Current Opinion in Solid State and Materials Science 4 (1999) 553558

Kinetics of phase transitions in block copolymers

N.P. Balsara *,1
Polytechnic University, Brooklyn, New York, USA

Abstract

A rich variety of equilibrium phases have been identified in block copolymer melts. In this paper we study the kinetics of phase
transitions from one equilibrium state to another, from both experimental and theoretical points of view. The formation of ordered phases
is often mediated by non-equilibrium intermediate states. In addition the phase transitions can proceed by either conventional nucleation,
or by spinodal decomposition. 2000 Elsevier Science Ltd. All rights reserved.

1. Introduction mean-field theories [2,3] indicate the presence of addition-

Block copolymers exhibit a variety of ordered microph-
ases with crystalline and liquid crystalline symmetry. At
high temperature, entropic factors dominate and a dis-
ordered, liquid-like phase is obtained. At low temperatures,
repulsive interactions between the blocks become increas-
ingly important, and this results in a series of phase
transitions. Lamellae, cylinders arranged on a hexagonal
lattice, and spheres arranged on a body centered cubic
(bcc) lattice are common, and we refer to these as classical
phases. The phase obtained at a given temperature (and
pressure) depends on the interactions between the blocks
(often expressed as the FloryHuggins interaction parame-
ter, x ), and the architecture of the block copolymer
molecule (total number of monomers per chain, N, and the
volume fraction of one of the blocks, f ). This article deals
with the kinetics of phase transitions from disorder to order
and from one ordered phase to another. These transitions
can be initiated either by changing temperature or pressure,
which in turn changes x.
2. Theory
We restrict our attention to weakly ordered systems. A
mean-field theory for predicting the formation of the
classical block copolymer phases was proposed in a
pioneering publication by Leibler [1]. Leibler also iden-
tified the stability limit for the disordered phase with
respect to the ordered phases. The results of more elaborate
*Tel.: 11-510-642-8973; fax: 11-510-642-4778.
E-mail address: nbalsara@cchem.berkeley.edu (N.P. Balsara).
1
Present address: Department of Chemical Engineering, University of
California, Berkeley, CA 94720, USA.
al phases: a disordered phase composed of spherical block
copolymer micelles, and a bicontinuous gyroid phase [4].
Brazovskii [5] recognized the importance of fluctuations in
weakly ordered systems. Fredrickson and Helfand [6]
applied this theory to block copolymers and found that all
of the classical ordered phases were metastable with
respect to the disordered phase. The two widely accepted
theories [1,6] thus predict different mechanisms for sam-
ples quenched from the disordered phase to lamellar or
cylinder phase. The former predicts nucleation and growth
for extremely shallow quenches and spinodal decomposi-
tion for deeper quenches, while the latter predicts nuclea-
tion and growth, regardless of quench depth.
During nucleation and growth, grains of the ordered
phase consume the surrounding disordered phase. Fredric-
kson and Binder [7] proposed a theory for the nucleation
and growth of lamellar phases, based on the Fredrickson
Helfand theory. Goveas and Milner [8] formulated a theory
for nucleation and growth based on the mean-field theory
of Leibler. Both theories yield expressions for, v, the
average velocity at which the ordered phase invades the
disordered phase. The expression obtained by Goveas and
Milner is given below
v 5 gRN( x 2 xcoexist ) /t, (1)
where g is an order 1 constant that depends on block
copolymer architecture, R is the average end-to-end dis-
tance of the block copolymer molecule, t is the molecular
relaxation time, and xcoexist is the value of x under
coexistence conditions (the two phases have identical
Gibbs energies at this point and v is therefore equal to
zero). The temperature dependence of v can thus be
predicted if the temperature (T ) dependence of x and t are
known.

