Polymer 55 (2014) 1028e1039

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Polymer
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Methanol diffusion in polyimides: A molecular descriptionq

Michele Galizia a, Pietro La Manna a, b, Marianna Pannico b, Giuseppe Mensitieri a,
Pellegrino Musto b, *
a
Department of Chemical, Materials and Industrial Production Engineering, University of Naples Federico II, p.le Tecchio 80, 80125 Naples, Italy
b
Institute of Chemistry and Technology of Polymers, National Research Council of Italy, Via Campi Flegrei, 34, 80078 Pozzuoli, Italy

a r t i c l e i n f o a b s t r a c t

Article history: In this contribution the diffusion of methanol in two commercial polyimides (6FDA-ODA and UltemÒ
Received 16 October 2013 1000) is investigated in detail by gravimetric analysis and in-situ, time-resolved FTIR spectroscopy. Two
Received in revised form methods of spectral data analysis are employed, namely difference spectroscopy (DS) and least-squares
20 December 2013
curve fitting (LSCF). These approaches provided complementary information about the overall diffusivity,
Accepted 6 January 2014
Available online 17 January 2014
the interactions and the dynamics of the molecular species present in the investigated systems. Spec-
troscopic measurements on thin film samples (2e4 mm) allowed us to identify the interaction site(s) on
the polymer backbone and to propose likely structures for the H-bonding molecular aggregates.
Keywords:
Polyimides
By coupling gravimetric and spectroscopic data collected in the same experimental conditions it was
Methanol possible to evaluate the molar absorptivities of the different molecular species, and hence their pop-
FTIR spectroscopy ulations, in both polyimides. The results highlighted the relevance of the H-bonding interaction and of
the substrate molecular structure on the final transport properties of the systems.
Ó 2014 Elsevier Ltd. All rights reserved.

1. Introduction fact, their good performances in dehydration of alcohols [5e12] are

Polyimides displaying different molecular architectures have
attracted, in the last decades, an increasing scientific and techno-
logical interest, in view of their widespread applications ranging
from microelectronics to the process industry. In the latter field, the
membrane separations of liquid and gas mixtures are some of the
most relevant applications of these materials [1]. Many routes have
been developed to optimize and tune mechanical and transport
properties of polyimides. Among them, the partial or total fluori-
nation of the polymer backbone and the introduction of crosslinks
appear to be of particular effectiveness [2,3]. Such chemically
modified polyimides display improved mechanical properties, high
gas permeability and selectivity, and strong resistance to organic
solvent, that makes it possible to use these materials in aggressive
environments or in extreme conditions of temperature and
pressure.
The interest of methanol/polyimides systems stems from the
fact that polyimides have been identified as membrane materials
with high separation factors for water/alcohol separations [4]. In
q Presented in part to the Conference “Frontiers in Polymer Science 2013”, Sitges,
Spain, 21e23rd May 2013.
* Corresponding author. Tel.: þ39 081 8675202.
E-mail addresses: pellegrino.musto@ictp.cnr.it, musto@ictp.cnr.it (P. Musto).
exploited in pervaporation and vapour permeation processes that
provide a feasible alternative to conventional distillation for
alcoholewater mixtures, warranting a lower energy demand [13].
The analysis of methanol sorption and transport in polyimides is of
interest not only with reference to water/methanol separation but
also for other processes involving the removal of methanol from
azeotropic mixtures with several organic compounds in all those
cases where methanol is used as reactant or reaction product (e.g.
esterification, transesterification).
The optimal design of separation processes involving alcoholic
compounds, requires a molecular level understanding of the in-
teractions between the penetrant and the polymer matrix. Indeed,
it has been demonstrated that both water and alcohol are able to
form hydrogen bonds with polymers displaying proton acceptor
groups on their backbone, and that such an occurrence strongly
affects the transport properties and the separation performances of
these systems. The occurrence of self-association of the penetrant
to form larger molecular aggregates has been also documented for
the water/polyimide system [14]. The vast majority of literature
contributions report only experimental data on alcohol dehydra-
tion using polyimides, while there is a lack of information about the
molecular mechanisms of these processes, and the role played by
the different types of H-bonding interactions.
Modelling of alcohol sorption thermodynamics in glassy poly-
mers endowed with hydrogen bonding interactions is rather

