – 8 (1964).
talline Polymers by Inverse Gas Chromatography. 2. 63. R.L. Scott, M. Magat, ‘Thermodynamics of High Poly-
A Blend of Poly(vinylidene fluoride) and Poly(ethyl mer Solutions. III. Swelling of Cross-linked Rubber’, J.
methacrylate)’, Macromolecules, 24, 3788 – 3795 (1991). Polym. Sci., 4, 555 – 571 (1949).
46. J.J. Van Deemter, F.J. Zuiderweg, A. Klinkenberg, 64. K. Ito, J.E. Guillet, ‘Estimation of Solubility Parameters
Chem. Eng. Sci., 5, 271 (1956). for Some Olefin Polymers and Copolymers by Inverse
47. D.G. Gray, J.E. Guillet, ‘Studies of Diffusion in Poly- Gas Chromatography’, Macromolecules, 12, 1163 – 1167
mers by Gas Chromatography’, Macromolecules, 6, (1979).
223 – 227 (1973). 65. N.F. Brockmeier, R.W. McCoy, J.A. Meyer, ‘Gas Chro-
48. J.-M. Braun, S. Poos, J.E. Guillet, ‘Determination of matographic Determination of Thermodynamic Proper-
Diffusion Coefficients of Antioxidants in Polyethylene ties of Polymer Solutions’, Macromolecules, 5, 130 – 132
by Gas Chromatography’, J. Polym. Sci., Polym. Lett. (1972).
Ed., 14, 257 – 261 (1976). 66. W.E. Hammers, C.L. DeLigny, ‘The Thermodynamics
49. J.C. Giddings, ‘Advances in the Theory of Plate Height in of Solutions of Some Normal and Branched Alkanes
Gas Chromatography’, Anal. Chem., 35, 439 – 449 (1963). in Polyisobutylene: an Investigation by Gas – Liquid
DOI: 10.1002/9780470027318.a2016
Chromatography’, J. Polym. Sci., Part C: Polym. Symp., 80. J.R. Condor, J.H. Purnell, ‘Gas Chromatography at
39, 273 – 280 (1972). Finite Concentrations. Part 4. Experimental Evaluation
67. Y.-K. Leung, B.E. Eichinger, ‘Gas Liquid Chromatog- of Methods for Thermodynamic Study of Solutions’,
raphy on Polymers. I. Polyisobutylene-hydrocarbons at Trans. Faraday Soc., 65, 839 – 848 (1969).
25 ° C’, J. Phys. Chem., 78, 60 – 64 (1974). 81. D. Patterson, A. Robard, ‘Thermodynamics of Polymer
68. W.E. Hammers, C.L. DeLigny, ‘A Gas Chromato- Compatibility’, Macromolecules, 11, 690 – 695 (1978).
graphic Investigation of the Thermodynamics of Solu- 82. O. Olabisi, ‘Polymer Compatibility by Gas – Liquid
tions of Some Tetrachloromethane in Polyisobutylene’, Chromatography’, Macromolecules, 8, 316 – 322 (1975).
Recl. Trav. Chim. Pays-Bas, 90, 912 – 931 (1971). 83. M. Galin, M.C. Rupprecht, ‘Gas Chromatographic Study
69. W.R. Summers, Y.B. Tewari, H.P. Schreiber, ‘Thermo- of the Interactions in Styrene – Dimethylsiloxane Block
dynamic Interaction in Polydimethylsiloxane – Hydro- Copolymers and Blends’, Macromolecules, 12, 506 – 511
carbon Systems from Gas – Liquid Chromatography’, (1979).
Macromolecules, 5, 12 – 16 (1972). 84. J.S. Aspler, D.G. Gray, ‘Gas Chromatographic and
70. M. Galin, ‘Gas Chromatographic Investigation of the Static Measurements of Solute Activity for a Polymeric
Thermodynamic Interactions of Poly(dimethylsiloxane) Liquid Crystalline Phase’, Macromolecules, 12, 562 – 566
or Poly(diethylsiloxane) with Some Solvents between 60 (1979).
and 180 ° C’, Macromolecules, 10, 1239 – 1244 (1977). 85. N.F. Brockmeier, R.E. Carlson, R.W. McCoy, ‘Gas
71. W.E. Hammers, B.C. Bos, L.H. Vaas, Y.J.W.A. Loom- Chromatographic Determination of Thermodynamic
ans, C.L. DeLigny, ‘Partial Molar Excess Free Enthalpies Properties of Polymer Solutions at High Temperatures’,
of n-Alkenes in Apiezon M and Alkanes in Squalane AIChE J., 19, 1133 – 1139 (1973).
and Polydimethylsiloxane, and the Solution Theories of 86. D.D. Liu, J.M. Prausnitz, ‘Solubilities of Gas and
Prigogine and Flory: an Investigation by Gas Chromatog- Volatile Liquids in Polyethylene and in Ethylene – Vinyl
raphy’, J. Polym. Sci., Polym. Phys. Ed., 13, 401 – 417 Acetate Copolymers in the Region 125 – 225 ° C’, Ind.
(1975). Eng. Chem. Fundam., 15, 330 – 335 (1976).
72. W.E. Hammers, C.L. DeLigny, ‘Determination of the 87. T. Sugiyama, T. Takeuchi, Y. Suzuki, ‘Thermodynamic
Flory – Huggins c Parameter, the Heat of Dilution, Properties of Solute Molecules at Infinite Dilution
and the Excess Heat Capacity of Some Alkanes Determined by Gas – Liquid Chromatography. 1. Inter-
in Polydimethylsiloxane by Gas Chromatography’, J. molecular Energies of n-Alkane Solute in C28 – C36
Polym. Sci., Polym. Phys. Ed., 12, 2065 – 2074 (1974). n-Alkane Solvents’, J. Chromatogr., 105, 265 – 272
