154 P. H.

Geil
2.2. Polyfbutylene terephthalate)
To the best of our knowledge, only one paper describes FT-IR studies of
the conformation of amorphous PBT. Yamato et al have reported FT-
IR results for the effect of sub-T^ annealing [96]. The physical aging is
accompanied by the development of conformations similar to those in the
crystals, z.e., there is an intermolecular interaction, as in PET.
Several papers describing the crystal structure in oriented PBT fibers
were published in the 1970s [97-103]. Three of them [100-102] identified
two reversible, triclinic crystal structures for the relaxed and stressed PBT
fibers, -form and /3-form, with unit cell parameters for each of them. Jake-
ways et al. [100] suggested that the unit cell parameters for the stressed
/3-form differed depending on the strain conditions of the fiber during the
X-ray exposure. However, in a note added in proof, this suggestion was
withdrawn, newer results indicating that the c-axis dimension changed dis-
continuously from that for a (11.6 A) to a new reflection, corresponding
to c = 12.9 A at 4% strain; by 6% strain, the a spacing had disappeared.
There was then a slight increase in c, to 14% strain, after which it re-
mained constant. This phenomenon is very much like that for PET X-ray
fiber patterns for which the c-axis spacing is a function of processing history
[44,79,8O]. Therefore, it is believed that, like PET, there are no universal
unit cell parameters that can be said to be appropriate for all PBT /3-form
crystals under different strain conditions. On the other hand, upon removal
of the stress, PBT -form reverts to the relaxed a-form (more about the
polymorphic transition can be found in Chapter 21). All of the a-form
unit cell parameters reported are in fairly close agreement even though the
fibers had been stressed to different initial strains. These -form unit cell
parameters are listed in Table 2. A comparative study [104] suggested that
all of these discrepancies are within experimental error, and therefore a best
estimate of the a-form unit cell parameters was suggested by taking aver-
ages of all the published data together with an error spread to account for
Table 2. PBT a-form unit cell parameters
Mencik [98]
JoIy et al. [99]
Jakeways et al. [100]
Yokouchi et al. [101]
Hall and Pass [102]
Desborough [103]
Average [104]
Bornschlegl and Bonart [77]
Huo et al. [105]
Liu and Geil [106]

(A)
4.83
4.87
4.88
4.83
4.89
4.87
4.86
0.03
4.82
4.83
4.94
b
(A)
5.96
5.96
5.94
5.94
5.95
5.99
5.96
0.03
5.93
6.00
5.98
c
(A)
11
11
11
11
11
11
11
.62
.71
.65
.59
.67
.67
.67
0.06
11
11
11
.74
.61
.56
(deg)
99,
100,
98,
99,
98,
99,
99,
.9
.1
.9
.7
.9
.8
.7
0.6
100,
100,
99,
.0
.3
.8

