Polymer 47 (2006) 234–242

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FTIR spectra of pure helical crystalline phases of syndiotactic polystyrene

Alexandra R. Albunia a,*, Pellegrino Musto b, Gaetano Guerra a
a
Dipartimento di Chimica, Università degli Studi di Salerno, via S. Allende, 84081 Baronissi (SA), Italy
b
Institute of Chemistry and Technology of Polymers, National Research Council of Italy, via Campi Flegrei 34, 80078 Pozzuoli (Na), Italy
Received 8 March 2005; received in revised form 11 August 2005; accepted 28 October 2005
Available online 28 November 2005

Abstract

By quantitative evaluation of the spectral changes associated with guest removal from clathrate films as well as by infrared dichroism
measurements on uniaxially oriented films, three infrared absorbance peaks (at 1379, 1154 and 841 cmK1) prevailingly associated with the
amorphous phase have been located for syndiotactic polystyrene (s-PS) samples with helical crystalline phases. A detailed study relative to the
infrared peaks in the wavenumber range 870–820 cmK1, corresponding to phenyl C–H out-of-plane bending, has shown that the 841 cmK1 peak is
fully associated with conformationally disordered sequences only for samples including trans-planar crystalline phases (a and b) but not for
samples including helical crystalline phases (g, d and clathrates). This result has been rationalized on the basis of different intermolecular
interactions between phenyl rings, occurring for trans-planar and helical s-PS crystalline phases. Moreover, a preparation procedure leading to
fully unoriented films has been described for helical semicrystalline films, which generally present different kinds of uniplanar orientation. FTIR
spectra of these fully unoriented semicrystalline films, by subtracting out the amorphous phase contribution with a procedure based on the
1379 cmK1 peak, have allowed a straightforward isolation of the spectra of the helical s-PS crystalline phases and the quantitative determination
of the amorphous content.
q 2005 Elsevier Ltd. All rights reserved.

Keywords: Syndiotactic polystyrene; Unoriented helical crystalline phases; Degree of crystallinity

1. Introduction have been thoroughly characterized [12], and presents a very

low density (0.98 g/cm3), also lower than the density of the
Syndiotactic polystyrene (s-PS) is characterized by a amorphous phase (1.05 g/cm3) [11]. Sorption studies have
complex polymorphic behavior, which, making some simpli- shown that the nanoporous d form rapidly and selectively
fications, can be described in terms of two crystalline forms, a absorbs, both from solutions [13–16] and gas phase [9,17–20],
and b, containing planar zigzag chains and two forms, g and d, molecules of suitable volatile organic compounds even at very
containing s(2/1)2 helical chains generated by TTGG low activities, thus transforming into the corresponding
conformational serquences [1]. clathrate forms. Hence, it has been suggested that this
Moreover, by solution crystallization or by sorption of thermoplastic material is promising for applications in
suitable compounds (e.g. methylene chloride, toluene, chloro- chemical separations and air/water purification [13–19], as
form, etc.) in amorphous s-PS samples as well as in samples in well as in sensorics [20].
the a, g or d form, clathrate crystalline phases, always Several Fourier transform infrared (FTIR) studies of the
containing s(2/1)2 helical chains, can be obtained [1–7]. As a different crystalline [21–33] and clathrate [13,17,25,34–42]
consequence of suitable treatments [8–10], guest molecules phases of s-PS have been reported in the literature. These
can be removed and all clathrate phases can be transformed studies have clearly established characteristic absorption peaks
into the nanoporous d phase [11]. of the trans-planar conformation which occurs for a and b as
The d form presents in place of the guest molecules two well as of the s(2/1)2 helical conformation, which occurs for g
identical cavities per unit cell [11], whose shape and volume and d crystalline phases and in all s-PS molecular complex
phases [1].
As for the crystalline forms including trans-planar chains, a
* Corresponding author. Tel.: C39 89 965362; fax: C39 89 965296. number of structural order effects has been identified and
E-mail address: [email protected] (A.R. Albunia). spectral subtraction analyses on FTIR spectra have allowed to
0032-3861/$ - see front matter q 2005 Elsevier Ltd. All rights reserved. isolate the spectra of the pure hexagonal a and orthorhombic b
doi:10.1016/j.polymer.2005.10.135 crystalline phases. As a consequence FTIR spectral subtraction
 A.R. Albunia et al. / Polymer 47 (2006) 234–242 235

analyses [32,43–46] allow an easy evaluation of the degree of

0.20
crystallinity and of the amount of a and b phases (often
simultaneously present in melt-crystallized samples). As
discussed in detail in Ref. [32], spectral subtraction procedures 0.15

