140 P. H.

Geil
tut. This phase transforms into triclinic when annealed at 80 or 10O
0
C,
depending on the aut hr. Auriemma et al [57] suggest the mesomorphic
phase differing from the intermediate phase in that the latter is present in
semicry st alline (triclinic) samples that have been annealed above 10O
0
C,
with the 10.3 spacing being absent. However, Wunderlich and co-workers
[44-46] report the presence of a 10.4 distance (fifth layer line) in their
intermediate-phase, partially cry st alline samples. Since in both types of
samples broad equatorial reflections are present, domains of liquid crystal
order are suggested. We thus conclude that the differences are more a result
of the processing conditions, leading to formation of such domains and their
resultant morphology. Clearly, there is need for further research (see also
Chapter 4).
2.1.2. Conformation in the cry stalline phase; crystal structure
Since PET is the first and still most commercially important polyester, its
crystal structure has been intensively studied for more than 50 years (e.g.,
[17,24,44,54,55,67-86]). The earliest report on the unit cell dimensions of
PET was in 1946 by Astbury and Brown [67], measured from X-ray ber
diffraction photographs. Later, in 1954, using better oriented specimens,
Daubeny, Bunn, and Brown [17] observed additional reflections which did
not fit Astbury and Brown's cell. Another unit cell, now considered the
conventional unit cell for PET and often described s Bunn's cell, was sug-
gested, hving = 4.56, b = 5.94, c = 10.75, a = 98.2, = 118,
and 7 = 112, with a calculated crystal density of p
c
= 1.455g/cm
3
. The
chain conformation and atomic positions in the crystals were also deduced
from the relative intensities of the X-ray reflections. Ten years later, in
1964, Tomashpolskii and Markova [70] used electron diffraction to obtain
patterns from solution-cast PET films that had been stretched 700% and
subsequently heated at 18O
0
C, and proposed similar, but slightly different
cell parameters (see Table 1). At about the same time, Yamashita reported
the morphology of PET folded-chain, single, solution-grown crystals, but
only obtained [101]* ED patterns [71]. In 1975, Fakirov et al [72] rechecked
the unit cell dimensions using X-ray diffraction from 5.5x drawn samples of
l mm thick "amorphous" bristles annealed taut for 6 h at various tempera-
tures between 100 and 26O
0
C; these authors suggested another set of unit
cell parameters with a higher calculated density of the crystalline phase
(pc = 1.515 g/cm
3
) for samples annealed above 14O
0
C and a slightly larger
cell for lower annealing temperatures (p
c
= 1.484 g/cm
3
at 10O
0
C). They
also suggested the presence of "highly distorted paracrystalline nuclei" dur-
ing low temperature stretching based on an X-ray pattern similar to that
for the mesomorphic phase.
*Use is made of italics, i.e., [hkl] in this chapter to represent zones in ED patterns
t o prevent confusion with the use of [xxx] t o represent references.
Handbook of Thermoplastic Polymers: Homopolymers, Copolymers, Elends, and Composites
Edited by Stoyko Fakirov
Copyright 2002 WILEY-VCH Verlag GmbH, Weinheim
ISBN: 3-527-30113-5
Crystal Structure, Morphology, and Orientation of Polyesters 141
More recently, Kitano et ai. [81] reported a highly crystalline PET sam-
ple, obtained by annealing stepwise under vacuum up to 29O
0
C for a period
of ca. 2 years after direct esterification. Using X-ray diffraction, they re-
ported the same unit eeli parameters, with p
c
= 1.501 g/cm
3
for this highly
crystalline PET, as they had reported for a fiber sample in 1979 [76], but
now with a high melting point of 302.5
0
C (the usually reported T
7n
is ca.
26O
0
C). The reflections in all their diffraction patterns were arced, sug-
gesting that these "highly crystalline PET" samples were still far from a
"perfect" single crystal, despite the extended annealing treatment at high
temperature. As indicated by the different sets of unit eeli parameters listed
in Tablel, "the" unit eeli of PET is not as well defined as that for many
low molecular weight materials; the effect of the variations can most easily
be seen in the values listed for p
c
.
