Polymer 52 (2011) 2085e2093

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

Formation mechanism, chain folding, and growth behavior of the intriguing

fiber-like crystal of poly (ethylene oxide-b-e-caprolactone) block copolymer
in ultrathin films
Junchai Zhao a, *, Jianmin Zhang a, Xiaoli Duan b, c, Zheng Peng a, Shaohui Wang a
a
School of Material Science and Engineering, Shijiazhuang Tiedao University, Shijiazhuang 050043, PR China
b
CAS Key Laboratory of Engineering Plastics, Joint Laboratory of Polymer Science and Materials, Beijing National Laboratory for Molecular Sciences, Institute of Chemistry,
The Chinese Academy of Sciences, Beijing 100190, PR China
c
Graduate School, Chinese Academy of Sciences, Beijing 100049, PR China

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

Article history: The morphologies, crystallization behavior and chain orientation of a highly asymmetric poly (ethylene
Received 30 September 2010 oxide-b-e-caprolactone) (PEO-b-PCL) block copolymer ultrathin films were investigated by using wide-
Received in revised form angle X-ray diffraction (WAXD), atomic force microscopy (AFM) and grazing incidence X-ray diffraction
24 February 2011
(GIXRD) techniques. It is shown that the intriguing fiber-like crystal which seems to be an individual flat-
Accepted 25 February 2011
Available online 4 March 2011
on lamella was first observed in PEO-b-PCL ultrathin film according to our knowledge. The possible
mechanism of forming the fiber-like crystals is chiefly ascribed to the rather low molecular weight of
PEO-b-PCL and the mutual interaction between crystallization and microphase separation. At the same
Keywords:
Fiber-like crystal
time, solution concentration and substrate surface energy play a crucial role. Subsequently, chain folding
Poly (ethylene oxide-b-e-caprolactone) of the fiber-like crystal of PEO-b-PCL in ultrathin films was deduced based on the cell parameters and the
Ultrathin film lamellar thickness. Isothermal crystallization tests revealed that in the whole growth process, the crystal
growths can be divided into two stages, both of which followed the diffusion-limited (DL) mechanism.
Ó 2011 Elsevier Ltd. All rights reserved.

1. Introduction Li et al. [7] ascertained that the morphological similarity between

Copolymers consisting of both PEO and PCL blocks exhibit drug
permeability and degradability and have been proposed for a wide
range of medical applications. It is known that the physical prop-
erties and degradability of the crystalline biodegradable materials
are close correlated with their microstructure, crystallinity, and
crystalline structure [1,2]. When one or more block copolymer
components can crystallize, a competition between micophase
separation and crystallization will lead to major changes in
microstructure [3]. Up to now, some studies have been published
on the morphology and the crystallization properties of PEO-b-PCL
block copolymer [4e9]. An interesting morphology of the concen-
tric spherulites [5] which developed through a unique crystalliza-
tion behavior was seen in symmetric PEG-b-PCL by polarized
optical microscopy (POM) while the ring-band spherulites [4]
formed in asymmetric one. Using in situ simultaneously small
and wide-angle X-ray scattering (SAXS/WAXS) as well as AFM,
* Corresponding author. Tel.: þ86 311 87939440; fax: þ86 311 87935416.
E-mail address: f-angle@163.com (J. Zhao).
highly asymmetric PEO-b-PCL and some homopolymers suggested
coupling and competition between crystallization and microphase
separation as a similar underlying mechanism. From the work
mentioned above, it is easy to find that morphology and crystalli-
zation behavior of PEO-b-PCL block copolymer in bulk have been
investigated in detail but few in ultrathin films so far.
In contrast to polymers in bulk, formation of thin film structure
of semicrystalline block copolymer on solid substrates is very
complicated. Firstly, thin films introduce one-dimensional
confinement. Under such circumstance, crystallization process and
the final morphology of semicrystalline block copolymer may be
quite different from that in bulk due to the effects of confinement
and interface. Secondly, both orientation of the lamellar structure
and crystal stems need to be considered. Because orientation of the
lamellae is controlled by thermodynamic aspects (e.g., surface
tension) in amorphous copolymer, while in semicrystalline block
copolymer the morphology is dictated by the kinetics of the crys-
tallization process [10].
In the past decade, some studies mainly focused on the
behavior of block copolymer thin films with at least one crystal-
lizable block [5,6,10e17]. Reiter et al. [10] reported the morphology

