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Polymer 52 (2011) 6097e6109

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Polymer
journal homepage: www.elsevier.com/locate/polymer

Crystal structure and disorder in Poly(L-lactic acid) d form (a0 form) and the phase
transition mechanism to the ordered a form
Kaewkan Wasanasuk, Kohji Tashiro*
Department of Future Industry-oriented Basic Science and Materials, Graduate School of Engineering, Toyota Technological Institute, Hisakata 2-12-1, Tempaku,
Nagoya 468-8511, Japan

a r t i c l e i n f o a b s t r a c t

Article history: Crystal structure of poly(L-lactic acid) (PLLA) a0 form (or the newly-termed “d” form) has been analyzed
Received 10 July 2011 on the basis of the X-ray diffraction data. The oriented d form was obtained by stretching and annealing
Received in revised form the melt-quenched sample at ca. 100  C. The unit cell parameters were a ¼ 10.80 Å, b ¼ 6.20 Å, c (fiber
14 October 2011
axis) ¼ 28.80 Å and a ¼ b ¼ g ¼ 90 . As seen from the lack of even-numbered 00l reflections (002, 004, ..)
Accepted 22 October 2011
Available online 28 October 2011
except the 0010 reflection, the chain conformation of the d form was found to be more remarkably
disordered than that of the regular a form. As already reported, the a form takes the (10/3) helix with
approximately 21 screw symmetry although, more strictly speaking, this screw symmetry is not actually
Keywords:
Poly(L-lactic acid)
existent. The d form does not possess any symmetry along the chain axis although the local torsional
Disordered a form angles are not very much different from each other. As for the chain packing structure, the two different
Crystal structure analysis possibilities were assumed in the structural refinement procedure: (i) the corner and center chains direct
upward and downward along the chain axis, respectively, just like the case of regular a form (alternate
packing mode) and (ii) the upward and downward chains are located at the same lattice site at 50%
probability (statistically-disordered packing mode). The structure analysis using the Bragg reflections
suggested the preferability of the model (i). The diffuse and streaky lines were observed along the layer
lines, originating from the relative-height disorder between the neighboring chains in the d form. The
X-ray diffuse scatterings coming from the various types of the disordered structure have been simulated,
among which the disordered multi-domain structure model was found to be the most plausible model,
where the domains constructed by the alternate arrangement of upward and downward chains are
gathered together with the mismatch in the relative height between the neighboring domains. In this
way the disorder-to-order phase transition from the d to a form was found to occur through the
conformational ordering of the chains accompanied with the chain packing regularization as well as the
matching of the neighboring domain height to give a large single domain of the a form.
Ó 2011 Elsevier Ltd. All rights reserved.

1. Introduction the two distorted (10/3) helical chains are packed in the orthogonal
cell of space group P212121, where the (10/3) chain indicates the 10
Poly(L-lactic acid) (PLLA) (e[eCH(CH3)COOe]ne) shows the monomeric units are included in the fiber period and the helix
various types of crystal modifications (a, b, and g forms) depending turns 3 times in this period. One upward chain and one downward
on the crystallization conditions [1e18]. The molecular chain chain are located at the center and corner positions of the unit cell,
conformation and the packing mode in the crystal lattice have been respectively, where the direction of the chain is defined along the
proposed for these crystalline forms on the basis of X-ray and C(CH3)eC(¼O)eO sequence. Approximately speaking, the molec-
electron diffraction data [1e13]. For example, the a form is the most ular chains had been considered to take the 21 screw symmetry
frequently obtained crystal modification when crystallized from along the chain axis, i.e., the 5 monomeric units are included in
the melt or annealed from the glass. The X-ray structure analysis a crystallographically asymmetric unit. However, more strictly
was reported by several researchers including us [1e13]. Basically speaking, the molecular chains are more or less deformed from the
21 screw symmetry and all the 10 monomeric units do not possess
any symmetrical relation between them as known from the more
* Corresponding author. Tel.: þ81 52 809 1790; fax: þ81 52 809 1793.
detailed analysis using the synchrotron X-ray diffraction data as
E-mail addresses: ktashiro@toyota-ti.ac.jp, ktashiro_001@yahoo.co.jp well as the 00l reflections [1e3,6,13]. A new idea has been intro-
(K. Tashiro). duced to interpret the 00l reflections. Several numbers of the unit

0032-3861/$ e see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.polymer.2011.10.046
6098 K. Wasanasuk, K. Tashiro / Polymer 52 (2011) 6097e6109