73. N.F. Brockmeier, R.W. McCoy, J.A. Meyer, ‘Gas Chro- (1978).
matographic Determination of Thermodynamic Prop- 88. T. Sugiyama, T. Takeuchi, Y. Suzuki, ‘Thermodynamic
erties of Polymer Solutions. I. Amorphous Polymer Properties of Solute Molecules at Infinite Dilution
Systems’, Macromolecules, 5, 464 – 470 (1972). Determined by Gas – Liquid Chromatography. 2. Inter-
74. Y.B. Tewari, H.P. Schreiber, ‘Thermodynamic Interac- action Energies of Contact Pairs of Methyl and
tions in Polymer Systems by Gas – Liquid Chromatogra- Methylene Segments’, J. Chromatogr., 105, 273 – 277
phy’, Macromolecules, 5, 329 – 332 (1972). (1978).
75. H.P. Schreiber, Y.B. Tewari, D. Patterson, ‘Thermody- 89. D.D. Liu, J.M. Prausnitz, ‘Solubilities of Volatile Solutes
namic Interactions in Polymer Systems by Gas – Liquid in Poly(vinyl acetate) from 125 to 200 ° C’, J. Polym. Sci.,
Chromatography. III. Polyethylene-hydrocarbons’, J. Polym. Phys. Ed., 15, 145 – 153 (1977).
Polym. Sci., Polym. Phys. Ed., 11, 15 – 24 (1973). 90. D.P. Maloney, J.M. Prausnitz, ‘Solubility of Ethylene in
76. G. DiPaola-Baranyi, J.E. Guillet, H.-E. Jeberien, J. Kle- Liquid, Low-density Polyethylene at Industrial Separa-
in, ‘Thermodynamics of Hydrogen Bonding Polymer – tion Pressures’, Ind. Eng. Chem. Process Res. Dev., 15,
Solute Interactions by Inverse Gas Chromatography’, 216 – 220 (1976).
Makromol. Chem., 181, 215 – 226 (1980). 91. D.P. Maloney, J.M. Prausnitz, ‘Solubilities of Ethylene
77. J.R. Condor, J.H. Purnell, ‘Gas Chromatography at and Other Organic Solutes in Liquid Low-density
Finite Concentrations. Part 1. Effect of Gas Imperfection Polyethylene in the Region 124° to 300 ° C’, AIChE J.,
on Calculation and the Activity Coefficient in Solution 22, 74 – 82 (1976).
from Experimental Data’, Trans. Faraday Soc., 64, 92. P.A. Small, ‘Some Factors Affecting the Solubility of
1505 – 1512 (1968). Polymers’, J. Appl. Chem., 3, 71 – 80 (1953).
78. J.R. Condor, J.H. Purnell, ‘Gas Chromatography at 93. G. DiPaola-Baranyi, J.E. Guillet, ‘Estimation of Sol-
Finite Concentrations. Part 2. A Generalized Retention ubility Parameters by Gas Chromatography’, Macro-
Theory’, Trans. Faraday Soc., 64, 3100 – 3111 (1968). molecules, 11, 228 – 235 (1978).
79. J.R. Condor, J.H. Purnell, ‘Gas Chromatography at 94. J.E.G. Lipson, J.E. Guillet, ‘Studies of Polar and Non-
Finite Concentrations. Part 3. Theory of Frontal and polar Probes in the Determination of Infinite-dilution
Elution Techniques of Thermodynamic Measurement’, Solubility Parameters’, J. Polym. Sci., Polym. Phys. Ed.,
Trans. Faraday Soc., 65, 824 – 838 (1969). 19, 1199 – 1209 (1981).
DOI: 10.1002/9780470027318.a2016
95. W. Mendenhall, R. Schaeffer, Mathematical Statistics 112. C.S. Su, D. Patterson, H.P. Schreiber, ‘Thermodynamic
with Applications, Duxbury Press, North Scituate, MA, Interactions and the Properties of PVC – Plasticizer
1973. Systems’, J. Appl. Polym. Sci., 20, 1025 – 1034 (1976).
96. G. DiPaola-Baranyi, J.E. Guillet, H.-E. Jeberien, J. Kle- 113. T.W. Card, Z.Y. Al-Saigh, P. Munk, ‘Inverse Gas Chro-
in, ‘Estimation of Solubility Parameters for Poly(vinyl matography. 2. The Role of ‘‘Inert’’ Support’, Macro-
acetate) by Inverse Gas Chromatography’, J. Chro- molecules, 18, 1030 – 1034 (1985).
matogr., 166, 349 – 356 (1978). 114. M.G. Prolongo, R.M. Masegosa, A. Horta, ‘Polymer –
97. C.M. Hansen, A. Beerbower, ‘Solubility Parameters’, Polymer Interaction Parameter in the Presence of a
Kirk – Othmer Encyclopedia of Chemical Technology, Solvent’, Macromolecules, 22, 4346 – 4351 (1989).
2nd edition, suppl., ed. A. Standen, Interscience, New 115. E.G. Lezcano, C.S. Coll, M.G. Prolongo, ‘Thermody-
York, 889 – 910, 1971. namic Study of Poly(4-hydroxystyrene)/Poly(vinyl
98. R. Kumar, J.M. Prausnitz, ‘Solvents in Chemical Techno- acetate) Blends by Inverse Gas Chromatography’,
logy’, in Solutions and Solubilities, Part I, ed. M.R. Dack, Macromolecules, 25, 6849 – 6854 (1992).
Wiley-Interscience, New York, 259 – 326, 1976. 116. Z.H. Shi, H.P. Schreiber, ‘On the Application of Inverse
99. P.J. Flory, Principles of Polymer Chemistry, Cornell Gas Chromatography to Interactions in Mixed Station-
University Press, Ithaca, NY, 1953. ary Phases’, Macromolecules, 24, 3522 – 3527 (1989).
