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SPECTROCHIMICA
ACTA
PART A
ELSEVIER Spectrochimica Acta Part A 51 (1995) 2117-2124

The Raman spectra of oriented isotactic polypropylene

M. Arruebarrena de B~ez, P.J. Hendra*, M. Judkins

Department of Chemistry, University of Southampton, Highfield, Southampton SOl7 I BJ, UK

Received 16 June 1995; accepted 26 June 1995

Abstract

Measurements of the relative band intensity changes with orientation can be made in the FT
Raman spectrometer on a wide range of isotactic polypropylene specimens. The usefulness of these
changes in estimating orientation at the sampled point is considered. It is concluded that the
method can be applied with caution.

I. Introduction

Many years ago, it was pointed out that illuminating an oriented polymer specimen
such as fibres of polypropylene with a polarized laser gave Raman spectra sensitive to the
sample's orientation [1-4]. This is hardly surprising in view of the well understood
anisotropic characteristics of the scattering. The technique used in the 1960s and 1970s
was based on the use of back scatter but involved a spectrometer operating in the visible
(the Cary Model 81L using He/Ne excitation). Back scatter made the measurements easy
and convenient, but fluorescence limited the value. Now that easy and simple measure-
ments are available using back scattering FT near-infrared machines, it is worth
re-appraising the method.
There have been many studies on the crystal structure and the vibrational spectrum of
isotactic polypropylene. The individual chains in micelles of crystalline order lie in 3t
helices with four chains per unit cell [6]. Two of these chains screw upwards and two
downwards in each cell producing a space group C2h [5]. Isolated chains would of course
have only Ca symmetry. Vibrational analyses have been carried out assuming the latter,
the modes lying in pairs of A and E class, e.g. for any C H 3 rocking vibration there are
three modes, one of higher symmetry, the remainder being doubly degenerate [7].
Assignment is fairly straightforward because the A class modes are infrared perpendicu-
lar dichroic while the E class modes are parallel (see Table 1). Of course this analysis is
naive and an attempt should be made to consider the polypropylene molecules as
crystalline. If one does, each A class isolated mode becomes a close quartet in the
crystals, two of the modes being infrared and two Raman active. In the E class features,
the degeneracy is lifted and again each mode so defined splits into quadruplets as for the
A species [8].

* Corresponding author.

0584-8539/95/$09.50 © 1995 Elsevier Science B.V. All rights reserved

SSDI 0584-8539(95)01512-4
2118 M. Arruebarrena de Bdez et al./Spectrochimica Acta Part A 51 (1995) 2117-2124

The various vibrational analyses and reports on the infrared spectra are to be found
collected in Ref. [8]. Raman data have been given in the same source and have included
a partial explanation of the results assuming that the full crystal structure be considered.
In Table 1 we list the assignments widely accepted for the infrared and Raman data on
isotactic polypropylene.
In the much earlier analysis of anisotropic scattering in polypropylene [1], direct
correlations were made between the behaviour in Raman scattering and in infrared
dichroic absorption and it was then suggested the orientational data could be acquired
using either method. Clearly, this is an oversimplification but was acceptable at that time.
In this paper, we explore this issue in some depth using newly acquired Raman data. The
account given here is not the first on the Raman spectra of oriented polypropylene, a
rigorous analysis appearing some years ago [7].

2. Experimental

Raman sepctra were recorded on a Perkin Elmer Model 1760 FT Raman spectrometer
powered by a CW Nd:YAG laser supplied by Spectron Lasers Ltd. and operating at
1.064 ~tm wavelength. The laser is polarized vertically and the instrument operates
exclusively in backscatter.
The highly isotactic polypropylene samples were cut from extruded sheet approxi-
mately 1.0 mm thick. They were irreversibly stretched using a modified mechanic's lathe.
One end of the specimen is held in a clamp bolted to the bed and the other end clamped
to the tool post with the thread cutting facility providing a range of crosshead speeds.

Table I
Raman and infrared spectra results for isotactic polypropylene; Ref. [5]

Raman Infrared

Frequency/cm- t Intensity Frequency/cm- ~ Intensity Polarization Symmetry Assignment

- 2965 vvs ]l A vCH3 asym.

