VIBRATIONAL

CTROSO)In/
S
ELSEVIER Vibrational Spectroscopy 10 (1996) 79-87

Review

Polymer crystallinity studied using Raman spectroscopy

B.H. Stuart
Department of Materials Science, University of Technology, Sydney, P.O. Box 123, Broadway, NSW, Australia
Received 17 March 1995

Abstract

The application of Raman spectroscopy to the study of crystaUinityin polymers has been examined. In particular, Fourier
transform (FT)-Raman spectroscopy has been applied in a number of studies in recent years to investigate crystallinity in a
variety of polymers. The polymers discussed in this review are polyethylene, polystyrene, poly(ether ether ketone),
polyamides, poly(ethylene terephthalate), elastomers, liquid crystalline polymers, inorganic polymers and certain polymer
blends.

Keywords: Raman spectrometry, Fourier transform; Polymers; Crystallinity

1. Introduction crystallinity. Studies of the following crystalline

The degree of crystallinity in polymers is an
important property which needs to be taken into
account when considering the manufacturing and
applications of such materials. Historically, infrared
spectroscopy has been an analytical technique used
more widely than the complimentary technique, Ra-
man spectroscopy, for the investigation of polymer
structure. However, in recent years, particularly with
the advent of Fourier transform (FF)-Raman spec-
troscopy, Raman has emerged as an equally useful
method for the investigation of polymer structure
(reviewed in [1-5]). FT-Raman spectroscopy avoids
the problems of sample fluorescence, a common
occurrence when studying polymers with conven-
tional Raman, as these materials often contain addi-
tives and/or impurities [3].
Raman spectroscopy has been used in a number
of studies to examine the structural changes in a
variety of polymers due to the differing degrees of
polymers have been reported in recent literature and
are discussed in this review: polyethylene,
polystyrene, poly(ether ether ketone), polyamides,
poly(ethylene terephthalate), elastomers, liquid crys-
talline polymers, inorganic polymers and certain
polymer blends.
2. Polyethylene
Polyethylene (PE) has been widely studied using
vibrational spectroscopy. Spectroscopic studies have
demonstrated that the crystallinity of PE may be
estimated by examination of the modes associated
with the trans and gauche rotational isomers of this
polymer (reviewed in [4,5]). The trans conformation
of PE is associated with the crystalline phase, while
the amorphous phase is predominantly gauche. The
frequencies and widths of the C - C stretching (1160-
1020 cm-1), CH 2 twisting (1350-1250 cm -1) and