The Variation in unit eeli parameters is clearly not due to experimen-
tal errors, but must be attributed, primarily, to variations in sample his-
tory. It has been reported that the unit eeli parameters of PET crystals
vary with crystallization temperature, draw ratio, and subsequent anneal-
ing temperature and time. For instance, Fakirov et ai. [72] showed that
the d-spacings varied slightly for annealing temperatures between 100 and
26O
0
C. When a drawn, amorphous bristle was annealed taut at 10O
0
C, the
010, 100, and 011 spacings were larger than those for samples crystallized
at higher temperatures while the c-axis spacing was the same (10.75).
The p
c
for 10O
0
C and 25O
0
C crystallized PET samples were calculated as
being 1.484 and 1.515 g/cm
3
, respectively. The latter value was also ob-
tained for an undrawn PET film annealed at 25O
0
C. Fakirov et ai. point
out the problems in determining the crystallinity of a PET sample from
density measurements if the density of the crystal varies with processing
history (see also Chapter 7). Wakelyn ([78], not listed in the table since nei-
ther the c-axis spacing nor angles were determined) found different (100)
and (010) spacings for fibers and films, while Sauer et ai. [83] reported
a difference in these spacings during elongation. Wakelyn suggested that
Tomashpolskii and Markova's eeli is applicable to PET films, and the eeli
of Daubeny et ai. refers to PET fibers. Sun et ai. [80] have reported the
unit eeli parameters of stress-induced PET crystallites in solid-state extru-
dates (coextruded amorphous PET samples, a method similar to channel
die extrusion, resulting in uniaxial extension of solid samples) as a function
of extrusion draw ratios from 3.5 to 4.4, at extrusion temperatures of 70
and 9O
0
C. They found that the higher the extrusion draw ratio, the larger
the c value, the shorter the and b values, and the smaller the unit eeli vl-
ume. Sun et ai. density values are considerably lower than those reported
by others. For the highest elongation, the c dimension is nearly 10% larger
than that in the Daubeny et ai. eeli. On the other hnd, when extruded at
5O
0
C, no crystallinity developed for any draw ratio, with 50% of the mate-
rial hving a "mesophase" (oriented amorphous) structure, the remainder
being isotropic. They do not comment on the presence of mesophase in the
samples extruded at 70 and 9O
0
C.
142 R H. Geil
Table 1. PET unit cell parameters
Astbury, Brown [67]
Daubeny, Bunn, Brown [17]
Tomashpolskii, Markova [70]
Fakirov etal. [72]
Bornschlegl, Bonart [61]
Hall [84]
Heuval, Huisman [85]
Kinoshit a, Kitano et al [76,81]
Sun, etal.
b
[80]
Thistlethwaite
c
etal. [82]
Zhang etal.
d
[79]
Fu etal. [44]
Liu, Geil [86]

(A)
5.54
4.56
4.52
4.48
4.44
4.52
4.48
4.50
4.46
4.46
4.42
4.48
4.43
4.37
4.54
4.53
4.81
4.77
4.68
4.64
4.64
4.61
4.5609
4.5221
4.5087
4.62
b
(A)
4.14
5.94
5.98
5.85
5.91
5.92
5.88
5.90
6.06
5.89
5.93
5.98
5.93
5.87
5.87
5.87
6.14
6.08
5.92
5.90
5.87
5.82
5.9531
5.9214
5.8818
5.92
c
(A)
10.86
10.75
10.77
10.75
10.67
10.70
10.71
10.76
11.29
11.31
11.43
11.38
11.45
11.57
10.71
10.73
11.10
10.95
10.79
10.70
10.63
10.51
10.7605
10.7792
10.7873
10.68
Oi
(deg)
107.
98.
101
99.
100.
99.
100.
100.
99.
