Review

Cite This: Chem. Rev. 2018, 118, 1840−1886 pubs.acs.org/CR

Multiscale and Multistep Ordering of Flow-Induced Nucleation of

Polymers
Kunpeng Cui,† Zhe Ma,*,‡ Nan Tian,§ Fengmei Su,† Dong Liu,∥ and Liangbin Li*,†
†
National Synchrotron Radiation Laboratory, Chinese Academy of Sciences Key Laboratory of Soft Matter Chemistry, and Anhui
Provincial Engineering Laboratory of Advanced Functional Polymer Film, University of Science and Technology of China, 96
Jinzhai Road, Baohe District, Hefei 230026, People’s Republic of China
‡
Tianjin Key Laboratory of Composite and Functional Materials, School of Materials Science and Engineering, Tianjin University,
92 Weijin Road, Nankai District, Tianjin 300072, People’s Republic of China
§
Ministry of Education Key Laboratory of Space Applied Physics and Chemistry and Shanxi Key Laboratory of Macromolecular
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Science and Technology, School of Science, Northwestern Polytechnical University, 127 Youyi West Road, District Beilin, Xi’an
710072, People’s Republic of China
∥
Key Laboratory of Neutron Physics and Institute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, 64
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Mianshan Road, Mianyang, Sichuan 621999, People’s Republic of China

ABSTRACT: Flow-induced crystallization (FIC) is a typical nonequilibrium phase

transition and a core industry subject for the largest group of commercially useful
polymeric materials: semicrystalline polymers. A fundamental understanding of FIC can
benefit the research of nonequilibrium ordering in matter systems and help to tailor the
ultimate properties of polymeric materials. Concerning the crystallization process, flow
can accelerate the kinetics by orders of magnitude and induce the formation of oriented
crystallites like shish-kebab, which are associated with the major influences of flow on
nucleation, that is, raised nucleation density and oriented nuclei. The topic of FIC has
been studied for more than half a century. Recently, there have been many
developments in experimental approaches, such as synchrotron radiation X-ray scattering, ultrafast X-ray detectors with a
time resolution down to the order of milliseconds, and novel laboratory devices to mimic the severe flow field close to real
processing conditions. By a combination of these advanced methods, the evolution process of FIC can be revealed more
precisely (with higher time resolution and on more length scales) and quantitatively. The new findings are challenging the
classical interpretations and theories that were mostly derived from quiescent or mild-flow conditions, and they are triggering
the reconsideration of FIC foundations. This review mainly summarizes experimental results, advances in physical
understanding, and discussions on the multiscale and multistep nature of oriented nuclei induced by strong flow. The multiscale
structures include segmental conformation, packing of conformational ordering, deformation on the whole-chain scale, and
macroscopic aggregation of crystallites. The multistep process involves conformation transition, isotropic−nematic transition,
density fluctuation (or phase separation), formation of precursors, and shish-kebab crystallites, which are possible ordering
processes during nucleation. Furthermore, some theoretical progress and modeling efforts are also included.

CONTENTS 3.3.3. Ordering Parameter of Flow-Induced

Precursors 1849
1. Introduction 1841 3.4. Influences of Precursor on Crystallization 1850
2. Conformational Ordering Induced by Flow 1842 3.4.1. Nucleation 1850
2.1. Flow-Induced Conformational Ordering 1842 3.4.2. Crystallization Kinetics 1850
2.1.1. Coil−Helix Transition 1842 3.4.3. Morphologies 1852
2.1.2. Gauche−Trans Transition 1844 4. Factors Influencing the Formation of Flow-
2.2. Flow-Induced Isotropic−Nematic Transition 1845 Induced Precursors 1852
3. Precursors Induced by Flow 1845 4.1. Flow Parameters 1852
3.1. Flow-Induced Precursors 1846 4.2. Temperature 1853
3.2. Theoretical Considerations for Flow-Induced 4.3. Molecular Parameters 1855
Precursors 1846 5. Correlation between Deformation at Whole-
3.3. Nature of Flow-Induced Precursors 1847 Chain Scale and Nucleation 1855
3.3.1. Existence of Flow-Induced Precursors 1847 5.1. Shish-Kebab Crystallite 1855
3.3.2. Are Flow-Induced Precursors Crystalline
or Not? 1848
Received: August 17, 2017
Published: January 19, 2018

© 2018 American Chemical Society 1840 DOI: 10.1021/acs.chemrev.7b00500

Chem. Rev. 2018, 118, 1840−1886
Chemical Reviews
5.2. Hierarchical Structure of Shish-Kebab
5.3. Coil−Stretch Transition in Polymer Solution
5.4. Shish-Kebab Formation in Polymer Melt
5.5. Other Mechanisms for Shish-Kebab Forma-
tion
5.6. Advances in Understanding of Shish-Kebab
5.6.1. Coil−Stretch Transition or Stretched
Network Model?
5.6.2. Is Long Chain the Only Contributor for
Shish Formation?
5.6.3. How Does Polydispersity Influence the
Threshold for Shish Formation?
5.6.4. How Does Short-Chain Matrix Influence
Shish Formation?
5.6.5. In Situ Observation of Evolution of
Shish-Kebab
5.6.6. Shish Formation under Near-Equilibrium
and Far-from-Equilibrium Conditions
5.6.7. Is Shish Formation a Single-Stage or
Multistage Process?
5.6.8. Is Shish a Thermodynamic Phase or a
Kinetic State?
6. Theories and Models of Flow-Induced Nucleation
6.1. Molecular Theory of Flow-Induced Nuclea-
tion
6.1.1. Crystallization Induced by Stretching of
Cross-Linked Network
6.1.2. Flow-Induced Nucleation in Free Melt
6.1.3. Quantitative Description of Extension-
Induced Nucleation
6.2. Macroscale Continuum Modeling
7. Final Remarks
Author Information
Corresponding Authors
ORCID
Notes
Biographies
Acknowledgments
References
1. INTRODUCTION
Semicrystalline polymers cover more than two-thirds of the
global applications of polymeric materials. Just due to their
intrinsic capability to arrange macromolecular segments into
three-dimensionally ordered crystal units, even in various
modifications, the ultimate products are endowed with rich
and unique properties.1−3 In practice, polymer processing often
starts with molten materials and subsequently utilizes flow to
transport the polymeric melt and/or to shape into final
products.4−8 This means that flow is an unavoidable factor in
polymer processing, and flow-induced crystallization (FIC) is a
general phenomenon for semicrystalline materials. Moreover,
crystallization is a typical first-order phase transition existing in
macromolecular systems. A polymer is a unique substance with
anisotropic molecular properties, where atoms along the chain
direction are connected by chemical bonds. Thus, a polymer that
initially is in quiescent random-coil conformation can be easily
deformed into an oriented or stretched state, and the
thermodynamic state of the system is varied correspondingly.9,10
The system under such disturbed molecular ordering and
thermodynamic state crystallizes in a different manner with
respect to the quiescent case or small-molecule system, and this
Review
1856 has become a unique aspect in the crystallization field.