0924-2031/96/$15.00 © 1996 Elsevier Science B.V. All rights reserved

SSDI 0 9 2 4 - 2 0 3 1 ( 9 5 ) 0 0 0 4 2 - 9
80 B.H. Stuart/Vibrational Spectroscopy 10 (1996) 79-87
CH 2 bending (1510-1390 cm -1) Raman modes have
been shown to be strongly related to the degree of
crystallinity in the sample.
PE is known to contain a third phase of intermedi-
ate order, in addition to the amorphous and crys-
talline phases. Strobl and Hagedorn [6] were able to
demonstrate that Raman spectroscopy could be used
to determine the relative amounts of these phases
present in samples of PE. The intensity of the band
at 1416 cm -~, due to CH 2 bending, is related to the
amount of orthorhombic crystalline material present
in the sample. Bands at 1303 and 1080 cm -1 can
also be used to estimate the amorphous content of
PE. This method has also been used in more recent
studies in an improved form [7-9].
Low-frequency Raman modes of PE have also
been investigated. Longitudinal acoustic modes
(LAM) are based on the idea that molecular chains
with a lamellar unit vibrate along their length in an
accordion-like motion and the frequency depends on
the length of the vibration. LAM bands may be used
to measure the long-range ordered segments of poly-
mer chains that comprise lamellae in crystalline
polymers. Snyder et al. [10] identified a LAM band
which is characteristic of long-range conformational
disorder in PE in the Raman spectrum of the semi-
crystalline polymer. They observed a Raman band at
206 cm-1 for semi-crystalline PE, while a broader
band at 202 cm-~ was observed for molten PE. The
intensity of the LAM band for crystalline PE is
closely related to the level of crystallinity in the
polymer.
3. Polystyrene
Jones and Wesley [11] carried out Fourier trans-
form Raman studies of polystyrene (PS) of varying
tacticity and differing thermal history. A comparison
of atactic and isotactic PS provides information about
the crystallinity-dependent Raman modes for this
polymer. Isotactic PS is known to be helical and
crystalline, while atactic PS is completely amor-
phous. Jones and Wesley suggested that bands near
842, 1198 and 1209 cm -1 are dependent on the
degree of crystallinity in the sample. The mode at
842 cm -1, attributed to the aromatic C - H out-of-
plane bending deformation, is significantly more in-
tense in the isotactic sample compared to the mode
observed for the atactic sample. Similarly, the shoul-
ders appearing at 1198 and 1209 cm -~ only occur in
the spectra of the partially crystalline samples. How-
ever, because the mode at 842 cm-a is not compli-
cated by other modes, the intensity of the band is
regarded as a more useful indicator of PS crys-
tallinity if quantitative analysis is to be attempted.
A low-temperature ( - 130°O FF-Raman study of
PS by Wesley and Hendra [12] also showed a crys-
tallinity-dependent mode at 1006 cm -1. This study
also provided evidence that the difficulty in forming
the 3 / 1 helix in isotactic PS contributes largely to
the slow rate of crystallisation and the low crys-
talline content in this form of PS.
4. Poly(ether ether ketone)
Raman spectroscopy has proved to be a particu-
larly fruitful technique for the examination of the
morphology of poly(ether ether ketone) (PEEK).
Louden [13] used Raman spectroscopy to investigate
a series of PEEK films annealed at different tempera-
tures. Correlations were found between changes in
the Raman spectrum and the crystallinity as mea-
sured by multiple internal reflection spectroscopy.
The relative intensity ratios of the 830 c m - 1 / 8 1 0
cm -1 and 1600 c m - 1 / 1 6 1 0 cm -1 peaks, and the
frequency position of the C---O stretching mode,
were shown to be dependent on the percentage crys-
tallinity. Agbenyega et al. [1] also noted that the
intensity of a PEEK Raman mode observed at 1596
cm -~ increases relative to that of a mode at 1607
cm-1 with increasing crystallinity. Fig. 1 shows the
FT-Raman spectra of both amorphous and semi-
crystalline PEEK [15].
Raman spectroscopy has proved to be a conve-
nient spectroscopic technique for the estimation of
the nature of the thermal changes induced in PEEK.
The relative intensity of the symmetric C - O - C
stretching mode has been followed as a function of
temperature in order to examine the crystallisation
process of PEEK [14,15] (Fig. 2). The results ob-
tained by Briscoe and co-workers [14,15] support the
theory developed by Nguyen and Ishida [16] using
infrared spectroscopy that the polymer undergoes
two processes during crystallisation. The first pro-
 B.H. Stuart/Vibrational Spectroscopy 10 (1996) 79-87
~ hous
1750 1550 135o 1150" " 9~0' ' "7~0
wavenumber/ era-1
Fig. 1. FF-Raman spectra of amorphous and semi-crystalline
PEEK [14].
cess occurs in the region of 120-130°C and is
associated with the partial bond rotation of the ether
linkages prior to crystallisation. This is manifested
by a decrease in relative intensity of the symmetric
C - O - C stretching mode. At temperatures above the
glass transition temperature Tg (143°C) a second
process involving the motion of the whole chain
occurs and is characterised by the rotation of the
benzophenone linkages near the melting temperature
Tm (334°C). In the Raman spectrum, an increase in
the intensity of the C - O - C stretching mode is ob-
served at this temperature.
One particularly important property of PEEK has
been its ability to resist chemical attack; there are a
very limited number of solvents for PEEK. Despite
this, a series of recent studies has shown that certain
solvents can be absorbed by PEEK and cause de-
tectable plasticisation and induce crystallisation. The
effect of toluene on the Raman spectra of PEEK was
examined by Briscoe et al. [14]. The relative inten-
sity of the symmetric C - O - C Raman stretching
mode of the polymer was affected by the presence of
toluene. Comparison with thermal experiments
showed that the presence of toluene in the polymer
at room temperature mimics the spectral characteris-
tics of the unsolvated polymer at a temperature of
about 120°C. Thus, Briscoe and co-workers were
81
able to assign a "fictive" temperature of 120°C to
the toluene solvated polymer. The presence of the
solvent induced additional molecular mobility and
the mechanical characteristics of the polymer ap-
peared to be similar to those of the unsolvated
polymer at some higher temperature. Similar find-
ings were observed in a spectroscopic study of the
effect of dodecane lubricant systems on the frictional
properties of PEEK [15]. The Raman spectra of
PEEK exposed to dodecane with the surfactant addi-
tives dodecylamine and decanoic acid showed that
these systems also produced a fictive temperature in
the region of 120-130°C.
Exposure of amorphous PEEK to various chlori-
nated aliphatic hydrocarbons was found to have con-
siderable effects on the spectral properties of the
polymer [17,18]. The solvents methylene chloride,
chloroform and tetrachloroethane (TCE) were found
to cause swelling and induce crystallisation in PEEK.
In particular, tetrachloroethane was shown to pro-
duce unusually dramatic swelling of the polymer
[17]. The Raman spectra of such solvated PEEK
systems showed that the frequency of the C = O
stretching mode is shifted to lower values compared
2.3
2.1
1.9
1.7
1.5
1.3 m I I I i I i
0 i00 2o0 3oo 4oo
temperatme/ *C
Fig. 2. Relative intensity of the symmetric C-O-C stretching
Raman mode of PEEK as a function of temperature[14].
82 B.H. Stuart/Vibrational Spectroscopy 10 (1996) 79-87