0032-3861/$ e see front matter Ó 2014 Elsevier Ltd. All rights reserved.
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 M. Galizia et al. / Polymer 55 (2014) 1028e1039
complex since one needs to account both for the out-of-equilibrium
state of the glassy system and for the occurrence of specific in-
teractions. Approaches based on the classical adsorption theories of
BET (BrunauereEmmetteTeller) or GAB (Guggenheim, Anderson,
de Boer) or their modifications are mainly phenomenological and
lack a physically sound description of the molecular mechanism
since do not supply a realistic microscopic picture of the interaction
mechanism between polar molecules and the internal structure of
the polymeric sorbent [15]. Another simple way to interpret sorp-
tion of low m.w. penetrants within glassy polymers is represented
by the so-called Dual Sorption model [16,17] that, properly modi-
fying the original theory, can be used to deal with specific poly-
merepenetrant interactions. This approach is suitable for
correlation purposes but it is not predictive. More recently, many
efforts have been devoted to the development of a theoretical
framework grounded on rational non-equilibrium thermody-
namics aimed at extending the equilibrium mixture theories,
suitable for the description of low m.w. sorption thermodynamics
in rubbery polymers endowed with hydrogen bonding interactions
to the case of non-equilibrium glassy polymer/penetrant mixtures
[18e20]. In the present contribution the thermodynamic modelling
issue is not addressed. Work is in progress to model the experi-
mental spectroscopic and gravimetric results presented herein, by
applying an extension of a thermodynamic model for rubbery
polymers to nonequilibrium glassy polymers. To this aim, the in-
formation gathered from the spectroscopic analysis is of primary
relevance.
In the present context, attention has been focused to the infor-
mation at the molecular level that can be gathered from FTIR
spectroscopy. This technique has recently emerged as a powerful
tool to investigate mass transport phenomena in polymers. For
example, in Ref. [14], by combining gravimetric and spectroscopic
approaches, an investigation of water transport in polyimides was
carried out and a reliable method was devised to quantify the
different populations of water molecules absorbed in the polymer
matrix.
In this work, a gravimetric and spectroscopic analysis of meth-
anol transport in two commercial polyimides differing for their
molecular structure has been performed. The spectral data have
been analysed by complementary techniques, namely difference
spectroscopy (DS) and least squares curve fitting (LSCF), which
provided information on the nature and the number of penetrant
species present in the systems. Coupling gravimetric and spectro-
scopic data collected in the same conditions, it was possible to
evaluate the molar absorptivity of the different species and to
Scheme 1. Molecular structure of A) 6FDA-ODA and B) UltemÒ 1000.
1029
Table 1
Properties of the investigated polyimides (in parentheses are indicated estimated
standard deviations).
M w (g/mol)a Mn (g/mol)a Tg ( C)b Density (g/cm3)c
6FDA-ODA 9.7  104 5.1  104 302 (0.5) 1.488 (0.001)
UltemÒ 1000 3.0  104 1.2  104 210 (0.5) 1.260 (0.001)
a
Measured by GPC.
b
Measured by differential scanning calorimetry: heating rate 20  C/min.
c
Measured by a helium pycnometer.
quantify their populations. Finally, spectroscopic measurements on
thin samples (2e4 mm) enabled us to identify the interaction site(s)
on the polymer backbone.
2. Experimental
2.1. Materials
The structure of the two investigated polyimides is reported in
Scheme 1. Poly(hexafluoroisopropilydene-2,2-bis-phthalicanhy-
dride-oxydianiline) (6FDA-ODA) was synthesized according to the
procedure described in Ref. [14].
Poly([2,20 -bis(3,4-dicarboxyphenoxy)phenylpropane]-2-
phenylene-bisimide), commercially available under the trade-
name of UltemÒ 1000, was kindly supplied by General Electric.
Table 1 summarizes the main characteristics of the two polyimides.
Methanol used for sorption experiments was purchased from
SigmaeAldrich (Milano, I) with purity higher 99.6%; it has been
further purified and degassed through freezingethawing cycles.
Free standing films of 6FDA-ODA, 30 mm thick, were obtained by
spreading the polyamic acid solution [13 wt% in N-methyl-2-pyr-
rolidone (NMP)] on a clean glass support with a Gardner knife. The
nascent films were then dried 1 h at room temperature and 1 h at
80  C, allowing the solvent to evaporate. The castings were then
thermally treated in a stepwise manner at 100, 150, 200, 250 and
290  C for 1 h at each temperature. Finally, the films were detached
from the glass support by immersion in distilled water at 80  C.
Free standing films of UltemÒ 1000 were prepared by casting of
a 5 wt% solution of the polyimide in chloroform. The nascent film
was first dried at atmospheric conditions for 2 days and then in a
vacuum oven at 120  C for 24 h, to remove residual solvent traces.
The thickness of the film used in gravimetric and FTIR experiments
was 43  1 mm.
1030 M. Galizia et al. / Polymer 55 (2014) 1028e1039