1857 Obviously, a fundamental understanding of FIC is of great
1857 importance for both industrial and academic communities.
After decades of effort, two major influences of flow on
1858 crystallization have been revealed: acceleration of crystallization
1859 kinetics and formation of oriented crystallites, which are
associated with raised nucleation density and oriented
1859 nuclei.11−15 According to the ultimate morphology (spherulites
or oriented texture), flow-induced nuclei can be roughly divided
1861 into pointlike nuclei and oriented nuclei. Formation of pointlike
nuclei has been recently reviewed by Peters et al.16 and will not
1861 be included in the present review. However, a more complex
situation is the formation of flow-induced oriented nuclei. A full
1862
understanding of oriented nuclei has not been reached yet, even
after decades of effort.17−19 Typical unsolved questions include
1862
the ordering nature and precise evolution process of the oriented
1863 nuclei. On one hand, for a polymer chain, the intrinsic structures
at various length scalessuch as segmental conformation,
1864 segmental orientation, density fluctuation, stretch of the whole
chain, and so oncan all be arranged in an orderly fashion
1866 during the crystallization process, especially under the effort of
1867 flow. Is there a basic ordering parameter or a combination of
multiscale orderings to define nuclei? Do these flow-induced
1867 ordering processes at various length scales evolve simultaneously
or sequentially? On the other hand, numerous experimental
1867 results indicate that nucleation under flow does not simply
1869 follow the classical nucleation theory to form stable crystalline
nuclei directly and may undergo some intermediate states. In
1871 this case, when and how the structural intermediates, if they
1873 exist, occur during flow-induced nucleation (FIN) should be
1878 answered.
1879 This review attempts to emphasize the possible processes of
1879 ordering in various length scales. For this purpose, this work is
1879 organized by mainly following a bottom-up length scale. We first
1879 focus on the formation of conformational ordering on a
1879 segmental scale (e.g., helix) in section 2, which acts as a basic
1879 ordering unit to arrange into a three-dimensionally ordered
1879 crystal unit. Then we introduce flow-induced precursors (FIP),
the presence of which can be demonstrated but about which
detailed structural information has not been revealed, and their
structural analysis in section 3. Concerning precursors, the
factors influencing their appearance are summarized to shed
light on the formation mechanism in section 4. Then, whether
deformation on the whole-chain scale is essential for FIC is
discussed with the discovery of shish in section 5. At last, some
theoretical and modeling efforts are compared and validated
with experimental results in section 6 to explore possible
molecular origins. In the meantime, possible multistep processes
for structure formation are also discussed for FIP and shish in
sections 3 and 5, respectively.
Note that the following multiscale and multistep aspects of
FIN are generic for polymer crystallization. Especially, the
nonequilibrium ordering understood from macromolecular
systems may be valid for other types of matter, like small
molecules. However, the concrete manifestation of these aspects
depends on the polymer investigated. For example, conforma-
tional ordering arranges into zigzag conformation for poly-
ethylene (PE),20 syndiotactic polystyrene (sPS),21 and poly-
(ethylene terephthalate) (PET)22 but forms helices for isotactic
polypropylene (iPP),23 isotactic polystyrene (iPS),24 and
poly(ethylene oxide) (PEO).25
1841 DOI: 10.1021/acs.chemrev.7b00500
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Chemical Reviews Review

Figure 1. Sketch of coil−helix transition at strained end-to-end distance R. The chain is simplified into a diblock polymer composed of coil and helical
domains.

2. CONFORMATIONAL ORDERING INDUCED BY conformational ordering including coil−helix transition (section

FLOW 2.1.1) and gauche−trans transition (section 2.1.2) will be
discussed.
Since a long-chain polymer needs to orderly arrange its short
2.1.1. Coil−Helix Transition. On the premise of dense
stems into a crystal lattice, the short stems must adopt proper
accumulation and positioning into a crystal unit, polymer chains
conformations for ultimate regular packing. For FIN, basic
adopt conformations with the lowest energy. Helix is a preferred
structural ordering concerns the change of segmental con-
state not only in crystals of synthetic polymers, like iPP, iPS, and
formation. However, in classic nucleation theory, FIN was
PEO, but also in some biological macromolecules, such as DNA
described in a coarse-grained way. It was often thought that
and actin filaments.39,40 The coil−helix transition of biopol-
when external flow is imposed, polymer chains are deformed
ymers induced by deformation has gained much attention
into an oriented or stretched state. The resulting orientation or
because biological functions are closely associated with the
stretch of the chain reduces system entropy and consequently
specific structure of the formed helices.41 To better understand
elevates the melting temperature according to the entropy-
the coil−helix transition, we first have a look at some theoretical
reduction model (ERM),26 which introduces an extra under-
works about how flow influences conformational transition, and
cooling for crystallization. This physical picture is essentially
then we discuss the relevant experimental results.
reasonable, since it has been widely demonstrated that flow can
Theoretical understanding of coil−helix transition can be
effectively enhance crystal nucleation.27 However, molecular
dated back to the work of Zimm and Bragg,42 in which the
details like intramolecular conformational ordering, intermo-
transition was described on a coarse-grained level. In the
lecular positional ordering, and orientation ordering28,29 are
Zimm−Bragg model,43 segments along a polymer chain are
ignored in ERM. In principle, flow can not only give rise to
assumed to have only two states, random-coil and helical. The
orientation or stretch of individual chain but also change
state of a long chain can be described by a simple sequence of
conformational ordering. Moreover, recent ultrafast X-ray
segmental status (cchhcchccchh...), where c and h represent coil
scattering results revealed a constant critical strain for nucleation
and helix, respectively. A monomer within a helix gains potential
in a wide temperature range under strong flow, which invalidates
energy Δh by forming hydrogen bonds but bears a loss of
the prediction of strain−temperature equivalence in classical
entropy Δs. (Here the notation for energy or entropy is
ERM.30 In this section, we mainly discuss the change of
lowercase for monomer, but uppercase for total system.) The
molecular details induced by flow. The ultrafast X-ray scattering
free energy of each monomer in the helical state can be
results will be discussed in section 5.6.6.
estimated by Δf = Δh − TΔs. The monomer located at the
Flow can induce conformational ordering. When the
interface between helical and coil domains suffers entropy
concentration or length of conformational ordering segments
reduction but does not form hydrogen bonds, resulting in an
exceeds a certain threshold, those ordered stiff segments may
increase in free energy of Δf t = −Δh compared to the monomer
spontaneously aggregate and organize, as happens in isotropic−
in helical state. Knowing the microscopic state of the whole
nematic transition.31,32 If this is the case, nucleation seems to be
chain and the energetic contributions of each segment, the total
completed via multiple steps from the melt, which has been
free energy ΔF can be obtained by a statistical mechanics
evidenced by experimental observations, especially under flow
method. This approach was further extended to deal with the
conditions.33−35 In this section, we decouple the global
case where an external extension is imposed by Tamashiro and
nucleation induced by flow into two ordering aspects: (i) how
Pincus36 and Buhot and Halperin.44,45 In their approaches, the
flow induces conformational ordering of individual segments
chain is simplified into a diblock polymer composed of coil and
and (ii) possible aggregation and parallel permutation of the
helical domains with an interface energy of Δf t (Figure 1). This
formed stiff segments.