Table 1 showed similarities. As this paraffin is known to

Crystallinity-dependent Raman modes of PEEK [17]
Sample C=O stretching Symmetric C-O-C
frequency (cm- i) stretching intensity
Amorphous 1651 1.51
Crystalline 1644 1.35
Tetrachloroethane- 1644 1.65
treated
to the untreated polymer, indicating an increase in
crystallinity. In addition, the relative intensities of
the symmetric C - O - C stretching modes are also
affected by the presence of certain chlorinated sol-
vents. Lewis acid-base interaction theory was used
to rationalise why such solvents affect PEEK in this
way. PEEK acts as a soft organic base owing to the
presence of the C=O, C - O - C and aromatic groups
in the structure, all of which act as electron donors.
The chlorinated solvents act as electron donors ow-
ing to the electron-deficient hydrogen atoms which
are activated by the strong electron-withdrawing in-
fluence of the chlorine groups. Fictive temperatures
were also assigned to the afore-mentioned chlori-
nated solvents. These solvents have a greater plasti-
cising effect than, say, toluene [14], and it was
shown that methylene chloride, chloroform and TCE
mimic the unsolvated polymer at temperatures near
250°C, close to the Try. The effect of TCE on the
crystallise in the triclinic form with one chain per
unit cell, it was concluded by both Hendra et al. [19]
and Maddams and Royaud [20] that both single and
double Nylons must also have one chain per unit
cell.
The effect of increasing temperature on the Ra-
man spectra of Nylon 6 has been investigated [21]
and the observed changes were interpreted in terms
of the "loosening" of the intermolecular hydrogen-
bonding within Nylon and a redistribution of the
hydrogen-bond energies. Modes associated with the
amide group (the amide I band at 1636 cm -1, the
amide III band at 1280 cm -1 and the N - H stretching
mode at 3301 cm -1) show a reduction in intensity
(Fig. 3). The amide I band, largely due to C = O
untreated
~ ) 25: C
V
w a t e r

crystallinity-sensitive Raman modes of PEEK is

summarised in Table 1 [18].

5. Polyamides

The presence of the amide group in polyamides

means that hydrogen-bonding makes an important 200° C
contribution to the crystalline regions of this class of
polymers. The FT-Raman spectra of a series of both
single-number and double-number Nylons have been
reported [19,20]. Information regarding the crys-
talline regions of these polyamides was derived from
examination of the CH 2 bending region (1500-1400
cm -1) of the spectra. Comparison of the mode at d • - - , • - , - - • , • • - , , • , • -
3400 2900 2400 1900 1400 900