2957 2953 vvs ± A vCH 3 asym
2920 m 2921 vvs X A vCH 2 asym
2905 m
2883 s 2877 vs ± A vCH 3 sym
2871 w 2869 vs Z A vCH 3 sym
2840 m 2840 vs A vCH 2
1457 vs 1456 s Z A t~CH 3 asym + 6 C H 2
1435 w 1434 m ± A, E 6CH.~ asym
1371 sh 1376 s ± A, E 6CH3 sym + CH 2 wag
1360 s 1357 m Z A, E C H 3 sym ben + a C H
1300 vs 1326 vw ± A, E 6 C H + tCH 2
1307 vw 1305 w Z A ¢oCH2 + tCH2
1296 vw 1296 wv ± E toCH 2 + ~CH
1257 w 1255 w II A ~ C H + tCH 2 + rCH 3
1220 s 1218 vw ± E tCH2 + ~ C H + v C - C
1167 sh 1166 m I1 A v C - C + rCH 3 + ~ C H
1152 vs 1153 w ± E v C - C + v C - C H 3 + 6 C H + rCH 3
1102 w II01 vw ± E v C - C + rCH 3 + toCH 2 + tCH + 6 C H
1034 s 1043 vw II E vC-CH.a + v C - C + ~ C H
998 m 998 m I1 A rCH 3 + ¢oCH 2 + 6 C H
973 s 974 m II 4, E rCH~ + v C - C chain
941 m 940 vw 2 E rCH_, + v C - C chain
900 m 900 w ± A,E vCH.~ + rCH 2 + 6 C H
841 vs 841 m II A rCH2 + v C - C H ~
809 vs 808 w ± A, E t,CH 2 + v C - C + t , C - C H
530 m 528 v ± E ¢oCH 2 + t,C-CH~ + rCH 2
458 m 456 vw ± A ~,~CH2
398 s 396 vvw II A ~oCH 2 + 6 C H
321 m 318 vvw ± E ~oCH2
252 m 248 vvw I/ A ~oCH 2 + ~CH
 M. Arruebarrena de B(tez et al./Spectrochimica ,4eta Part A 51 (1995)2117-2124 2119

Table 2
Depolarization ratios in glassy polypropylene

Band frequency pa Band frequency pa

/cm - i lcm -

400 0.408 1169 0.876

459 0.492 1220 0.867
809.5 0.492 1331 0.924
842 0.336 1360 0.993
974 0.812 1436 1.005
999 0.510 1460 1.002
1152 0.879

Peak area I ± / I .

After drawing, the specimens are white. To reduce this turbidity which may well
scramble the polarized laser radiation in the Raman experiment, each sample was
compressed under a force of about 20 tonnes for two minutes. Precise pressure can-
not be quoted due to inequalities in sample thickness and width.
Draw ratios were determined by measuring the cross-sectional area and ratioing
this with the undeformed section.
To enhance the intensity of the spectra recorded, a small piece of aluminium foil
was taped to the rear of the sample to enhance reflection of both the laser and the
Raman scatter into the collection lens.
All spectra were recorded at 2 cm -~ resolution and 200 scans were co-added.

3. Results and discussion

3. I. Unoriented specimens

The interaction of polarized radiation with an unoriented sample and the analysis
of the scattering polarized parallel and perpendicular to the beam can yield two
familiar behaviour patterns. Where the intensity ratio /±//11 = 0.75 the so called "de-
polarized" bands will derive from the E class modes while those with I±/Ill <0.75
and described as "polarized" will originate from the .4 class modes.
There are several difficulties associated with the carrying out and interpretion of
this type of measurement.
(1) The glassy sample of polypropylene contains an unknown and uncontrollable
concentration of 31 helices; the vibrational behaviour in which we are interested is
confined to these species rather than any disordered fragments of the chains.
(2) The depolarization performance of the instrument is known to be poor (the v~
mode in CC14 does not give a depolarization ratio close to zero as expected). Fur-
ther, polymer samples invariably scramble the polarization of the source and scatter
beams to variable extents.
As a consequence, depolarization data can only be used as an indicator; bands
with small depolarization ratios are assignable with confidence to .4 class features.
In Table 2 we offer a set of data taken from a quenched, cooled glassy specimen.
Several points are clear: the instrumental problem explained in (2) above may well
apply, but nevertheless a wide range of p values is observed. Further, although
scrambling must be present, the data are not ruined.
2120 M. drruebarrena de Bdez et al./Spectrochimica Acta Part A 51 (1995) 2117-2124

Candidates for assignment to the A class must include the features at 400, 459, 809,
842 and 999 cm -~. It is worthwhile at this stage to consider the established assignments
of the infrared spectra. Perhaps the most thorough of these, by Tadokoro et al. [7] is
based on the observation of infrared dichroism in polypropylene and its deutero
derivatives supported by normal coordinate analysis. Based on infrared data, the
assignments listed above are very inaccurate, e.g. prominent features at 809 and
842 cm-~ are assigned by Tadokoro to E and A classes, respectively. However, the
experimental acquisition of the infrared spectra is not without its difficulties. Although
scrambling is modest, it is hard to be certain of the dichroic behaviour of the weak
features and in a spectrum as complex as that of polypropylene, overlapping can also
cause uncertainties. The prominent Raman features highlighted above face just such a
problem. The observed intensities in absorption of the 842 and 809cm t bands are
medium and weak, respectively.