98.
98.
99.
99.
100.
99.
99.
99.
97.
95.
94.
93.
93.
99.
99.
100.
99.
.5
.5
.5
.1
.8
.1
.3
.5
.5
.6
.0
.8
.1
.1
.6
.2
.6
.1
.2
.9
.8
.85
.96
.01
.8

(deg)
112.
118
118
.2
118.4
117.
117.
117.
118.
114.
113.
114.
114.
113.
113.
119.
119.
118.
119.
119.
119.
119.
119.
118.
118.
118.
127.

.5
.9
.6
.5
.7
.6

.8
.4
.2
.6
.7
.2
.3
.5
.6
.9
.20
.08
.36
.6
(deg)
92.
112
111
111.
111,
111,
110,
110,
111,
112,
112,
114,
113,
111,
110,
110,
111,
112,
113,
113,
113,
114,
111,
111,
110,
104,
.23
.3
.8
.4
.7
.8
.9
.0
.7
.0
.8
.4
.1
.6
.7
.3
.1
.7
.9
.7
.37
.19
.56
.9
Pc
(g/cm
3
)'
1.471
1.455
1.479
1.515
1.515
1.479
1.501
1.501
1.338
1.351
1.367
1.359*(1.
1.381*(1.
1.357
1.486
1.501
1.312
1.353
1.421
1.454
1.473
1.533*(1.
1.465
1.479
1.487
1.578
l
.33)
.35)
.52)
a
)The density values have been calculated from the parameters listed in the references.
In several cases, indicated by an asterisk, they differ from those given, in parentheses,
by the authors. In those cases we suggest an error in the listed cell parameters.
b
)The values listed are, successively, for samples extruded in the solid state at 7O
0
C,
extrusion ratios 3.5, 5.0 and 6.0 and at 9O
0
C, extrusion ratios 3.5, 6.0 and 10.0, s listed
in [79]. This differs from [8O].
c
)The values listed are for an annealed film with initial draw ratios of 5.4 and 6, respec-
tively.
d
)The values listed are, successively, for an unset fiber and after annealing taut at 130,
160, 190, 22O
0
C for 15 min and 22O
0
C for 4 h.
Of particular interest relative to the relationship between internal stress
and unit cell parameters in PET bers is a later paper by Zhang et al.
[79]. For a high speed spun PET ber, a crystal density of 1.31 g/cm
3
was
determined, increasing with annealing temperature and time, s shown in
Table l, to 1.52 g/cm
3
when annealed at 22O
0
C for 4h. These authors also
examined the diffuse scattering (amorphous) peak centered at 20 = ca. 22
Crystal Structure, Morphology, and Orientation of Polyesters 143
(4) in solid-state extruded PET, as a function of extrusion ratio at 5O
0
C.
With increasing draw ratio, the width of the peak decreased, thus indicating
that not only the crystalline scattering, but also the amorphous scattering
varies as a function of processing history.
In a recent, comprehensive work, the relation between the unit eeli di-
mensions of crystallites in PET bers and the processes of annealing and
tension during annealing has been reported by Fu et ai. [44] (see also [46])
utilizing the full-pattern ber X-ray diffraction refinement also used for
characterization of the anisotropic amorphous (intermediate) phase dis-
cussed above. Both the structure and morphology were found to be depen-
dent on the heat and tension treatments. All of their unit eeli parameters
are also listed in Table 1.