Absorbance
are made straightforward by the presence of the low absorption
peak centered at 841 cmK1, which upon crystallization is 1190 1160 1130
cm-1 870 850 830
shifted to higher frequencies. In fact, its exact position was 0.10 cm-1
found to depend on the crystalline phase a or b as well as on the
degree of perfection of crystallites (that is on the occurrence of
0.05
a 0 or a 00 modifications [1]) and the shifts are large enough
(from 11 up to 17 cmK1) to afford spectroscopic resolution of
the amorphous and the crystalline components. 1400 1300 1200 1100 1000 900 800
Recently, by following the approach developed earlier for cm-1
the a and b forms, an attempt to isolate the spectrum of the pure
crystalline monoclinic d phase has been reported [17]. Fig. 1. FTIR spectra for the spectral range 1400–800 cmK1of: (thin line) a s-
PS/acetone clathrate film with an acetone content close to 15 wt%; (thick line) a
However, in that case, application of difference spectroscopy
nanoporous d form film, obtained after 1 day of acetone desorption at room
was not straightforward, not only owing to the difficulty of temperature.
identifying well-resolved purely amorphous peaks [17] but also
due to the not fully recognized presence of uniplanar
orientation of the crystalline phase. In fact, recent studies The s-PS/acetone films whose FTIR and WAXS spectra are
have pointed out the nearly general occurrence of uniplanar reported in Figs. 1 and 2 were obtained by casting at room
orientation (of three different kinds) [47–51] for clathrate temperature from 5 wt % solutions in chloroform. The cast
phases as obtained by solution casting [47,48] and by solvent films were subsequently immersed in acetone for 3 h and then
induced crystallization procedures [49–51] (as well as for the allowed to desorb in air for few minutes, before measurements.
derived d and g crystalline phases) [48–51], which produce The s-PS/1,2-dichloroethane (DCE) clathrate films of Figs. 4
large variations of relative intensities of infrared absorbance were prepared by DCE absorption into a nanoporous d form film
peaks [49,50]. It is also worth noting that these kinds of from a 0.5 wt% DCE aqueous solution. The DCE amount sorbed
uniplanar orientation are present in most s-PS films presenting at equilibrium was 8.0 wt%. In turn, the d form film was
helical crystalline phases, whose spectra have been reported in prepared from a chloroform cast films, after treatment with
the literature [17,21–42]. boiling acetone for 5 h followed by desiccation at 60 8C for 2 h.
In this paper, an analysis aimed at identifying possible Both s-PS/acetone and s-PS/DCE clathrate films, as well as
amorphous peaks, for helical semicrystalline samples of s-PS, the corresponding d form films, present a degree of uniplanar
has been afforded by quantitative evaluations of the spectral orientation (ac plane tendentially parallel to the film surfaces
changes associated with guest removal from clathrate phases in [47,48]) close to 0.7.
different conditions (Section 3.1), and by linear infrared
dichroism measurements on uniaxially oriented s-PS films
(Section 3.2). In the central part of the paper the achievement
of films including fully unoriented g, d and clathrate s-PS
phases is described (Section 3.3). These unoriented semicrys-
talline films can be used for easier FTIR spectral subtraction A δacetone
procedures. In fact, in the final section of the paper, we have
Intensity (a.u.)

isolated the spectra of the pure crystalline g and d phases from

those of semicrystalline unoriented films, by subtracting out the B δ
contribution of the amorphous phase (Section 3.4), as
established on the basis of the results of Sections 3.1 and 3.2. _ 111
_ 111
210 _ δacetone
2. Experimental section A' 111

2.1. Materials B' δ

5 10 15 20 25 30 35
Syndiotactic polystyrene was supplied by Dow Chemical 2θ deg
under the trademark Questra 101. 13C nuclear magnetic
resonance characterization showed that the content of syndio- Fig. 2. X-ray diffraction patterns (Cu Ka) of the films of Fig. 1, before (A) and
after (B) acetone desorption: (A,B) obtained by an automatic powder
tactic polystyrene triads was over 98%. The weight-average
diffractometer; (A 0 ,B 0 ) obtained with beams perpendicular to the film plane
molar mass obtained by gel permeation chromatography (GPC) by using a photographic cylindrical camera. These data indicate that the
in trichlorobenzene at 135 8C was found to be MwZ3.2!105 acetone desorption involves a transition from the s-PS/acetone clathrate toward
with the polydispersity index, Mw/MnZ3.9. the nanoporous d phase.
236 A.R. Albunia et al. / Polymer 47 (2006) 234–242