cells are gathered together to form the domain of a finite size. These layer lines cannot be detected clearly, and many reflections are
domains are aggregated together to form a crystallite but they are diffuse and broad and overlap with the continuous streak lines.
disordered in relative height between the neighboring domains. These streak lines suggest that the crystal structure of the a0 phase
That is to say, the PLLA a form is not necessarily created as a perfect might be a disordered crystal phase. But, no detailed analysis has
single domain structure but it consists of the aggregation of been reported so far about the crystal structure of the a0 form. The
coherent domains, which can reproduce the observed X-ray structural disorder may occur in both of the molecular chain
diffraction data reasonably. conformation and the chain packing mode. These structural infor-
The molecular chains of the crystalline form b takes the (3/1) mation should give us an important hint for the discussion about
helical conformation and they are packed in the trigonal lattice the phase transition behavior among the a, a0 and b forms. It should
[3,5,7]. These chains are packed with an orientational disorder be emphasized here that the a0 form is not simply the a form with
around the chain axis (frustration) as well as with the upward and some degree of structural disorder due to the imperfect packing
downward directional disorder along the chain axis. mode and the small crystallite size, as seen for many kinds of
Another type of crystalline modification was proposed on the polymer substances, but it is a crystalline form independent of the
basis of the several experimental facts [12e24]. For example, in the a form and it shows the discontinuous solid-state phase transition
isothermal crystallization process from the melt, the crystallization in a relatively narrow temperature region. In such a sense, it might
rate showed an abnormal maximum at the crystallization be better to use the other name like “d form” for “the a0 form” in
temperature Tc of 100e120  C [14,15,22]. The sample, which was order to avoid the confusion coming from the similar name, the
obtained by melt-quenching followed by annealing in this a form.
temperature region, showed the X-ray diffraction peaks broader
and small in number compared with those of the a form [12]. The 2. Experimental section
uniaxially-oriented sample, which was prepared by stretching the
unoriented sample at around 100  C, showed the diffuse layer lines 2.1. Samples
and some of them were too weak to detect as shown in Fig. 1. The
total number of the observed spot-like reflections is one order PLLA samples were purchased from Polysciences, Inc. The
smaller than that of the regular a form. Besides the reflection peak molecular weight was 700,000 g/mol with the polydispersity of 1.8.
positions were not necessarily the same as those of the a form, The thin films of ca. 40 mm thickness were prepared by casting from
indicating the slightly different unit cell parameters in these two the chloroform solution at room temperature. These films were
cases. The similar situation is seen also in the infrared and Raman melted at 220  C and cooled rapidly to 100  C and annealed for 2 h
spectra [12,23,24]. The spectral profile looks similar to that of the to obtain the unoriented d form. The oriented d sample was
a form, but the bands are broader as a whole and some bands are prepared by stretching the melt-quenched sample 4 times the
intrinsic to the d form. These diffuse X-ray diffraction and vibra- original length at 100  C followed by heat treatment at the same
tional spectral profiles changed discontinuously to those of the temperature for 2 h under tension. The oriented a form was ob-
a form when the sample was heated above 120  C [16,17]. From tained by heat treatment of the oriented d sample at 150  C for 1 h
these experimental evidences the PLLA sample crystallized below under tension.
120  C was concluded to be a new crystalline form independent of
the a form. This crystalline phase was named the a0 form as re- 2.2. X-ray diffraction measurements
ported in our previous paper [12,16]. On the other hand, the b form
is obtained by stretching the a form at a high draw ratio [25,26]. The 2-dimensional X-ray diffraction patterns were measured for
The transition from a to b form was reported to occur indirectly via the uniaxially-oriented samples at room temperature by irradiating
the transformation to the a’ form (a / a0 / b) although the detailed a graphite-monochromatized Mo-Ka X-ray beam generated from
structural transition behavior has not yet been clarified [27]. a Rigaku R-axis Rapid-II X-ray diffractometer equipped with
The purpose of the present paper is to analyze the crystal a cylindrical imaging plate camera as a detector. The temperature
structure of this new crystal modification, the a0 form. As dependence of the X-ray diffraction diagrams was measured by
mentioned above, the X-ray diffraction pattern of the a0 form is at setting the oriented d form into the home-made heater, which was
a glance similar to that of the a form. But the reflection profiles mounted on a goniometer head of a Rigaku R-axis VII X-ray
along the layer lines are different including the peak positions. diffractometer with flat imaging plate (Mo-Ka line). The tempera-
Then, the unit cell is also different from that of the a form. Some ture dependence of the meridional 00l reflections was measured in
a transmission mode using a Rigaku TTR-III X-ray diffractometer
where the Cu-Ka line was used as an incident X-ray beam.

2.3. X-ray structure analysis

The analysis of the observed X-ray diffraction data was per-


formed using a home-made software in the following way [28,29].
The peak positions (x, y) were read from the 2-dimensional X-ray
diffraction pattern recorded on the imaging plate film, from which
the cylindrical coordinates (x, z) in the reciprocal lattice system
were calculated and utilized for indexing the observed reflections
to determine the unit cell parameters. The integrated intensity
I(hkl) of each reflection was estimated by encircling the reflection
on the computer screen, where the background correction was
made also at the same time. The overlapped reflections were
separated by the curve fitting of the X-ray diffraction profiles traced
Fig. 1. Observed X-ray diffraction diagrams of uniaxially-oriented PLLA: (a) a form and along the x axis. The structure factors were calculated from the
(b) d form. thus-obtained integrated intensity data using an equation
K. Wasanasuk, K. Tashiro / Polymer 52 (2011) 6097e6109 6099

3. Results and discussion

3.1. Crystal structure analyses based on regular structure models

The 2-dimensional X-ray diffraction pattern of the uniaxially-


oriented d form is shown in Fig. 1 (b) in comparison with that of
the a form [Fig. 1 (a)]. At a glance the whole pattern of the d form is
similar to that of the a form, but the details are appreciably
different from each other as already mentioned above. More
detailed investigation reveals the following several points. The
observed reflections of the d form are broader as a whole compared
with those of the a form. The 3rd, 6th, 7th, and 10th layer lines
contain the relatively intense spots but the reflections appearing in
the wide angle region are extremely weak and diffuse. The 1st, 4th,
8th and 9th layer lines are as a whole diffuse and weak although
there are a few spot-like reflections overlapped together. Most of
the layer lines show the continuous streaks along the lines. High
Fig. 2. Observed X-ray 00l reflection profiles: (a) a form and (b) d form.

I(hkl) ¼ m∙L∙p∙A∙jF(hkl)j2, where m, L and p are the multiplicity,


the Lorentz factor and the polarization factor, respectively. The
absorption effect was ignored (A ¼ 1). The structure analysis was
performed using a Shelx program [30,31] installed in the software
wingx (version 1.80.05) [32] on the basis of the full-matrix least
squares method under the constraining conditions about some
structural parameters.

2.4. Computer simulation of X-ray diffraction patterns

The 2-dimensional X-ray diffraction pattern and the layer line


profiles were calculated using a commercial software Cerius2
(version 4.6, Accelrys Inc.) on the basis of the structure derived by
the X-ray diffraction analysis.