0032-3861/$ e see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.polymer.2011.02.044
2086 J. Zhao et al. / Polymer 52 (2011) 2085e2093
of low-molecular-weight hydrogenated poly(butadiene-b-ethyl-
eneoxide) (PBh-PEO) diblock copolymers thin films before and after
crystallization, and tried to relate the observed morphologies to
the kinetics of chain folding. Recently, Fan et al. [18] found that the
lamellar orientation parallel to the silicon surface prevailed for low
molar mass symmetric oxyethylene/oxybutylene diblock copol-
ymer, but perpendicular ones existed in high molar mass block
copolymers, and substrate also has a distinct effect on the lamellar
orientation in thin film. In addition, crystallization in block
copolymer thin films has been explored using in situ AFM [12,16],
and impact of the melt structure on the crystallization process was
assessed in detail [12].
In general, polymer crystallization is involved in the two processes
of nucleation and growth. The kinetics of crystal growth is usually
governed by one of the two: a mass transport process via diffusion or
a nucleation process via molecular attachment and detachment.
Crystal growth is controlled by the slowest step, either nucleation-
limited (NL) or diffusion-limited (DL) [19e24]. In thin film with the
thickness comparable to the radius of gyration (Rg) of polymer chains,
the thin layer can anisotropically suppress the polymer density
fluctuation so that the crystal growth may be altered as compared
with that of bulk crystallization. Crystal growth rate in thin and
ultrathin films was explored extensively in both experiments
[15,21e23,25,26] and simulations [24]. It is reported [15] that
a remarkable slowing down of the crystal growth is observed for films
with a thickness of less than w100 nm for poly(ethylene oxide) (PEO),
which is considered to be related to the reductions of the mobility of
chains at the crystal/amorphous interface. Recently, changes in the
crystal growth mechanism [22] were discerned in pseudo-dewetted,
thin layers of low molecular weight PEO on mica surface. It is found
that both the end-group chemistry of the PEO molecules and super-
cooling can effectively switch the growth mechanisms between the
NL and DL processes. Afterward, fractal crystal growth in PEO
monolayer [26] was detected by in situ AFM, it is shown that the
growth is linear, i.e., a surface kinetic process, which is consistent
with those predicted by simulation [24].
Despite the work mentioned above, there are still some unre-
solved problems, especial chain folding, lamellar structure and
orientation in thin films of semicrystalline block copolymers, which
are not explored clearly [18,27,28]. Moreover, understanding of the
crystal growth of an individual lamella in thin layers, particularly in
semicrystalline block copolymer ultrathin films, is still far from
complete. So, it is essential to detect the crystal growth mechanism
in semicrystalline block copolymer thin films thoroughly. In this
contribution, the formation mechanism and the chain folding of the
fiber-like crystal of PEO(4k)-b-PCL(20k) in ultrathin films is pre-
sented, then effect of substrate on the formation of the fiber-like
crystal, and its growth behavior are detected in detail, respectively.
2. Experimental section
2.1. Sample characterization and preparation
PEO-b-PCL block copolymers were synthesized by the ring-
opening polymerization [29]. In this paper, block copolymer of PEO
(4k)-b-PCL(20k) was selected. And PCL homopolymer with
Mn ¼ 42 500 and Mw ¼ 65 000, purchased from Aldrich, was used as
compare.
The PCL weight fraction of the PEO-b-PCL diblock copolymer
was calculated by using the relative intensities of the characteristic
peak of 1H NMR at 2.28e2.33 ppm for PCL and that at 3.65 ppm for
PEO, which are determined by 1H NMR (AV400). The apparent
molecular weight and polydispersity of PEO-b-PCL diblock copol-
ymer were also measured by gel permeation chromatography
(GPC) (Waters 2414) using polystyrene standard. Parameters of the
block copolymer and the corresponding homopolymer are
summarized in Table 1.
The samples for AFM observation were prepared by spin-coating
(2500 rpm, 30 s) solutions of PEO(4k)-b-PCL(20k) in chloroform
with concentrations between 0.05 and 2 mg/mL (film thickness
between 7 and 39 nm) onto clean silicon, mica, and octadecyltri-
chlorosilane (OTS), respectively, and then airing for 24 h, followed
by drying in vacuum at room temperature for 24 h. The film
thickness was determined by scanning the edge of the scratches on