(deg)
115.
116.
116.
115.
116.
116.
116.
,2
,6
,6
,2
,6
,2
,0
0.7
115.
115.
116.
,5
,0
,5
(deg)
111.3
110.3
110.9
110.8
110.9
110.9
110.8
0.5
111.0
111.3
111.15
P
a
c
(g/cm
3
)
1,
1,
1,
1,
1,
1,
1,
1,
1,
1,
.407
.396
.399
.404
.392
.392
.396
.403
.404
.397
Handbook of Thermoplastic Polymers: Homopolymers, Copolymers, Blends, 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 155
Figure 41. CTFMP PBT single crystals polymerized at 19O
0
C, 8h [106]
the variation in individual values. The averaged unit cell parameters, with
deviations for the a-form, as determined by Desborough and Hall [104],
are also listed in Table 2. It should be pointed out that these averaged unit
cell parameters, as well as all other data listed in Table 2, except for those
of Liu and Geil [106], describe the a-form crystal structure in PBT fibers,
since all these data were obtained from X-ray fiber patterns.
Micrographs of PBT lamellar crystals prepared by the CTFMP method
are shown in Figures 41 and 42a-c. At 19O
0
C for 8h, relatively large flat
lamellar crystals with smooth surfaces were grown (Figure 41) [106]. The
lamellar thickness is ca. 100 A with possible doubled layers in some regions
(arrows). Cracks similar to those here are common to most of our CTFMP
single crystals; they are believed to be due to differential crystal-substrate
thermal shrinkage when the lamellar crystals cooled down from the poly-
merization temperature. Like other CTFMP lamellar crystals, the surfaces
of these cracks are aligned in planes which are approximately parallel to the
phenyl rings. If the two sequential phenyl rings in a molecular chain are ro-
tated by a certain angle, such as the ca. 120 in poly(p-oxybenzoate) [107],
the cracks always bisect the smaller angle between the two phenyl rings
in the b projection. Electron diffraction indicates that the molecular
chains in these PBT single crystals are tilted to the substrate at differ-
ent angles, depending on polymerization temperatures and, possibly, local
concentrations (thicknesses) of the monomers before polymerization.
CTFMP of PBT at 21O
0
C resulted in large two-dimensional spherulites
composed of many ribbons or fronds which, in turn, are composed of many
thin (ca. 100 A) lamellae (Figure42a-c) [106]. Interestingly, it seems that
156 P. H. Geil
Figure 42. CTFMP PBT single crystals polymerized at 21O
0
C, 2Oh. A twinned
[ 0 1 0 ] ED pattern is inset in (c) [106]
Crystal Structure, Morphology, and Orientation of Polyesters 157
all of these fronds have backbones, making them very much like the fronds
of some plants. The thin lamellae overlap each other and grow along these
backbones with the lattice -axis aligned in the long direction of the fronds,
as indicated by ED patterns. ED shows that the molecular chains are also
tilted to the substrate in these crystals. An example of frequently observed
(010) twin ED patterns is shown in the inset in Figure 42c. These (010)
twins are very much like those in PET crystals [86], although they are
relatively less frequently observed in PBT crystals. The mechanism of for-
mation and the structure of the backbones, often buried under the lamellae,
are not yet clear.
By tilting the crystals in the TEM, six different zones of ED patterns
were obtained [106]. Typical patterns are shown in Figure43; the [ O i l ] ,
[ O i l ] , and [JlI] patterns are clearly tilted, resulting in the asymmetry. The
unit cell, modeled with Cerius
2
, is shown in Figure 44 with four projections.
The unit cell parameters, also listed in Table 2, were refined on the basis
of 14 independent reflections; they are similar to the averages reported by
Desborough and Hall [104], except for c and a. Our c is slightly shorter, pos-
sibly because of residual strain in the fibers used for X-ray studies, while
is larger. Figure 44d indicates that the phenyl rings with the two connected
ester groups are substantially planar, with the plane tilted at ca. 17.5 to
the c-axis. The glycol groups are rotated out of the phenyl ring plane in
the a-axis directions and have a gauche-trans-gauche conformation.
The simulated [001], [101], [SlJ], [OJl], [ O i l ] , and [JlI] ED patterns for
the "perfect" PBT single crystal are shown in Figure 45a-g. The calculated
[001], [101], and [SlJ] patterns (Figure 45a-c) of the "perfect" single crystal
reproduce well the corresponding observed patterns (Figure 43a-c) in terms
of both spacings and intensities. The spot size for the reflections in the
calculated patterns only approximately indicates the predicted intensities;
in order to show the weaker reflections, the more intense ones have been
"saturated" (comparisons of measured and calculated structure factors and
d-spacings are given in [106]). The simulated patterns for [OJl], [ O i l ] , and
[JlI] agreed in terms of spacings, but not of intensities, with the examples
in Figure 43; the difference was attributed to tilt of the patterns.
Although the unit cell parameters obtained from the ED patterns agree
well with X-ray-determined values, the conformation of the chain in the
crystal proposed by Liu and Geil [106] differs from that proposed ear-
lier [98,101,102,108]. The differences, primarily in the ethylene glycol unit,
were attributed to differences in the equations, intensity scaling factors,
and atomic radii used; in the conformation proposed by Liu and Geil, the
C-C-C-C bonds are gtg, with the g torsion angles being 50; for the other
proposed conformations, the angles were ca. 78 [102], 68 [101], and
-88 [98,108], i.e., far from the normal "gauche" angle of 60.
Changes in the -form parameters with temperature have been de-
scribed by Huo et al. [105]. The large c-axis expansion was attributed to
the low elastic modulus in this direction, due to the "kinked" conformation
of the tetramethylene unit. With the SAXS pattern also being measured at
158 P. H. Geil
133
Figure 43. PBT ED patterns from the CTFMP single crystals: (a) [ 0 0 1 ] , (b) [ 1 0 1 ] ,
(c) [ SIl]
9
(d) [ Oli\, (e) [ 0 1 1 \, and (f) [ ill] [106]
elevated temperature, these authors conclude that the thermal expansion
coefficient of the amorphous regions between the lamellae is three times
that of the c-axis.
As indicated, the -form lattice parameters vary with the strain on the
Crystal Structure, Morphology, and Orientation of Polyesters 159
(a)
'-0, 1/ 2
"0 0,1/2
./2
*
(c)
(b)
O
3
---4..
(d)
Figure 44. Proposed PBT -phase unit cell. The projection at the lower right
shows the coplanar phenyl ring and ester groups. The open circles in (a) are the
inversion centers for the symmetry [106]
160 P. H. Geil
(a)
[0011 (b) 10
(c)
[31]
(d)
LOlIJ
(e) '
lim
(f)
[ITl]
d " A-
1
Figure 45. Simulated ED patterns corresponding to the zones in Figure 43a-f
[106]
Crystal Structure, Morphology, and Orientation of Polyesters 161
Figure 46. Simulated /3-phase unit cell
proposed by Grasso et a l Asterisks in-
dicate centers of symmetry [109]
crystal. Figure 46 shows the Cerius
2
modeled -form unit cell, using the
lattice parameters from Grasso et a l. [109]. As indicated by comparison
of Figures 44 and 46, the transformation involves a straightening of the
tetramethylene glycol moiety. In the fibers, the c-axis is tilted 1.5 away
from the fiber axis, giving rise to displacement of the reflections above
and below the layer lines, similarly to the situation in PET (see, e.g., Fig-
ure 26a). These authors indicate that the a-form is energetically preferred
over the -form because of intermolecular packing contributions. Based
on work with copolymers, Muramatsu and Lando [110,111] indicate that
the transformation requires a high amorphous modulus, rather than being
crystallinity driven. Unit cell parameters from several reports are listed in
TableS.
Table 3. PBT /3-form unit cell parameters
Yokouchi et a l. [101]
Hall and Pass [102]
Desborough and Hall [104]
Grasso et a l. [109]