Crystal structure of PLLA α Form

δ Form model (i) δ Form model (ii)


(alternate up/down packing) (statistical up/down packing)

Introduction of Disorder

Disorder in relative Disorder in relative


height of domains height of chains
(A) (B)

Disordered structure models


(A-i) (A-ii) (B-i) (B-ii)

Crystal structure of δ form


(A-i)

Fig. 3. Flowchart showing the structural analysis route on the basis of the observed X- Fig. 4. Crystal structures of PLLA: (a) crystalline form a, (b) The model (i) and (c) model
ray diffraction data. (ii).
6100 K. Wasanasuk, K. Tashiro / Polymer 52 (2011) 6097e6109

contrast is seen in the X-ray diffraction pattern of the a form, which be seen in the observed X-ray 00l reflection profiles shown in Fig. 2
shows many intense and spot-like reflections and the streaks on as well as the X-ray diffraction profiles along the 6th and 7th layer
the layer lines become quite weak. The reflections of the 1st, 4th, lines (see Fig. 15 in a later section). In the case of the regular a form
5th, 7th, 8th layers etc. are also spot-like and strong in intensity. the 002, 004 etc. can be seen clearly, indicating the existence of the
Even the higher-angle reflections can be detected clearly. The 21 screw symmetry along the chain axis. But, more strictly
apparent similarity of the whole pattern between these two forms speaking, the odd-numbered reflections such as 007 and 009 can
indicates that they take the similar chain conformation as well as be also detected although the intensities are too weak. As already
the similar chain packing structure. But, the decisive difference can reported in the previous paper [13], it may be said that the chain
conformation of the regular a form basically takes the 21 screw
symmetry along the chain axis although some degree of deviation
Table 1
from the regular shape occurs more or less. Quite contrarily, in the
Atomic fractional coordinates and isotropic temperature factors of one chain in the case of the d form, the most remarkably observed reflection is 0010,
unit cell of PLLA crystalline form d. indicating simply that the 10 monomeric units are included in
x y z Uiso/Å2
a repeating period along the chain axis. A lack of 002, 004, 006 etc.
and the observation of 007 and 009 reflections indicate clearly the
O1(1)a 0.0253 0.0324 0.0714 0.20
C2(1) 0.0820 0.2330 0.1163 0.15 deformation of the chain conformation from the 21 screw
C3(1) 0.0839 0.4685 0.0971 0.15 symmetry. In this way the molecular chains of the d form are
C4(1) 0.0727 0.0562 0.0783 0.15 appreciably disordered in the conformation compared with the
O5(1) 0.1713 0.0892 0.0524 0.20 a form. In the next section we will describe the quantitative
O1(2) 0.0348 0.2385 0.0243 0.20
C2(2) 0.1633 0.0098 0.0059 0.15
structural analysis of the d form on the basis of the observed 2D X-
C3(2) 0.2872 0.0321 0.0214 0.15 ray diffraction pattern.
C4(2) 0.0749 0.0599 0.0340 0.15 The outline of the crystal structure analysis of the d form is
O5(2) 0.0235 0.1212 0.0509 0.20 shown in Fig. 3. At first the crystal structure of the d form was built
O1(3) 0.1217 0.1089 0.1303 0.20
up by referring to the crystal structure of the a form [13]. Then, the
C2(3) 0.0552 0.0392 0.0883 0.15
C3(3) 0.1145 0.2468 0.1075 0.15 structural refinement was performed by comparing the reflection
C4(3) 0.0114 0.0874 0.1266 0.15
O5(3) 0.0647 0.1606 0.1589 0.20
O1(4) 0.0077 0.0670 0.2257 0.20
C2(4) 0.0177 0.2938 0.1969 0.15 Table 2
C3(4) 0.1262 0.4010 0.2231 0.15 Comparison of observed and calculated structure factors of model (i) of pLLA d form.
C4(4) 0.0376 0.1194 0.2283 0.15
h k l jFoj jFcj Phase/
O5(4) 0.1010 0.2063 0.2623 0.20
O1(5) 0.0531 0.1312 0.3276 0.20 2 0 0 269.22 243.84 0
C2(5) 0.1541 0.0650 0.2976 0.15 4 0 0 24.44 25.41 0
C3(5) 0.2642 0.1680 0.3234 0.15 1 1 0 249.17 252.05 346.9
C4(5) 0.0413 0.0264 0.3287 0.15 3 1 0 59.15 52.72 356
O5(5) 0.0622 0.1651 0.3470 0.20 0 2 0 38.84 62.31 325.2
O1(6) 0.0760 0.0709 0.4288 0.20 2 2 0 11.25 12.94 357.4
C2(6) 0.0224 0.2029 0.3857 0.15 1 0 1 2.25 3.30 180
C3(6) 0.0157 0.4405 0.3954 0.15 0 1 1 32.71 29.57 262.9
C4(6) 0.0197 0.0327 0.4242 0.15 2 1 1 56.43 53.87 223.8
O5(6) 0.1136 0.0564 0.4536 0.20 1 0 3 23.12 23.78 0
O1(7) 0.0127 0.1716 0.5266 0.20 2 0 3 104.78 97.93 90
C2(7) 0.1170 0.1004 0.4916 0.15 1 1 3 100.03 84.92 125.9
C3(7) 0.2485 0.1231 0.5117 0.15 0 1 4 47.53 41.48 62.9
C4(7) 0.0207 0.0150 0.5261 0.15 2 1 4 3.74 3.46 133.4
O5(7) 0.0251 0.1727 0.5517 0.20 3 1 4 1.84 3.02 270.8
O1(8) 0.0793 0.0236 0.6297 0.20 0 2 4 2.37 2.26 39.1
C2(8) 0.1020 0.1120 0.5912 0.15 2 0 6 66.60 54.19 180
C3(8) 0.1735 0.3031 0.6127 0.15 3 0 6 43.33 66.26 90
C4(8) 0.0317 0.0113 0.6290 0.15 1 1 6 60.94 46.34 267.9
O5(8) 0.1095 0.1131 0.6564 0.20 2 1 6 30.33 43.54 170.5
O1(9) 0.0363 0.1710 0.7250 0.20 3 1 6 34.84 42.26 213
C2(9) 0.0584 0.2071 0.6988 0.15 4 1 6 51.01 46.85 129.4
C3(9) 0.1559 0.3193 0.7296 0.15 0 2 6 17.97 14.59 215.9
C4(9) 0.0169 0.0190 0.7296 0.15 1 2 6 47.96 53.83 215.7
O5(9) 0.0572 0.1141 0.7596 0.20 1 0 7 63.43 39.13 180
O1(10) 0.0895 0.0035 0.8262 0.20 2 0 7 33.09 36.95 90
C2(10) 0.1097 0.0364 0.7933 0.15 3 0 7 65.47 6.73 0
C3(10) 0.2098 0.0820 0.8222 0.15 1 1 7 32.20 45.31 30.3
C4(10) 0.0139 0.1230 0.8122 0.15 2 1 7 50.43 43.48 281.4
O5(10) 0.0421 0.2135 0.8478 0.20 2 0 9 10.92 17.71 270
a
1 1 9 16.83 22.28 24.4
The numbering of the atoms is shown below. For example, C3(2) indicates the 2 0 10 48.75 42.62 180
carbon atom of methyl group belonging to the 2nd monomeric unit in the repeating 3 0 10 66.82 35.25 90
period. 4 0 10 24.98 22.94 180
1 1 10 50.58 44.03 171.7
3 1 10 21.10 32.94 169.8
0 2 10 7.23 7.61 300.8
2 2 10 22.12 11.94 117.2
2 0 13 20.95 17.80 270
3 0 13 36.86 26.28 0
1 1 13 15.92 12.38 343.1
K. Wasanasuk, K. Tashiro / Polymer 52 (2011) 6097e6109 6101