1440 and 1473 cm -1 with those observed in the

Raman spectrum of PE indicated that the Nylons do wavenumber / cm" l
not contain two chains per unit cell. However, com- Fig. 3. FT-Raman spectra of Nylon 6 at 25°C, 200°C and after
parison with the spectrum of the paraffin Cz6H54 exposure to water [21].
 B.H. Smart/Vibrational Spectroscopy 10 (1996) 79-87
stretching, also shifts to greater frequencies with
increasing temperature. Modes due to vibrations in
the hydrocarbon chain of Nylon 6 were also affected
by an increase in thermal energy.
The changes in the FT-Raman spectra of Nylon 6
due to the presence of water have also been exam-
ined [21] (Fig. 3). It was postulated that water
molecules disrupt the inter-chain hydrogen-bonding
which exist in the polyamide; water molecules have
a greater propensity to interact at the basic carbonyl
sites of Nylon than adjacent Nylon chains. Conse-
quently the Raman spectra of water-treated Nylon
demonstrate that water produces augmented hydro-
gen-bonding in Nylon 6.
Schmidt and Hendra [22] have reported the results
of a Fr-Raman study of the conformation of poly(~-
caprolactam), which is also known as Nylon 6. They
were able to assign Raman bands characteristic of
planar (a-crystalline) and non-planar (~/-crystalline
and mesomorphous) conformation of the e-caprolac-
tam units. These bands were then used to investigate
the conformational composition of ~-caprolactam se-
quences in several e-caprolactam-butadiene copoly-
mers. It was observed that at higher concentrations
of the butadiene units, the content of the planar
conformation of caprolactam units in these copoly-
mers considerably decreases.
6. Poly(ethylene terephthalate)
The vibrational spectra of poly(ethylene tereph-
thalate) (PET) have been reported in a number of
papers. In the amorphous state PET has a gauche
structure of the ethylene glycol units, while in the
crystalline state the ethylene glycol units of PET
have a trans structure. McGraw [23] reported the
Raman spectrum of PET and examined the effects of
high-temperature annealing on the PET spectrum.
The intensity of the 1096 cm-1 band was shown to
correlate linearly with density. However, a later study
by Melveger [24] demonstrated that using the inten-
sity of the 1096 cm -1 mode as an indicator of
crystallinity was not reliable as the correlation
changes with orientation of PET. Melveger [24] found
that the bandwidth at half-height of the C= O stretch-
ing mode at 1730 cm -1 correlates with density in
PET. The carbonyl mode is notably broader for
83
amorphous PET in comparison to that of the crys-
talline polymer. This correlation is valid for unori-
ented as well as highly oriented materials. Stokr et
al. [25] have made comprehensive assignments of the
Raman modes of PET and spectral substraction was
used to separate the amorphous and crystalline com-
ponents of PET.
7. Liquid crystalline polymers
Thermotropic liquid crystalline polymers (LCPs)
consist of two main types depending on the position
of the mesogenic unit. Side-chain LCPs have meso-
genic units attached to the polymer backbone, while
main-chain LCPs have mesogenic units attached ei-
ther directly or via spacers to the polymer chain.
Raman studies of LCPs have been limited because of
a particular problem with fluorescence. However, in
recent years several successful FT-Raman studies of
LCPs have been reported.
Ellis et al. [26] have examined the crystallisation
of poly(bis-4-m e t h o x y p h e n o x y p h o s p h a z i n e )
(PBMOPP). Changes observed in the difference
spectra were attributed to a reduction in the mobility
of the aromatic ring side-chains in the crystalline
material. An aromatic ring breathing mode and an
aromatic C - H stretching mode both shift in fre-
quency on crystallisation. The relative band intensi-
ties of several modes were also observed to change
on crystallisation, including the C = C stretching
modes, which increase in intensity with increasing
crystallinity. Polyphosphazines exhibit thermotropic
behaviour dependent on their thermal history and the
nature and packing of the side-chains attached to the
flexible P - N backbone. The Raman results support
the view that the arrangement of the substituent
groups influences the properties of the polymer.
A thermotropic main-chain LCP, poly(hepta-
m e t h y l e n e terephthaloyl-bis-4-oxybenzoate)
(PHMTOB) has been studied using FT-Raman spec-
troscopy. Ellis et al. [27] have examined PHMTOB
as a function of temperature and thermal history. The
relative intensity of certain modes (with respect to
the C = C stretching mode at 1605 cm-1) were found
to correlate with the degree of erystallinity deter-
mined using wide angle X-ray scattering (WAXS).
The crystallinity-dependent modes of PHMTOB are
84 B.H. Stuart/Vibrational Spectroscopy 10 (1996) 79-87