For both polyimides, thinner films (2e4 mm) were prepared by a the 3650e2750 cm1 range, corresponding to the v(OH) and v(CH)
two-step spin-coating process, using a Chemat KW-4A apparatus modes of methanol. To separate the individual components in the
(Northridge, CA). Spinning conditions were 12 s at 700 rpm for the case of unresolved bands, a curve fitting algorithm was applied,
first step and 20 s at 1500 rpm for the second step. After removal of based on the LevenbergeMarquardt method [23,24]. The peak
the films from their glass support in distilled water at room tem- functions used throughout were a log-normal and a mixed Gausse
perature, they were treated in the same conditions as for the Lorentz line shape, which are expressed respectively in the form
thicker samples. [24]:
" "  # #
2.2. Gravimetric sorption experiments ðx  x0 Þ r2  1
ln 2 2
f ðxÞ ¼ H exp ln þ1 (1)
 C,
ðln rÞ2 w
Methanol sorption experiments were performed at 30 using
a Quartz Spring Balance equipped with a couple of digital CCD " 2 #
  x  x0 H
cameras. Experimental sorption isotherms were obtained by f ðxÞ ¼ 1  lf H exp 4 ln 2 þ lf  (2)
w 2
increasing stepwise the penetrant relative pressure p/p0, p0 being xx0
4 w þ1
the penetrant vapour pressure at the experimental temperature.
Before each sorption test, the polymer sample was dried overnight
under vacuum at the experimental temperature, up to constant where x0 is the peak position, H the peak height, w the full-width at
weight. Full details about the experimental procedure are given in half height (FWHH), lf the fraction of Lorentz character and r the
Ref. [21]. asymmetry index (half width ratio). In order to keep the number of
adjustable parameters to a minimum, the baseline, the number and
2.3. FTIR sorption experiments the shape of the components were fixed, allowing the curve-fitting
algorithm to optimize the FWHH and the position of the peaks.
Time-resolved spectra were collected in the transmission mode
during sorption of methanol in polyimides. To this aim, a vacuum- 3. Results and discussion
tight FTIR sorption cell was used, in which a free standing polymer
film is exposed to methanol vapour at constant temperature (30  C) 3.1. Gravimetric measurements
and different penetrant relative pressures. The sorption cell,
equipped with a recirculation water bath to keep the temperature Sorption isotherms of methanol in 6FDA-ODA and UltemÒ 1000,
constant to within 0.1  C, was connected through service lines to a as obtained from gravimetric experiments, have been reported in
methanol reservoir, a turbo-molecular vacuum pump and an MKS Fig. 1 as a function of the penetrant relative pressure.
Baratron 121 (Andover, MA) pressure transducer (full scale Since the penetrant molecules are able to establish attractive
100 Torr, resolution 0.01 Torr and accuracy 0.5% of the reading). interactions with the carbonyl group on the polymer backbone in
Full details of the experimental setup are reported elsewhere [22]. the whole range of relative pressures inspected, the sorption iso-
Before each sorption measurement, the polymer film was placed in therms display in the low-medium p/p0 range a downward con-
the sorption cell and dried overnight under vacuum at the exper- cavity that, in the light of the Dual Sorption model [25,26], can be
imental temperature. ascribed to the ‘adsorption’ on polymer excess free volume
The sorption cell was coupled with a Spectrum GX spectrometer microvoids and specifically interacting sites. The slight upturn
from PerkineElmer (Norwalk, CT), equipped with a Ge/KBr beam observed in 6FDA-ODA at p/p0 higher than 0.5 can be ascribed to
splitter and a wide-band DTGS detector. The transmission spectra the onset of penetrant clustering, whereby molecular aggregates
were collected by setting the following instrumental parameters: larger than the dimer start to occur (more on this, later).
resolution ¼ 4 cm1; Optical Path Difference (OPD)
velocity ¼ 0.5 cm/s; spectral range 4000e600 cm1. Spectra were
acquired in the single-beam mode using a dedicated software
package for time-resolved spectroscopy (Timebase, PerkineElmer).
Differential sorption tests were performed by increasing step-
wise the relative pressures of methanol vapour within the range 0e
0.6.
Finally, for both polyimides, sorption experiments were also
performed on a much thinner film, to identify the functional
group(s) in the polymer backbone directly involved in H-bonding
interaction with the penetrant.

2.4. FTIR data analysis

Full absorbance spectra (i.e. polyimide plus absorbed methanol)

were obtained using a background collected on the cell with no
sample inside, at the test conditions. The spectra representative of
absorbed methanol were obtained by using as a background in the
single-beam spectrum of the cell containing the dry polymer film. It
is explicitly noted that this data processing approach is equivalent
to the more general difference spectroscopy method, provided that
no significant change in sample thickness takes place during the
sorption measurement, which was experimentally verified in the
present case. The above procedure allows us to eliminate the Fig. 1. Gravimetric sorption isotherms of methanol in 6FDA-ODA (open symbols) and
interference of the polymer spectrum in the regions of interest, i.e. UltemÒ 1000 (filled symbols). The continuous lines are a guide for the eye.
 M. Galizia et al. / Polymer 55 (2014) 1028e1039 1031

Fig. 2. Absorbance spectra (polyimide þ methanol) for A) 6FDA-ODA and B) UltemÒ 1000.

3.2. Absorbance and difference FTIR spectra
In Fig. 2AeB are reported the absorbance spectra of dry 6FDA-
ODA and UltemÒ 1000, respectively, before (black trace) and after
(blue in web version trace) equilibration in methanol vapour at the
highest relative pressure inspected.
The spectrum representative of sorbed methanol can be iso-
lated, at each relative pressure, after suppression of the polymer
interference by means of the subtraction analysis (see
Experimental section). As reported in Fig. 3AeB, the difference
spectrum of methanol shows a quite complex band shape in the vOH
region, indicating the occurrence of different species of methanol
involved in H-bonding interactions with the polymer matrix.
In particular, in both polyimides a relatively sharp, partially
resolved component at around 3570 cm1 is superimposed onto a
much broader band approximately centred at 3440 cm1. The latter
feature is significantly more pronounced in 6FDA-ODA than in
UltemÒ 1000. It is anticipated that the intensity ratio between the
two components changes with the amount of sorbed methanol,
with the low frequency bands getting more and more pronounced
as the penetrant concentration grows. This effect is more marked for
UltemÒ 1000 than for 6FDA-ODA. A quantitative assessment of this
behaviour will be presented in a forthcoming paragraph. Below
3000 cm1 is located the n(CH) pattern of sorbed methanol, showing
a three component profile centred at 2945 cm1, plus a fully
resolved peak at 2830 cm1. This profile remains completely un-
perturbed in the case of 6FDA-ODA (coincident with the reference
state, vide infra), while showing a typical first-derivative feature in
UltemÒ 1000 at 2970 cm1. This effect is indicative of a (limited)
perturbation in the v(CH) range of the UltemÒ 1000 spectrum.
3.3. Sorption kinetics
Sorption kinetics of methanol in 6FDA-ODA and UltemÒ 1000
has been investigated by using gravimetric and spectroscopic ap-
proaches. In view of the linear response of the spectroscopic ob-
servables with respect to concentration values (LamberteBeer
behaviour, see Fig. 4AeB), the time evolution of the v(eCH) band

Fig. 3. Difference spectra collected at increasing relative pressures during sorption experiments of methanol in polyimides: A) 6FDA-ODA, and B) UltemÒ 1000.