intensities between the calculated and observed data. As another constant and the structural parameters were not changed anymore
possible structural model we introduce here the directionally- self-consistently. The final R factor was 19.8%, where the R factor is
disordered model in which the upward and downward chains are a measure of agreement between the observed and calculated X-
disposed at the same lattice site at 50% probability. As will be shown ray diffraction intensities and it is defined as below.
later, this type of statistically-disordered structure does not give the X X
streak lines but it affects the relative intensities of the Bragg R ¼ ðjjFobs j  jFcalc jjÞ= jFobsd j
reflections. In this way, we assume here the two kinds of crystal
structure: In the model (i) the alternately arrayed upward and The Fobs and Fcalc are the observed and calculated structure
downward chains are packed in the unit cell similarly to the a form. factors, respectively, and the summation is made over all the
Another one [model (ii)] is the statistical arrangement of the upward observed reflections. The unit cell structure of the model (i) is
and downward chains at the same lattice site at 50% probability. shown in Fig. 4 (b) in comparison with that of the a form [Fig. 4 (a)].
The atomic fractional coordinates of a single chain in the model (i)
are listed in Table 1. In Table 2 are compared the observed structure
3.2. Structure analysis of model (i)
factors with the calculated ones.
In Fig. 5 the skeletal torsional angles are compared between the
The 41 reflection spots were picked up from the observed X-ray
a and d forms. The torsional angles are deviated remarkably from the
diffraction pattern given in Fig. 1 (b), and their positions and inte-
regular uniform helix. The difference in torsional angles between the
grated intensities were evaluated. From the reflection positions the
a and d forms is not very serious, allowing us to say that these two
unit cell parameters were determined as below.
crystalline forms take the similar local structure along the chain
direction. In fact, the 002, 004, 006 and 008 reflections, which are
a ¼ 10:80 
A; b ¼ 6:20 
A and cðfiber axisÞ ¼ 28:80 
A
detected clearly in the a form crystal, disappeared almost perfectly
The cell parameters are a little different from those of the in the d form, and only the odd-numbered reflections were detected
regular a form (a ¼ 10.86 Å, b ¼ 6.16 Å and c ¼ 28.86 Å), in which the as shown in Fig. 2. The similar situation can be seen also about the 2-
2 chains are packed in the unit cell. To build up the initial model for dimensional X-ray diffraction pattern. Figs. 6 and 7 shows the X-ray
the structural analysis of the model (i), the molecular chain diffraction diagram and the layer line profiles simulated for the
conformation and the chain packing mode of the a form were model (i), respectively. In this calculation the crystallite sizes and
transferred as they were [13]. Since the total number of the Bragg lattice strains were assumed as follows: the a form: the crystallite
reflections observed for the d form was only 41, the constraining sizes La ¼ Lb ¼ Lc ¼ 200 Å, lattice strains εa ¼ εb ¼ εc ¼ 0.1%, the degree
conditions were introduced for the bond lengths and bond angles. of chain orientation ¼ 2 , and the isotropic temperature factor
The structure refinement was performed repeatedly by adjusting B ¼ 8 Å2 (common to C and O atoms); the d form: La ¼ Lb ¼ Lc ¼ 100 Å,
the skeletal torsional angles of the two chains in the unit cell. The εa ¼ εb ¼ εc ¼ 0.2%, the degree of chain orientation ¼ 3 , and B ¼ 10 Å2
isotropic temperature factor was assumed to be common to both of As seen in these figures, the relative intensities of some partic-
carbon and oxygen atoms and varied in the structural refinement. ular reflections show the remarkable difference between the a and
These processes were repeated until the R factor was almost d forms, consistent with the observed data.

Fig. 5. Comparison of molecular chain conformation between the crystalline forms a and d [model (i)].
6102 K. Wasanasuk, K. Tashiro / Polymer 52 (2011) 6097e6109

3.3. Structure analysis of model (ii)

The second structural model [model (ii)] was built up from the
model (i) shown in Fig. 4 (b). The upward and downward chains are
assumed to locate at a lattice site at 50% probability as shown in
Fig. 4 (c). The structural refinement was performed in a similar way.
The relative heights of the upward and downward chains were also
modified so that the calculated layer line profiles were in good
agreement with the observed ones as much as possible. The finally
obtained R factor was 22.0%. The 2D X-ray diffraction pattern and
the layer line profiles are compared with the observed data in
Figs. 6 and 7, respectively.
Judging from all of these results, it may be said that the model (i)
gives as a whole the better reproduction of the observed X-ray
diffraction data than the model (ii). However, the difference in R
factor is not very significant between these two models. At this
stage, therefore, we keep these two models as the most plausible
candidates of the basic structure of the d form.

3.4. Introduction of structural disorders

As immediately speculated from the diffuse scatterings along


the layer lines (Fig. 1), the structure disorder is needed to introduce
into these two models, which is the disorder in relative height
between the neighboring chains. Before the detailed analysis is
made, it may be good to check again the following several char-
acteristic points about the X-ray diffraction patterns of the d form.
Fig. 6. The calculated 2-dimensional X-ray diffraction patterns of uniaxially-oriented
PLLA d form: (a) model (i) and (b) model (ii).
(1) Some layer lines are appreciably hard to detect (for example,
the 1st, 4th, 5th, and 8th layers).
(2) The reflections of the 3rd, 6th, 7th and 10th layer lines have the
strong intensities.