Table 2 gauche conformation of the alkyl side-chains of the

FT-Raman modes of PHMTOB dependent on the thermal history
of the sample [27]
Frequency (cm- 1) Assignment
3077 C-H stretching
1736 C=O stretching
1285 ring C=O stretching, O-C stretching,
C-H in-plane stretching
1269 CO-O stretching
1078 ester CO-O stretching or C-C stretching
858 CH 2 rocking
summarised in Table 2. The spectral changes ob-
served were associated with the mesogenic unit, as
well as the flexible methylene spacer.
8. Inorganic polymers
The thermal transitions of a germanium-based
polymer, poly(di-n-hexylgermane) (PDHG), have
been investigated using FT-Raman spectroscopy [28].
A correlation between the band splitting of the CH 2
bending modes at 1444, 1453 and 1469 c m -1 and
the packing of the hexyl side-chains was observed.
Below 12°C the spectrum shows sharp bands which
may be attributed to a trans planar zigzag conforma-
tion. Notable changes in the Raman spectrum of
PDHG were observed as the temperature was raised
above 12°C, the thermochromic transition tempera-
ture. The sharp intense bands in the 1150-1000
cm -1 region are replaced by broader and weaker
bands and these changes were associated with a
polymer. A similar observation was made for the
behaviour of poly(di-n-hexylsilane) above the ther-
mochromic transition temperature [29].
9. Elastomers
Wang et al. [30] have reported the results of a
Raman spectroscopic study of the pressure-induced
glass transitions of polyisoprene. Examination of the
spectra recorded over a pressure range of 0-2 GPa
showed that the frequencies and intensities of certain
Raman modes change as a function of pressure. The
frequencies of the =CH 2 rocking (493 c m -1 ) and
CH 2 stretching (2913 cm -1) modes shift to lower
frequencies before the low-pressure glass transition.
Additionally, the intensity of the CH 3 rocking mode
(1038 cm-1) relative to the intensity of the = CHCH 2
rocking mode (996 cm- 1) was examined and turning
regions were noted at 0.7 and 1.7 GPa, respectively.
The spectral changes allowed Wang et al. [30] to
assign the transition near 0.7 GPa to the glass transi-
tion characterising the "forced freezing" of main-
chain motion. The transition at 1.7 GPa was associ-
ated with the fl-transition characterising the "forced
freezing" of side-chain motion.
FT-Raman spectroscopy has been used to study
the crystallisation of polychloroprene. Wallen [31]
observed changes in frequency and intensity on com-
parison of the spectra of amorphous and semi-crys-
talline (predominantly trans) polychloroprenes. The
assignments of the amorphous and crystalline modes

Table 3
Amorphous and crystalline FF-Raman modes of polychloroprene [31]
Frequency (cm- 1) Assignment
Amorphous Crystalline
1344 1340 saturated and olefinic C-H bending
1291,1277 1289, 1255 saturated C-H bending, C-C stretching
1082 1079 C-C stretching
1007 1010 C-C stretching, C - C - C bending
826 saturated C-H bending, C-C1 bending, C-C1 stretching
783 saturated C-H bending
671 olefinic C-H bending, C-C1 stretching, C=C twisting
580 C - C - C bending, C = C - C bending, saturated C-H bending, C-C1 stretching
479 476 C - C - C bending, C = C - C bending, CI-C=C bending
 B.H. Smart/Vibrational Spectroscopy 10 (1996) 79-87 85

of polychloroprene are summarised in Table 3. It

was noted that many of the bands related to the
crystallinity are also related to the C-C1 vibration
1652 "'"
modes, and that during the crystaUisation process the amorphous region

environment of the chlorine atoms must be changed. 1650"

Fr-Raman spectroscopy has been applied to the
study of the crystallisation of dicumyl peroxide cured 1648 "
natural rubber under stress. Stevenson [32] has car-
ried out a study of the polymer with the samples 1646 "

stretched such that the polymer chain axes were

parallel to the plane of polarisation of the incident
laser. It was noted that bands at 1364, 1286, 1130,
1644-
ii 50% PEEK 150% pEI
iiiiii crystallineregion