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554 N.P. Balsara / Current Opinion in Solid State and Materials Science 4 (1999) 553 558
If the formation of the ordered phase occurs by spinodal
decomposition, then microstructure formation in different
regions within the sample will begin as soon as the system
is quenched. However, periodic concentration profiles,
representing the precursors of the ordered phase, will
develop simultaneously and incoherently throughout the
sample. The interference effects and the presence of
defects will be important during all stages of the disorder
order phase transition. Theories that describe these com-
plex processes have not yet been developed. In contrast,
spinodal decomposition during certain kinds of order
order phase transitions can be considered without including
defects if it is assumed that the daughter and mother
phases share an epitaxial relationship.
Qi and Wang [9] studied the kinetics of the orderorder
phase transitions by spinodal decomposition. A perturba-
tion analysis of the order parameter about the equilibrium
state led to the conclusion that the dominant fluctuations
Fig. 1. Theoretical images of the lamellae to cylinders transition at selected time steps. See Qi and Wang [9] for details. Reprinted from Polymer
1998;39:46394648. Copyright 1998, with permission from Elsevier Science.
are anisotropic and with certain preferred symmetries (see
also Ref. [10]). For example, the preferred fluctuations on
a lamellar phase have ABABAB stacking with either
hexagonal or body centered cubic symmetry. These fluc-
tuations are amplified when the lamellar phase is quenched
to a region of the phase diagram where it is unstable. The
formation of cylinders from lamellae obviously requires
perforating the lamellae. Anisotropic fluctuations that exist
in the pre-quenched equilibrium state, provide preferred
directions along which the perforations take place. The
theoretical prediction for the pathway for the lamellae to
cylinder transition is shown in Fig. 1. The free energy
landscape of block copolymers contains features such as
saddles and ridges in addition to minima corresponding to
the equilibrium structures (lamellae and cylinders). Per-
forated states, obtained by the amplification of the pre-
existing fluctuations, are located at these features, and they
appear as long-lived intermediates during the lamellae to
 N.P. Balsara / Current Opinion in Solid State and Materials Science 4 (1999) 553 558 555

Fig. 2. Classical nucleation of lamellar grains in a sea of the disordered phase in a polystyrene-block-polyisoprene copolymer. The polyisoprene phase is
stained and appears dark. (a) Micrograph. (b) Micrograph with some lamellar grains outlined in white. See Sakamoto and Hashimoto [12] for details.
(Reprinted from Macromolecules 1998;31:32923302, with permission from the American Chemical Society.)

cylinder transition. Similar effects are seen in other order

order transitions, e.g. cylinders to spheres.

3. Experiments

The nature of block copolymer phases can be studied

experimentally in position space by electron microscopy,
or in reciprocal space by locating Bragg peaks in small
angle X-ray and neutron scattering (SAXS and SANS)
data. Depolarized light scattering has been used to detect
the presence of the liquid crystalline phases (e.g. lamellae
and cylinders), due to their birefringent character. Changes
in the rheological properties of the sample can also be used
to follow phase transitions due to the (soft) solid-like
character of ordered phases and the liquid-like character of
disordered phases. Time-resolved scattering methods are
best suited for kinetic measurements because they provide
a direct measure of microstructural changes in the sample.
However, complimentary position space data is often Fig. 3. The dependence of dimensionless average grain growth velocity
required to identify complex structures such as perforated v* 5 vt /R on quench depth (1 /T 2 1 /T coexist ) in a polystyrene-block-
lamellae. polyisoprene copolymer. The grains are anisotropic and v represents the
rate of change of the average grain dimension. The line represents the
The transformation from disorder to bcc spheres was theoretical prediction (Eq. (1)) with no adjustable parameters. See Balsara
studied in pioneering small angle X-ray scattering experi- et al. [13] for details. (Reprinted from Macromolecules 1998;31:5301
ments by Singh et al. [11]. Clear signatures of the ordering 5302, with permission from the American Chemical Society.)
556 N.P. Balsara / Current Opinion in Solid State and Materials Science 4 (1999) 553 558

process were obtained due to the presence of second and disordered phase first transforms into a phase consisting of
third order Bragg peaks in the ordered state and their disordered spheres, similar to the prediction of Semenov
absence in the disordered state. It was shown that the [2]. The spheres subsequently organize themselves on a