Fig. 7. The comparison of X-ray layer line profiles observed for PLLA d form with those calculated for the models (i) and (ii).
K. Wasanasuk, K. Tashiro / Polymer 52 (2011) 6097e6109 6103

(3) The diffuse streaks are observed along almost all the layer lines. the chain axis. Poly(b-propiolactone) shows the totally continuous
(4) The higher-angle reflections are more diffuse and weaker. lines along all the layer lines, which was interpreted reasonably by
assuming almost perfect randomness in the relative height of the
As mentioned above, the streaks along the layer lines indicate neighboring chains [35]. This is to say, there is no structural
the disorder in the relative height of the neighboring chains. But, correlation between the neighboring chains, and so the observed X-
the diffuse X-ray diffraction patterns should be affected sensitively ray diffraction pattern is almost similar to that predicted for an
depending on the type of the disorder. We need to clarify the isolated chain. Poly-p-phenylene benzobisoxazole shows the
relation between the structural disorder and the corresponding X- characteristic X-ray fiber pattern, in which some of the layer lines
ray diffraction profiles, from which we may be able to assign the include both of the spot-like reflections and the continuous
most plausible type of disorder to the d form. intensity distribution, but the other layer lines are streak [36e38].
This characteristic pattern was interpreted reasonably in such
3.4.1. Various types of translational disorder a way that the neighboring chains are shifted by a fixed value
For example, polytetrafluoroethylene shows the spot-like (0.22c) along the chain axis but the plus/minus direction of shift is
reflections (and continuous distribution of intensity) on the 6, 7, 8 random. This type of disorder was called the registered disorder.
and 15th layer lines, but the 2 to 5th layer lines are totally contin- To know the systematic relation between the X-ray streak
uous when this polymer is heated up to 25  C [33,34]. The two patterns and the structural disorder of polymer chains, the various
types of disorder are introduced as the possible origins of streaky X- types of translational disorder model have been constructed and
ray patterns: the relative-height disorder of the neighboring helices the corresponding X-ray diffraction profiles were calculated. Only
along the chain axis and the orientational disorder of chains around one example is shown here. At first one large unit cell was built up,

Fig. 8. X-ray diffraction patterns predicted for the various kinds of disordered crystal structure of (4/1) helical chains.
6104 K. Wasanasuk, K. Tashiro / Polymer 52 (2011) 6097e6109

in which the 25 chains of (4/1) helical conformation were packed layer lines are strong and diffuse, corresponding to those of the
and the arbitrarily-chosen 12 chains were shifted along the chain isolated chain. Fig. 8 (h) is the case of an isolated domain consisting
axis in the various ways. The corresponding X-ray streak patterns of 16 chains. The X-ray pattern is similar to that of original regular
were calculated using the Cerius2 software as summarized in Fig. 8. pattern but with some diffuse lines. As the domain size becomes
For example, when these randomly chosen 12 chains are shifted larger, the X-ray diffraction pattern becomes sharper. Another type
by c/4 along the chain axis, the 0, 4 and 8th layer lines are spot-like of disorder is about the rotational orientation of the chains. If the
but the other layer lines consist of the overlap of spots and (4/1) helical chains are oriented randomly around the chain axis
continuous distribution of intensity. When the shift is c/3, the 0, 3, 6 with arbitrary angles, all the layer lines are streaky in addition to
and 9th layer lines are spots and the others are streaky. Similarly, if the spot-like Bragg reflections, but the degree of streak is not very
the 12 chains are shifted by c/2 randomly, the reflections on the significant compared with the case of translational shift along the
even-numbered layer lines are spot-like but the odd-numbered chain axis. We may summarize these simulation results as follows.
layer lines are streaky. In this way, if the translational shift is
made for randomly chosen chains by a fixed value (c/m), the layer Type (I): Higher degree of random translation along the chain
lines of m, 2m, 3m, . are spot-like but the other layer lines are axis gives the X-ray diffraction pattern similar to that of an
streaky. This type of Xeray diffraction pattern was observed for the isolated chain except the spot-like equatorial line. The streaks
above-mentioned poly-p-phenylene benzobisoxazole fiber, i.e., the along the layer lines become more remarkable. Extreme case is
registered disorder. In Fig. 8, we have also the X-ray diffraction seen for poly(b-propiolactone) [35].
patterns coming from the other types of disorder. For example,
Fig. 8 (e) is the case in which all the 25 chains in the unit cell are
randomly shifted along the chain axis, giving the streaky patterns
along all the layer lines. The whole pattern is similar to that pre-
dicted for an isolated (4/1) helical chain as shown in Fig. 8 (g).
Sometimes we have the crystal structure including both of the
upward and downward chains. If these chains are disordered in
relative height, of course, we have remarkably streaky layer lines as
likely the case shown in Fig. 8 (e). However, it is noticed here that if
the upward and downward chains are located statistically
randomly at the same lattice point without any random trans-
lational shift, then the X-ray diffraction pattern does not give any
streaks but the relative intensities of reflections change depending
on the relative height between the upward and downward chains.
An introduction of the translational disorder to these upward and
downward chains gives the streak lines. If the several chains are
packed together to form a finite domain and these domains are
gathered together to form a crystallite with some statistically
random translational shift along the c axis, then the X-ray diffrac-
tion pattern of Fig. 8 (f) is obtained. The X-ray diffraction pattern is
similar to that of the regular packing structure as a whole, but some

Fig. 10. Schematic illustration of the two structure disorder models: (A) the relative
Fig. 9. 2-dimensional X-ray diffraction pattern predicted for an isolated PLLA (10/3) height of the neighboring domains is randomly shifted, and (B) the relative height of
helical chain. the neighboring chains is randomly shifted.
K. Wasanasuk, K. Tashiro / Polymer 52 (2011) 6097e6109 6105

Type (II): Different from the case (I), the upward/downward


random shift of chains by a fixed value (c/m) results in the
streaks on the particular layer lines of m, 2m, 3m, etc.
Type (III): The disorder in relative height between the neigh-
boring domains gives also the streak layer lines, but the X-ray
diffraction pattern of the basic unit cell structure is kept
unchanged.
Type (IV): The rotational orientation disorder of chains gives
relatively weak streaks along all the layer lines.
Type (V): The aggregation of statistically-randomly-packed
upward/downward chains does not give any streaks along the
layer lines but the relative intensity of the Bragg reflections is
modified from the regularly-packed structure. The model (ii)
analyzed in the previous section corresponds to this case. Of
course, the random translational shift of the upward and
downward chains causes the streaky layer lines.