means that the mixing entropy from reordering of domains and
Before going into a deep discussion, it should be first clarified
the interfacial energy are disregarded. The detailed study of
that intermolecular and intramolecular orderings do not
Buhot and Halperin45 demonstrated that this simplification has
necessarily occur simultaneously but may happen individually.
a slight influence on the outcome only quantitatively but not
As an example, stretching-induced formation of protein α-helix
qualitatively. In this case, the total free energy can be expressed
in biopolymers is a conformational ordering without positional
as follows:
ordering.36 On the other hand, PE can crystallize into hexagonal
crystals under high pressure, which lacks full conformational
3(R − γaNϕ)2
ordering.37,38 ΔFch = ϕN Δf + 2Δft +
2(1 − ϕ)Na 2
2.1. Flow-Induced Conformational Ordering
Although early investigations on FIC can be dated back to the where N is the total number of monomers and ϕ is the
1960s, conformational ordering of chain segments did not get concentration of helical segments. The last term describes the
the attention it deserves. Here, the formation of intramolecular free energy of a coil domain, where R is the end-to-end distance
1842 DOI: 10.1021/acs.chemrev.7b00500
Chem. Rev. 2018, 118, 1840−1886
Chemical Reviews
Figure 2. (a) IR spectra of iPP under quiescent crystallization at 140 °C and (b) the time evolution of normalized relative intensities of different
conformational bands. Reprinted with permission from ref 50. Copyright 2007 American Chemical Society.
Figure 3. IR spectra of iPP before and after shear at 140 °C and (b) time evolution of normalized relative intensities of different conformational bands.
Reprinted with permission from ref 50. Copyright 2007 American Chemical Society.
of chain, γ is a factor to characterize the shortening of effective
polymer length due to formation of helix, and α is monomer
length. This model provides a quantitative correlation between
helix concentration and molecular deformation, which can be
used to study conformational transition in FIC, as synthetic
polymers and biological macromolecules share the same physics.
For network, Courty et al.41,46 and Kutter and Terentjev47
formulated a theoretical work by uniting statistical mechanisms
of single helix-forming chain under extension (as just described)
with the phantom-chain network approach. It was theoretically
predicted that extension promotes the formation of helical
domains under appropriate conditions, which is in agreement
with experimental results.47
Compared with biological macromolecules, flow-induced
coil−helix transition was less studied in synthetic polymers,
either theoretically or experimentally. As polymer melt is a
transient network constructed by entanglements, change of end-
to-end distance by flow should influence the coil−helix
transition, as in biological macromolecules. However, it is not
easy to trace the coil−helix transition in polymers. Helix is a
short-range order and cannot be characterized with regular
scattering techniques like X-ray scattering, which is sensitive to
long-range correlation. In this aspect, IR spectroscopy shows
superiority to probe conformational ordering. Middle IR bands
are mainly vibrational bands due to the existence of dipole
moment. Therefore, even though the vibrational modes are the
same, differences in helical length and local environment can
vary the wavenumber of absorption bands. This was revealed by
the calculations of Snyder and Schachtschneider48 and the
experiments of Zhu et al.49 Length and concentration of helices
are two important parameters for coil−helix transition, which
can be characterized by the position and intensity of the
characteristic absorption peaks, respectively. iPP with 3/1 helix
conformation is chosen here as a representative, as the one-to-
one correspondence between helix length of segments and
1843
Review
absorption bands in Fourier transform infrared spectra (FTIR)
has been well documented.50,51 For iPP, the absorption bands at
940, 1220, 1167, 1303, 1330, 841, 998, 900, 808, 1100, and 973
cm−1 indicate helical structures with different ordering degrees
from high to low, of which the 1220, 841, 998, and 973 cm−1
bands correspond to helical lengths with monomer numbers 14,
12, 10, and 5, respectively.49,52 Besides, the concentration of
these helices can be indicated by the absorbance intensity.
Flow-induced conformational ordering of iPP coil−helix
transition has been studied by An et al.50,51 and Geng et al.53
Figures 2 and 3 compare the IR spectra of quiescent
crystallization and FIC of iPP at 140 °C. In Figure 2a, the
observation of bands at 973, 808, and 900 cm−1 demonstrates
that the short helices already exist in amorphous iPP melt. Under
quiescent conditions, the intensities of those IR bands remain
almost unchanged in the initial 4 h (see Figure 2b). However,
when flow is applied, the intensities of IR bands rise sharply just
after flow, suggesting the increase in population of helices. As
crystallization proceeds further, long helices appear and grow.
The saturation time for those IR bands, which under quiescent
conditions is 20 h (see Figure 2b), is shortened to around 100
min by shear flow (see Figure 3b). The observation of long
helices is often considered as a signature of crystallization.
Obviously, these results demonstrated that flow can promote
formation of helices and thus crystallization in synthetic
semicrystalline polymers.
According to the Zimm−Bragg model,46 end-to-end distance
is an essential parameter to determine the ratio between coil and
helix. This is qualitatively confirmed in a cross-linked iPP by Su
et al.,54 who observed a direct correlation between helical
content and stress. As stress is determined by the end-to-end
distance, helical content is related to end-to-end distance in
cross-linked iPP. However, polymer melt is a transient network
constructed by entanglements, and there must exist a
competition between deformation and relaxation of polymer
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Chemical Reviews
Figure 4. Schematic of three growth pathways for flow-induced coil−helix transition. Reprinted with permission from ref 50. Copyright 2007 American
Chemical Society.
chain. Thereby, the fraction of helix formed in total sequence is
influenced not only by flow strength, like strain or strain rate, but
also by temperature that determines chain relaxation. An et al.51
employed the ratio between height values of band 998 cm−1 after
and before shear flow to indicate a conformational order ratio
(COR) and assessed the effect of various external parameters on
flow-induced helix quantitatively. Under a fixed flow strength
with strain rate of 13.5 s−1 and strain of 3375%, COR induced at
temperatures below 150 °C decreases linearly with increasing
temperature due to the competition between deformation and
relaxation. For temperatures above 205 °C, COR has negligible
change after flow, probably because relaxation dominates this
process. On the other hand, at a constant temperature of 145 °C
with strain rate of 6 s−1, a minimum strain is required to
significantly vary COR, in line with the prediction of Kutter and
Terentjev47 that a threshold extension is required to induce
coil−helix transition. As strain increases, COR first increases and
then reaches saturation at strain larger than about 4000%.