1.2 1.2
840
1154
1154 840
1.1 1.1 1379

1069
1181
1181 1.0

A t /A 0
1.0 1069
1169
A t /A0

934
1391
0.9
0.9 1169 571

1320
1320 0.8
0.8
571
0 500 1000 1500 2000 2500 3000 3500
0 200 400 600 800 1000 1200 1400 t (minutes)
t (minutes)
Fig. 5. Quantitative comparison of the variations of the s-PS peak intensities,
Fig. 3. Quantitative comparison of the variations of the s-PS peak intensities, obtained from FTIR spectra like those of Fig. 4, upon DCE removal at 40 8C.
obtained from FTIR spectra like those of Fig. 1, upon acetone removal at room
temperature.
The preparation of the unoriented semicrystalline g and d
form films of Figs. 9 and 10 is described in detail in Section 3.3.
Uniaxially oriented films of Figs. 6 and 7 were obtained by
monoaxial stretching of extruded s-PS films, at different draw
ratios up to lz3 and at constant deformation rate of 0.1 sK1, in 2.2. Techniques
the temperature range 105–110 8C with a Brukner stretching
machine. The stretched films, still essentially amorphous, were Infrared spectra were obtained at a resolution of 2.0 cmK1
crystallized into the nanoporous d form by exposure for three with a Vector 22 Brucker spectrometer and/or with a Perkin
days to CS2 vapor, followed by treatment under vacuum at Elmer System 2000 spectrometer. Both instruments were
40 8C for other 3 days. The clathrate films were obtained from d
form films by exposure to DCE vapors for 2 h. Films in g and a
semicrystalline forms, were obtained from films in d form by δDCE
increasing the temperature (z2 8C/min) from room tempera-
E
ture up to 160 and 220 8C, respectively, and then maintaining
the samples at those temperature for 30 min.
Unoriented amorphous s-PS films with thickness 40–60 mm D
were obtained by compression molding process at 300 8C,
δ
followed by quenching in ice-water.
C
840
DCE
(T)
γ
0.7

B
0.6
DCE
(G) 870 850 830
β
Absorbance

cm-1
0.5
1379
1154

0.4
A α
0.3
1380 1330 1180 1140 840
1400 1300 1200 cm-1
cm-1
Fig. 6. FTIR spectra for three different wavenumber ranges of uniaxialy
Fig. 4. FTIR spectra for the spectral range 1400–1130 and 870–820 cmK1 oriented s-PS films (lz3 and Herman’s orientation factor fz0.95), taken with
(inset) of: (thin line) a s-PS/DCE clathrate film with a DCE content close to polarization plane parallel (thin lines) and perpendicular (thick lines) to the
8 wt%; (thick line) the same clathrate film with a DCE content close to 4 wt%, draw direction. The spectra of semicrystalline samples presenting the a, b, g, d
obtained after 60 h of DCE desorption at 40 8C. and DCE-clathrate phases are presented by curves (A)–(E), respectively.
 A.R. Albunia et al. / Polymer 47 (2006) 234–242 237

δDCE δ film

Intensity (a.u.)
D
D

C δ powder

δ
B γ film
C
γ powder
Intensity (a.u.)

5 10 15 20 25 30 35
γ 2θ (deg)

B Fig. 9. X-ray diffraction patterns of unoriented s-PS samples: (A) g form

powder; (B) g form film; (C) d form powder; (D) d form film.