the films with AFM. The clean and fresh mica surface was obtained
by stripping the first several layers on the top of the mica. The
silicon wafers were cleaned using ultrasonic bath in oil of vitriol for
half an hour, subsequently cleaned by using acetone, ethanol, and
deionic water, respectively. Afterward, dry it under vacuum.
Hydrophobic surface was prepared by treating the silicon wafer
with OTS by a vapor deposition method [30].
2.2. Wide-angle X-ray diffraction (WAXD)
For WAXD measurements, the samples were hot-pressed at
80  C to obtain the film with about 100 mm thickness. WAXD was
carried out by a D/Max2500 (Japan) X-ray diffractometer with a Cu
Ka radiation (l ¼ 0.1546 nm) at room temperature. The scanning
rate was 4  C/min. The selected voltage and current were 40 kV and
200 mA, respectively.
2.3. Tapping mode atomic force microscopy (AFM)
Tapping-mode AFM observations were performed by using
NanoScope III MultiMode AFM (Digital Instruments). Both height
and phase images were recorded simultaneously during scanning.
The height and phase images were flattened using AFM software to
eliminate the height error from the sample. The resonant frequency
and the force constant of the probe are about 280 kHz and 34 Nm1,
respectively.
The measurements at elevated temperatures were conducted
with a commercial thermal accessory supplied by the microscope
manufacturer. The detailed experimental conditions of high-
temperature AFM can be found elsewhere [31,32].
2.4. Grazing incidence X-ray diffraction (GIXRD)
Grazing incidence techniques were carried out to probe the
chain orientation of the crystal stems in PEO-b-PCL ultrathin films.
A Bruker D8-Advance reflectometer with a Cu Ka radiation source
was used. The diffracted beam is in the plane defined by the inci-
dence beam and the surface normal. This geometry is sensitive to
the structure parallel to the surface. Grazing incidence angle of 0.2
was tested. The XRD curves were scanned in the 2q range of
5.0e30 .
3. Results and discussion
3.1. Crystal structure of PEO(4k)-b-PCL(20k) block copolymer
The crystal structure of PEO(4k)-b-PCL(20k) at room tempera-
ture was characterized by WAXD, as shown in Fig. 1. One can see
Table 1
The physical parameters of PEO-b-PCL and PCL.
Sample Mn of PCL Mn of PEO-b-PCL Mw/Mn
PEO(4k)-b-PCL(20k) 20,000 24,000 1.63
PCL 42,500 1.53
 J. Zhao et al. / Polymer 52 (2011) 2085e2093
that, only characteristic diffraction peaks of (110) and (200) planes
locating at 2q ¼ 21.0 and 2q ¼ 23.4 , respectively, for PCL are
detected. It can be inferred that the PEO blocks in this block
copolymer can not crystallize at room temperature due to
confinement by the crystalline PCL blocks, which has been proved
by other researchers [5,6]. However, it is interesting to note that
why the PEO block gradually become uncrystallizable when chain
length of PCL exceeds the critical length [6]. The essence is that
during crystallization, the long molecules first crystallize then short
ones in turn, just like the fractional crystallization [33]. Therefore,
the long PCL blocks which correspond to the higher melting point
(Tm) first crystallize in PEO(4k)-b-PCL(20k). After PCL blocks crys-
tallize, the PCL lamellae restrict the movement of PEO blocks. The
mobility of PEO blocks reduces so that it greatly affects the nucle-
ation process and makes the crystallization difficult. But very high
supercooling can stimulate the crystallization of PEO blocks to
occur, that is, the confined PEO blocks can crystallize at very high
supercooling.
3.2. As-spun thin film morphology of PEO(4k)-b-PCL(20k) block
copolymer with different film thickness
Fig. 2 presents the AFM images of PEO(4k)-b-PCL(20k) block
copolymer thin film on mica with film thickness of about 39, 14, 10,
and 7 nm, respectively. From thicknesses of 39 nm down to 7 nm,
one can see that big spherulitic morphology, the dendritic spher-
ulite, branched lamellae with two layers, and fiber-like crystals are
seen in turn. In Fig. 2a, for the film thickness of 39 nm, normal
spherulite with the overgrowth is observed. And the dendritic
patterns are seen in a 14 nm film (Fig. 2b). Crystals with two layers
can be detected when the film thickness is 10 nm or so. The height
of each layer is very close to the thickness of monolayer crystal, as
shown in Fig. 2c. A further decrease of the film thickness down to
7 nm (Fig. 2d) shows the monolayer lamella with a fiber-like
structure. In Fig. 2d, the average height and lateral width of the
fiber-like crystals are about 7.5 nm and 118 nm, respectively, which