Furthermore, when temperature and strain are both fixed, COR
increases with rising strain rate. Therefore, An et al.51 pointed
out that, due to relaxation effect on COR, a combination of
intense flow (high strain rate or/and high strain) and high
temperature has a similar effect as combining weak flow (low
strain rate or/and low strain) and low temperature.
Besides helical population, Geng et al.53 also revealed the
influence of flow on length of formed helices. Unlike the short
helices that already exist in original amorphous melt, long helices
with more than 12 monomers can be found only under flow. A
critical flow strength is required to generate long helices. At 150
°C, an 841 cm−1 band (representing the helix with 12
monomers) appears only for flow rates larger than 18 mm3/s,
while a flow rate of 45 mm3/s is required to induce the
occurrence of a 1220 cm−1 band (corresponding to the helix
with 14 monomers). The flow rate thresholds for appearance of
the 1220 and 841 cm−1 bands increase with temperature,
suggesting that stronger flow is necessary to generate longer
helices at higher temperatures. Geng et al.53 also found that, at
temperatures close to the melting point, the intensity of 841
cm−1 band or helices with 12 monomers increases monotoni-
cally with time upon cessation of flow, which is accompanied by
a decrease in band intensity of short helices. In addition, an
induction time exists for helices with 12 monomers. On the basis
of those results, they proposed three pathways for the formation
of long helices (see Figure 4). The first way is flow-induced
growth of the short helices that already existed in amorphous
melt, without primary nucleation, known as propagation. The
second path is to generate long helices via nucleation and
1844
Review
growth. The third one is the merging of short helices, that is, an
incorporation process.
Yamamoto55 used molecular simulation to study the coil−
helix transition by quickly drawing an amorphous iPP to about 9
times elongation within about 350 ps. Statistical results showed
that the weight-average length of helical sequence increases with
elongation, while elongation has no influence on the length of
nonhelical sequences. The detailed distribution of the
population of helical sequences as a function of their length
indicated that short sequences dominate the initial stage of
elongation and long sequences increase considerably with
further elongation. A threshold length of helix with about 13
monomers was observed during elongation, in line with the IR
experimental results of An et al.50
2.1.2. Gauche−Trans Transition. In addition to helical
conformation, planar zigzag is another conformation in
crystallites of many polymers, such as sPS,24 nylon,56 PET,57
and PE.20,58 For example, sPS has a trans sequence of (TT)2 in
crystals, with T representing trans conformation. It was reported
that within the crystallization induction period the content of all-
trans sequence increases, whereas the sequence containing
gauche conformation decreases.24 For nylon, all-trans sequence
can be induced by strong flow, as happens in electrospinning.56
In drawing of PET film, gauche−trans transition may also take
place to form a mesomorphic phase constituted of trans
conformation. 57 In the following, PE is chosen as a
representative to discuss the gauche−trans transition.
PE is the simplest semicrystalline polymer and often serves as
a model material to study phase transitions such as
crystallization, melting, and so on.4,59,60 PE can crystallize in
various modifications depending on crystallization conditions.
For instance, mobile hexagonal crystals may appear under high
pressure and then transform to orthorhombic crystals with
increasing thickness.61−63 Here we discuss the formation and
evolution of locally ordered trans-rich structure in the early stage
of crystallization studied with Raman and FTIR spectrosco-
py.20,58,64,65
Using time-resolved FTIR and small-angle X-ray scattering
(SAXS), Sasaki et al.65 concluded that, in the early stage of
quiescent crystallization, disordered conformation of trans
sequence first increases and then remains at the maximum for
a while. After that, the content of regular trans sequences, which
can be used to indicate the formation of orthorhombic crystals,
increases simultaneously with the decrease of disordered trans
sequences. In contrast, the structural intermediate composed of
all-trans configurations can be induced by flow even before the
onset of crystallization. Flow orientates polymer chains and
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increases the number of trans bonds, which in turn enhances the
possibility for formation of all-trans configurations. Combining a
homemade shear device and Raman, Chai et al.58 performed a
quantitative study on how shear rate influences all-trans C−C
bonds. Three peaks in the Raman spectrum of PE are assigned to
intrachain bands, where sharp Raman peaks at 1065 (C−C
asym) and 1130 (C−C sym) cm−1 stem from consecutive trans
vibrations, and the broad peak at 1080 cm−1 originates from
gauche bonds in the amorphous component. When PE melt is
sheared at 140 °C, the Raman bands at 1065 and 1130 cm−1
appear and their band intensities increase with increasing shear
rate, suggesting the generation of all-trans sequences induced by
flow. The all-trans sequence can survive for several hours after
cessation of flow, indicating that the flow-induced all-trans
sequence is not only oriented but also stable. The experimental
results of Chai et al.58 are consistent with the simulation of
Meier,64 who calculated vibrational frequencies and intensities
of various hexadecanes to address how long a trans sequence is
needed for PE to contribute to the all-trans Raman bands. These
results showed that sequences with more than 10 trans bonds are
responsible for the all-trans Raman bands at 1065 and 1130
cm−1. As only disordered trans sequences exist in PE melt, the
appearance of all-trans structure can be expected under strong
nonequilibrium conditions before the onset of crystallization,
such as under flow field. In addition, trans and gauche
conformations may differentiate in the response to external
flow. The work of Pigeon et al.20 demonstrated that the trans
conformation in amorphous phase is easily oriented along the
flow direction, whereas flow has negligible influence on
orientating gauche sequences.
2.2. Flow-Induced Isotropic−Nematic Transition
The helix induced by flow can be considered as a rigid rod or stiff
segment with length L and diameter b. The increased rigidity
induced by conformational changes may cause the occurrence of
nematic ordering, although flexible polymers have no intrinsic
mesogenic unit. The statistical mechanical theory of isotropic−
nematic transition for rodlike molecules was first proposed by
Onsager66 in colloidal particles and then developed by Flory
(see ref 67) for polymers. According to this theory, the excluded
volume (Vexcl) of stiff segments increases with increasing helical
length. The excluded volume Vexcl can be calculated as Vexcl =
2bL2|sin θ|, where θ is the angle between neighboring stiff
segments. When the helical sequences exceed a critical length,
they start to orient parallel to each other to reduce the excluded
volume or free energy of the system. The critical length of stiff
segments for orientation occurrence is given as L = 4.19M0/
bl0ρNA, where ρ is density, NA is Avogadro’s number, and l0 and
M0 are the length and molecular weight of monomer,
respectively. With this correlation, the critical helical length
for parallel ordering of iPP calculated by Zhu et al.49 is 11
monomers, which agrees well with their FTIR experimental
observations. It was indicated that the segmental conformation
is stable when the length of helical sequences is shorter than 10
monomers, while the helix conformation extends quickly and
starts crystallization as soon as the helical length exceeds 12
monomers.