β mounted in the spectrometer for the real time process

monitoring. The isothermal measurements were carried out at
A room temperature and 40 8C under a nitrogen atmosphere at a
pressure of 760 mmHg.
α Polarized infrared spectra were recorded by the use of a
SPECAC 12500 wire grid polarizer. The degree of axial
5 10 15 20 25 30 35 40 orientation relative to the crystalline phase has been formalized
2θ (deg) on a quantitative numerical basis using the Hermans’
Fig. 7. X-ray diffraction patterns (Cu Ka) of the uniaxially stretched films, orientation function. In particular, as described in Ref. [38],
whose FTIR spectra are shown in Fig. 6(A)–(E), respectively. the order parameter of the 1222 and 571 cmK1 bands has been
directly used as a measure of the axial orientation function
equipped with a deuterated triglycine sulphate (DTGS) (fc,IR, which is equal to unity for perfect alignment and null for
detector and a Ge/KBr beam splitter. The frequency scale random orientation) for trans-planar and helical crystalline
was internally calibrated to 0.01 cmK1 using a He–Ne phases, respectively.
reference laser. Thirty-two scans were signal averaged to Wide-angle X-ray diffraction patterns with nickel filtered
reduce the noise. The thickness of films used for infrared Cu Ka radiation were obtained, in reflection, with an automatic
measurements was always comprised between 20 and 40 mm, Bruker diffractometer. The X-ray based degree of crystallinity
in order to keep the peaks of interest in the range of has been determined by resolving the diffraction pattern in a
absorbance–concentration linearity. selected range (5–388) into two areas Ac and Aa that are taken as
The infrared based degree of crystallinity, expressed as weight being proportional to the crystalline and amorphous weight
fraction Xc, can be evaluated according to K Z l=l 0 ð1KXc Þ fractions, respectively, and calculated through the expression
[13,17], where K is the subtraction coefficient, l and l 0 are the 100Ac/(AcCAa).
thickness of the sample and of an amorphous reference film. The The X-ray diffraction patterns of Fig. 2(A 0 ) and (B 0 ) were
ratio l/l 0 is estimated from the absorbance ratio of a confor- obtained with X-ray beam perpendicular to the film plane, and
mationally insensitive peak (i.e. at 1601 cmK1). the diffracted radiation was collected with a cylindrical camera
The desorption measurements were carried out in an (radiusZ57.3 mm), recorded on a BAS-MS Imaging Plate
environmental chamber (SPECAC Mod 20100) directly (FUJIFILM) and processed with a digital imaging reader
(FUJIBAS 1800).

3. Results and discussion

3.1. FTIR spectral changes of s-PS clathrate films upon

guest removal

This section describes changes of FTIR spectra associated

with guest removal from s-PS clathrate phases, wich generally
occurs with some loss of cristallinity [52].
Fig. 8. Side view of models of syndiotactic polystyrene in the: (A) trans-planar The FTIR spectrum of a s-PS/acetone clathrate film,
conformation; (B) s(2/1)2 helical conformation. obtained by acetone treatment of a s-PS/CHCl3 clathrate cast
238 A.R. Albunia et al. / Polymer 47 (2006) 234–242