100. I.C. Sanchez, R.H. Lacombe, ‘Statistical Thermody- 117. A.M. Farooque, D.D. Deshpande, ‘Studies of Polysty-
namics of Polymer Solutions’, Macromolecules, 11, rene – Polybutadiene Blend System by Inverse Gas
1145 – 1156 (1978). Chromatography’, Polymer, 33, 5005 – 5018 (1992).
101. D.R. Paul, S. Newman (eds.), Polymer Blends, Aca- 118. M.J. El-Hibri, P. Munk, ‘Recent Developments in Inver-
demic Press, New York, 1978. se Gas Chromatography of Polymer Blends’, Polym.
102. O. Olabisi, L.M. Robeson, M.T. Shaw, Polymer – Poly- Prepr. (Am. Chem. Soc. Div. Polym. Chem.), 28(1),
mer Miscibility, Academic Press, New York, 1979. 262 – 263 (1987).
103. P. Munk, P. Hattam, A.A. Abdel-Azim, Q. Du, ‘Ther- 119. Z. Tan, G.J. Vancso, ‘Molecular Probing of Polymeric
modynamics of Miscible Polymer Blends Studied Microstructure and Nonrandom Partitioning of Solvents
by Inverse Gas Chromatography’, Makromol. Chem., Absorbed in Polymers by Inverse Gas Chromatography’,
Macromol. Symp., 38, 205 – 220 (1990). Macromolecules, 30, 4665 – 4673 (1997).
104. J. Pouchly, A. Zivny, K. Solc, ‘Thermodynamic Equi- 120. A.B. Garcia, A. Cuesta, M.A. Montes-Moran, A. Marti-
librium in the System Macromolecular Coil – Binary nez-Alonso, J.M.D. Tascon, ‘Zeta Potential as a Tool
Solvent’, J. Polym. Sci., Part C: Polym. Symp., 23, to characterize Plasma Oxidation of Carbon Fibers’, J.
245 – 256 (1968). Colloid Interface Sci., 192, 363 – 367 (1997).
105. Z.Y. Al-Saigh, P. Munk, ‘Study of Polymer – Polymer 121. M.N. Belgacem, G. Czeremuszkin, S. Sapieha, ‘Cellu-
Interaction Coefficients in Polymer Blends Using Inverse lose, Surface Characterization of Cellulose Fibers by
Gas Chromatography’, Macromolecules, 17, 803 – 809 XPS and Inverse Gas Chromatography’, Cellulose, 2,
(1984). 145 – 157 (1995).
106. O.S. Tyagi, S.M. Sajjad, S. Husain, ‘Polymer – Polymer 122. J.T. Guthrie, M. Kunaver, ‘Interactions in Coatings
Interaction Parameter Determined by Inverse Gas Formulations. Part 3. The Influence of Selected Pigment
Chromatography’, Polymer, 28, 2329 – 2334 (1987). Paste Assemblies’, Dyes Pigment. 26, 201 – 215 (1994).
107. D.D. Deshpande, D. Patterson, H.P. Schreiber, C.S. Su, 123. P.L. Jackson, M.B. Huglin, A. Cervenka, ‘Use of Inverse
‘Thermodynamic Interactions in Polymer Systems by Gas Chromatography to Quantify Interactions in
Gas – Liquid Chromatography. IV. Interactions between Amine Cured Epoxy Resins’, Polym. Int., 35, 119 – 133
Components in a Mixed Stationary Phase’, Macro- (1994).
molecules, 7, 530 – 535 (1974). 124. P.L. Jackson, M.B. Huglin, A. Cervenka, ‘Investigations
108. C.S. Su, D. Patterson, ‘Determination by Gas – Liquid by Inverse Gas Chromatography Relevant to Coated
Chromatography of the Polystyrene – Poly(vinyl methyl Glass Fiber Epoxy Composites’, Polym. Int., 35, 145 – 152
ether) Interaction’, Macromolecules, 10, 708 – 710 (1977). (1994).
109. G. DiPaola-Baranyi, S.J. Fletcher, P. Degré, ‘Gas Chro- 125. P.L. Jackson, M.B. Huglin, A. Cervenka, ‘Use of Inverse
matographic Investigation of Poly(vinylidene fluo- Gas Chromatography to Quantify Interactions in Anhy-
ride) – Poly(methyl methacrylate) Blends’, Macromole- dride Cured Epoxy Resins’, Polym. Int., 35, 135 – 143
cules, 15, 885 – 889 (1982). (1994).
110. G. DiPaola-Baranyi, P. Degré, ‘Thermodynamic Char- 126. M. Kazayawoko, J.J. Balatinecz, M. Romansky, ‘Ther-
acterization of Polystyrene-Poly(n-butyl methacrylate) modynamics of Adsorption of n-Alkanes on Maleated
Blends’, Macromolecules, 14, 1456 – 1460 (1981). Wood Fibers by Inverse Gas Chromatography’, J. Col-
111. Z.Y. Al-Saigh, ‘Inverse Gas Chromatography for the loid Interface Sci., 190, 408 – 415 (1997).
Characterization of Polymer Blends’, Int. J. Polym. Anal. 127. S. Rebouillat, J.B. Donnet, H. Guo, T.K. Wang, ‘Surface
Charact., 3, 249 – 291 (1997). Energy Mapping of Kevlar Fibers by Inverse Gas
DOI: 10.1002/9780470027318.a2016
Chromatography’, J. Appl. Polym. Sci., 67, 487 – 500 142. A. Robard, D. Patterson, ‘Temperature Dependence
(1998). of Polystyrene – Poly(vinyl methyl ether) Compatibility
128. L.I. Kuzub, A.I. Efremova, E.N. Raspopova, O.S. Svec- in Trichloroethene’, Macromolecules, 10, 1021 – 1025