Fig. 4. Non-classical nucleation and growth of a perforated lamellar phase during the lamellar to gyroid phase transition in a polystyrene-block-
polyisoprene copolymer. The polyisoprene phase is stained and appears dark. The arrows point to grains with perforated lamellae that coexist with ordinary
lamellar grains during the lamellae to gyroid transition. These results are consistent with the theoretical results shown in Fig. 1. See Hajduk et al. [14] for
details. The bar in the micrograph is 100 nm in length. (Reprinted from the Journal of Physical Chemistry B 1998;102:13561363, with permission from
the American Chemical Society.)
 N.P. Balsara / Current Opinion in Solid State and Materials Science 4 (1999) 553 558
bcc lattice. These experiments demonstrate the possibility
of non-classical nucleation and growth wherein the trans-
formation from one equilibrium phase to another is
mediated by a non-equilibrium intermediate phase (dis-
ordered spheres in this case). In many cases, however, the
disorder to order transition proceeds by classical nucleation
and growth, as stipulated by Fredrickson and Binder. Fig.
2 shows striking images of individual lamellar grains
growing in a sea of disorder obtained by electron
microscopy [12]. The disordered phase that surrounds the
ordered grains is not devoid of structure. The alternating
dark and light regions indicate the presence of large
concentration fluctuations with a characteristic length scale
that is similar to the repeat distance of the lamellar phase.
However, SAXS experiments under these conditions failed
to reveal higher order Bragg reflections corresponding to
the lamellar phase. It appears that some weakly ordered
block copolymer systems exhibit higher order reflections
(e.g. Ref. [11]) while others do not (e.g. Ref. [12]). In the
cases where higher order peaks are not obtained, following
the kinetics of order formation by SAXS or SANS is
difficult because the primary Bragg peak usually occurs at
the same location in reciprocal space as the peak due to
disordered concentration fluctuations (see Fig. 2).
Depolarized light scattering is related to the grain
structure in ordered block copolymers [13]. The grain
growth velocity, v, can thus be monitored by studying
changes in the depolarized light scattering profiles. The
results of these measurements were used to test the
theoretical prediction of Goveas and Milner. The interest-
ing feature of block copolymers is that all of the parame-
ters that govern ordering kinetics (the right hand side of
Eq. (1)) can be obtained from independent experiments: R
and x from SANS, t from rheology, and N from polymer
characterization tools such as gel permeation chromatog-
raphy. The experimentally determined grain growth veloci-
ties can thus be compared with theory without resorting to
any adjustable parameters. Such a comparison is shown in
Fig. 3.
Experimental studies of phase transitions that involve
exotic intermediate states such as perforated lamellae have
been conducted by Hajduk et al. [14]. Electron microscopy
was used to demonstrate that this phase is formed during
the lamellae to gyroid transition. The microstructure during
the intermediate stage of this transition is shown in Fig. 4
where coexisting grains of (regular) lamellae and per-
forated lamellae are shown. Ordered fluctuations have also
been detected in cylindrical block copolymers near the
cylinder to sphere transition [15]. These experiments
demonstrate the importance of anisotropic fluctuations on
transitions from one ordered phase to another. However, a
quantitative understanding of factors that govern the
kinetics of such transformations have not been established.
For example, the experimental results of Hajduk et al.
suggest that the mechanism for the phase transformation is
nucleation and growth while the theory that predicts the
557
formation of perforated lamellae assumes that the mecha-
nism is spinodal decomposition.
The presence of stability limits or spinodal curves in the