3.2. Oriented specimens

The interaction of the polarized laser with highly oriented samples gives rise to several
experiments defined in Fig. 1. One would expect that different modes would interact more
or less effectively in these experiments. Tests confirm that once an extension of 300% has
been induced in a specimen of isotatic polypropylene, the effect is well developed and
increases little as further extension is forced upon samples [9].

I
I

fA~t.
/
/
/

/
/"
/
/
/

Fig. 1. Anistropic scattering experiments for cylindrically oriented specimens. Porto's nomencla-
ture [I 5] is used to describe each. The experiments described are those involved in Fig. 2.
 M. Arruebarrena de B6e- et al./Spectrochimica Acta Part A 51 (1995) 2117-2124 2121

~oo-/MI IH

IN1

ol-

o3-

ol-

0 DO.
I
tSO0 0
1400 13~ 12001 1100 I0O0 ~o 800 700 600 50O 40O 3O0
20O 0

(a)

100 "I IH

o,g-

Ofl-

07"

06-

INT 0b-

03-

02-

01-

0 O0 I
1400 1300
1500.0 200.0

CN-I
(b)
Fig. 2. Three of the anisotropic Raman scattering experiments for an oriented specimen of
polypropylene. Laser polarized vertically. (a) chains vert:anal.vert.; (b) chains vert:anal.hor.: (c)
chains hor:anal.hor. (see Fig. I).

The bands thought from infrared dichroic evidence to derive from A class isolated
chain modes tend to be stronger in the Raman spectrum. It will be seen from the spectra
given in Fig. 2 that the degree of anisotropy in the scattering is relatively modest and
certainly not nearly so marked as it is in ultra high modulus polyethylene. However, the
A-class modes tend to predominate when the plane of polarization of the source lies
parallel to the direction of draw and hence presumably that of molecular orientation.
Apparently the E class features interact more effectively with radiation polarized perpen-
dicular to the draw direction. There are, however, some ambiguities in the experimental
data. The efficiency of scattering and light collection varies from experiment to experi-
2122 M. Arruebarrena de B{te: et al.tSpectrochimica Acta Part ,4 51 (1995) 2117-2124

i.
'°°
09-
tHI
08-

0&
1

05-
INI

04-

02-

Ol-

° ° ° 115000 ,+00 ,+0 ,,00 +0 ,0; BJ0 ..... I

~000

CN-
(c)
Fig. 2. (continued).

ment; hence there is error in normalizing the intensities before comparison. This is not a
problem, of course, in infrared spectra as the electric vector of the polarizer is rotated
between experiments carried out on an undisturbed specimen. As we stated in our study
of the unoriented specimen, there are problems with assignments. Some of those made by
Tadokoro et al. [7] are not confirmed by the Raman evidence. Our data on anisotropy
clearly assign the band at 809 c m - 1 to an A class motion as suggested above. One might
argue that the infrared is an inherently more reliable method of measuring anisotropy
than Raman scattering. As has been suggested earlier, each band in the infrared and
Raman is an unresolved multiplet [8]. In infrared, the dichroic absorption of each
component of the multiplet should be similar, but the Raman scattering of each
component is not, because the multiplets are mixtures of A and E class modes. Therefore
the approximation of an isolated molecule is adequate to interpret infrared spectra, but
too simplistic for Raman spectra. Clearly an overall detailed appraisal of the interpreta-
tion is needed and this has been attempted to some extent in several papers by Cambon
and his co-workers [10,11].
For the purpose of routine analysis of sample orientation, it is sufficient to understand
how the anisotropic behaviour exhibited relates to the orientation being measured.
Strong bands with marked anisotropy of reliable characteristics are most useful. We
propose the use of the combination of 842/809 bands for determining orientation in
polypropylene.
At this stage the Raman technique can provide an estimation of orientation rather
than a quantitative determination thereof, but the "dichroism" found is not the same as
that deduced from infrared measurements. However, Raman scattering is a measurement
which can be performed on samples which are too thick for infrared and of course little
or no sample preparation is required. Further, for industrial usage it may be sufficient to
only change the direction of polarization of the incident laser and avoid using an
analyser. The advantage here is the convenience and the greater signal strength resulting
from the elimination of the analyser. The two sepctra recorded in these conditions are
shown in Fig. 3. The anisotropy is clearly visible.
In their contributions Cambon and co-workers [10,11] suggest that the disoriented
material contributes heavily to the intensity of the Raman bands and hence any
anisotropy therein can mask effects originating in the crystals. Their point is that such
 M. Arruebarrena de B6ez et al./Spectrochimica Acta Part A 51 (1995) 2117-2124 2123