hnikova, N.I. Shut, V.I. Irzhak, ‘Properties of the Sur- (1977).
face Layer of Ultrahigh Modulus Polyethylene Fiber’, 143. M.J. Fernandez-Berridi, G.M. Guzman, J.M. Elorza,
Vysokomol. Soedin., Ser. B, 35, 308 – 311 (1993). L. Garijo, ‘Study by Gas – Liquid Chromatography of
129. H. Chtourou, B. Riedl, B.V. Kokta, ‘Surface Character- the Thermodynamics of the Interactions of Poly(vinyl
izations of Modified Polyethylene Pulp and Wood Pulps acetate) with Various Solvents’, Eur. Polym. J., 19,
Fibers Using XPS and Inverse Gas Chromatography’, J. 445 – 450 (1983).
Adhes. Sci. Technol., 9, 551 – 574 (1995). 144. C.P. Doubé, D.J. Walsh, ‘Studies of Poly(vinyl chlo-
130. W. Shen, I.H. Parker, Y.J. Sheng, ‘The Effects of Surface ride)/Solution Chlorinated Polyethylene Blends by
Extractives and Lignin on the Surface Energy of Eucalpt Inverse Gas Chromatography’, Eur. Polym. J., 17, 63 – 67
Kraft Pulp Fibers’, J. Adhes. Sci. Technol., 12, 161 – 174 (1981).
(1998). 145. T. Nishi, T.T. Wang, ‘Melting Point Depression and
131. A. Lundqvist, L. Oedberg, J.C. Berg, ‘Surface Charac- Kinetic Effects of Cooling on Crystallization in Poly(vin-
terization of Non-chlorine-bleached Pulp Fibers and ylidene fluoride) – Poly(methyl methacrylate) Mixtures’,
Calcium Carbonate Coatings Using Inverse Gas Chro- Macromolecules, 8, 909 – 915 (1975).
matography’, Tappi J., 78, 39 – 42 (1995). 146. T.P. Russell, H. Ito, G.D. Wignall, ‘Neutron and X-ray
132. M.H. Abraham, G.S. Whiting, ‘Hydrogen Bonding. Scattering Studies on Semicrystalline Polymer Blends’,
Part 22. Characterization of Soybean Oil and Predic- Macromolecules, 21, 1703 – 1709 (1988).
tion of Activity Coefficients in Soybean Oil from Inverse 147. C.A. Barron, S.K. Kumar, J.P. Runt, ‘Crystal – Amorph-
Gas Chromatographic Data’, J. Am. Oil Chem. Soc., 69, ous Interphases in Semi-crystalline Polymers and Poly-
1236 – 1238 (1992). mer Blends’, Polym. Prepr. (Am. Chem. Soc. Div. Polym.
133. J.W. King, ‘Determination of the Solubility Parameter Chem.), 33(2), 610 – 611 (1992).
of Soy Bean Oil by Inverse Gas Chromatography’, Food 148. D.J. Walsh, J.S. Higgins, S. Rostami, K. Weeraperuma,
Sci. Technol. (London), 28, 190 – 195 (1995). ‘Compatibility of Ethylene – Vinyl Acetate Copolymers
134. M. Lagoudaki, P.G. Demertzis, G. Panagiotis, ‘Equilib- with Chlorinated Polyethylenes. 2. Investigation of
rium Moisture Characteristics of Dehydrated Food the Thermodynamic Parameters’, Macromolecules, 16,
Constituents as Studied by a Modified Inverse Gas Chro- 391 – 396 (1983).
matographic Method’, J. Sci. Food Agric., 65, 101 – 109 149. M.J. Fernandez-Berridi, G.M. Guzman, J.K. Iruin, J.M.
(1994). Elorza, ‘Determination of the Interaction Parameter c of
135. R. Gavara, R. Catala, P. Hernandez-Munoz, ‘Study of Poly(ethylene oxide) by Gas – Liquid Chromatography
Aroma Scalping Through Thermosealable Polymers below the Melting Temperature’, Polymer, 24, 417 – 422
Used in Food Packaging by Inverse Gas Chromatog- (1983).
raphy’, Food Addit. Contam., 14, 609 – 616 (1997). 150. F.H. Covitz, J.W. King, ‘Solute Absorption into Molten
136. M. Lagoudaki, P.G. Demertzis, M.G. Kontominas, Leb- Polystyrene’, J. Polym. Sci., Part A-1: Polym. Chem., 10,
ensm. Wiss. Technol., 26, 512 (1993). 689 – 699 (1972).
137. K.A. Riganakos, P.G. Demertzis, M.G. Kontominas, 151. M.J. El-Hibri, W. Cheng, P. Hattam, P. Munk, ‘Inverse
‘Water Sorption by Wheat and Soy Flour: Compar- Gas Chromatography of Polymer Blends: Theory and
ison of Three Methods’, J. Cereal Sci., 20, 101 – 106 Practice’, in Inverse Gas Chromatography, Characteriza-
(1994). tion of Polymers and Other Materials, eds. D.R. Lloyd,
138. K.A. Riganakos, M.G. Kontominas, ‘GC Study of the T.C. Ward, H.P. Schreiber, ACS Symposium Series
Effect of Specific Heat Treatment on the Sorption of no. 391, Washington, DC, Chapter 10, 1989.
Water by Wheat and Soy Flour’, Z. Lebensm. Unters. 152. R.D. Newman, J.M. Prausnitz, ‘Polymer – Solvent Inter-
Forsch., 198, 47 – 51 (1994). actions from Gas – Liquid Partition Chromatography’, J.
139. H. Kumagai, M. Iwase, H. Kumagai, A. Mizuno, Phys. Chem., 76, 1492 – 1496 (1972).
T. Yano, ‘Application of Solution Thermodynamics to 153. W. Merk, R.N. Lichtenthaler, J.M. Prausnitz, ‘Solubili-