Fig. 4. Absorbance of the v(OH), v(CH) and v(CeO) bands as a function of methanol concentration: A) 6FDA-ODA and B) UltemÒ 1000.
1032 M. Galizia et al. / Polymer 55 (2014) 1028e1039
intensities can be exploited to monitor the diffusion kinetics, which
have been analysed by reporting, in the Fick’s diagram, the
normalized absorbance A(t)/Ainf as a function of the ratio t0.5/L,
where t represents the sorption time and L the film thickness. Here
and in the following, A(t) is the integrated absorbance at time t and
Ainf the final integrated absorbance, after reaching equilibrium
conditions.
The higher diffusivity of methanol in 6FDA-ODA as compared to
PEI is likely due the higher Fractional Free Volume (FFV) of the
former. In fact FFV of PEI has been reported to be equal to 0.112 as
opposed to the value of 0.165 for 6FDA-ODA [27]. This effect is
related mostly to the presence of CF3 groups in 6FDA-ODA that
significantly increase the stiffness of the chain and reduce the
effective chain packing [28].
The same analysis can be performed by considering the gravi-
metric data and reporting, in the Fick’s diagram, m(t)/minf as a
function of t0.5/L. Fig. 5AeB demonstrates that the gravimetric and
spectroscopic data are essentially coincident and can be satisfac-
torily fitted by the Fick’s model, which is described, in the case of a
plane sheet, by the following equations in terms of mass absorbed
(eq. (3)) or, equivalently, in terms of absorbance (eq. (4)) [29,30]
" #
mðtÞ 8 X
N
1 Dð2m þ 1Þ2 p2 t
¼ 1 2 exp
minf p m ¼ 0 ð2m þ 1Þ2 L2
" #
AðtÞ 8 X
N
1 Dð2m þ 1Þ2 p2 t
¼ 1 2 exp
Ainf p m ¼ 0 ð2m þ 1Þ2 L2
In eqs. 3 and 4, D represents the mutual diffusivity and is the
sole parameter used to fit the experimental points. The Fickian
behaviour of the systems at hand is confirmed by the linearity of
the sorption curves as a function of t0.5/L, up to A(t)/Ainf and m(t)/
minf values of 0.6.
The diffusivity values estimated from gravimetric and FTIR data
are in excellent agreement one to another for both the systems
investigated and compare very well with literature data [31] (see
Table 2).
3.4. Detecting the polymer active site(s)
With the aim of identifying the interaction site(s) on the poly-
mer backbone, a methanol sorption test has been performed on
much thinner films of 6FDA-ODA and UltemÒ 1000. The samples
used for this kind of analysis have been obtained by a dual step
spin-coating process, as described in the Experimental section:
Fig. 5. Methanol sorption kinetics in A) 6FDA ODA and B) UltemÒ 1000. Red symbols refer to gravimetric data, blue symbols are relative to FTIR data. Continuous lines represent the
best fitting provided by 2nd Fick’s law (eqs. (3) and (4)). (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)
Table 2
Methanol diffusivity in 6FDA-ODA and UltemÒ 1000 as estimated from gravimetric
and FTIR experiments (in parentheses are indicated estimated standard deviations).
Dgrav (cm2/s) DFTIR (cm2/s)
6FDA-ODa 6.0  1010 (2  1011) 7.0  1010 (1  1011)
UltemÒ 1000b 2.0  1010(2  1011) 2.5  1010(1  1011)
a
Measured at p/p0 ¼ 0.20.
b
Measured at p/p0 ¼ 0.04.
their thickness has been estimated spectroscopically, according to
the relationship:
Athin
Lthin ¼ L (5)
Athick thick
The analytical peak of the polymer spectrum (located at
1015 cm1) was chosen so as to be fully resolved and of intensity
lower than the saturation threshold in both thicker and thinner
specimens. The thickness of the thin films resulted to be 2 mm for
6FDA-ODA and 4 mm for UltemÒ 1000. The sorption test was per-
formed at four different relative pressures; in this case only equi-
librium data were meaningful, owing to the very fast sorption
(3)
kinetics.
In Fig. 6AeC the absorbance spectrum of dry 6FDA-ODA is
compared with the spectrum of the same polyimide after equili-
bration in methanol vapour at p/p0 ¼ 0.6 in three different fre-
(4)
quency ranges. The difference spectra (equilibrated  dry) are also
reported. In Fig. 6DeF is shown the same comparison for UltemÒ
1000 equilibrated at p/p0 ¼ 0.5.
The chosen frequency ranges are those where the most likely
proton-acceptor groups of the two polyimides display their major
features. For 6FDA-ODA, we observe a well resolved carbonyl
doublet at 1785e1727 cm1 [vsym(C]O) and vasym(C]O), respec-
tively] and a band at 1378 cm1 which, according to previous
literature reports [32] and to a recent normal coordinate analysis
[33], has been assigned to a highly coupled normal mode
comprising a significant contribution from the NeCeO in-plane
deformation. Finally, the prominent band at 1241 cm1 originates
from the ether linkage of the ODA unit (the asymmetric stretching
vibration of the CeOeC bond [32]). Both carbonyl peaks display a
red-shift which is clearly detected in the difference spectrum as a
pronounced first-derivative feature with the negative lobe pre-
ceding the positive (see Fig. 6A). Also for the 1378 cm1 band a first-
derivative pattern is apparent in the difference spectrum, but this
time the positive lobe occurs at higher frequencies than the
 M. Galizia et al. / Polymer 55 (2014) 1028e1039 1033