Flow may induce isotropic−nematic transition in flexible
polymers even above the melting temperature. From the rheo-
FTIR experiments of iPP conducted by Geng et al.,53 it was
found that flow-induced helices with 12 monomers can exist at
170 °C and the intensity of the corresponding absorption band
increases after flow. According to coil−helix transition theory, an
1845
Review
individual isolated long helix is not stable in free polymer melt, as
the raised end-to-end distance of chain tends to relax back to
that of coil state due to entropy effects. The growth of long
helices suggests the occurrence of coupling between conforma-
tional and orientational orderings. This means that flow-induced
coil−helix transition provides the necessary stiff segments for
isotropic−nematic transition, which further form intermolecular
ordering that in turn stabilizes the long helices. The recent works
of Kanaya and Matsuba and co-workers68−71 in iPS melt gave
indirect evidence to support this mechanism. Stringlike objects
of iPS with micrometer dimensions were generated by flow
above the melting temperature. Microbeam SAXS and wide-
angle X-ray scattering (WAXS) characterization demonstrated
that those structures are not stacks of lamellae and have no or
very limited crystallinity.68 The conformational information in
those intermediate structures was further examined with two-
dimensional (2D) FTIR. The IR band of long helix was observed
in the center and edge of those structures, whereas in the
amorphous domain only short helical bands were detected. In
addition, the works of Alfonso and co-workers72,73 suggested
that the intermediate structure consisted of bundles with
conformational ordering and oriented chain segments. Hsiao
and co-workers74,75 inferred that the intermediate structure is
liquid-crystal phase. It seems reasonable and likely that flow
induces the occurrence of isotropic−nematic transition in
polymer melt.
For a certain helical length, a threshold concentration of stiff
segment is also needed to induce the isotropic−nematic
transition. Combining extensional rheometry and ultrafast
SAXS/WAXS measurements, Cui et al.30 found a constant
critical strain to observe iPP intermediate structure for a broad
temperature range from 130 to 170 °C. Based on flow-induced
coil−helix transition47 and fluctuation−dissipation theories,76,77
the content of helical sequence was calculated as a function of
helical length. For helical length exceeding 14 nm, flow not only
facilitates compatible alignment of the helical sequences but also
increases the helical concentration for the isotropic−nematic
transition. In addition, flow may vary the critical concentration
for isotropic−nematic transition. With time-resolved birefrin-
gence, Lenstra et al.78 studied isotropic−nematic transition in
suspensions of fd virus and found that the critical concentration
under shear flow is much smaller than in the quiescent case.
The formation of conformational ordering discussed in
section 2.1, including coil−helix and gauche−trans transitions,
can be effectively influenced by external stimuli such as strain,
strain rate, and temperature. Some qualitative conclusions can
be drawn: (i) flow promotes segmental ordering not only in
sequence length but also in content; (ii) the combination of high
flow intensity and high temperature has a similar effect to the
combination of low flow intensity and low temperature; (iii)
stronger flow is needed for the formation of ordering segments
with long sequence length than for short ones. However, the
quantitative relationship between flow intensity, length, and
content of ordering segments is still lacking and requires more
investigation. The rigidity of ordering segments leads to
intermolecular ordering, that is, isotropic−nematic ordering,
which is commonly considered as an intermediate state and will
be discussed in section 3.
3. PRECURSORS INDUCED BY FLOW
Although segmental conformations are the basic ordering for
ultimate crystallites, polymer crystallization often starts with the
formation of nuclei, of which the length scale is larger than the
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segmental conformation. According to the classical nucleation
theory (CNT),79 crystalline nuclei are directly generated from
initial random coil and no further structural intermediate is
considered. However, numerous experimental observations
suggest that FIN may be a multistep process and may undergo
an intermediate ordered state (also commonly termed as
precursor, preordering, mesomorphic ordering, and so
on).11,68,80,81 In our opinion, precursors are the structures
whose existence can be solidly demonstrated by their substantial
influences on crystallization (i.e., kinetics, orientation, morphol-
ogy, and so on) but whose fundamental ordering nature is still
unclear yet.
Structural intermediates may exist even in quiescent
crystallization. A liquid−liquid phase separation, known as
spinodal decomposition, was observed in the first step of
polymer crystallization by Kaji et al.,31 and then the relevant
theoretical effort was made by Olmsted et al.35 Strobl33
conjectured that crystallization starts with formation of a
mesomorphic layer that then develops into a granular crystal
layer, followed by a merging process of crystal blocks. Flow is an
effective external stimulus to reveal the intermediate state before
crystallization, if there is one, because the formation of structural
intermediates with mesomorphic ordering in flexible-chain
polymers is often attributed to the rigidity based on conforma-
tional ordering, which could be considerably enhanced by flow
as discussed in section 2.
The theory developed by Kim and Pincus82 and experiment
conducted by Li and de Jeu83 showed that the coupling between
coil−helix transition and orientational ordering could induce a
nematic state. Recent results from a combination of FTIR,
SAXS, and WAXS suggested that coil−helix transition and
orientational ordering indeed happen before crystallization in
cross-linked iPP.54 For long-chain polymers, the highly
asymmetric nature provides enormous possibility to form
precursors with orientational ordering. In this section, the
observations of structure intermediatesthat is, precursors
will be discussed for FIN to shed light on the detailed process
and formation mechanism of stable nuclei.
3.1. Flow-Induced Precursors
Katayama et al.84 probably were the first to report the formation
of flow-induced precursors (FIP) in the 1960s. They studied a
melt spinning process by combining a special model-spinning
apparatus with an in-house X-ray setup. Their results showed
that the structural signal in SAXS is observed much earlier than
the crystalline signal in WAXS, which indicates that density
fluctuations on the length scale of several tens of nanometers
occur before crystallization. This mesomorphic state was
deemed as FIP, bridging the transformation from melt to
crystals. Several other groups also provided results to support
the presence of FIP in PET.85−88 Bonart85 reported that nematic
and smectic phases form sequentially during stretching of an
amorphous PET sample. Using synchrotron characterization,
Blundell and co-workers86−88 announced the existence of
mesophase during drawing of PET homopolymer and
copolymer, which act as a precursors in strain-induced
crystallization. At that time, the investigations of FIP were
mainly concentrated on steady melting spinning or polymers
with slow crystallization kinetics such as PET,85,86 poly(ethylene
naphthalate) (PEN),87,88 and polystyrene (PS),24,89 due to the
limitation of time resolution of detection techniques. Besides,
the experiments were mostly performed in complex processing
conditions like molding or spinning. This means complex flow
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and thermal histories were imposed on the polymers, which
influence both nucleation and growth steps. Despite all
aforementioned limitations, some features of FIP are still
captured: the formation of FIP can strongly influence the
crystallization rate, change the crystallite morphology, and even
induce the appearance of new crystal modification.