It is clear, as has been pointed out by a number of the above authors,
that there are no universal unit eeli parameters which can be said to be
appropriate for all PET crystals prepared by different procedures. During
the manufacturing of PET fibers and films, the internal strain apparently
can affect the dimensions of the unit eeli, and the PET crystals in many,
probably all, of the samples cannot be in an equilibrium state. Thus, it
would be of interest to know the crystal structure and morphology in a
"perfect" PET single crystal under equilibrium conditions. By comparing
a specific PET crystal structure with the "perfect" PET unit eeli, one
might then estimate how much deformation or residual internal stress is
introduced by a specific manufacturing procedure. Solution crystallization
of PET single crystals might be a method to grow "perfect" crystals, with
electron diffraction then being appropriate for characterizing the crystal
structure. Although such crystals have been grown, they have not yet been
used for crystal structure determination; only single zone ED patterns have
been obtained. In addition, one has to keep in mind that PET (at least the
commercial one) is a copolyester containing some amount of diethylene
glycol, which strongly affect s its structure, although this would not cause
the differences observed for the same initial sample prepared by different
subsequent processing techniques (see also Chapter 7).
As indicated above, although X-ray diffraction characterization of poly-
mer conformation (in crystalline regions) is aided by the use of fibers, it
stiil requires development of a model from which calculated intensities of
the reciprocal lattice "points" are compared with those measured. The X-
ray fiber pattern corresponds to the rotationally averaged projection of
the reciprocal lattice, with rotation about c (rather than c*, which compli-
cates the determination of crystal structures of triclinic and monoclinic unit
eelis). We have contended for some time [87] that if appropriate samples
are available, electron diffraction is a better method (simpler to Interpret
than X-ray diffraction) of determining crystal structure either by itself or at
least in conjunction with X-ray diffraction. The potential of using ED has
been greatly enhanced recently by Dorset's development [88,89] of ab initio
direct phasing of the ED patterns, allowing direct calculation of electron
144 P. H. Geil
density projections. For general discussions of the application of electron
diffraction to crystal structure determination see [90,91], with a number of
papers on its application to synthetic and natural macromolecules in [92].
If appropriate samples are available, the advantage of electron diffrac-
tion is that single-crystal or, if necessary, ber diffraction patterns can be
obtained. The single-crystal patterns are displays of the intensity distribu-
tion on a single plane (or zone, due to the flatness of the sphere of reflection,
resulting from the small value of ) of the reciprocal lattice from which,
using Dorset's technique, the electron density of the unit cell projected on
the corresponding real space plane can be calculated. On the other hand,
with the Simulation techniques using, e.g., Cerius
2
, the calculated inten-
sities can be compared directly with the measured ones, with the results
of small changes in conformation, packing, and various types of disorder
being "immediately" visualized. However, the easy application of ED to
crystal structure determination is restricted by the need for "appropriate"
samples; methods of sample preparation are described in [6]. Needed for
crystal structure characterization are: (i) preferably single crystals with
lateral dimensions of the order of at least l (to yield sufficient intensity
within the lifetime of the crystal, as determined by beam damage and to
permit Isolation by selected area apertures) and ca. 100 thick (to reduce
or eliminate dynamic (double) diffraction). (ii) If single crystals are not
available, fibers (usually sheared films) can be used. Generally, these are
annealed t o develop as high crystallinity as possible, but still usually yield
only rotationally averaged patterns. The advantage over X-ray patterns is
that the flatness of the sphere of reflection permits obtaining 00/ reflections
(meridian), as well as the averaged hkO and hkl (equator and quadrant)
reflections, without tilting the sample, (iii) For most studies, it is required
that the samples used are representative (same crystal structure) of the bulk
samples of interest (fibers, films, or molded objects). This can be done by
comparison with X-ray results. The single-crystal samples are often more
perfect and may have different packing. For instance, parallel chain packing
in crystals grown by simultaneous polymerization-crystallization, antipar-
allel chain packing in folded chain crystals, and statistically random chain
direction in drawn fibers and films are to be expected, with different chain
conformations in all three. In addition, the presence of the folds on the
surface of folded-chain lamellae, whether "tight" (regulr adjacent reentry)
or loose loops, may affect the unit cell parameters in comparison with the
crystals in extended-chain fibers.