the Water Sorption Isotherms of Food Materials’, Biosci. ties of Fifteen Solvents in Copolymers of Poly(vinyl
Biotechnol. Biochem., 58, 475 – 481 (1994). acetate) and Poly(vinyl chloride) from Gas – Liquid
140. H. Balard, A. Saada, J. Hartmann, O. Aouadj, E. Papir- Chromatography. Estimation of Polymer Solubility
er, ‘Estimation of Surface Energetic Heterogeneity of Parameters’, J. Phys. Chem., 84, 1694 – 1695
Fillers by Inverse Gas Chromatography’, Macromol. (1980).
Symp., 108, 63 – 80 (1996). 154. A. Heintz, R.N. Lichtenthaler, J.M. Prausnitz, ‘Solubili-
141. G. DiPaola-Baranyi, P. Degré, ‘Thermodynamic Char- ties of Volatile Solvents in Polyvinyl Acetate, Polyvinyl
acterization of Polystyrene – Poly(n-butyl methacrylate) Chloride, and Their Random Copolymers’, Ber. Bunsen-
Blends’, Macromolecules, 14, 1456 – 1460 (1981). ges. Phys. Chem., 83, 926 – 928 (1979).
DOI: 10.1002/9780470027318.a2016
155. A. Voelkel, E. Andrzejewska, R. Maga, M. Andrzejew- of Polypropylene Transitions’, Makromol. Chem., 175,
ski, ‘Characterization of Dispersive and Acid – Base 2975 – 2982 (1974).
Properties of Crosslinked Polymers by Inverse Gas 171. L.Q. Xie, ‘Measurement of Solute Diffusion in Polymers
Chromatography’, Polymer, 34, 3109 – 3111 (1993). by Inverse Gas Chromatography Using Fused-silica
156. C.T. Chen, Z.Y. Al-Saigh, ‘Characterization of Poly(eth- Open Tubular Columns’, Polymer, 34, 4579 – 4584 (1993).
yl methacrylate) by Inverse Gas Chromatography’, 172. J.S. Vrentas, C.M. Vrentas, ‘Solvent Self-diffusion in
Polymer, 31, 1170 – 1176 (1990). Glassy Polymer – Solvent Systems’, Macromolecules, 27,
157. P. Munk, P.J. Hattam, Q. Du, ‘Thermodynamic Inter- 5570 – 5576 (1994).
actions in Mixtures’, J. Appl. Polym. Sci., 43, 373 – 399 173. S. Prager, F.A. Long, ‘Diffusion of Hydrocarbons in
(1989). Polyisobutylene’ J. Am. Chem. Soc., 73, 4072 – 4075
158. A. Voelkel, J. Janas, ‘Inverse Gas Chromatographic (1951).
Determination of Solubility Parameter and Binary 174. P. Hattam, P. Munk, ‘Inverse Gas Chromatography. 5.
Parameters of a,w-Diamino Oligoethers’, J. Chro- Computer Simulation of Diffusion Processes on the
matogr., A, 669, 89 – 95 (1994). Column’, Macromolecules, 21, 2083 – 2090 (1988).
159. A. Voelkel, J. Janas, ‘The Solubility Parameters of 175. D. Arnould, R.L. Laurence, ‘Size Effects on Solvent
Fluorine-containing Oxyethylates’, J. Fluorine Chem., Diffusion in Polymers’, Ind. Eng. Chem. Res., 31,
67, 75 – 81 (1994). 218 – 228 (1992).
160. A. Voelkel, J. Janas, ‘Solubility Parameters of Broad and 176. R.E. Balthus, M.A. Alger, T.J. Stanley, ‘Solubility and
Narrow Distributed Oxyethylates of Fatty Alcohols’, J. Diffusivity of Cyclic Oligomers in Poly(dimethylsilo-
Chromatogr., 645, 141 – 151 (1993). xane) Using Capillary Column Inverse Gas Chromatog-
161. P.L. Jackson, M.B. Huglin, ‘Use of Inverse Gas Chro- raphy’, Macromolecules, 26, 5651 – 5656 (1993).
matography to Assess the Compatibility of Polyurethane 177. M.F. Grenier-Loustalot, G. Mouline, P. Grenier, ‘Inverse
Foam with Liquids at Different Temperatures’, Polym. Gas Chromatography Used to Follow Kinetics of Epoxy-
Int., 33, 409 – 411 (1994). amine Reactions in the Molten State’, Polymer, 28,
162. P. Munk, Z.Y. Al-Saigh, T.W. Card, ‘Inverse Gas Chro- 2275 – 2281 (1987).
matography. 3. Dependence of Retention Volume on 178. G.J. Price, K.S. Siow, J.E. Guillet, ‘The Use of Gas
the Amount of Probe Injected’, Macromolecules, 18, Chromatography to Determine the Degree of Cross-
2196 – 2201 (1985). linking of a Polymer Network’, Macromolecules, 22,
163. J.E. Guillet, A.N. Stein, ‘Study of Crystallinity in Poly- 3116 – 3119 (1989).
mers by the Use of ‘‘Molecular Probes’’ ’, Macro- 179. M.L. Abel, M.M. Chehimi, ‘Comments on ‘Character-
molecules, 3, 102 – 105 (1970). ization of Dispersive and Acid – Base Properties of
164. A. Lavoie, J.E. Guillet, ‘Estimation of Glass Transition Crosslinked Polymers by Inverse Gas Chromatography’
Temperatures from Gas Chromatographic Studies on by A. Voelkel et al.’, Polymer, 35, 1789 – 1790 (1994).
Polymers’, Macromolecules, 2, 443 – 446 (1969). 180. Z. Tan, R. Jaeger, G.J. Vancso, ‘Crosslinking Studies
165. G. Boiteux-Steffan, J.P. Soulie, D. Sage, J.-M. Letoffe, of Poly(dimethylsiloxane) Networks: a Comparison of