1037 and 998 cm-1 showed an increase in intensity 1642"

on crystallisation. In a stress-crystallised material • 100% PEEK

three distinct regions exist: ordered crystalline, or- 1640

dered amorphous and disordered amorphous.
Jones [33] has carried out an FT-Raman study of
the cold crystallisation of natural rubber and depro-
teinised rubber. Changes in the spectrum of natural
rubber were observed upon cold crystallisation. Cold
crystallisation occurs in rubber when it is maintained
at temperatures in the range - 5 0 to 0°C. Dramatic
changes in the C - H stretching region and new bands
at 469, 489 and 684 cm -1 occur uniquely in the
spectrum of the cold-crystallised natural rubber.
These changes increase with increasing cold soaking
indicating that they are related to further crystal
formation. Jones' examination of the Raman spec-
trum of deproteinised rubber also indicated that pro-
tein impurities facilitate the formation of an addi-
tional crystal structure. Stress-induced crystallisation
in cross-linked natural rubber was also investigated
using Raman spectroscopy in this study. However, it
was shown that the cross-linked material is pre-
vented from forming crystalline regions in the
stressed state by the restriction of chain movement
imposed by the cross-links. However, it has been
shown in other studies that cross-linked poly(iso-
prene) can undergo stress-induced crystallisation [34].
10. Polymer blends
Raman spectroscopy has also been used in a
number of studies of PEEK blends. FT-Raman spec-
troscopy was used by Briscoe et al. [35] to examine
the crystallisation processes of PEEK blended with
poly(ether imide) (PEI). Both the intensity of the
0
. . . . ,
100
. . . . ,
200
. . . . ,
300
. . . .
400
tem~/'~C
Fig. 4. Frequencies o f the C = O stretching m o d e o f P E E K a n d a
5 0 % P E E K - 5 0 % PEI b l e n d as a function of temperature [35].
C - O - C stretching mode and the frequency of the
C=O stretching mode of PEEK in this blend were
shown to change as a function of temperature. The
temperature dependence of the frequency of the car-
bonyl mode of PEEK, before and after blending with
50% PEI, is shown in Fig. 4. Through examination
of initially amorphous blend samples, the study
showed that the rate of crystallisation of PEEK is
inhibited by the presence of PEI up to the Tg of
PEEK, after which crystallisation proceeds rapidly.
The total amount of crystallinity induced in PEEK is
increased by blending with PEI and in the case of a
50% PEEK-50% PEI blend, the increase was com-
puted to be on the order of 5%.
Raman spectroscopy has also been used to study
blends of PEEK and poly(tetrafluoroethylene) (PTFE)
of various compositions [36]. Stuart and Briscoe [36]
showed that the addition of PTFE to PEEK to form
an immiscible blend caused changes in the Raman
spectrum of PEEK. The narrowing of the Raman
modes of PEEK were taken as an indication of more
order in the PEEK molecules. In addition, the reduc-
tion of the intensity of the C - O - C stretching mode
with increasing PTFE concentration provided evi-
dence of an increase in crystallinity in PEEK (Fig.
5). Another important observation was that the most
significant change to this crystallinity-dependent
mode occurs when about 10 wt.% PTFE is added to
86 B.H. Smart/Vibrational Spectroscopy 10 (1996) 79-87
1.4'
1.3"
1.2'
1.1 • i • | • i
• 20 40 60 80
PTFE concentration/ %
Fig. 5. Relative intensity of the symmetric C - O - C stretching
mode of PEEK-PTFE blends as a function of PTFE concentration
[36].
PEEK as this composition appears to produce the
most generally effective bearing material where this
blend is used in engineering applications [37].
11. Conclusions
Crystalline polymers possess a number of charac-
teristics which have been examined using Raman
spectroscopy. In this review it has been demonstrated
that the technique may be used to assign characteris-
tic modes of vibration to the amorphous and crys-
talline regions of certain polymers. Additionally,
trans and gauche conformations of polymer chains
may be differentiated. Long-range order, particularly
that associated with lamellae, may be studied using
LAMs observed in the low-frequency region of the
Raman spectrum. Crystal packing may be examined
and the number of chains per unit cell can be deter-
mined. Tacticity and its relationship with crys-
tallinity have been investigated. The effect of ther-
mal history on the crystallinity of some polymers has
been examined using Raman spectroscopy. Polymer
samples may also be observed at different tempera-
tures and thermally induced crystallisation in poly-
mers has been investigated. In particular, well-estab-
lished thermal transitions have been identified for a
number of polymers. Solvent-, pressure-and stress-
induced crystallisation have also been examined in a
number of studies. Finally, the effect of copolymeri-
sation and blending with other polymers have also
been investigated using Raman spectroscopy.
In summary, recent examples of the application of
Raman spectroscopy to the study of crystallinity in
polymers have been reported here. This review serves
to demonstrate the already wide application of the
technique and also the potential for the investigation
of a large number of established crystalline poly-
mers.
.
100
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