film, is shown by a thin line in Fig. 1, for the spectral range leads to a nearly complete disappearance of the DCE gauche
1400–800 cmK1. This spectrum, beside s-PS peaks, presents peak at 1285 cmK1, to a much lower reduction of the DCE
acetone peaks (e.g. at 1360, 1219 and 1089 cmK1) indicating a trans peak at 1234 cmK1, while only minor changes occur for
concentration close to 15 wt%. The FTIR spectrum of the same the s-PS peaks. As shown in Fig. 12 of Ref. [14], the difference
film, after 1 day of acetone desorption at room temperature, is in the desorption rate between the two phases is dramatic. After
shown by a thick line in Fig. 1 and indicates that the acetone about 60 h the DCE content in the amorphous phase has
content becomes lower than 1%. decreased by about 85% of its initial value while in the
X-ray diffraction patterns of the same film of Fig. 1, before crystalline phase the reduction is lower than 10%. As a
and after acetone desorption, obtained by an automatic powder consequence, contrary to the case of acetone desorption of
diffractometer (Fig. 2(A) and (B)), are typical of semicrystal- Figs. 1 and 2, the crystalline clathrate phase remains nearly
line films with a nanoporous d or clathrate phases, presenting a unaltered upon DCE desorption at 40 8C, since its guest content
(010) uniplanar orientation [48]. The corresponding X-ray decreases only from about 4 to 3.5 wt%.
diffraction patterns obtained with beams perpendicular to the Nevertheless, the quantitative comparison of the intensity
film plane by using a photographic cylindrical camera variations of relevant s-PS peaks upon the isothermal DCE
(Fig. 2(A 0 ) and (B 0 ), show that, upon acetone desorption, the desorption at 40 8C (Fig. 5) is similar to that one observed upon
(210) reflection decreases markedly while the 111 reflection acetone desorption (Fig. 3). In fact, the intensities of all helical
increases, thus clearly indicating that the starting material peaks are substantially reduced (depending on the peak from 5
presents a clathrate phase [11,47–51], which includes acetone up to 15%) while the other s-PS peaks remain essentially
guest molecules. Hence, the X-ray diffraction data of Fig. 2 constant, with the exception of the 1379, 1154 and 841 cmK1
indicate that the acetone desorption shown by the FTIR spectra peaks, which present an intensity increase close to 15%. The
of Fig. 1 also involves a transition from the s-PS/acetone data of Figs. 3 and 5 can be rationalized by assuming that both
clathrate toward the nanoporous d phase. kinds of desorption lead to a reduction of crystallinity and that
On inspection of Fig. 1, it is apparent that upon guest 1379, 1154 and 841 cmK1 peaks are prevailingly amorphous
removal the FTIR helical peaks (e.g. those at 1320, 1277, 1169, peaks, for d and clathrate s-PS samples.
943, 935 cmK1) reduce their absorbances, while the only peaks As for the vibrational origin of the 1379 cmK1 band, it is
which clearly increase their absorbances are those at 1154 and worth noting that a strong absorption has been found in all-
841 cmK1 (insets of Fig. 1). A quantitative comparison of the trans crystalline forms at 1376 cmK1. According to one normal
variations of the peak intensities upon guest removal has been coordinate analysis [28] this band was assigned to a complex
obtained by curve fitting analysis of the relative frequency mode to which both backbone vibrations (C–C–H bending, CC
ranges (i.e. 1410–1255, 1215–1135, and 865–825 cmK1). The stretching) and ring vibrations (C–H bending and C–C
results, in terms of peak heights, are shown in Fig. 3 and clearly stretching) contribute. Conversely, Gupta et al. [31] associated
indicate that the intensities of all helical peaks are substantially this peak to a phenyl ring mode with contribution from H–C–C
reduced (depending on the peak from 10 up to 25%) while the ring bending (potential energy distribution, PED, 54%) and
other s-PS peaks remain essentially constant, with the ring C–C stretching (PED 39%). According to both studies
exception of the 1154 and 841 cmK1 peaks, presenting an [28,31], also the peaks at 1154 and 840 cmK1 are almost pure
intensity increase close to 15%. ring modes. In particular, the former is ascribed to a ring H–C–
It is worth noting that the 1379 cmK1 peak, which has been C bending (PED 83%), and the latter to a ring C–H out-of-
already identified as an amorphous peak [17], is not shown in plane bending (PED 83%) and a ring C–C torsion (PED 16%).
Figs. 1 and 3, due to its superposition with the intense The three above absorptions share the common feature that
1360 cmK1 acetone peak. their dispersion curves are essentially flat and are therefore
FTIR spectral changes associated with guest removal have expected to be conformationally insensitive [31]. The
been analogously studied for s-PS/1,2-dichloroethane (DCE) observation that their intensity increases considerably with
clathrate films. This guest choice was motivated by the the amorphous content could be tentatively interpreted taking
additional information, which comes from its conformational into account the effect of the intermolecular interactions
equilibrium. In fact, as described in detail in previous papers between adjacent chains within the crystal lattice. Thus, a
[13–16,53], since essentially only its trans conformer is sufficient perturbation of the force constants involved may
included into the clathrate phase while both trans and gauche arise upon the formation of the crystalline phase, so as to
conformers are included in the amorphous phase, quantitative induce a more or less significant shift and/or an in-phase and
evaluations of vibrational peaks associated with these out-of-phase splitting of the original band (correlation or
conformers allow to evaluate the amount of DCE confined as Davidov splitting). This effect is well documented for isolated
guest in the clathrate phase or simply absorbed in the vibrations such as carbonyl stretching in polyesters [54,55] or
amorphous phase. aromatic ring modes in syndiotactic polystyrene [13].
The FTIR spectrum of a clathrate film containing about It is also worth noting that, upon guest desorption, the
8 wt% of DCE (thin line) is compared with the spectrum of the reduction of intensity of the helical peak at 1169 cmK1 is smaller
same film after 60 h of desorption at 40 8C (containing 4 wt% than those associated with other helical peaks (Figs. 3 and 5). This
of DCE, thick line) for the spectral range 1400–1130 and 870– contradicts the previous suggestion that the peak at 1169 cmK1
820 cmK1 (inset), in Fig. 4. The isothermal desorption at 40 8C would be not only characteristic of the s(2/1)2 helical
 A.R. Albunia et al. / Polymer 47 (2006) 234–242 239