Fig. 6. Spectra of the dry polyimide (black trace), of the polyimide after equilibration in methanol vapour at the higher p/p0 value (blue trace) and difference spectra (equilibrated
sample  dry sample, red traces). Spectra are reported in three different frequency regions. AeC): 6FDA-ODA; DeF) UltemÒ 1000. (For interpretation of the references to colour in
this figure legend, the reader is referred to the web version of this article.)

negative, i.e. the band is blue-shifted (see Fig. 6B). These observa-
tions can be accounted for by assuming the involvement of the
carbonyl groups in H-bonding interactions with methanol. In fact,
the red shift is a direct consequence of the lowering of the C]O
force constant caused by the interaction between the proton
acceptor and the OeH groups. Conversely, it is known that H-
bonding determines a stiffening of force constant of in-plane
deformation modes of the proton acceptor [33], which according
to our previous assignments, accounts for the blue-shift of the
1378 cm1 band. The v(CeOeC) band is not significantly perturbed
in the presence of methanol, which rules out the involvement of
ether linkages in H-bonding with the penetrant.
In summary, the above analysis demonstrates that, in the pre-
sent system the only proton acceptors are the imide carbonyls,
while the ether oxygens are not appreciably affected.
In view of the spectral features shown in Fig. 6DeF, exactly the
same conclusions can be drawn for UltemÒ 1000.
The reason why the sp3 oxygen does not participate to the
overall interaction equilibrium is not easily accounted for. Possible
steric effects can be invoked, originating from the well established
propensity of the polyimide chains to form charge-transfer in-
teractions among the aromatic rings of the backbone. These induce
the formation of mesophases in which the chains assume prefer-
ential conformations such that the carbonyls may be more
1034 M. Galizia et al. / Polymer 55 (2014) 1028e1039

Fig. 7. A): The absorbance spectra in the v(C]O) frequency range (1820e1640 cm1) collected on 6FDA-ODA (thin film) equilibrated at different vapour pressures of methanol; B):
Difference spectra (equilibrated sample  dry sample). The colour code is: black trace: p/p0 ¼ 0 (dry sample); blue trace: p/p0 ¼ 0.06; red trace: p/p0 ¼ 0.2; green trace: p/p0 ¼ 0.4;
cyan trace: p/p0 ¼ 0.6. In B) the black trace corresponds to the difference between the fully desorbed sample (eq. at p/p0 ¼ 0.6) and the initial, dry sample (reversibility test). (For
interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

accessible than the ether groups. Similar effect has been already
reported for the system polyimide/water [14].
Figs. 7 and 8AeB display the carbonyl range of 6FDA-ODA and
UltemÒ 1000 in the films equilibrated at different relative pressures
of methanol vapour. The extent of the red-shift, which is reflected
in the peak-to-peak height of the difference spectra, is found to
increase gradually with increasing methanol concentration and is
fully reversible upon methanol removal, which further confirms
that the observed effects originate from the established in-
teractions, and are not due to spectroscopic artefacts.
3.5. Quantitative assessment of the different methanol species
The quantitative analysis is based on the curve fitting of the
spectral profiles in the v(OH) region; typical results are demon-
strated in Fig. 9A, relative to 6FDA-ODA, and in Fig. 9BeC relative to
UltemÒ 1000. For both polyimides two components are sufficient to
satisfactorily reproduce the experimental profiles. However, the
band shapes of the two components are significantly different.
Luckily, for UltemÒ 1000 at the lowest activity only the sharp peak
at 3578 cm1 is present: the broad band at lower frequency starts to
develop at p/p0 ¼ 0.20 and keeps increasing therefore. The spectral
parameters of the first component are therefore experimentally
available: it is explicitly noted that the 3578 cm1 peak displays an
intrinsic band asymmetry (that is, due to the vibrational relaxation
mechanism rather then to an unresolved component) which has
been satisfactorily simulated by use of a log-normal band-shape
(see Fig. 9B). This model has been demonstrated to be well suited
for vibrational relaxation processes affected by multiple interfering
mechanisms [34].
For the band at around 3440 cm1 the best fit over the whole
experimental profiles was achieved with a mixed LorentzeGauss
line shape [23]. The results of the LSCF analysis are summarized in
Table 3. It explicitly noted that the n(OH) profile invariably displays
a feature at around 3480 cm1 which resembles a partly resolved
component (see Figs. 3 and 9). We assign this feature to a
derivative-type profile appearing in the difference spectrum as a
consequence of the downward shift of the 3484 cm1 peak of the
polyimides [a combination mode of the stretching fundamentals of
the imide carbonyls (niph þ nooph)]. The effect is similar to that
represented in Figs. 7 and 8 for the n(C]O) vibration but amplified
twice (roughly) due to the non-fundamental nature of the vibration

Fig. 8. A) The absorbance spectra in the v(C]O) frequency range (1820e1640 cm1) collected on UltemÒ 1000 (thin film) equilibrated at different vapour pressures of methanol; B):
Difference spectra (equilibrated sample  dry sample). The colour code is: black trace: p/p0 ¼ 0 (dry sample); blue trace: p/p0 ¼ 0.05; red trace: p/p0 ¼ 0.2; green trace: p/p0 ¼ 0.3;
cyan trace: p/p0 ¼ 0.5. In B) the black trace corresponds to the difference between the fully desorbed sample (eq. at p/p0 ¼ 0.5) and the dry sample (reversibility test). (For
interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)
 M. Galizia et al. / Polymer 55 (2014) 1028e1039 1035