The understanding of FIP was further improved by progress
in experimental methods. Recently, Lamberti12 produced a
review paper on methods to investigate and quantify
crystallization. Modeling approaches and main factors acting
on crystallization are also included in this review. Here, we just
give a brief introduction to the progress in experimental
methods. In 1993, Liedauer et al.90 designed a new flow
apparatus and proposed a short-term shear protocol, in which
the flow duration is short enough to separate nucleation from
crystallization processes. This method allows one to study FIP
by looking at the subsequent crystallization kinetics and
morphology. A similar flow apparatus was developed by
Kumaraswamy et al.,91 which allows one to study structural
evolution in real time by optical and X-ray probes with only a
small amount of sample (several grams). At the same time, the
commercial Linkam shear cell with parallel-plate geometry was
widely used by the community due to its convenience for X-ray
and optical measurements.11 In 2011, Liu et al.92 developed an
extensional-type flow device, which can control strain and strain
rate independently. More importantly, stress recording and real-
time X-ray measurement can be realized simultaneously by this
device. Meanwhile, various structure characterization techni-
ques such as optical microscopy,93 light scattering,94 birefrin-
gence, 95 atomic force microscopy (AFM),96 and X-ray
scattering97 have been combined to reveal the formation and
evolution of FIP. Especially with the development of
synchrotron ultrafast X-ray scatting30,98 and X-ray micro-
diffraction scanning,68,99 new understanding of FIP has been
obtained.
3.2. Theoretical Considerations for Flow-Induced
Precursors
Flow can induce intrachain conformational ordering, but the
conformational ordering alone cannot cause a phase separation
in polymer melt. However, the conformational ordering may
couple with density. The aggregation and parallel arrangement
of oriented segments with conformational ordering may work
together to induce phase separation. As mentioned earlier, Kaji
et al.31 proposed a spinodal (SD) type of phase-separation
model for the induction period of polymer crystallization. In this
model, the amorphous random coil first transforms into a stiff
helical conformation. As soon as both length and concentration
exceed their thresholds, the stiff segments tend to orient with
each other. The increase in chain stiffness induces the parallel
ordering of polymer segments due to excluded volume effect.
According to isotropic−nematic theory67 mentioned in section
2, the completely parallel orientation gives an excluded volume
of zero, while the perpendicular orientation gives the maximum
value. Such parallel orientation does not occur homogeneously
in the system, but it involves a microphase separation into
oriented and unoriented domains. Those oriented dense
domains grow in size by reactions and diffusion of clusters.
Olmsted et al.35 developed a more general phenomenological
theory to illustrate the coupling between chain conformation
and density for phase separation. Figure 5 shows the
temperature-density diagram calculated by use of phenomeno-
logical free energy, which contains three regions: coexistence
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Figure 5. Generic phase diagram for a polymer melt. Tm, Tc, and Ts are
the melting, liquid−liquid binodal and spinodal temperatures,
respectively. Dotted line represents quench path. Reprinted with
permission from ref 35. Copyright 1998 American Physical Society.
region of melt and crystals, metastable region, and unstable
region. In Figure 5, the horizontal axis indicates the product of
normalized density ρ and w, which is defined as a product of the
average mass density ρ of melt and the specific volume w of
monomer core. This phase diagram is analogous to the binary
component case but has a different ordering parameter, that is,
density. While the melt is quenched to a temperature below
spinodal temperature Ts (that is, the melt is in an unstable
region), SD-type phase separation takes place. The melt
separates into two coexisting liquids, which differ in con-
formation distributions (see Figure 6). In the region of denser
Figure 6. Schematic representation of the late stage of spinodal
decomposition for coexisting liquid phases with different conforma-
tions. Thin and thick lines represent disordered and helical
conformations, respectively. Reprinted with permission from ref 35.
Copyright 1998 American Physical Society.
liquid, density and conformation are both closer to the state
needed for crystal packing than that in the original melt, which
lowers the energy barrier for crystallization.100
In fact, numerous experimental results reported the
emergence of SAXS signal before crystal diffraction in WAXS,
indicating the occurrence of density fluctuation prior to
crystallization.31,101−103 For example, Imai et al.101,104,105
investigated the induction period of PET in cold crystallization.
In their experiments, the peak position in SAXS is smaller than
the ordinary peak position of the intercrystal correlation peak.
SAXS signal shows an increase of scattering intensity and a shift
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of diffraction maximum before crystal growth. The SAXS
evolution can be well fitted with the theory for spinodal
decomposition, indicating that the scattering behavior obeys the
predication of spinodal kinetics in the early stage of
crystallization.
Spinodal phase separation was mainly observed in melt
crystallization under flow. This is because flow aligns polymer
chains and enhances density, which thereby increases the
possibility of liquid−liquid separation. Recently, crystallization
studies on the extrusion process of iPP, PS, and PET were
conducted by Ryan et al.,106−108 where large-scale ordering
before growth of crystals was observed. Moreover, melt spinning
investigation of poly(vinylidene fluoride) conducted by Cakmak
et al.109 and annealing study of iPP from a highly extended melt
conducted by Schultz et al.110 also showed spinodal-type phase
separation.
3.3. Nature of Flow-Induced Precursors
Although the formation of FIP has been demonstrated by a large
amount of experimental observations, the nature of FIP is still
under debate. In this section, we review the debates on the
existence (section 3.3.1), structure (section 3.3.2), and ordering
parameter (section 3.3.3) of FIP. The concept of FIP is rather
vague and is commonly used to describe structures that are not
clearly revealed. The term FIP can include various structures; for
example, Ma et al.111 sorted four types of FIP according to the
sensitivities of different detection techniques. Up to now, there
has been no consensus yet reached on the existence and
structure of FIP. Various experimental techniques have been
employed to characterize dynamic and thermal abilities of FIP.
Since scattering methods are powerful for probing structure with
long-range ordering, most experimental results presented in this
section are based on X-ray scattering.
3.3.1. Existence of Flow-Induced Precursors. Many FIC
studies have shown the appearance of metastable FIP before
crystallization, among which most experiments were based on
the combination of SAXS and WAXS methods. SAXS can detect
density fluctuations without long-range order, and WAXS can
probe crystalline order. For crystallization with nucleation and
growth mechanism, WAXS should appear at the same time as
SAXS. However, if FIP forms, development of SAXS due to
density fluctuation may occur prior to that of WAXS due to
crystalline order. Most early evidence for the appearance of FIP
was obtained from extrusion processes. The pioneering works of
Katayama et al.,84 Cakmak et al.,109 Ryan et al.,107,108 and
Schultz et al.110 showed earlier observation of SAXS than WAXS
in various systems like iPP, PE, and PET. They concluded that
density fluctuation with large-scale order occurs and that it plays
an important role in crystallization. However, Wang et al.112,113
pointed out that the time lag between SAXS and WAXS may be
attributed to detector sensitivity. In other words, WAXS may not
be able to detect crystals with low volume fraction in the early
stage of crystallization, whereas SAXS is capable of probing the
structure as long as its density contrast with the surrounding
melt is sufficient. Thus, caution should be exercised when
comparing the first appearance of SAXS and WAXS. Heeley et
al.114 further addressed this issue by using an updated WAXS
detector, which has an improvement in count rate with a factor
of 104 over that used in previous experiments. Their results
demonstrated that the lag between SAXS and WAXS is not
caused by detector sensitivity, and the appearance of SAXS
before WAXS indicates the formation of unknown structure.