PET single crystals were grown from dilute solution by solvent (ni-
trobenzene, diphenyl ether, or a diphenyl ether/phenol mixture) evapora-
tion a number of years ago by Yamashita [71]. However, only five indepen-
dent reflections were observed in a [101] ED pattern. The PET crystals
were seen t o consist of platelets about 100 thick, and the chain molecules
were inclined at about 25-35 to the normal direction of the basal plane
of the single crystals. An example, crystallized from dimethyl phthalate
Crystal Structure, Morphology, and Orientation of Polyesters 145
Figure 34. Solution grown,
folded chain single crystal of
PET crystallized from 0.005%
dimethyl phthalate solution by
solvent evaporation at 145
0
C
on glass (a) and by immersion
of a freshly cleaved NaCl crys-
tal in a 0.05% dimethyl phtha-
late solution at 12O
0
C for 5 min
(b). An ED pattern and its se-
lected area are shown in the in-
set in (b), the strong reflections
being 110 and lil; 105 was
very weak (arrow). The lamel-
lae are on edge in (b), with the
molecular axes lying at an an-
gle to the lamella normals [93])
by solvent evaporation, is given in Figure 34a [93]. Figure 34b shows PET
epitaxially crystallized on NaCl; the lamellae are on edge, with the ED
pattern indicating that the molecules are tilted within them. Although
these crystals could have been used with a tilting stage to obtain other
zones of reflections and thus the unit eeli parameters, that was not done.
146 P. H. Geil
(b)
Figure 35. CTFMP crystals of PET polymerized at (a) 20O
0
C, 10h and (b)
225
0
C, 6h. The inset ED pattern in (a) was obtained by tilting the crystal 27;
the surface roughness in the inset image was suggested to be due to sheared
molecular tilt [86]
105 was visible in the pattern in Figure 34b, but was extremely weak and
partially buried in the Pt shadowing ring, making it difficult to measure.
Recently, we described confined thin-film melt and solution polymerization
techniques (CTFMP and CTFSP) for preparing lamellar, single crystal
samples suitable for ED [94]. Initially applied to thermotropic liquid crys-
talline polyesters (for which lamellar single disclination domains, s well s
single crystals, were grown), it appears more broadly applicable to conden-
sation polymers in general, including copolymers (for a partial review, see
[95]). The CTFMP technique involves the simultaneous polymerization-
crystallization (in some cases, initially in the liquid crystal form) of the
monomers in a t hin film between glass cover slips; the result is extended-
chain lamellae, which, for reasons unknown s yet, are often ~100 thick,
regardless of polymerization times and temperatures. This technique has
been applied to prepare single crystals of all of the polyesters discussed in
this chapter.
Figure 35 shows micrographs and ED patterns of PET crystals prepared
by the CTFMP technique [86]. Since PET has a triclinic unit cell, if the
b real space plane is parallel to the Substrate, c will lie at a substantial
angle to the beam direction (which is normal to the Substrate), s well s
a* and & *. This appears to be the case for the PET crystals polymerized-
crystallized at temperatures between 100 and 215
0
C, with a representative
Crystal Structure, Morphology, and Orientation of Polyesters 147
. . .
* i
[001]
Hoi]
(a)
(b)
Figure 36. (a) [001] ED pattern from a PET CTFMP lamellar single crystal
polymerized at 225
0
C, 6h; (b) [101] ED pattern obtained by tilting a 20O
0
C,
10 h polymerized CTFMP lamellar single crystal [86]
200C/10h sample shown in Figure 35a. OnIy a few or no reflections could
be obtained without tilting the sample in t he microscope; t he sample was
tilted 27 for the pattern in the inset. On the other hnd, for the crystals
in Figure 35b, c is parallel to the beam, a* and fr* Iie in the plane of the
Substrate, and hkO ED patterns with several Orders of reflections were ob-
tained (Figure 36a). However, the thickness of these crystals, which consist
of numerous (twinned) lamellae lying at an angle to the Substrate, is such
that dynamic diffraction is occurring; the relative intensities of the various
reflections are "incorrect", and normal kinematic diffraction equations for
the relationship between intensity (amplitude) and atomic positions can-
not be used. Thus, thinner crystals, such s those in Figure 35a were used,
the crystals being tilted in the beam to obtain both [101] (Figure 36b) and
[001] zones. The Au rings in the pattern in Figure 36b were of the type
used for the in situ spacings calibration. Sixty (18 independent) reflec-
tions in a [001] ED pattern, and nearly twenty (7 additional independent)
reflections in a [101] pattern were obtained, sufficient to permit determi-
nation of the unit eeli parameters for a "perfect" PET crystal. Although
other zone patterns, e.g., [Hl], [102], [101], [114], [H% ]i were also observed,
fewer reflections could be seen than in the [101] pattern and thus they were
not used. Yamashita [71] also found (010) twinned [001] ED patterns for
lamellar crystals grown by solvent evaporation at 12O
0
C. Many more re-
flections are visible in the patterns from the CTFMP samples than from
the solution-crystallized samples.