‘Multiple Transitions in Poly(allylbenzene): 1. Thermo- Inverse Gas Chromatography, Swelling Experiments,
physical Properties’, Polymer, 26, 1443 – 1447 and Mechanical Analysis’, Polymer, 35, 3230 – 3236
(1985). (1994).
166. A.B. Wojcik, ‘Porous Bead Aliphatic – Aromatic Metha- 181. J. Guillet, M. Romansky, G.J. Price, R. van der Mark,
crylate Copolymers. VII. TG, DTA, DSC, and Inverse ‘Studies of Polymer Structure and Interactions by
Gas Chromatography Studies’, J. Appl. Polym. Sci., 39, Automated Inverse Gas Chromatography’, in Inverse
179 – 187 (1990). Gas Chromatography: Characterization of Polymers
167. R. Sanetra, B.N. Kolarz, A. Wlochowicz, ‘Determination and Other Materials, eds. D.R. Lloyd, T.C. Ward,
of the Glass Transition Temperature of Poly(styrene- H.P. Schreiber, ACS Symposium Series no. 391, Wash-
co-divinylbenzene) by Inverse Gas Chromatography’, ington, DC, Chapter 3, 1989.
Polymer, 26, 1181 – 1186 (1985). 182. F. Chen, ‘Study of Acceptor – Donor Interactions at the
168. C.T. Chen, Z.Y. Al-Saigh, ‘Characterization of Semicrys- Polymer Interface by Inverse Gas Chromatography Data
talline Polymers by Inverse Gas Chromatography. 1. Analysis’, Macromolecules, 21, 1640 – 1643 (1988).
Poly(vinylidene fluoride)’, Macromolecules, 22, 2974 – 183. O.S. Tyagi, D.D. Deshpande, ‘Inverse Gas Chromatog-
2981 (1989). raphy of Poly(n-butylmethacrylate): Effect of Flow
169. C. Bonnerup, P. Gatenholm, ‘The Effect of Surface Rate on Specific Retention Volume and Detection of
Energetics and Molecular Interdiffusion on Adhesion Glass Transition Temperature’, J. Appl. Polym. Sci., 34,
in Multicomponent Polymer Systems’, J. Adhes. Sci. 2377 – 2388 (1987).
Technol., 7, 247 – 262 (1993). 184. J.Y. Wang, G. Charlet, ‘Use of Moment Analysis in
170. S. Galassi, G. Audisio, ‘The Application of the Molecu- Inverse Gas Chromatography’, Macromolecules, 22,
lar Probes Gas Chromatographic Technique to the Study 3781 – 3788 (1989).
DOI: 10.1002/9780470027318.a2016
185. P. Hattam, Q. Du, P. Munk, ‘Computer Simulation of ed. J.V. Dawkins, Applied Science Publishers, Barking,
Elution Behavior of Probes in Inverse Gas Chromatogra- Chapter 2, 1982.
phy: Comparison with Experiment’, in Inverse Gas Chro- 199. Z.Y. Al-Saigh, ‘Recent Advances in the Characteri-
matography: Characterization of Polymers and Other zation of Polymers and Polymer Blends Using the
Materials, eds. D.R. Lloyd, T.C. Ward, H.P. Schreiber, Inverse Gas Chromatography Method’, Polym. News,
ACS Symposium Series no. 391, Washington, DC, Chap- 19, 269 – 279 (1994).
ter 4, 1989. 200. J.-M. Braun, J.E. Guillet, ‘Study of Polymers by Inverse
186. A.E. Bolvari, T.C. Ward, P.A. Koning, D.P. Sheehy, Gas Chromatography’, Adv. Polym. Sci., 21, 107 – 145
‘Experimental Techniques for Inverse Gas Chromatog- (1976).
raphy’, in Inverse Gas Chromatography: Characteriza- 201. P. Munk, ‘Polymer Characterization Using Inverse Gas
tion of Polymers and Other Materials, eds. D.R. Lloyd, Chromatography’, Chem. Anal. (N.Y.), 113, 151 – 200
T.C. Ward, H.P. Schreiber, ACS Symposium Series (1991).
no. 391, Washington, DC, Chapter 2, 1989. 202. G. DiPaola-Baranyi, ‘Thermodynamics of Polymer
187. M.J. El-Hibri, P. Munk, ‘Marker Retention in Inverse Blends by Inverse Gas Chromatography’, in Inverse
Gas Chromatography Experiments on Polymers’, Mac- Gas Chromatography, Characterization of Polymers
romolecules, 21, 264 – 266 (1988). and Other Materials, eds. D.R. Lloyd, T.C. Ward,
188. H. Becker, R. Gnauck, ‘Determination of Dead Times H.P. Schreiber, ACS Symposium Series no. 391, Wash-
for Inverse Gas Chromatography: Measurements by Use ington, DC, Chapter 9, 1989.
of Methane’, J. Chromatogr., 366, 378 – 381 (1986). 203. S.P. Wesson, R.E. Allred, ‘Surface Energetics of Plasma-
189. R. Zhang, J. Jagiello, J.F. Hu, Z.Q. Huang, J.A. Schwarz, treated Carbon Fiber’, in Inverse Gas Chromatography,
A. Datye, ‘Effect of Tungsten Trioxide Loading on the Characterization of Polymers and Other Materials, eds.
Surface Acidity of WO3/Alumina’, Appl. Catal., A, 84, D.R. Lloyd, T.C. Ward, H.P. Schreiber, ACS Sympo-
123 – 139 (1992). sium Series no. 391, Washington, DC, Chapter 15, 1989.