(A)
4.73
4.69
4.73
4.73
b
(A)
5.75
5.80
5.83
5.88
C
(A)
13,11
13.00
12.90
13.06
OL
(deg)
104.2
101.9
101.9
103.3

(deg)
120.8
120.5
119.4
119.8
7
(deg)
100.9
105.0
105.1
104.4

(g/cm
3
)
1.33
1.36
1.33
1.32
162 R H. Geil
Following suggestions by Lu and Spruiell [112], and Perry et a l. [113],
Roebuck et a l. have described a method of producing /3-form crystals that
are stable in the absence of stress [114]. They redrew pre-spun fibers and
tapes, quenching them after extension. Figures 47-50 show meridional scans
40 35
20 (deg)
30
Figure 47. Meridional X-ray diffraction scan of the as-spun fiber; a small amount
of /3-phase is present [114]
45 40 35 30
20 (deg)
Figure 48. Meridional X-ray diffraction scan of the fiber in Figure 47 after cold
drawing 2 x; substantial /3-phase is present [114]
Crystal Structure, Morphology, and Orientation of Polyesters 163
as a function of processing history for a high take-up speed as-spun PBT
fiber. The initial fiber consisted primarily of -phase crystals and was of
low crystallinity (Figure 47). Cold drawing 2 resulted in an increase in -
form crystals (Figure 48). Annealing of the as-spun fibers at 155
0
C for 21 h
resulted in the development of a high degree of crystallinity (Figure 49)
which was also converted to if the annealed sample was subsequently
cold drawn (Figure 50). /3-Phase crystal sizes in the annealed and then cold
106/3
104/3
45 40 35
20 (deg)
30
Figure 49. Meridional X-ray diffraction scan of the fiber in Figure 47 after an-
nealing at 155
0
C, 21 h; the sample is primarily -phase [114]
105
104
45 40 35 30
(deg)
Figure 50. Meridional X-ray diffraction scan of the fiber in Figure 47 after an-
nealing at 155
0
C, 21 h, and cold drawing 2x; substantial /3-phase is present [114]
164 P. H. Geil
104
Thru view "~
105
Edge view
104
010
445
0
C
10 20 30 40 50 60
Scattering angle (deg)
O 10 20 30 40 50 60 70
Scattering angle (deg)
Figure 51. WAXS scans of PBT films uniaxially stretched (width restrained) as
a function of stretch temperature, (a) Meridional scans; (b) equatorial scans [93]
drawn fibers were 44 and 30 A laterally ((01O) and (100) directions) and
31A in the 06 direction (nearly along c), i.e., considerably smaller than in
drawn annealed fibers or tapes in which the X-ray patterns were taken while
the samples were held under tension. Lu and Spruiell concluded that the -
form crystals could be stable if sufficiently small, with a length about twice
the diameter, and that they were poorly connected to the bulk polymer. A
model developed by these authors suggests that relaxation to the -form
would involve a smaller reduction in free energy than the increase due to
the deformation of the adjoining amorphous regions. However, they do not
describe the lattice parameters of these crystals.
Song [115] has recently described the relative amounts of a- and -form
crystals in samples drawn "uniaxially" at various temperatures while held
constrained in the lateral direction. As shown in Figure 51, when drawn 4
at 45
0
C, a sharp low-angle peak (11.69 A, the same as the -phase repeat
distance) as well as weak 04 and strong 06 /3-phase reflections appeared.
With increasing temperature of draw, the ^-spacing gradually decreased
to that of 001 (a) (Figure 52). The 100 spacing increased gradually from
Crystal Structure, Morphology, and Orientation of Polyesters
1.20
1.10
1.00
ooi
O
100
D
165
D
OH
0.39/
0.38
0.37
0.36
0.30
0.28
0.26
0.24
0.22
0.20
--