can be determined from cross-section analysis. It is well-known
that three kinds of modes of crystallization which are broken out,
templated, and confined exist in the semicrystalline block copoly-
mers [34]. Images in Fig. 2 demonstrate that crystallization in PEO
(4k)-b-PCL(20k) block copolymer belongs to the first case. Namely,
the crystallization breaks out the microdomains produced by the
microphase separation. Generally, when block copolymer
Fig. 1. WAXD pattern (measured at room temperature) of PEO(4k)-b-PCL(20k) after
crystallization at room temperature.
2087
crystallizes from homogeneous or weakly segregated melt, where
neither component is vitreous, it would exhibit structures and
crystallization kinetics qualitatively similar to those of leading
components in semicrystalline homopolymers. Moreover, in the
recent research paper [7], both SAXS and rheological data corrob-
orated that the crystallization in PEO-b-PCL does take place in
a homogenous phase rather than in the microphase separated
domains. Therefore, some of the crystallization morphologies of
PEO(4k)-b-PCL(20k) should exhibit the similarity to those of the
major component of PCL homopolymer [21,35]. As we expected, the
morphologies presented in Fig. 2a and b confirm this speculation.
But when the film is very thin, a special fiber-like crystal will be
observed on mica, which is completely different from that of PCL
homopolymer. The intriguing fiber-like crystal is first reported in
this system to our best knowledge.
3.3. Formation mechanism and the chain folding of the fiber-like
crystal of PEO(4k)-b-PCL(20k) in ultrathin films
Fig. 3 reveals that the intriguing fiber-like crystal can be only
observed in PEO(4k)-b-PCL(20k) but not in homopolymer of PCL,
inferring that it is probably particular for PEO-b-PCL block copol-
ymers. The proposed mechanism for the formation of the fasci-
nating fiber morphology in PEO-b-PCL block copolymers is
analyzed below.
In general, to minimize the Gibbs-energy, an equilibrium degree
of chain folding in the crystalline layer is introduced. But for the
noncrystallized component, randomly coiled chains are taken. For
PEO(4k)-b-PCL(20k) at room temperature, only PCL segments can
crystallize while PEO segments can not due to the confinement by
the crystalline PCL blocks. When ultradilute solution is spun onto
the hydrophilic mica, hydrophilic PEO chains will absorb on the
mica surface. And incompatibility between PEO and PCL blocks
makes the hydrophobic PCL segments stretch perpendicular to the
interface, folding and forming the flat-on lamellae. Obviously, the
pattern formation originates from the strongly different affinities of
the building blocks toward the substrate. Meanwhile, the rather
low molecular weight and the mutual interaction between crys-
tallization and microphase separation for PEO(4k)-b-PCL(20k) play
a key role. While, for PCL homopolymer, when the ultradilute
solution is spun onto the hydrophilic mica, hydrophobic PCL will
dewet on the mica surface, forming the droplets to minimize the
free energy (see Fig. 3b). Moreover, the high surface tension of the
droplets prevents them from crystallization, making the droplets
very difficult to turn into lamellar morphology, as reported in
literature [17].
As is known, in crystalline state, the orthorhombic unit cell
parameters of PCL crystals determined from X-ray data [36] are
a ¼ 0.748  0.002 nm, b ¼ 0.498  0.002 nm, and
c ¼ 1.726  0.003 nm, i.e., the PCL crystal unit cell has a length of
1.726 nm that corresponds to two e-caprolactone repeat units. The
thickness of the fiber-like crystal of PEO(4k)-b-PCL(20k) in ultrathin
films is about 7.5 nm, which is quite in agreement with the previously
reported literature on the thickness of PCL lamellae obtained from
LangmuireBlodgett Films of PCL homopolymer [37], PEO-b-PCL star-
shaped [38] and linear block copolymer [39], respectively. It is clear
that the lamellar thickness of 7.5 nm indicates that the chains fold
approximately every eight e-caprolactone repeat units if it is assumed
that the PCL chains orient perpendicularly to the mica substrate. We
try to prove whether the fiber-like crystals are of flat-on view by the
GIXRD experiment. Fig. 4a presents the GIXRD pattern of fiber-like
crystals of PEO(4k)-b-PCL(20k) in ultrathin film on mica at an inci-
dence angle of 0.2 . According to the geometry of GIXRD, only the
reflections parallel to the substrate surface can be detected [40,41].
The penetration depth of the X-rays into the thin films is dependent
2088 J. Zhao et al. / Polymer 52 (2011) 2085e2093