conformation but would also increase as a consequence of host– five phenyl C–H bonds is restricted by the crystalline
guest interactions occurring in the clathrate phase [53,56]. environment while for the helical crystalline phases a similar
restriction would occur only for one phenyl C–H bond. This is
3.2. Linear dichroism of infrared peaks of crystalline in good qualitative agreement with the available information
and clathrate phases of s-PS relative to the packing of s-PS crystalline phases, which for
trans-planar a [1,57–60] and b [61–63] phases is dominated by
This section describes some information relative to the the parallel stacking of the phenyl rings (see a side view of the
nature of the s-PS FTIR peaks which can be achieved by linear trans-planar chain in Fig. 8(A) and, e.g. for the packing of the a
dichroism measurements on uniaxially stretched films. form, Fig. 3 in Ref. [57]) while for the helical d [11] and
FTIR spectra for three different wavenumber ranges of clathrate [3–7] phases is dominated by the formation of ac
uniaxially oriented s-PS films (lz3 and Herman’s orientation parallel layers of s(2/1)2 helices (see a side view of these
factor fc,IRz0.95), taken with polarization plane parallel and helices in Fig. 8(B) and, e.g. for the packing of the d form,
perpendicular to the draw direction, are shown in Fig. 6 by thin Fig. 4 in Ref. [11]), leading to short intermolecular contacts
and thick lines, respectively. In particular, the spectra of between only few phenyl CH groups [11].
semicrystalline samples presenting the a, b, g, d and DCE- In summary, the present results indicate that, for all
clathrate phases are presented by curves (A)–(E), respectively. semicrystalline s-PS samples, the crystalline peaks in the
The occurrence of these crystalline phases has been clearly wavenumber range 860–850 cmK1 should be attributed to the
established by the X-ray diffraction patterns of uniaxially same vibrational mode of the 841 cmK1 (ring C–H opb [28]).
stretched films, as collected by an automatic diffractometer, However, only for the trans-planar (a and b) phases, the
shown in Fig. 7(A)–(E), respectively. For instance, the patterns intermolecular packing produces a substantial shift of the peak
of Fig. 7(A)–(D) present the typical (110), (020),(200) and position for all the ring C–H opb of the crystalline phase while
(010) reflections, at 2wCu Kaz6.7, 6.15, 9.25, and 8.48, typical for the helical (g, d and clathrate) phases, the intermolecular
of a, b, g and d phase, respectively. The pattern of Fig. 7(E) packing would produce a substantial shift of the peak position
presents beside the (010) reflection also the ð210Þ only for a fraction of the ring C–H opb of the crystalline phase.
reflection at 2wCu Ka z10.78, as typical of s-PS clathrate As a consequence, for samples including trans-planar crystal-
phases [3–5,11,12]. line phases, the 841 cmK1 peak can be considered as fully
The occurrence for samples presenting the helical crystal- associated with conformationally disordered sequences, and
line phases of a reduced dichroism for the 1379, 1154 and hence used as basis of quantitative evaluations of crystallinity,
841 cmK1 peaks (Fig. 6(C)–(E)) with respect to other s-PS as already suggested in a previous report [32]. On the other
peaks is in good agreement with their prevailingly amorphous hand, for semicrystalline s-PS samples with helical crystalline
nature, as pointed out by the results of Section 3.1. phases, the 841 cmK1 peak is not only associated with
However, an accurate examination of the whole FTIR conformationally disordered sequences but also with a large
spectra of the uniaxially oriented s-PS films shows that only the fraction of the ring C–H of the crystalline phase, and hence it is
841 cmK1 peak, corresponding to ring C–H out-of-plane not suitable as basis of quantitative evaluations of crystallinity.
bending (opb) [28], presents a complete absence of dichroism, More in general, for semicrystalline films with helical
but only for a form samples (Fig. 6(A)), or for b form samples crystalline phases (g, d and clathrate), FTIR spectra like those
(Fig. 6(B)), while the same peak, for all semicrystalline films of Fig. 6 shows that some noticeable dichroism occurs for all
presenting helical conformations (g, d and clathrate, infrared peaks, thus indicating that no isolated infrared peak
Fig. 6(C)–(E)) presents a noticeable dichroism (for a can be fully associated with the amorphous phase.
comparison of FTIR spectra of different a and b form samples,
see also Fig. 6 of Ref. [32]). 3.3. Fully unoriented films presenting the helical s-PS
It is also worth noting that the peaks in the wavenumber crystalline phases
range 860–850 cmK1 (at 857 and 852 cmK1 for the a phase, at
858 cmK1 for the b phase and for g, d and clathrate phases) are To get infrared spectra of pure crystalline phases by spectral
fully dichroic and their transition moment vectors are parallel subtraction procedures, good quality spectra, like those
to the chain axes (and hence perpendicular to the phenyl rings obtained for films samples, are generally needed. Moreover,
for the trans-planar crystalline phases). These results clearly both semicrystalline and amorphous films have to be
suggest that the peaks in the wavenumber range 860–850 cmK1 characterized by the absence of molecular orientation, since
correspond to the same C–H opb mode of the 841 cmK1 peak, this can substantially alter the relative intensities of the
for the conformationally ordered chains of all crystalline measured absorbances.
phases. However, although the degree of crystallinity for all the As for s-PS, it is quite easy to get fully unoriented
samples of Fig. 6 is similar, the absorbance of the crystalline amorphous films (by quenching procedures from the melt
858 cmK1 peaks, for all helical crystalline phases, is markedly state [1]) as well as fully unoriented semicrystalline films
smaller (roughly 1/5) with respect to the corresponding presenting the trans-planar crystalline phases (a and/or b, e.g.
crystalline peaks of trans-planar phases. by melt crystallization techniques [1]). However, as for
These results can be rationalized by assuming that for the semicrystalline films presenting the helical crystalline phases
trans planar crystalline phases the out-of-plane bending of all (g, d and clathrate), which are obtained by solution
240 A.R. Albunia et al. / Polymer 47 (2006) 234–242