In order to compare with "Bunn's" unit eeli [17], the [001] ED pattern
of the Bunn cell was simulated with the Cerius
2
program (see Figure 40).
148 P. H. Geil
Space group
Pl
, /2
"oO,l/2
Figure 37. Three projections of the "perfect" PET unit cell. The 8 Inversion
centers are indicated by the sniall open circles [86]
From a direct comparison, significant differences are found. The 7* in our
patterns is 62.5, while it is 60 in Bunn's cell; the d-spacing ratio cfoio/^ioo
is 1.6, while it is 1.44 in Bunn's cell.
Based on the ED results and the refined cell parameters, the chain
conformation for this "perfect" PET crystal was simulated by the Cerius
2
program with a Dreiding force field with three projections of the unit cell
shown in Figure 37 [86]. The phenyl ring and its two connected carbonyl
groups are substantially planar. This plane is tilted at ca. 7 to the c-
axis and the glycol group is rotated out of the phenyl ring plane. The
space group is PL In order to compare the structural differences between
our "perfect" PET single crystals and the crystals in oriented PET bers,
Crystal Structure, Morphology, and Orientation of Polyesters 149
7 = 106.6
7 =
112
.
(a) "Perfect" crystal Bunn's crystal
Figure 38. (a) ab and (b) (see next page) ac projections of Computer simulated
PET unit eelis based on the ED patterns and the unit eeli parameters of Daubeny
et ai [86]
Bunn's unit eeli, as a typical structure for PET fibers, was also simulated
as above; the results are shown in Figure 38 with several projections, based
on the Universal force field (see also Figure 29).
Comparing the "perfect" single crystal eeli with Bunn's cell [17], as
would be expected, there are no significant changes for the a, fr, and c di-
mensions, especially for b along which direction the planes of the phenyl
rings are aligned in the b projection. It is understandable that the a, fr,
and c dimensions are relatively stable, since the bond lengths and angles
changed little and the a, fr, c dimensions are primarily affected by chain
conformation. In an oriented PET fiber, the phenyl rings may be more
perfectly aligned in the b c plane when the sample is drawn, resulting
in smaller and larger c dimensions. On the other hnd, the angles, es-
pecially and 7, changed significantIy, with an almost 10 increase for
and a 7 decrease for 7 in the single crystal, compared to that in Bunn's
crystal. In the CTFMP single crystals, which are believed to be in an equi-
150 P. H. Geil
= 128.3
= 118
%
(b) "Perfect" crystal Bunn's crystal
Figure 38. (b)
Crystal Structure, Morphology, and Orientation of Polyesters 151
Figure 39. A diagram showing crystal deformation in PET fiber formation and
processing. The lengths of the arrows indicate the relative extent and direction
of the deformation during fiber draw [86]
librium condition without internal strain, the phenyl rings on two neighbor-
ing molecules in the -direction are more separated along the c-axis than
in Bunn's eeli, allowing a more Condensed packing in the single crystals. In
oriented fibers, the molecules are apparently brought, by the processing,
to positions in which phenyl rings on two neighboring molecules in the a-
direction are closer to each other, which can be balanced by the decrease of
the angle 7, the plane of the phenyl ring also tilting closer to the c-axis. A
diagram showing the proposed lattice deformation in PET fiber processing
is given in Figure 39; the lengths of the arrows indicate the relative extent
and direction of the deformation. This type of unit eeli deformation is easy
because of the low symmetry of the single-chain, triclinic unit eeli.