Fig. 2. Tapping mode AFM height images (10  10 mm2) of PEO(4k)-b-PCL(20k) films crystallized at room temperature at film thicknesses of (a) 39, (b) 14, (c) 10, (d) 7 nm.

on the incidence angle. The larger the incidence angle, the deeper the
penetration of the X-rays. In our case, an incidence angle of 0.2 was
selected because of the thinnest film. From Fig. 4a, it is obvious that
the characteristic diffractions of (110) and (200) planes locating at
about 2q ¼ 21.0 and 2q ¼ 23.4 (marked by two dashed lines),
respectively, for PCL blocks do not be observed, in principle indicating
that the crystal stems of fiber-like crystals are perpendicular to the
substrates. That is, the fiber-like crystals are of flat-on view. However,
it can not still conclude that the fiber-like crystals are flat-on lamellae.
Because the coverage of the mica surface by the PEO(4k)-b-PCL(20k)
is very low, it is possible that the GIXRD pattern does not embody the
diffraction peaks of PCL blocks at all. Evidently, the diffractions from
mica (such as 2q ¼ 9.2 ) also appear in Fig. 4a. Although the GIXRD
result does not give strong proofs to the chain orientation of crystal
stems of the fiber-like crystals, the thickness of the fiber-like crystals
obtained in our study is very in agreement with the lamellar thickness
for flat-on PCL lamellae grown in spin-coated films as reported in
literature [37]. Based on these results, the possible sketch maps of