crystallization procedures, oriented semicrystalline films are //

generally obtained.
In fact, solution casting [47,48] as well as solvent induced
crystallization procedures [49–51] lead to s-PS films which
generally present oriented clathrate phases. In particular, the
occurrence of three different kinds of uniplanar orientation,
which present a preferential orientation parallel to the film
plane for the (010), (002) or ð210Þ crystal planes, has been
recently pointed out [47–51]. High degrees of uniplanar
orientations are generally observed also for d and g crystalline
A
phases which are obtained by guest removal or thermal
δ +am

a. u.
treatments, respectively [48–51]. Moreover, it has been clearly
pointed out that these uniplanar orientations produce large
variations of relative intensities of the infrared absorbance
B
peaks corresponding to the conformationally ordered helical γ +am
sequences [49,50].
Fully unoriented films presenting the g phase can be
obtained by solvent induced crystallization by guests giving C am
rise to unstable clathrate phases, like acetone [49] or carbon
dioxide [64]. This is shown, for instance, by the similarity of
the X-ray diffraction patterns of a g form powder (Fig. 9(A)) D δ
and of a g form film (Fig. 9(B)), obtained by supercritical
carbon dioxide treatment (at 40 8C and 200 atm for 90 min) and E γ
subsequent annealing at 150 8C for 2 h of a quenched
amorphous film. //
1400 1300 1200 1100 1000 900 600 500
By treatment of these unoriented g form films with suitable
cm-1
guest molecules, unoriented films presenting clathrate phases
can be obtained. After guest removal from the latter films, Fig. 10. FTIR spectra in the range 1400-500 cmK1 of unoriented s-PS films: (A)
unoriented films presenting the nanoporous d phase can be also semicrystalline d, of Fig. 9(D); (B) semicrystalline g, of Fig. 9(B); (C)
achieved. This is shown by the similarity of the X-ray amorphous; (D) subtraction spectrum (A)–(C), pure crystalline d phase; (E)
subtraction spectrum (B) and (C), pure crystalline g phase.
diffraction patterns of a d form powder (Fig. 9(C)) and of a d
form film (Fig. 9(D)) obtained from a g form film after 12 h
immersion in tetrahydrofuran, followed by supercritical carbon attempting to reduce the three above selected prevailingly
dioxide extraction. amorphous peaks (at 1379 and 1154 and 841 cmK1) to the
baseline.
3.4. Spectra of the pure crystalline g and d phases
It is apparent that a reduction close to the baseline is
possible only for the 1379 cmK1 peak, since after spectral
The results reported in Sections 3.1 and 3.2 clearly show
subtraction only two minor crystalline peaks (located at 1376
that, for d and clathrate s-PS samples, the 1379 and 1154 and
and 1387 cmK1 for the g phase and at 1378 and 1390 cmK1 for
841 cmK1 peaks are prevailingly, although not fully, associ-
the d phase) are left. It is worth adding that this crystalline
ated with conformationally disordered chains and they are
doublet is possibly responsible for the dichroic behaviour of the
sufficiently isolated from neighboring absorptions and of
sufficiently high intensity to be employed for quantitative peak at 1379 cmK1 in the helical semicrystalline samples
purposes. As a consequence, these peaks have been considered (Fig. 6(C)–(E)). The 1154 and 841 cmK1 peaks, although
for a possible isolation of the spectra of pure g and d crystalline heavily reduced with respect to the other peaks, are well
phases, by following a spectral subtraction procedure analo- apparent in the spectra of the pure crystalline g and d phases
gous to that one previously described for a and b form samples, and hence are not helpful to the spectral subtraction procedure.
based on the 841 cmK1 peak [32]. This indicates that, for semicrystalline samples presenting
The FTIR spectra of the semicrystalline g and d form films helical crystalline phases, the 1379 cmK1 peak is the most
of Fig. 9, being fully unoriented and hence suitable for this kind suitable for crystallinity evaluation. In particular, the crystal-
of spectral subtraction procedures, are shown in the upper part linity degrees, evaluated according to this spectral subtraction,
of Fig. 10. The FTIR spectrum of a unoriented amorphous film, by following the procedure of Refs. [32,17], is 40 and 38% for
which has been subtracted to the spectra of the semicrystalline g and d phase, respectively. These values are in agreement with
films is shown by a thin line in the middle of Fig. 10. The the crystallinity degrees evaluated by X-ray diffraction (39%
subtraction spectra, which can be assumed as the spectra of the for g and 36% for d).
pure crystalline g and d phases, are shown in the lower part of A close comparison between the spectra of the pure
Fig. 10. The spectral subtraction was accomplished by crystalline g and d phases shows, in several spectral regions,
 A.R. Albunia et al. / Polymer 47 (2006) 234–242 241