190. P.J. Kalaouzis, P.G. Demertzis, ‘Influence of a Monome- 204. A.J. Vukov, D.G. Gray, ‘Properties of Carbon Fiber
ric Plasticizer on the Water-sorption Behavior of Food- Surfaces’, in Inverse Gas Chromatography, Characteri-
grade Plastics Packaging Materials’, Polym. Int., 32, zation of Polymers and Other Materials, eds. D.R. Lloyd,
125 – 130 (1993). T.C. Ward, H.P. Schreiber, ACS Symposium Series
191. A. Voelkel, J. Janas, J.A. Garcia-Dominguez, ‘Inverse no. 391, Washington, DC, Chapter 13, 1989.
Gas Chromatography in Characterization of Surfac- 205. J. Schultz, L. Lavielle, ‘Interfacial Properties of Carbon
tants’, J. Chromatogr., A, 654, 135 – 141 (1993). Fiber-epoxy Matrix’, in Inverse Gas Chromatography,
192. M.F. Grenier-Loustalot, P. Grenier, ‘The Mechanism of Characterization of Polymers and Other Materials, eds.
Epoxy Resin Curing in the Presence of Glass and Carbon D.R. Lloyd, T.C. Ward, H.P. Schreiber, ACS Sympo-
Fibers’, Polymer, 33, 1187 – 1199 (1992). sium Series no. 391, Washington, DC, Chapter 14, 1989.
193. H. Balard, E. Papirer, ‘Characterization and Modifica- 206. E. Osmont, H.P. Schreiber, ‘Surface Characteristics of
tion of Fillers for Paints and Coatings’, Prog. Org. Coat., Glass Fibers’, in Inverse Gas Chromatography, Char-
22, 1 – 17 (1993). acterization of Polymers and Other Materials, eds.
194. J. Jagiello, T.J. Bandosz, J.A. Schwarz, ‘Study of Carbon D.R. Lloyd, T.C. Ward, H.P. Schreiber, ACS Sympo-
Microstructure by Using Inverse Gas Chromatography’, sium Series no. 391, Washington, DC, Chapter 17, 1989.
Carbon, 32, 687 – 691 (1994). 207. Z. Tan, G.J. Vancso, ‘Polymer – Polymer Interaction
195. M.M. Chehimi, M.L. Abel, E. Pigois-Landureau, M. De- Parameters by Inverse Gas Chromatography. A Novel
lamar, ‘Characterization of Conducting Polymers by Molecular Interpretation of Nonrandom Partitioning of
Inverse Gas Chromatography. Part II. Effect of Dopant Solvent Probes in Polymer Blends’, Macromol. Theory
on the Dispersive and Specific Properties of Polypyrrole’, Simul., 6, 467 – 478 (1997).
Synth. Met., 60, 183 – 194 (1993). 208. P.J.T. Tait, A.M. Abushihada, ‘Use of a Gas Chromato-
196. E. Pigois-Landureau, M.M. Chehimi, ‘Quantitative Ass- graphic Technique for the Study of the Variation of
essment of Acid – Base Properties of Chloride Doped the Interaction Energy Parameter with Temperature’,
Polypyrrole by Inverse Gas Chromatography’, J. Appl. Macromolecules, 11, 918 – 922 (1978).
Polym. Sci., 49, 183 – 186 (1993). 209. F.L. Imken, D.R. Paul, J.W. Barlow, ‘Transition Behav-
197. M.M. Chehimi, E. Pigois-Landureau, M. Delamar, ior of Poly(vinylidene fluoride)/Poly(ethyl methacry-
‘Characterization of Conducting Polymers by Inverse late)’, Polym. Eng. Sci., 16, 593 – 601 (1976).
Gas Chromatography. Part 1. Dispersive and Acid – Base 210. F. Feraz, A.S.H. Hamou, S. Djadoun, ‘Miscibility of
Properties of Conducting Polypyrrole and its Related Poly(styrene-co-acrylic acid) with Polymethacrylates or
Insulating Form’, J. Chim. Phys., 1173 – 1178 (1992). Poly(methacrylate-co-vinylpyridine)’, Eur. Polym. J., 31,
198. J.E.G. Lipson, J.E. Guillet, ‘Study of Structure and 665 – 669 (1995).
Interactions in Polymers by Inverse Gas Chromatogra- 211. S. Djadoun, F.E. Karasz, A.S.H. Hamou, ‘Blends of
phy’, in Developments in Polymer Characterisation – 3, Poly(isobutyl methacrylate) with Poly(styrene-co-acrylic
DOI: 10.1002/9780470027318.a2016
acid) and of Poly(isobutyl methacrylate-co-acrylic acid) 213. D.E. Cherrak, S. Djadoun, ‘A Study of Mixtures of
with Poly(styrene-co-N,N-dimethyl aminoethyl metha- Poly(ethylene oxide) with Polystyrene or Poly(styrene-
crylate)’, Thermochim. Acta, 282/283, 399 – 410 (1996). co-acrylic acid) by Inverse Gas Chromatography and
212. D.E. Cherrak, S. Djadoun, ‘Inverse Gas Chromatogra- Viscosimetry’, Polym. Bull., 27, 289 – 295 (1991).
phy of Poly(ethylene oxide) with Poly(ethyl methacry- 214. G.J. Price, J.E. Guillet, ‘The Determination of Thermo-
late) or Poly(ethyl methacrylate-co-methacrylic acid)’, dynamic Properties of Polymer Solutions Using Finite
J. Appl. Polym. Sci., Appl. Polym. Symp., 51, 209 – 219 Concentration Gas Chromatography’, J. Macromol. Sci.,
(1992). Chem., A23, 1487 – 1502 (1986).
DOI: 10.1002/9780470027318.a2016