Fig. 3. Tapping mode AFM height images (10  10 mm2) of (a) PEO(4k)-b-PCL(20k), and (b) PCL ultrathin films crystallized at room temperature on mica. Ultrathin films for each
polymer were prepared by spin-coating chloroform solution with concentration of 0.05 mg/mL onto the mica surface.
 J. Zhao et al. / Polymer 52 (2011) 2085e2093 2089

crystals on silicon is shorter than that on mica (see Fig. 5b). By cross-
section analysis, the average height and width of the fiber-like
crystals on silicon wafer can be obtained and are approximate 8.0
and 120 nm, respectively. For the size of the fiber-like crystals on the
mica and silicon the subtle distinction between them gives a clue to
the possible similarity of chain organization of the fiber-like crystals
on the two kinds of substrate. However, the stretch of PEO chains on
the mica is greater than that on silicon wafer because the former is
more hydrophilic. In Fig. 5c, two layers of lamellae formed by PCL
blocks on OTS are detected. The average height of the bottom and
the top layers obtained by AFM software is 4e5 nm and 12e15 nm,
respectively. Moreover, the top layers are not with uniform width. It
is considered that both the bottom and the top layers are highly

Fig. 4. (a) GIXRD pattern of fiber-like crystals of PEO(4k)-b-PCL(20k) in ultrathin film

on mica at an incidence angle of 0.2 ; (b) the possible sketch maps of chain organi-
zation in fiber-like crystals of PEO(4k)-b-PCL(20k).

chain organization in fiber-like crystals of PEO(4k)-b-PCL(20k) are

deduced, as shown in Fig. 4b. In short, for PEO(4k)-b-PCL(20k) at
ambient temperature, only PCL segments can crystallize, the chain
organization in the fiber-like crystal is probable such a case, i.e.,
amorphous PEO chains strongly stretch on the mica surface and PCL
segments crystallize as chain folding approximately every eight e-
caprolactone repeat units on it. It can be said that the fiber-like
crystals of PEO(4k)-b-PCL(20k) in ultrathin film seem to be an indi-
vidual flat-on lamella in fact.