Fig. 9. LSCF analysis of the vOH region (3800e3100 cm1): A) 6FDA-ODA/methanol system, p/p0 ¼ 0.07; B) UltemÒ 1000/methanol system, p/p0 ¼ 0.04; C) UltemÒ 1000/methanol
system, p/p0 ¼ 0.5.

involved. According to this interpretation, the feature was consid- first-shell species (second and higher layers in the BET nomencla-
ered as an artefact and neglected in the subsequent curve fitting ture). A schematic representation of the spectroscopically detected
analysis (see Fig. 9). species is reported in Scheme 2.
As demonstrated by Fig. 9AeC and by the data presented in Work is in progress to optimize the geometry of the above
Table 3, the simulation of the experimental data by the selected molecular aggregates by first principles computational approaches
curve-fitting model is satisfactory and consistent. so as to calculate theoretically the vibrational spectra and compare
Taking into account the whole of the spectroscopic results, we these simulations with the experimental results.
can assign the 3575 cm1 component to the OeH groups of It is useful to compare the spectrum representative of methanol
methanol directly bound to the imide carbonyls, which represent sorbed in the polyimides with that of the penetrant in the un-
the first shell layer of sorbed methanol in the frame of the multi- perturbed, reference state, which is represented by a dilute solu-
layer adsorption model of BrunauereEmmetteTeller (BET) [35]. tion in a low polarity, non-interacting solvent (CCl4). In Fig. 10 are
The band at 3440 cm1 is representative of self-associated meth- reported the spectra of three solutions of methanol in CCl4,
anol molecules, whereby the H-bond is established between the differing for their concentrations. At the highest dilution (0.012 M)
OeH group of this molecular species and the oxygen of the only the monomer is present, giving rise to a very sharp peak at
3643 cm1. Increasing the concentration, dimers start to appear,
producing a well resolved and symmetrical band at 3525 cm1.
Table 3
Results of the LSCF analysis. (Standard errors in parentheses). Note the considerable increase in FWHW when passing from the
monomer to higher aggregates, which is a direct consequence of
6FDA-ODA
the H-bonding interaction. Finally, at 0.1 M the equilibrium in-
p/p0 ¼ 0.07 p/p0 ¼ 0.20 p/p0 ¼ 0.40 p/p0 ¼ 0.60 volves also trimers and tetramers [36], which produce a further
Peak 1 Position (cm1) 3579 (0.1) 3577 (0.1) 3575 (0.2) 3573 (0.1) broad band centered at 3350 cm1. The spectrum of methanol
FWHH (cm1) 73.6 (0.2) 79.8 (0.3) 86.0 (0.2) 88.1 (0.1) sorbed in 6FDA-ODA displays a fully resolved component which,
Area (cm1) 9.4 (0.1) 16.3 (0.1) 23.9 (0.1) 28.4 (0.1) by comparison with the reference state, can be safely associated
r 0.64 (0.001) 0.66 (0.002) 0.62 (0.001) 0.60 (0.001)
Peak 2 Position (cm1) 3465 (0.1) 3445 (0.2) 3430 (0.1) 3423 (0.1)
with a monomeric species. However, the larger value of FWHH
FWHH (cm ) 1
198.8 (0.2) 231.5 (0.3) 236.7 (0.2) 249.5 (0.3) (from 22 to 90 cm1) and, especially, the considerable red-shift
Area (cm1) 13.1 (0.1) 30.8 (0.1) 52.9 (0.1) 82.1 (0.1) (68 cm1) demonstrates that in the polymer, the monomeric
lf 0 0 0 0 species is not free as in the CCl4 solution, but is involved in an H-
R2 0.993 0.996 0.982 0.990
bonding interaction of non-self-association type. Self-association
is connected with the broad band at 3440 cm1. Its rather sym-
UltemÒ 1000
metrical shape suggests the occurrence of a single molecular
p/p0 ¼ 0.04 p/p0 ¼ 0.20 p/p0 ¼ 0.35 p/p0 ¼ 0.5
aggregate (dimers) or, at least, a large predominance of this species
1
Peak 1 Position (cm ) 3577 (0.2) 3575 (0.2) 3575 (0.1) 3575 (0.2) over higher order aggregates. The available spectroscopic evidence
FWHH (cm1) 94.7 (0.5) 95.4 (0.3) 97.0 (0.4) 97.3 (0.2) allows us to rule out the occurrence “free” monomers or dimers,
Area (cm1) 6.8 (0.1) 18.9 (0.1) 23.5 (0.2) 25.6 (0.1)
i.e. of penetrant molecules or aggregates thereof not directly
r 0.60 (0.01) 0.64 (0.02) 0.64 (0.02) 0.63 (0.01)
Peak 2 Position (cm1) 3442 (0.5) 3441 (0.6) 3441 (0.5) anchored to the polymer backbone. In fact the highly characteristic
FWHH (cm1) 136.2 (0.9) 168.5 (0.8) 195.7 (1.0) signal of “free” OeH bonds, which would occur in the case of a
Area (cm1) 4.8 (0.1) 10.4 (0.2) 17.1 (0.1) non-interacting monomer and/or an open dimer (the energetically
lf 0.17 (0.01) 0.11 (0.01) 0.30 (0.01)
favoured conformation on the basis of ab-initio calculations [36]) is
R2 0.994 0.996 0.993 0.990
absent.
1036 M. Galizia et al. / Polymer 55 (2014) 1028e1039

Scheme 2. Schematic representation of the methanol species identified by the spectroscopic analysis.