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INVERSE GAS CHROMATOGRAPHY IN ANALYSIS OF POLYMERS 1

Inverse Gas Chromatography 13.3 Coating the Support: the Pile

This article describes the application of inverse gas chro-

Figure 2 Retention diagram for a semicrystalline polymer. Tg is

Area A – C represents a nonequilibrium absorption of the

percentage crystallinity of the sample at any temperature,

5.1 Adsorption Isotherms

VR equal to Ka AL . The surface partition coefficient can

therefore be found by using a support of known surface

3 for the same polymer – probe system the surface area of

the stationary phase can be found. The surface partition

Vg0 D Ks A .17/ 6.1 Degree of Crystallinity

to remove particles larger than about 0.1 mm, will give

2.0 while using curvilinear extrapolation the curve leveled off

density measurements. Besides giving a more accurate

small molecules at infinite dilution in the polymer system

7.1 Determination of Diffusion Constants

phase, H values are calculated from the chromatographic 2

where f .a, µ/ is a function of the probe’s polarizability

[(δ12/RT ) –(χ/ V 1)] × 102

Solubility parameters provide another way of quantifying

13.4 Determination of Degree of Crosslinking of

Figure 14 Flow meter is calibrated using a thermostated soap VN D .tr tm /F .72/

Detector c D 0.344 C 0.004f1 .80/

Industrial Hygiene (Volume 5)

Polymers and Rubbers (Volume 8)

Volume fraction of solvent (φ) Polymers and Rubbers (Volume 9)

Gas Chromatography (Volume 12)

Sample Radiation dose (Mrad) 104 ve Mc REFERENCES

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