3.4. Effect of substrate on the formation of the fiber-like crystal of

PEO(4k)-b-PCL(20k) in ultrathin films

Surface energy of the substrate has a pronounced effect on thin

film morphology. A situation is well characterized for amorphous
block copolymers [42e45] in terms of theory and experiment. For
example, lamellar structures parallel to the substrate surface are
favorably formed when the substrate preferably absorbs one of the
components, while lamellar structures perpendicular to the
substrate surface are favorable for neutral substrates. Recently,
studies about the lamellar orientation in semicrystalline block
copolymers [14,18,46] show that both chain length and substrate
surface energy can significantly vary the lamellar orientation and
film morphology.
To further detect the impact of substrate on the morphology of
semicrystalline block copolymers in ultrathin films, the morphology
of nascent PEO(4k)-b-PCL(20k) thin film formed from highly dilute
chloroform solution onto different substrate was investigated and
Fig. 5. Tapping mode AFM height images (10  10 mm2) of PEO(4k)-b-PCL(20k) crys-
the results are presented in Fig. 5. It is obvious that the fascinating tallized at room temperature in ultrathin films on (a) mica, (b) silicon wafer, and (c)
fiber-like crystal can be observed on both mica and silicon wafer, OTS, respectively. Ultrathin films were prepared by spin-coating chloroform solution
while it can not on the OTS surface. Moreover, the length of fiber-like with concentration of 0.05 mg/mL onto the substrate.
2090 J. Zhao et al. / Polymer 52 (2011) 2085e2093
Fig. 6. Tapping mode AFM images (5  5 mm2) of a 7 nm thick PEO(4k)-b-PCL(20k) film isothermally crystallized at 26  C. The time interval for capture of the AFM images is given on
each height image.
reminiscent of flat-on lamellae. We suspect that the
hydrophobicehydrophobic interaction between PCL and OTS helps
the PCL segments to lie down when PEO(4k)-b-PCL(20k) ultradilute
solution is spun onto the hydrophobic OTS surface. But during the
crystallization induced by the solvent evaporation, PCL segments
can adjust their orientation from ‘lying down’ to ‘standing up’, giving
the flat-on crystals. The dominance of flat-on lamellae close to the
OTS surface can be related to the inhibited growth of edge-on
lamellae due to the hindered thickening of lamellae at the lateral
growth front [47]. And the small thickness of the bottom layers
implies that the chain conformation of PCL blocks at least in the
surface normal direction should be perturbed by the attraction force
between PCL and OTS, and the microphase separation of PEO(4k)-b-
PCL(20k). In a word, the formation of patterns for PEO(4k)-b-PCL
(20k) on different substrate originates from the strongly different
affinities of the building blocks toward the substrate. At the same
time, the effects of the crystallization and microphase separation can
not be ignored.
3.5. Growth behavior of the fiber-like crystals in PEO(4k)-b-PCL
(20k) ultrathin films on mica detected by using in situ AFM with
a hot-stage
Crystal growth from the molten droplets of PEO(4k)-b-PCL(20k)
was detected by in situ AFM with the hot-stage, as shown in Figs. 6
and 7. Fig. 6 presents the successive AFM images at different times
in an isothermal crystal growth experiment at 26  C. The detected
samples are prepared from chloroform solutions of PEO(4k)-b-PCL
(20k) with concentration of 0.05 mg/mL which is too dilute so that
dewetting would be happen during spin-coating. So the initial state
of the melt behaves a lot of droplets. From Fig. 6a, one can see that
the growth rate is very high at 26  C. After crystallization proceeds
for 8 min, the length of the fiber-like crystal (marked by the black
arrow) reaches about 725 nm. But when the crystallization time is
16 min, other two fiber-like crystals have grown from the same
molten droplet as the first fiber-like crystal but in different direc-
tions, as shown in Fig. 6b. Subsequently, these fiber-like crystals
grow right along (Fig. 6c). Simultaneously, it can be observed that
the number of droplets decreases with the growing of the fiber-like
crystals. Furthermore, most droplets around the fiber-like crystals
are gradually consumed when the crystallization time is 32 min, as
shown in Fig. 6d. With the rise of crystallization time further
(Fig. 6eej), the fiber-like crystals grow longer and longer, at the
same time, new fiber-like crystals appear now and then. Above
results indicate that not only the droplets which contain nuclei but
also those non-nucleus-containing droplets serve as material
“reservoirs” from which the molten PCL blocks in PEO(4k)-b-PCL
(20k) block copolymer transport toward the crystal growth fronts.
The growth behavior of the fiber-like crystals at 30  C is presented
in Fig. 7. Similarly, the droplets which contain nuclei will evolve
into fiber-like crystals at last with the crystallization time
increasing. However, the induction period of the crystal growth is
long compared with 26  C.
In polymer crystallization, important aspects besides
morphology are the lateral growth rate and the thickness of
a lamellar crystal. The growth rate of fiber-like crystal can be
 J. Zhao et al. / Polymer 52 (2011) 2085e2093
Fig. 7. Tapping mode AFM images (5  5 mm2) of a 7 nm thick PEO(4k)-b-PCL(20k) film isothermally crystallized at 30  C. The time interval for capture of the AFM images is given on
each height image.
quantitatively obtained from the AFM images shown in Figs. 6 and
7. Namely, in terms of the variation of relative length of the fiber-
like crystals with crystallization time, growth rate can be calcu-
lated. Fig. 8 presents the representative results. It is clear that the
relations between the crystal lateral growth size and time at 26 and
30  C are both non-linear (Fig. 8a), whereas it can be regarded as
two developing stages according to the changes of growth rate. And
for both stages (Fig. 8b and c), the crystal lateral growth size r can be
linearly proportional to crystallization time t0.5, which refers to a DL
crystal growth. For the crystallization temperature of 26  C, the
growth of the fiber-like crystals is accompanied by shrinking of the
neighboring non-nucleus-containing droplets. Once the droplets
around the fiber-like crystals are exhausted, the second stage will
start. Therefore, it is evident that at 26  C the growth rate in the first
stage is faster than that in the second stage. As for the crystalliza-
tion temperature of 30  C, no evident shrinking of the neighboring
non-nucleus-containing droplets is observed. And the growth rate
in the first stage is slower than that in the second stage. It is worth
noting that the growth rate of an individual lamella often varies
from lamellae to lamellae at each crystallization temperature but
with similar growth rule, which are in accord with the previous
literatures reported [16,48,49]. Compared the growth rate of fiber-
like crystal at 26  C with that of 30  C, some distinctions in growth
behavior between the two crystallization temperatures can be
found. As can be seen from Fig. 8b, the growth rate in the first stage
at 26  C is faster than that at 30  C. It is considered that at 26  C
polymer chains can move to the crystal growth front quickly
because shrinking of the neighboring non-nucleus-containing
2091
droplets and a decrease in the droplet number can be found around
the growing fiber-like crystal, that is, polymer chains enrich at the
crystal growth front for crystallization temperature of 26  C. But in
the second stage (Fig. 8c), the growth rates at 26 and 30  C are close
due to the longer time needed to transport the polymer chains to
the crystal growth front for both. Another difference in growth
behavior between the two crystallization temperatures of 26 and
30  C is that the growth rate in first stage at 30  C is slower than
that in second stage, which is distinct from crystallization
temperature of 26  C. The possible reason can be that at crystalli-
zation temperature of 30  C no enough polymer chains exist at the
crystal growth front in the first stage, while a lot of polymer chains
can move there after a period of time when crystallization begins.
This may result in the faster growth rate in second stage at 30  C. In
short, the growth of fiber-like crystals at crystallization tempera-
tures of 26 and 30  C can be both divided into two stages which all
follow the DL mechanism.
For the fiber-like crystals exhibited in Figs. 6 and 7, the typical
curves about evolution of the height with time at 26 and 30  C are
shown in Fig. 9. Like the crystal growth rate, variation of the height
of fiber-like crystals is different from one to another during crystal
growth. But the trend of variation is accordant, namely, at the initial
growth stage, the height of fiber-like crystals has obvious increase
with crystallization time, subsequently it approaches the satura-
tion, which embodies the thickening of lamellae during isothermal
crystallization.
According to the HoffmaneLauritzen theory [19], the expression
of the crystal growth rate can be used
2092 J. Zhao et al. / Polymer 52 (2011) 2085e2093