block copolymer phase diagram remains unresolved. Haj-
duk et al. [16] addressed this issue in their study of the
disorder to lamellae transition by SANS. They found a
discontinuity in the nature of the ordered phase when the
quench depth exceeded a critical value. They recognized
that this may be due to the presence of a stability limit for
the disordered phase. In a later study [17], the disorder to
cylinder transition was studied by monitoring the time
dependence of the second order Bragg peaks in SAXS and
depolarized light scattering. This combination of tech-
niques provides a method for monitoring the development
of microstructure along the liquid and crystalline direc-
tions, i.e. along the cylinder axis and in the hexagonal
plane perpendicular to the cylinder axis. At small quench
depths, microstructure formation along the liquid and
crystalline directions is strongly correlated. This is ex-
pected if the mechanism for the phase transition is classical
nucleation and growth. At large quench depths, however,
microstructure formation along the liquid and crystalline
directions is not correlated. The growth of crystalline order
occurs before the development of a coherent structure
along the liquid direction. It was suggested that the change
from correlated to uncorrelated microstructural growth
may be due to the presence of a stability limit.
References
[1] Leibler L. Theory of microphase separation in block copolymers.
Macromolecules 1980;13:160217.
[2] Semenov AN. Microphase separation in diblock copolymer melts:
ordering of micelles. Macromolecules 1989;22:284951.
[3] Matsen MW, Bates FS. Unifying weak and strong segregation
theories. Macromolecules 1996;29:10918.
[4] Hajduk DA, Harper PE, Gruner SM, Honeker CC, Kim G, Thomas
EL, Fetters LJ. The gyroid: a new equilibrium morphology in
weakly segregated diblock copolymers. Macromolecules
1994;27:406375.
[5] Brazovskii SA. Phase transition of an isotropic system to a
nonuniform state. Sov Phys-JETP 1975;41:859.
[6] Fredrickson GH, Helfand E. Fluctuation effects in the theory of
microphase separation in block copolymers. J Chem Phys
1987;87:697705.
[7] Fredrickson GH, Binder K. Kinetics of metastable states in block
copolymer melts. J Chem Phys 1989;91:726575.
[8] Goveas JL, Milner ST. Dynamics of the lamellarcylindrical
transition in weakly segregated diblock copolymer melts. Macro-
molecules 1997;30:260512.
[9] Qi S, Wang ZG. Weakly segregated block copolymers: anisotropic
fluctuations and kinetics of orderorder and orderdisorder transi-
tion. Polymers 1998;39:463948.
[10] Laradji M, Shi AC, Noolandi J, Desai RC. Stability of ordered
phases in diblock copolymer melts. Macromolecules 1997;30:3242
55.
[11] Singh MA, Harkless CR, Nagler SE, Shannon RF, Ghosh SS.
Time-resolved small angle X-ray scattering study of ordering
kinetics in diblock styrenebutadiene. Phys Rev B 1993;47:8425
35.
558 N.P. Balsara / Current Opinion in Solid State and Materials Science 4 (1999) 553 558
[12] Sakamoto N, Hashimoto T. Ordering dynamics of a symmetric
polystyrene-block-polyisoprene. 1. Ordering mechanism from the
disordered state. Macromolecules 1998;31:3292302.
[13] Balsara NP, Garetz BA, Chang MY, Dai HJ, Newstein MC, Goveas
JL, Krishnamoorti R, Rai S. Identification of the molecular parame-
ters that govern ordering kinetics in a block copolymer melt.
Macromolecules 1998;31:530915.
[14] Hajduk DA, Ho RM, Hillmyer MA, Bates FS, Almdal K. Transition
mechanisms for complex ordered phases in block copolymer melts. J
Phys Chem B 1998;102:135663.
[15] Ryu CY, Vigild ME, Lodge TP. Fluctuations with cubic symmetry in
a hexagonal copolymer microstructure. Phys Rev Lett
1998;81:53547.
[16] Hajduk DA, Tepe T, Takenouchi H, Tirrell M, Bates FS, Almdal K,
Mortensen K. Shear-induced ordering kinetics of a triblock co-
polymer melt. J Chem Phys 1998;108:32633.
[17] Balsara NP, Garetz BA, Newstein MC, Bauer BJ, Prosa TJ.
Evolution of microstructure in the liquid and crystal directions in a
quenched block copolymer melt. Macromolecules 1998;31:766875.