3.4.2. Structural disorder in PLLA d form


By referring to these simulated results, we may characterize the
structural disorder in PLLA d form. The observation of the intense
reflections on the 3rd, 6th, 7th and 10th layer lines comes from the
(10/3) helical conformation of the chains. In fact, an isolated (10/3)
helical chain gives the strong intensity distribution along these
layer lines as shown in Fig. 9. The type (II) disorder, which gives the
streaky lines on particular layer lines only, does not reproduce the
observation that all the lines are streaky. The type (I) disorder (the
random shift of the chains) and the type (III) simulation (the rela-
tive height disorder in multi-domains) are more suitable for the
reproduction of the observation that all the lines are streaky.
Then we introduced these two types of structural disorder into
the above-mentioned two crystal structure models (i) and (ii). One
is the disordered multi-domain model (A) as illustrated in Fig. 10
(a). A domain is constructed by the aggregation of finite number
of the unit cells, where the basic unit cell structure is kept
unchanged. These domains are gathered together with the relative
height disorder among the domains. The second type of disorder
Fig. 11. 2-dimensional X-ray diffraction diagrams calculated for the 4 types of disor- (B) is to shift the chains randomly in the unit cell with keeping the
dered structure of PLLA d form crystal: models (A-i), (A-ii), (B-i), and (B-ii) and for an
isolated single chain.
structural feature projected along the chain axis as shown in Fig. 10
(b). By combining the above-mentioned two models (i) and (ii) with

Fig. 12. X-ray layer-line profiles calculated for PLLA d form crystal models (A-i) and (A-ii).
6106 K. Wasanasuk, K. Tashiro / Polymer 52 (2011) 6097e6109

gives the 007 and 009 reflections in addition to the most intense
0010 reflection. The 002, 004, 006, and 008 were not detected at
all. This is quite contrast to the case of the regular a form, in which
the strong 002, 004, 006, 008 and 0010 reflections are detected
clearly in addition to the weak 003, 007 and 009 reflections. The
observation of odd-numbered 00l reflections indicates clearly the
breakage of 21 helical symmetry along the chain axis as already
discussed in the previous papers [1e3,6,13]. This tendency is
remarkable in the case of the d form. In this way the d form
possesses the appreciably deformed helical chain conformation. In
addition, we need to consider the effect of packing disorder on the
relative intensity of the 00l reflections [13]. The 00l reflections
were calculated for the two models (A-i) and (A-ii) as shown in
Fig. 13. Of course the profile of the model (A-i) is changed
depending on the degree of domain height disorder, but this model
seems to give better correspondence to the observed data as
a whole when compared with the case of the model (ii). In the
latter case the 002 and 004 reflections are detected with not very
negligible intensities. (In Fig. 13, the peak positions of the 007 and
009 and also other reflections are slightly deviated from the
observed positions. This might be due to the effect of small crys-
tallite. The total diffraction peak profile is determined by the
product of structure factor and Laue function. The Laue function
Fig. 13. The 00l reflection profiles calculated for the models (A-i) and (A-ii) in
comparison with the observed data (refer to Fig. 2). The calculation was performed profile becomes broader with a decrease in crystallite size,
using the following parameters: the crystallite size ¼ 100 Å , the lattice strain ¼ 0.1%, affecting the peak position sensitively after the multiplication with
B ¼ 8 Å2, and the domain size along the a axis ¼ 16e22 Å. The averaged shift of the the structure factor [39].)
neighboring domains was 0.15c along the c axis.
Here let us compare the degree of structural disorder between
the a and d forms. As mentioned above, the relative height disorder
the disorder types (A) and (B), we have four types of disordered between the neighboring domains is one of the major factors to
models; (A-i), (A-ii), (B-i) and (B-ii) as shown in Fig. 3. These four give the characteristic X-ray diffraction patterns. As shown in the
models may be described briefly as follows: (B-i) the random shift simulation of the X-ray diffraction patterns (Figs. 6 and 7), the
of two chains in the unit cell, (B-ii) the random shift of statistically- whole molecular chain shape is slightly different between them. At
packed up/down chains in the unit cell, (A-i) the random shift of the the same time, the crystallite size and lattice strain as well as the
domains consisting of the basic unit cell structure given in Fig. 4 (b), temperature factors are different between them. The half-width of
and (A-ii) the random shift of the domains consisting of the the observed X-ray reflection peaks was estimated for these two
statistically-disordered unit cell structure shown in Fig. 4 (c). Fig. 11 samples. The crystallite size was as below based on the Scherrer’s
shows the 2D-X-ray diffraction patterns calculated for these four equation.
models. The models (B-i) and (B-ii) did not give the X-ray diffrac-
tion patterns similar to the observed one. The X-ray diffraction a form ð200=110Þ300 
A; ð0010Þ170 
A
patterns calculated for the model (A-i) look better than those of the
model (A-ii), but the difference is not very significant.and the layer
d form ð200=110Þ100 
A; ð0010Þ75 
A
line profiles calculated for models (A-i) and (A-ii). The similar
situation can be seen also about the layer line profiles as shown in These values were not inconsistent with those used in the
Fig. 12. Then these two models (A-i) and (A-ii) are still kept here as simulation procedure mentioned in the previous section. The size
the two candidates of the disordered crystalline form d. of individual domains is difficult to estimate experimentally, but
Another important X-ray diffraction data to be checked is the d form should have smaller domains with random c-axial shift
a series of 00l reflections. As already mentioned in Fig. 2, the d form as already discussed above.