temperature region. For the DL crystal growth, the general feature

is the branched morphologies, which are normally formed at
relatively high supercooling. And the growth rate is usually power
law. It follows the scaling rule [21,22]

rft 0:5 (2)

Where r is the crystal lateral growth size, t is the crystallization
time.
Crystal growth kinetics at the supercooling condition has been
studied in both experiment [21e23] and simulation [24]. The
experimental results show the linear, RðtÞft 1 [23], and non-linear,
RðtÞft 0:5 [21,22] relations between pattern radius and time found
from different polymers at the different supercooling conditions.
The theoretical simulation [24] confirms that the growth of crystal
patterns is a surface kinetic process, that is, a linear growth. In our
study, the relationships between the crystal lateral growth size r
and crystallization time t0.5 in the two stages at 26 and 30  C,
respectively, are all linear, showing that the crystal growth mech-
anisms follow the DL process.
In summary, the outstanding features of the fiber-like crystals
during growth are as follows. Firstly, each fiber-like crystal grows
from the molten droplets which contain nuclei. However,
secondary nucleation [50] which is induced by trapping one end of
a polymer chain in a lamella has not been observed in our experi-
ment. It is great different from the results of Li et al. reported
[50,51], which showed that the edge-on lamellae could grow
becoming long lamellae before branching occurred when the
lengths of the lamellae reached 0.5e1.0 mm. However, no branching
and splaying of the lamella happens in our study even though the
lengths of the lamellae exceed the critical length of 1.0 mm. It is
considered that absence of branching and splaying is possible
connected with depletion of the melt due to no sufficient polymer
material to be transported to the growth fronts and the geometric
confinement. In addition, perhaps more importantly, it is also
ascribed to the coupling and competition between crystallization
and microphase separation in PEO(4k)-b-PCL(20k). Secondly, when
the single lamella impinges against other growing lamellae, the
growth of both would be stopped, just like the growth behavior of
spherulite in bulk. Thirdly, crystal growth at 26 and 30  C can be
both divided into two developing stages based on the changes of
growth rate. Moreover, the relationships between the crystal lateral
growth size r and crystallization time t0.5 in each stage at 26 and
30  C, respectively, are all linear, showing the DL crystal growth
mechanism. Fourthly, the height of the fiber-like crystals or the

Fig. 8. The length of fiber-like crystals in a 7 nm thick PEO(4k)-b-PCL(20k) film as

a function of time when samples were isothermally crystallized at 26 and 30  C (a) the
whole curve of the growth process, (b) and (c) are the first and second stage of the
growth process, respectively.

"  # 
*
G ¼ G0 exp U =RðT  T Þ exp Kg=T ðDTÞf (1)
c N c

Where G0 is the constant, U * is the activation barrier to chain

transport, R is the gas constant, Tc is the crystallization temperature,
TN ¼ Tg  30K. Kg is the nucleation parameter, ΔT is the super-
cooling, and f is calibrated temperature of fusion heat. For formula
(1), the first exponential term is related to the chain diffusion and
the second is related to the nucleation. In general, crystal growth is
controlled by the slowest step, either the NL or the DL mechanism Fig. 9. The height of fiber-like crystals in a 7 nm thick PEO(4k)-b-PCL(20k) film as
[19,20]. Namely, the crystal growth rate G is controlled by nucle- a function of time when samples were isothermally crystallized at 26 and 30  C,
ation in higher temperature region, while by diffusion in lower respectively.
 J. Zhao et al. / Polymer 52 (2011) 2085e2093
lamellar thickness increases initially and then reaches the satura-
tion with increasing crystallization time, i.e., thickening of lamellae
occurs during isothermal crystallization.
4. Conclusion
Ultrathin film morphology of PEO-b-PCL block copolymers on
mica was investigated by using AFM. It is shown that the intriguing
fiber-like crystal which seems to be an individual flat-on lamella
was first observed in PEO-b-PCL ultrathin film according to our
knowledge. The effects of solution concentration and substrate on
the formation of fiber-like crystal were examined. It is found that
the unique fiber-like crystal can be only observed in PEO-b-PCL
block copolymer at suitable concentration, while can not in corre-
sponding homopolymer. And it is most easily produced on the
highly hydrophilic mica surface. Moreover, it is worth mentioning
that the unique fiber-like crystal is different from the dendritic and
other fractal morphology. The possible mechanism of forming this
special fiber-like crystal is mainly assigned to the rather low
molecular weight of PEO-b-PCL and the corporate interaction
between crystallization and microphase separation. At the same
time, solution concentration and substrate surface energy play
a crucial role.
Isothermal crystallization tests reveal that in the whole growth
process, the crystal growth can be divided into two stages, and both
follow the DL mechanism.
Acknowledgement
The authors acknowledge financial support from the National
Natural Science Foundation of China (20804051) and Natural
Science Foundation of Hebei Province (B2010001055). The authors
also thank Dr. GQ Yu for supplying the samples of PEO-b-PCL. The
authors would like to thank Prof. XL Ji for the availability of the
Grazing Incidence X-ray facilities at Changchun Institute of Applied
Chemistry, Chinese Academy of Sciences. The authors also appre-
ciate the much helpful comments from the reviewers.
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