539 1379, 1154 and 841 cmK1 peaks, corresponding to ring

0.3 534
Absorbance

D vibrational modes, are prevailingly associated with the

0.2 amorphous phase. This suggestion is confirmed by linear
0.1 dichroism measurements on uniaxially stretched s-PS films,
0.0 indicating for these peaks a lower dichroism than for the other
s-PS peaks. However, the dichroism measurement indicate that
560 540 520 500 480
only the phenyl C–H out-of-plane bending peak at 841 cmK1,
0.04
Absorbance

C and only for samples including trans-planar crystalline phases

0.02 (a and b), can be considered as fully associated with
0.00
conformationally disordered sequences, and hence safely
used as basis of quantitative evaluations of crystallinity. This
behavior has been rationalized on the basis of the different
610 600 905 590
910
intermolecular interactions between phenyl rings occurring for
the chain packings of trans-planar and helical s-PS crystalline
Absorbance

0.2 B
phases.
0.1
As for helical (g, d and clathrate) s-PS semicrystalline films,
0.0 which generally present different kinds of uniplanar orien-
tation, a procedure leading to films with fully unoriented
960 920 880
0.2
crystalline phases has been described. The availability of these
fully unoriented semicrystalline films allows a more accurate
Absorbance

A
0.1 isolation of the spectra of the pure crystalline helical phases,
with respect to those achieved on the basis of FTIR spectra of
0.0 powder samples.
A comparison between the spectra of pure g and d
1400 1350 1300
crystalline phases has allowed to identify a number of
cm-1
structural order effects (corresponding to the same helical
Fig. 11. Comparison between the spectra of the pure crystalline phases of conformation) only in part described in the literature.
Fig. 10(D) and (E), for four different spectral regions: (thin lines) d phase (thick A satisfactory evaluation of the degree of crystallinity for g,
lines) g phase. d and clathrate s-PS samples, can be obtained by FTIR spectral
subtraction procedures based on the use of the 1379 cmK1
some clear differences (Fig. 11), some of which have been
peak. This procedure of crystallinity evaluation can be
already pointed out in the literature, on the basis of
particularly relevant for clathrate samples, for which the
unsubtracted spectra of semicrystalline samples. In particular,
traditional methods based on measurements of density or based
with reference to the (A)–(D) sections of Fig. 11: (A) A shift to
on X-ray diffraction spectra of unoriented samples are
higher frequencies of nearly 2 cmK1 for all the bands in the
practically useless, due to the presence of large and variable
range 1400–1250 cmK1 is observed for the d phase (as already
observed by Tashiro and co-workers for the 1354 and (from null up to 30–40 wt%) amounts of guest molecules,
1320 cmK1 peaks) [56]. (B) Substantial intensity and position which can be present in both amorphous and clathrate
variations for all the peaks in the range 980–920 cmK1 (as crystalline phases.
already pointed out in Fig. 3 of Ref. [25]) and the presence of a
shoulder at 938 cmK1 only for the g phase (as already pointed Acknowledgements
out in Refs. [33,39,56]). It is also worth noting that the g phase
presents an intense well defined peak at 910 cmK1, largely Financial support of the ‘Ministero dell’Istruzione, dell’U-
shifted with respect to the 905 cmK1 peak typical of niversità e della Ricerca’ (PRIN 2004 and FIRB2001) of
amorphous and d phases. (C) The band positions in the ‘Regione Campania’ (Legge 5 and Centro di Competenza per
615–595 cmK1 region are significantly different for the two le Attività Produttive) is gratefully acknowledged. We thank
crystalline phases (as already shown in detail by Tashiro and Dr Christophe Daniel, Dr Paola Rizzo and Dr Davide Alfano of
co-workers [36,56]). (D) Large shifts for all the peaks in the the University of Salerno for useful discussions.
range 560–480 cmK1 are observed, in particular well defined
and intense peaks are centered at 539 and 534 cmK1 for the g References
and d phase, respectively.
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