For comparison with experimental data, simulated [001] and [101] ED
patterns for the "perfect" PET single crystal and a simulated X-ray fiber
pattern with a 3 half-width orientation are shown in Figure 40a-c, where
the corresponding patterns for the Simulation of Bunn's cell are also in-
152 R H. Geil
Figure 40. The simulated (a) [001], (b) [101] ED, and (c) X-ray fiber patterns for
both the "perfect" PET crystals and Bunn's crystals [86]
Crystal Structure, Morphology, and Orientation of Polyesters 153
cluded. In Figure40a, the calculated [001] ED pattern of the "perfect"
single crystal reproduce well the observed [001] pattern (Figure36a). The
spot size for the reflections in the calculated patterns approximately indi-
cates the predicted intensities; numerical values of the calculated intensities
are giyen in [86]. Reflections 030, 030, 040, 040, 150, 150, 210, 120, 300,
300, 320, and 320 in the calculated [001] ED pattern match the experimen-
tal observations, while they are absent or have very small intensity values
in the calculated [001] ED pattern for Bunn's eeli. The two parameters
mentioned above for the single crystal [001] ED pattern are 7* = 62.5
and spacing ratio d
0
io/dioo = 1.6 in the calculated pattern, in excellent
agreement with experimental data. The calculated [101] ED pattern for
the PET single crystal is also in good agreement with the observed pattern
both in spacings and reflection intensities. The reciprocal angle between
the 212 and 010 planes is 87.5 in the calculated and observed patterns
for the single crystal while it is 90.7 for a Bunn eeli. The spacing ratio
is diQi/din = 1-04 for the single crystal and simulated pattern while it is
0.99 for Bunn's cell.
Significant differences were also found between an experimental X-ray
PET fiber pattern (see, e.g., [18]; here we use our simulated X-ray fiber
pattern based on Bunn's crystals) and our calculated X-ray fiber pattern
of the "perfect" crystalline PET [86]. In the calculated X-ray fiber pattern
for the "perfect" PET, compared to the one based on our Simulation of
Bunn's cell, the 105, 003, 111, and 002 reflections are much more distant
from the meridian, while the 205, 103, 113, and 112 reflections are much
closer to the meridian (Figure40c). The intensities of 103, 113, 205, Oli, and
1 are also much stronger for the "perfect" crystal. In addition, reflections
104, 014, 013, and 210 are absent in the "perfect" crystal pattern, while
213 and 102 are absent in an experimental fiber pattern.
As discussed above, a mesomorphic "crystal structure" has also been
described for PET, produced by deforming the presumably amorphous
polyester below T
9
. Although initially described by Bonart [53] as hv-
ing a 10.7 physical repeat, consisting of all trans, extended conforma-
tion chains, more recently the repeat has been said to be 10.3 , with
the ethylene unit being at almost right angles to the chain backbone. We
have not been able to find an explanation for this discrepancy. Probably,
Bonart's original description (as a smectic structure [53]) is stiil reasonable,
with broad equatorial (d = 4.6, 4.3, and 4.OA) reflections being reported
for some samples, and the 4.6 reflections being slightly off the equator
because of molecular tut in the drawn samples. This structure is trans-
formed into the triclinic cell when annealed slightly above T
9
. An oriented
or anisotropic amorphous material (intermediate phase) has also been de-
scribed as consisting of part of the amorphous component of oriented, par-
tially crystalline samples; the difference has been related to the visibility of
the meridional 001' and 003' reflections, as well as to different processing
histories [45].