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In addition to X-ray scattering, some other experimental
techniques also lead to the same conclusion on the existence of
FIP. As already discussed in section 2, the rheo-Raman study by
Chai et al.58 showed that flow can promote the formation of all-
trans bands, which can survive for several hours after cessation of
flow even above the melting temperature. The birefringence
experiments reported by Seki et al.95 and Ma et al.111 suggested
the appearance of oriented structure before crystallization.
Small-angle light scattering (SALS) experiments conducted by
Pogodina et al.115 and Zhang et al.116 indicated the formation of
highly elongated structures associated with crystallization by
flow.
The elegant works of Alfonso and co-workers72,117−119 about
the existence and lifetime of FIP deserve a separate discussion.
They imposed shear flow by pulling a fiber inside a thin layer of
molten polymer and chose the crystalline morphology at the
fiber−melt interface as a marker to study the existence and
memory of flow history. Melt was first sheared at a temperature
slightly above the melting point, followed by an annealing at this
temperature for different durations, and finally cooled to a lower
temperature for isothermal crystallization. For the sheared melt
after being annealed for 100 s, a cylindrical morphology was
found during isothermal crystallization, while the completely
relaxed melt after being annealed for 300 s led to the typical
spherulitic morphology (Figure 7). The lifetime of FIP could be
Figure 7. Morphological evolution of PS sample as a function of
isothermal time at shear temperature after cessation of flow. The
isothermal times were (a) 100, (b) 300, and (c) 500 s (pulling rate is 5
mm/s and pulling time is 1 s). Reprinted with permission from ref 118.
Copyright 2008 American Chemical Society.
estimated from the disappearance of transcrystalline morphol-
ogy. They investigated a series of isotactic poly(1-butene)s with
varying molecular weights and found that the temperature
dependence of FIP lifetime follows an Arrhenius-type relation-
ship.72 This relationship is independent of the molecular weight
of polymer, but the lifetime of FIP increases with increasing
molecular weight. Later, they used the same method to study a
series of very narrowly dispersed iPS and found that the
exponent of this Arrhenius-type relationship is about 2.118
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Although their experimental approach is simple, with that
method, the formation of FIP can be corroborated and the
lifetime can be quantitatively assessed.
3.3.2. Are Flow-Induced Precursors Crystalline or Not?
Concerning FIP, another debated question is whether they are
crystalline or not. In the early stage of nucleation, FIP must start
with a tiny amount. In addition, FIP is often studied at high
temperatures close to the nominal melting point. Those two
reasons lead to difficulty in justifying the structure of FIP. With
the development of synchrotron radiation and detection
techniques, noncrystalline rodlike structures from SAXS,
appearing earlier than crystalline scattering from WAXS around
the nominal melting point, have been observed by several
groups.59,120−122 In contrast, some recent work on PE blends
with low and high molecular weight components and lightly
cross-linked PE showed that FIP contains crystals at temper-
ature above the equilibrium melting point.59,120,123 However,
even with a synchrotron radiation source, the detection
sensitivity of SAXS and WAXS is still a disputed issue, which
poses an obstacle to understanding whether FIP are crystalline
or not. Therefore, experimental techniques with higher
detection sensitivity and delicate experimental design are
required.
Microdiffraction scanning with beam size of a few micro-
meters is a highly sensitive technique, which allows one to obtain
high-quality SAXS and WAXS patterns with high time and
spatial resolution. For FIP, some notable studies have been
carried out recently with this technique by Gutierrez et al.,117
Kanaya et al.,68 and Su et al.,99 just to name a few. Gutierrez et
al.117 observed that ordered FIP can be generated under intense
flow at temperatures above the nominal melting temperature in
iPS. They claimed that those ordered FIP are noncrystalline and
are made up by parallel chain bundles oriented along the flow
direction, while the lamellae developed subsequently with a
crystallinity less than 1%. Their results also suggested that the
smallest and least stable FIP may be destroyed by the relaxation
of orientation and loss of segments from the oriented clusters,
which is consistent with the finding of Balzano et al.120 that FIP
stability depends on size. Kanaya et al.68 reported that FIP has a
crystallinity of about 0.15% and has a higher melting
temperature than the nominal melting temperature of lamellar
crystals in iPS.
Su et al.99 performed systematic temperature-range research
to provide more evidence on the structure of FIP. Their
experimental protocol is similar to the fiber pulling experiment
of Gutierrez et al.117 A fiber was pulled through iPP films to
create an intense shear flow field in a temperature range covering
temperatures below and above the nominal melting point, and
then the sheared sample was kept at the shear temperature for 10
min, which was finally cooled to 138 °C for isothermal
crystallization; see Figure 8. For shear temperatures below 170
°C (slightly above the nominal melting point of iPP, 165 °C),
crystalline FIP is observed. For shear temperature at 175 °C, no
crystalline FIP is detected but transcrystalline morphology is
generated at the fiber−melt surface at 138 °C. The transcrystal-
line morphology indicates the formation of noncrystalline FIP
induced by shear at 175 °C. For shear temperatures above 180
°C, only spherulitic morphology appears at 138 °C. Some may
argue that the formation of tiny crystals cannot be detected due
to the detection limit of WAXS. This indeed cannot be
completely avoided, even with synchrotron radiation scanning
microdiffraction. If the structures induced by flow at 175 °C are
tiny crystallites below the detection limit, the absence of
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Figure 8. (a1−d1) Microscopic images after crystallization at 138 °C for about 10 min. (a2−d2) One-dimensional (1D) WAXS diffraction profiles
integrated from mapping diffraction patterns. (a3−d3) Distribution of crystallinity over time around the fiber surface (which is indicated in the
microscopic images) during the second mapping measurement of samples (a) S160−138, (b) S170−138, (c) S175−138, and (d) S180−138. Dashed line indicates
the position of fiber. S160−138, S165−138, S170−138, S175−138 and S180−138 represent samples sheared at 160, 165, 170, 175, and 180 °C, respectively.
Reprinted with permission from ref 99. Copyright 2014 American Chemical Society.
induction time is expected, because crystals formed could grow
straightforwardly when sample was cooled to 138 °C. However,
an induction time exists for the sample sheared at 175 °C
(S175−138), as shown in Figure 9. Thus, it seems that the existence
of induction time demonstrates the formation of noncrystalline
FIP, which further develop into stable nuclei during the
induction time.
Figure 9. Evolution of crystallinity during isothermal crystallization at
138 °C of samples after shear at different temperatures. Reprinted with
permission from ref 99. Copyright 2014 American Chemical Society.