30G
MI I ,~

?0-

15-

IO-
i

051

000
14 1300 i200 ItO0 I
1000 ~0
15000 200.0

O4-1
(a)

3.00 MI iH

2.5-

20-

15-

IO-

05-

0.00

1500.0 .~0.0

oq-I

Fig. 3. Two of the anisotropic Raman scattering experiments meaningful for an oriented
specimen of polypropylene where no analyser is used. Laser polarized vertically; (a) chains vert.:
(b) chains hor.

effects reduce once the sample is extended more and more. At 300% extension the value
used here, they contend that the crystallite orientation is low, but this is not supported
by X-ray and other evidence [12,13]. Certainly, the spectra do change with increasing
strain [9] and this is linked to the properties of orientation, but the explanation offered
seems simplistic. Further, we have repeatedly observed that in semi-crystalline polymers
the Raman scattering for the crystalline phase is sharper and more intense than that for
the disordered component, which again refutes the suggestions of Cambon and co-work-
ers [10,11].
2124 M. Arruebarrena de Bde: et al./Spectrochimica Acta Part ,4 51 (1995)2117-2124

4. Conclusions

The effect identified long ago a n d reemphasized recently is simplistic, but used with
c a u t i o n and bearing in m i n d the complex origin o f the a n i s o t r o p y it can be o f value in
estimating o r i e n t a t i o n a n d changes t h e r e o f in p o l y p r o p y l e n e m o u l d i n g s o r extruded
sections. There is no d o u b t that the m e t h o d w o r k s because it has been a p p l i e d in the past
to c o m p l e x m o u l d i n g s o f p o l y m e t h y l p e n t e n e [14]. W e a d v o c a t e the use o f the pair o f
b a n d s at 842 and 809 cm l for o r i e n t a t i o n d e t e r m i n a t i o n , but r e c o m m e n d that spectra be
interpreted carefully. In particular, as the degree o f crystallinity rises, the intensity o f the
b a n d at 809 cm 1 rises relative to that at 842 c m - m. This change should not be confused
with anistropic observations.

References

[1] P.J. Hendra and H.A. Willis, Dichroism in the laser Raman spectrum of stretched fibers of polypropylene
Chem. Ind., (1967) 2102.
[2] P.J. Hendra and J. Derouault, J. Chim. Phys., 71 (1975) 1395-1407 (Discusses Refs. [1], [3] and [4].)
[3] J. Derouault, P.J. Hendra, M.E.A. Cudby and H.A. Willis Chem. Commun., (1972) 1187.
[4] P.J. Hendra and H.A. Willis, Chem. Commun., (1968) 255.
[5] R.G. Snyder and J.H. Schachtschneider, Spectrochim. Acta, 20 (1964) 853.
[6] Z. Mencik, J. Macromol. Sci. Phys., B6 (1972) 101.
[7] H. Tadokoro, M. Kobayashi, M. Ukita, K. Yasufuku, S. Murahashu and T. Torii J. Chem. Phys., 42
(1965) 1432.
[8] P.J. Hendra, M.J. Gall, H.A. Willis, M.E.A. Cudby, G. Fraser and D.S. Watson, Spectrochim. Acta Part
A 29 (1973) 1525.
[9] M. Arruebarrena de B~ez, Ph.D. Thesis, University of Southampton, 1994.
[10] L.D. Cambon and D.V. Luu, J. Raman Spectrosc., 14(4) (1983) 291.
[11] L.D. Cambon, J.L. Ramonja and D.V. Luu, J. Raman Spectrosc., 18 (1987) 129.
[12] R.J. Samuels, Makromol. Chem., 4 (1981) 241.
[13] F.M. Mirabella, Jr., J. Polym. Sci., 25 (1987) 591.
[14] P.J. Hendra, DJ. Cutler and R. Sang, Faraday Discuss. Chem. Soc., 68 (1979) 320-327.
[15] T.C. Damen, S.P.S. Porto, and B. Tell, Phys. Rev., 142 (1966) 570.