The first step towards a quantitative assessment of the con- species, respectively (see Scheme 2). Substituting the Lamberte
centration of the different methanol species is the evaluation of Beer law in eq. (6), leads to:
their molar absorptivities. To this end, the mass balance for the total
absorbed methanol has been considered: Afs Ass
Ctot ¼ þ (7)
εfs L εss L
Ctot ¼ Cfs þ Css (6)
where Ai and εi are the integrated absorbance and the molar ab-
where Ctot is the total concentration as evaluated gravimetrically, sorptivity of the i-th species, while L represents the sample thick-
while Cfs and Css are the concentration of first shell and second shell ness. After some algebra, eq. (7) becomes:

Fig. 10. A): Spectra of methanol in CCl4 in the frequency interval 4000e2450 cm1. Concentrations as indicated. B) Comparison between the spectrum of a 0.10 M methanol solution
in CCl4 (upper trace) and the spectrum of methanol sorbed in 6FDA-ODA (bottom trace, p/p0 ¼ 0.07).

Fig. 11. Estimation of monomer and dimer molar absorptivity: A) 6FDA-ODA and B) UltemÒ 1000. Continuous line represents the best fit provided by eq. (8).
 M. Galizia et al. / Polymer 55 (2014) 1028e1039
 
Afs ε Ass
¼ εfs L  fs
Ctot εss Ctot
Thus, a linear correlation is expected between Afs/Ctot and Ass/
Ctot, whose slope directly provides the εfs/εss ratio, while the
intercept gives an experimental estimation of the product εfsL. In
Fig. 11AeB, the experimental correlations between Afs/Ctot and Ass/
Ctot are reported for the systems 6FDA-ODA/methanol and UltemÒ
1000/methanol, respectively. Accordingly to eq. (8), in both cases a
very good linear trend is observed (R2 w 0.92); the molar absorp-
tivity evaluated therefore is εfs ¼ 88 km/mol and εss ¼ 183.3 km/mol
for the 6FDA-ODA/methanol system; εfs ¼ 75.3 km/mol and
εss ¼ 108 km/mol for UltemÒ 1000/methanol. The closeness of the
εfs and εss values for the two polyimides provides a clue to the
consistency of our analysis. A value of εss higher that of εfs by a factor
of about two appears to be consistent, as an order of magnitude,
with previous results on molar absorptivity increase in similar H-
bonding systems [14,37].
As already mentioned, for UltemÒ 1000 the spectrum of sorbed
methanol at the lowest investigated value of p/p0 displays only the
3575 cm1 component (see Fig. 9B), thus indicating that, in these
experimental conditions, only the monomer is present in the sys-
tem. Accordingly, in this case εfs ¼ Afs/LCtot the value calculated in
this way is 77.0 km/mol, in excellent agreement with the estimation
provided by eq. (8), which confirms the reliability of the more
general quantitative approach.
A comparison of our εfs values with that of monomeric methanol
in CCl4 [36] indicates a fourfold increase of this parameter for
methanol sorbed in the polyimides with respect to the reference
state (76 and 88 km/mol vs 21 km/mol). Once again, the compari-
son indicates that the present estimates are reasonable in terms of
orders of magnitude; the higher values we observe can be readily
accounted for considering the well known increase of the absorp-
tivity value brought about by H-bonding formation.
With the absorptivity values at hand, the concentration of
methanol species is readily obtained from the relevant absor-
banceeconcentration relationships, i.e. Cfs ¼ A3575/εfsL and
Css ¼ A3440/εssL.
In Fig. 12AeB are reported the concentrations of first-shell and
second-shell methanol in 6FDA-ODA and UltemÒ 1000, respectively,
as a function of methanol relative pressure.
In the case of 6FDA-ODA the two above concentrations can be
considered coincident up to p/p0 values of 0.45, which infers that in
this relative-pressure range all absorbed methanol is present in the
form of dimers. At higher p/p0 values (>0.5) Css significantly offsets
Fig. 12. Concentration of first-shell (red circles) and second-shell (blue circles) methanol in A) 6FDA-ODA and B) UltemÒ 1000. Continuous and dotted lines are a guide for the eye.
(For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)
1037
Cfs, which may only occur when aggregates comprising more than
(8) two methanol molecules are formed. The plot of Fig. 12A allows us
to clearly identify the onset of the clustering phenomenon as the
point of departure between the Css and Cfs curves.
For UltemÒ 1000 Cfs largely exceeds Css in the whole p/p0 range:
in this case the predominant species is the monomer, and the self-
associated aggregate is likely to be the dimer.
An approach has been proposed to quantify the population of
proton acceptor groups in polymer/penetrant systems where H-
bonding interactions among the penetrant and the substrate are
formed. The method relies on the shift of the imide carbonyls,
brought about by the H-bonding interaction, which has been
described in detail in Refs. [33,14] and will be summarized here-
after. The observed carbonyl red-shift is actually due to the pres-
ence of two unresolved components originating, respectively, from
the interacting groups (at lower frequency) and the unperturbed
ones (at higher frequency). The direct resolution of the components
is not achieved because their Dn is comparable to their FWHH. The
unperturbed carbonyl peak is experimentally available (the peak of
the fully dry polyimide) and can be used as a reference for spectral
subtraction. Thus, the interacting carbonyl component, Adiff, can be
isolated as:
Adiff ¼ As  K,Ar (9)
where As and Ar refer, respectively, to the absorbance of the imide
peak in the sample spectrum (methanol saturated film) and in the
reference spectrum (dry film). Owing to the invariance of the film
thickness upon methanol sorption, the subtraction factor K is
quantitatively related to the relative concentration of proton
acceptor groups. The physical meaning of K, derived from the