Fig. 14. Temperature dependence of X-ray diffraction pattern measured for PLLA d form in the heating process.
K. Wasanasuk, K. Tashiro / Polymer 52 (2011) 6097e6109 6107

In summary, judging from the comparison in X-ray diffraction


pattern with the observed pattern, the model (A-i) structure seems
the most plausible model of the d form although the conclusion is
still not very confirmative. The size of the domains is appreciably
smaller than those of the regular a form. Besides, the c-axial shift of
the neighboring domains is also more significant in the d form. The
structural transformation phenomena between the a, d and b forms
may be interpreted using these structural information, as will be
discussed in the next section.

3.5. Mechanism of phase transition between the a, d and b forms

The d-to-a transition is discussed at first. Figs. 14 and 15 show,


respectively, the temperature dependence of the 2D X-ray diffrac-
tion diagrams and that of the hk6 and hk7 reflection profiles
measured in the heating process starting from the d form. As the
temperature is increased, the broader layer-line reflections become
sharper and the streaks are also weaker. Important observation is

Fig. 15. Temperature dependence of hk6 and hk7 layer line profiles traced from Fig. 14.

Fig. 17. Temperature dependence of (a) X-ray 0010 diffraction profile measured for
PLLA d form in the heating process and (b) The profiles obtained after subtraction of
Fig. 16. Temperature dependence of X-ray 00l diffraction profile measured for PLLA the reflection component of the d form measured at room temperature. It should be
d form in the heating process. noticed that the 0010 peak positions of the d and a forms are different appreciably.
6108 K. Wasanasuk, K. Tashiro / Polymer 52 (2011) 6097e6109

that the relative intensity and peak position of the reflections on seen in Fig. 17 (b). This data shows definitely that the repeating
these layer lines are not the same between the d and a forms and period along the chain axis is different between these two modi-
that they change the position and intensity significantly in the fications and that the transition from the d to a form occurs
transition process. Rather some reflections decrease in intensity discontinuously at around 120  C.
during this transition. This is again an evidence why the d form The transition process based on the model (A-i) may be
should be identified as a crystalline form independent of the described as follows, as illustrated in Fig. 18 (a) As the temperature
a form. The temperature dependence of the 00l reflection profile is is increased, the thermal motion of the chains is activated. The
also in the same situation as seen in Fig. 16. The even-numbered molecular chain conformation is regularized and the chain packing
reflections become stronger as the d form transforms to the becomes tighter in the domains. At the same time the small
a form. The 0010 reflections of the a and d forms are detected at the domains shift along the c axis to adjust the relative height with the
different positions as shown in Fig. 17 (a). The peak changes the neighborhoods, and they merge into a larger and more regular
position apparently continuously with increasing temperature, but domain. Once the temperature approaches 110e120  C, some of the
this is due to the overlapping effect of these two peaks. In fact, the larger domains transform to the a form. The domains of the d and
subtraction of the d form reflection from the original profiles gives a forms coexist in the crystallite. As the temperature increases
the reflection peaks of the a form at almost the same position as furthermore, more domains transform to the a form domain and

Fig. 18. Schematic illustration of the phase transitions between PLLA a, d and b forms. (a) The thermally-induced d-to-a form transition through the regularization of inner structure
as well as the aggregation structure of multiple domains. The model (A-i) is used as the most reliable structure of the d form. (b) The thermally-induced d-to-a form on the basis of
the d form model (A-ii). The translational movement of the statistically-upward/downward chains must occur in the ab plane to reach the alternately packed structure of the
upward and downward chains in the a form. (c) The tensile-force-induced transition of the a form to the b form via the d form.
K. Wasanasuk, K. Tashiro / Polymer 52 (2011) 6097e6109 6109