104
V 05
06/3

O- O
. , ,
50 75 100 125 150 OL
Temperature (
0
C)
Figure 52. Bragg spacings of lattice planes for 4 uniaxially drawn PBT films as
a function of stretch temperature [93]
that of the /3-phase to that of the -phase with increasing temperature
of draw, while the quadrant reflections remained essentially constant. The
pattern from the sample drawn at 45
0
C was interpreted in terms of a
smectic structure, suggested to be similar to the mesomorphic structure
of PET. The diffuse equatorial scattering up to a 9O
0
C draw temperature,
we suggest, implies a similar structure, although the diffuseness may also
be due to crystal imperfection, small size, and overlap of the and
reflections for the 100 and 010 planes, along with poor resolution by the
X-ray difrractometers.
The transformation has also been followed by Raman spectroscopy
[116]. No shifts in peak positions were observed up to 11% strain, but
166 P. H. Geil
780 800 820 840 860 880 900 920
Raman shift (cm"
1
)
Figure 53. Strain dependence of the Raman spectra of PBT during cyclic loading
(asterisks mean strain during unloading). The 808 and 885Cm"
1
bands (arrows)
are attributed to the gtg conformation (-phase) while the 798 and 856cm"
1
bands are attributed to the benzene ring [116]
changes in intensity did occur, with the bands in the 780-9OUCm"
1
region
showing the largest changes (Figure 53). The 808 and 885cm"
1
bands are
Crystal Structure, Morphology, and Orientation of Polyesters 167
attributed to the gauche-trans-gauche conformation of the glycol residue in
the a-form crystal, while the 798 and 856cm"
1
bands are assigned to ben-
zene ring modes [117]. The intensity of the 885Cm"
1
band, normalized by
that of the 856Cm"
1
band, changed linearly with increasing and decreasing
strain. Mak et al. [116] also showed small reversible increases in the 965,
1044, 1345, and 1405cm"
1
() bands, with corresponding small decreases
in the 1382 and 1450cm"
1
(a) bands. None of the bands totally disap-
pear in the relaxed sample nor do the bands disappear at 11% strain.
Roebuck et al. [114] also used the above Raman bands to characterize the
conformation in their samples and obtained similar results, with present
in the as-spun fibers and present in the stable beta sample. Roebuck et
al. reported similar results with FT-IR.
2.3. Polyftrimethylene terephthalate)
The recent development of economical methods for the production of 1,3-
propanediol has resulted in increased commercial interest in the produc-
tion and utilization, primarily as carpet yarn, of PTT (see also Chapter
12). We know of no reports on conformation or morphology of amorphous
PTT. Only one crystal structure has been reported, as determined by X-
ray diffraction. Values from several authors are given in Table 4, along with
values we described recently, obtained from several types of samples [118].
The results of Poulin-Dandurand et al. [119] were based on ED patterns
from solution-grown single crystals and X-ray fiber patterns. The results
of Poulin-Dandurand et al. [119] were based on ED patterns from solution-
Table 4. Unit cell data for poly(trimethylene terephthalate)
Poulin-Dandurand
et al. [119]
Desborough
et al. [120]
Tadokoro [121]
Hall [84]
(best estimates)
Wang et al. [122],
WAXS
(melt crystallized)
DuPont fiber
(WAXS) [118]
Bulk (180C/72h)
polymerized
(WAXS) [118]
ED (TEM) [118]

(A)
4.637
4.620
4.58
4.60
0.03
4.6(3)
4.42
4.57
4.53
b
(A)
6.266
6.200
6.22
6.22
0.01
6.1(2)
6.23
6.41
6.15
C
(A)
18.64
(fiber axis)
18.30
18.12
18.36
0.25
18.6(1)
18.75
18.65
18.61
a
(deg)
98.4
98.0
96.9
97.8
0.6
97.5
98.13
98.57
96.87

(deg)
93.0
90.0
89.4
90.8
1.9
92.1
91.24
91.45
92.21
(deg)
111.1
112.0
111.0
111.3
0.4
110
112.09
112.20
110.97
P
a
c
(g/cm
3
)
1.387
1.427
1.43
1.414 (unit cell)
1.35 (measured)
1.40
1.406
1.431
1.448