relevant absorbanceeconcentration relationships [33], is:
Cf C
K ¼ and b ¼ 1  K (10)
Ctot Ctot
where the subscripts f, b and tot refer, respectively, to the non-
interacting (free) imide groups, the imide groups H-bonded to
methanol molecules, and to their total population. The criterion to
correctly choose the subtraction factor K is described in Ref. [33].
In the light of the interaction model proposed in Scheme 2, the
concentration of carbonyl proton-acceptors is equal to the con-
centration of first-shell methanol. It is explicitly noted that in our
view, in terms of stoichiometry, the proton acceptor group is not
represented by the single carbonyl, but rather by the whole imide
1038 M. Galizia et al. / Polymer 55 (2014) 1028e1039
Fig. 13. Concentration of interacting carbonyls (red circles) and concentration of first-shell methanol (black triangles) as evaluated in the thin sample; concentration of first-shell
methanol (blue squares) as evaluated in the thick sample: A) 6FDA-ODA and B) UltemÒ 1000. The insets represent the analysis of C]O range in terms of difference spectroscopy,
with the main peak (black trace) representing the reference (dry sample). (For interpretation of the references to colour in this figure legend, the reader is referred to the web
version of this article.)
group. This because the formation of two H-bonds on the same
imide ring is unlikely both statistically and in terms of reactivity.
Statistically, because of the large excess of non-interacting car-
bonyls with respect to those involved in H-bonding; in terms of
reactivity, because in the imide ring the electronic density is
delocalized over the whole condensed system. A withdrawing of
electron density from one of the carbonyl by the OeH proton is also
experienced by the second carbonyl in the imide ring, which, as a
consequence, becomes an even weaker proton acceptor. From the
consideration enumerated so far, we can compare the concentra-
tion of imide acceptors as evaluated from the analysis of the
carbonyl region, with the concentration of first shell methanol as
estimated in the n(OH) range. The two estimates are simultaneously
available for the thin film, where the n(OH) band, albeit weak, is still
suitable for curve-fitting analysis. In the case of the thick sample
only the Cfs value can be estimated since the carbonyl region is fully
saturated (see spectrum in Fig. 2). In Fig. 13-A is reported, for 6FDA-
ODA, the comparison between the Cfs and the Cb curves as a func-
tion of p/p0. The figure inset displays the analysis of the carbonyl
region in terms of the difference spectroscopy method discussed
earlier. It is found that the data compare very satisfactorily: the Cb
curve is essentially coincident with the Cfs curve relative to the
same sample (thin film); also the Cfs curve for the thick sample is
very close (within experimental uncertainty up to p/p0 ¼ 0.4); the
slight difference found at higher p/p0 values could be related to an
influence of the film thickness on the sorption behaviour. Similar
effects have been documented in the literature on polyimide/water
and polyimideeoxygen systems [26,33]. The results discussed so
far confirm the robustness of the analytical methodology and verify
the reliability of the proposed molecular models.
For UltemÒ 1000 similar conclusions can be drawn (see Fig. 13-
B): in this case the CbeCfs curves for the thin sample are slightly
more separated. This is a consequence of the lower intensity of the
n(OH) band for this series of samples, due to the lower methanol
solubility compared to 6FDA-ODA. This makes the Cfs estimation on
the thin sample by curve-fitting analysis more uncertain. The Cbe
Cfs curves relative to the films of different thickness are even closer
than in the previous case.
4. Conclusions
In this work the transient and equilibrium sorption of methanol
in 6FDA-ODA and UltemÒ 1000 polyimides has been investigated
by coupling gravimetric and in-situ FTIR analysis in the trans-
mission mode. This approach allowed a detailed characterization of
the investigated systems at a molecular level.
The analysis of gravimetric and spectroscopic kinetic data pro-
vided two independent estimations of the diffusion coefficients
which were in good agreement with each other.
The spectral data were analysed by using two complementary
techniques, i.e. difference spectroscopy and least squared curve-
fitting analysis: both methods indicated the occurrence of two
distinct populations of penetrant, namely single methanol mole-
cules directly interacting with the carbonyls of the imide group
(first-shell species), and self-associated methanol molecules form-
ing second and higher shell layers. For 6FDA-ODA the dimer rep-
resents the largely predominant species up to p/p0 values of 0.5.
Afterwards, higher aggregates (higher shell layers) are formed; for
UltemÒ 1000 the isolated methanol molecules bound to the imide
carbonyls represent the predominant species over the whole p/p0
range investigated. Two independent methods to quantify the
population of the methanol species have been proposed and
compared. The first relies on the evaluation of the respective molar
absorptivities, the second employs the difference spectroscopy
technique in the carbonyl range. The results obtained with the two
approaches compare very satisfactorily to each other, thus con-
firming the robustness of the quantitative analysis and the reli-
ability of the proposed molecular models.
Acknowledgements
Thanks are due to Mr. G. Orefice for his assistance in performing
the time-resolved FTIR experiments. Financial support from the
National Research Council of Italy (CNR) in the frame of the Project
“Ricerca a Tema Libero” is acknowledged.
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