merge into larger domain by shifting along the chain direction. chains at the same lattice site. Among these two models, the multi-
These larger a domains should change finally to a single domain, domain structure model has been concluded to be more preferable
but such an ideal transformation does not occur actually and some than the other one judging from the various situations including
domains are existent still with some relative height disorder, as the observed X-ray diffraction data and the transition mechanism
understood from the structure analysis of the a form reported in to the a form. The thermally-induced phase transition from the d to
the previous paper. a form can be interpreted reasonably by imaging that the trans-
As mentioned already, another plausible candidate or the (A-ii) lational motion of the thermally-activated molecular chains along
model might be less preferable judging from the poorer repro- the chain axis causes the coalescence of the neighboring small
duction of the observed X-ray diffraction data. In the structure domains into the larger domains of the a form. The transformation
model (A-ii), the upward and downward chains are statistically from the a form to the b form can be also interpreted reasonably by
located at the same lattice point. On the other hand the a form taking the transient existence of the d form into account. The
consists of the alternate arrangement of upward and downward application of a tensile force to the a form induces the breakage of
chains at the center and corner of the unit cell. In the transition the large domain into smaller domains as well as the conforma-
process from the d to a form, the upward and downward chains tional disordering, resulting in the appearance of the d form.
must migrate from the random positions to the regular positions Further stretching transforms the d form into the b form of (3/1)
(Fig. 18 (b)). The conversion between the upward and downward helical conformation.
directions of a chain is not impossible in some special polymer It should be noticed here again that the d form is a crystal
cases. For example, poly(vinylidene fluoride) (PVDF) form II can modification independent of the a form, and the d form transforms
change the up/down direction through the trans-gauche confor- discontinuously to the more regular a form as known from the
mational exchange [40]. The situation is different in the present observed X-ray diffraction data.
case of PLLA. Since the PLLA chain has a directionality [C(CH3)e
C(¼O)-O], such an up/down inversion through the conformational
exchange is impossible. Judging from these discussions, the model References
(A-ii) is not suitable for the reasonable interpretation of the d-to-
[1] De Santis P, Kovacs J. Biopolymers 1968;6:299e306.
a phase transition. It may be said here that the model (A-i) or the [2] Kobayashi J, Asahi T, Ichiki M, Okikawa A, Suzuki H, Watanabe T, et al. Appl
multi-domain structure consisting of the alternately packed Phys 1995;77:2957e73.
upward/downward chains should be the actual crystal structure of [3] Hoogsteen W, Postema AR, Pennings AJ, ten Brinke G, Zugenmaier P. Macro-
molecules 1990;23:634e42.
the d form and it transforms to the a form through the c-axial-
[4] Alemán C, Lotz B, Puiggali J. Macromolecules 2001;34:4795e801.
translational motion of the thermally-activated chains. As a result [5] Eling B, Gogolewski S, Pennings A. J Polym 1982;23:1587e93.
the coalescence of the small domains occurs to give larger domains [6] Sasaki S, Asakura T. Macromolecules 2003;23:8385e90.
by adjusting the relative height of neighboring domains (Fig. 18 (a)). [7] Puiggali J, Ikada Y, Tsuji H, Cartier L, Okihara T, Lotz B. Polymer 2000;41:
8921e30.
Now the transition mechanism from a to b form is considered [8] Cartier L, Okihara T, Ikada Y, Tsuji H, Puiggali J, Lotz B. Polymer 2000;41:
here. An application of tensile force to the regular a form along the 8909e19.
chain axis was reported to cause the a-to-b transformation via the [9] Kang S, Hsu SL, Stidman HD, Smith PB, Leugers MA, Yang X. Macromolecule
2001;34:4542e8.
d form [27]. As illustrated in Fig. 18 (c), the tensile stress may cause [10] Okihara T, Tsuji M, Kawaguchi A, Katayama KJ. Macromol Sci Phys B 1991;
the breakage of a large domain into the smaller domains with the 30(1):119e40.
translational disorder. At the same time, the relatively regular (10/ [11] Ikada Y, Jamshidi K, Tsuji H, Hyon SH. Macromolecules 1987;20(4):904e6.
[12] Zhang J, Tashiro K, Domb AJ, Tsuji H. Macromol Symp 2006;242:274e8.
3) helix may change to the deformed (10/3) helix. As a result the [13] Wasanasuk K, Tashiro K. Polym Prepr Jpn 2009;58:3534.
d form is created with many smaller domains. By stretching the [14] Vasanthakumari R. Polymer 1983;24:175e8.
thus-transformed d form furthermore, the disordered (10/3) helical [15] Di Lorenzeo ML. Eur Polym J 2005;41:569e75.
[16] Zhang J, Tashiro K, Tsuji H, Domb AJ. Macromolecules 2008;41:1352e7.
conformation changes finally to the (3/1) helical form. These chains
[17] Zhang J, Li C, Duan Y, Domb AJ, Ozaki Y. Vib Spectrosc 2010;53:307e10.
are displaced to make the closely packed unit cell of the b form. The [18] Kawai T, Rahman N, Matsuba G, Nishida K, Kanaya T, Nakano M, et al.
orientational disorder of the chains might occur also during this Macromolecules 2007;40:9463e9.
[19] Pan P, Zhu B, Kai W, Dong T, Inoue YJ. Appl Polym Sci 2008;107:54e62.
process. The b form should include many multiple domains just
[20] Cho TY, Strobl G. Polymer 2006;47:1036e43.
likely the case of the d form. [21] Iannace S, Nicolais LJ. Appl Polym Sci 1997;64:911e9.
[22] Zhou ZH, Ruan JM, Zhou ZC, Zou JP. Polym.-Plast Technol 2007;46:863e71.
4. Conclusions [23] Zhang J, Duan Y, Sato H, Tsuji H, Noda I, Shouke Y, et al. Macromolecules 2005;
38:8012e21.
[24] Kalish JP, Aou K, Yang Z, Hsu SL. Polymer 2011;52:814e21.
In the present paper the structure of the disordered a form or [25] Sawai D, Takahashi K, Imamura T, Nakamura K, Kanamoto T, Hyon SH.
the d form has been analyzed on the basis of the 2-dimensional X- J Macromol Sci Phys B 2002;40:95e104.
[26] Sawai D, Takahashi K, Sasashige A, Kanamoto T. Macromolecules 2003;36:
ray diffraction pattern, the layer line profiles and the 00l reflection 3601e5.
profile. The difference in reflection peak positions and the reflec- [27] Zhang J, Tashiro K. Fiber Preprints Jpn 2007;62:89.
tion profiles indicates clearly that the d form is not simply the [28] Tashiro K, Anasaga H, Ishino K, Tazaki R, Kobayashi MJ. Polym Sci. Part B
Polym Phys 1997;35:1677e700.
disordered state of the a form but it should be the crystalline [29] Tashiro K, Ishino K, Ohta T. Polymer 1999;40:3469e78.
modification independent of the a form. The chain conformation is [30] Sheldrick GM. SHELXL-97-A program for crystal structure refinement. Got-
appreciably disordered as known from the total lack of the even- tingen, Germany: University of Gottingen; 1997. Release 97e2.
[31] Sheldrick GM. Acta Cryst 2008;A64:112e22.
numbered 00l reflections. The chain packing is also disordered as
[32] Farragia LJ. J Appl Cryst 1999;32:837e8.
known from the remarkable streak lines along the layer lines. These [33] Sperati CA, Starkweather Jr HW. Adv Polym Sci 1961;2:465e95.
several characteristic features of these X-ray diffraction data have [34] Clark ES, Muss LT. Z Krist 1962;117:108e19.
[35] Suehiro K, Chatani Y, Tadokoro H. Polym J 1975;7(3):352e8.
been successfully reproduced by assuming the two plausible types
[36] Martin DC, Thomas EL. Macromolecules 1991;24:2450e60.
of the disordered structure models. One is the multi-domain [37] Tashiro K, Yoshino J, Kitagawa T, Murase H, Yabuki K. Macromolecules 1998;
structure in which the domain consisting of the alternate upward 31:5430e40.
and downward chains are aggregated together with the relative [38] Tashiro K, Hama H, Yoshino JI, Abe Y, Kitagawa T, Yabuki K. J Polym Sci. Part B
Polym Phys 2001;39(12):1296e311.
height disorder along the chain axis. Another model is the [39] Kaji K, Yamagishi H, Kitamaru RJ. Appl Cryst 1981;14:223e5.
statistically-disordered packing of the upward and downward [40] Takahashi Y, Tadokoro H. Ferroelectrics 1984;57(1):187e201.