As suggested by the results of Su et al.,99 whether FIP is
crystalline or not depends on temperature. This dependence is
consistent with the findings from different groups.121,124−126
Polec et al.121 observed crystalline FIP for temperature below
155 °C, whereas noncrystalline FIP was found for temperatures
above 155 °C. Zhao et al.124 reported crystalline FIP of iPP at
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148 °C, while Somani et al.125,126 provided evidence of
noncrystalline FIP at 165 and 175 °C. In a nice review by
Hsiao and co-workers,11 it was pointed out that FIP may be
amorphous, mesophase, or crystalline. In the work of Balzano et
al.,127 kinetic analysis of early-stage crystallization indicates that
unidirectional propagation of a growth front may occur, which
facilitates development of crystalline FIP. However, even at low
temperature (much lower than the melting point), recent
molecular simulation by Yamamoto55 showed the growth of
smectic mesophase before crystallization in a highly stretched
amorphous iPP. Therefore, probably noncrystalline FIP can be
generated at low temperature, but the transformation process
from noncrystalline FIP to crystallites is too fast to be detected
by current experimental techniques. If this is the case, further
development of ultrafast structural detection techniques should
shed light on this long-standing problem.
3.3.3. Ordering Parameter of Flow-Induced Precur-
sors. Experimental data from X-ray scattering,83 birefrin-
gence,128 and simulation results55 all suggest the existence of
FIP. What is the fundamental ordering of FIP? This question is
still unrevealed for the polymer community. Therefore, the
definition of FIP is obscure and has been queried, just due to the
lack of full structural information and precise ordering
parameter.
Generally speaking, the order of polymer includes intrachain
and interchain orderings.28,29 Imposing a flow field first leads
polymer chains to be oriented or/and stretched, which is
accompanied by intrachain ordering. With Fourier transform
infrared (FTIR) spectroscopy, it had been demonstrated by Li
and co-workers50,51,53 that flow can indeed induce conforma-
tional order (helix) in iPP melt, where the effect is more
pronounced below the nominal melting temperature than
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above. Hence, intrachain ordering seems the starting point to
study FIP, which, however, is commonly neglected.
The effects of strain and strain rate on the coil−helix transition
were studied at various temperatures. It was noticed that long
helices induced by flow can relax or grow and align to induce
interchain ordering. Figure 10a shows an IR spectrum of the
Figure 10. (a) Intensities of 998 cm−1 band vs time after shear at (a)
164 °C; (b) 172, 177, and 200 °C; and (c) 168 °C (shear rate 13.5 s−1,
shear strain 3375%). Reprinted with permission from ref 51. Copyright
2008 American Chemical Society.
helix containing 10 monomers, with conformational band (998
cm−1), before and after shearing at 164 °C. First, flow leads to a
sharp increase of IR band intensity, indicating a strong
enhancement of long helices. Second, the IR intensity shows a
decay process after shear, which can be considered as the
melting of helical structures. Finally, crystallization starts and
leads to a second increase in intensity of the IR band. The
relaxation process of helices was analyzed with the model that
was widely used for protein.129 Two different relaxation
processes were identified, with the nominal melting point
(165 °C) as a boundary temperature. For temperatures above
the nominal melting point, the IR band intensity follows a first-
order decay process (Figure 10b), while for temperatures
around or below the nominal melting point, second-order decay
fitting is needed to model the relaxation process (Figure 10c).
Taking 168 °C as an example, two relaxation times of 315 and
16 428 s are obtained, suggesting the formation of two different
states of helices. It was tentatively speculated that the isolated
helices have a fast relaxation dynamic and aggregations of helices
with interchain ordering have a slow relaxation process. The
relaxation time of helices is influenced by strain, strain rate, and
temperature, which can reflect the ordered degree of helical
aggregation. Thus, Li and co-workers50,51,53 proposed that
relaxation time can be considered as an ordering parameter of
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FIP in some way. Of course, relaxation time is not enough to
define the structure of FIP, but the work of Li and co-workers
presented a good starting point. A more precise ordering
parameter is needed to describe and define the structure of FIP.
Interestingly, the crystallization begins after a relaxation
process of flow-induced helices rather than directly after
cessation of flow (Figure 10a), indicating that an arrangement
of helices is required for crystallization. This implies that the
helical aggregations induced by flow have a mesomorphic or
liquid-crystal ordering, consistent with the viewpoint of Somani
et al.74 that FIP are mesomorphic bundles of aligned chain
segments.
3.4. Influences of Precursor on Crystallization
Compared with disordered melt, precursors are easier to
transform into stable crystalline nuclei and consequently trigger
crystallization. This acceleration of transformation under flow is
due to two reasons. First, the barrier between crystal and
precursor is smaller than that between crystal and melt. Second,
the conformation and orientation of chain in precursor are closer
to the state in crystal than that of random-coil state. The former
is thermodynamically favorable while the latter is kinetically
favorable for this transformation, leading to accelerated
crystallization kinetics. In addition, with advanced character-
ization techniques, some other interesting phenomena were
observed recently about how the presence of precursors
influences the crystallization process, such as nucleation (section
3.4.1), crystallization kinetics (section 3.4.2), and final
morphologies (section 3.4.3).
3.4.1. Nucleation. The influence of precursor on nucleation
not only refers to its direct transformation into stable nuclei but
also facilitates the subsequent appearance of ultimate nuclei by
absorbing the surrounding molecules, creating new surface, and
even directly catalyzing the growth from relaxed melt.
Janeschitz-Kriegl and co-workers130−132 proposed the presence
of dormant nuclei even in quiescent melt, which are local
alignments or organized aggregates with a shape of fringe
micelle. When flow strength (stress in their work) exceeds a
critical level, the dormant nuclei become active as point nuclei
and align along the flow direction. With increasing stress, the
number and longitudinal dimension of those nuclei are both
significantly increased. At this stage, those nuclei have the ability
to induce growth of lamellae and can be considered as the
precursors for shish nuclei. As the intensity of the flow field
further increases, adjacent nuclei merge into shish nuclei.
Later in 2002, Seki et al.95 put forward a new model within the
framework of Janeschitz-Kriegl and co-workers130−132 that
emphasized the role of chain absorbing in the formation of
shish nuclei. In this new model (Figure 11), flow promotes the
formation of precursors, which interact with the adjacent chains
on the surfaces. The absorbed chains are easier to deform during
flow and generate more new precursors, which further adsorb
adjacent chains and ultimately lead to a trace of precursor
clusters, that is, shish nuclei. More recently, a ghost nucleation
model has been proposed by Cui et al.97 It was speculated that
the formed precursors have movement relative to their
surrounding matrix, which creates surface to form nucleation
sites. Such an effect can be generated by pulling fiber embedded
in polymer melt.133
3.4.2. Crystallization Kinetics. In most cases, FIP develops
into an effective nucleus and accelerates crystallization kinetics,
which has been demonstrated by many experiments. However,
FIP may be destroyed and consequently influence the early stage
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Figure 11. Schematic diagram of the nature of shear-induced
nucleation and subsequent growth of oriented lamellae during short-
term shearing. (a) A long chain (bold line) dispersed in a matrix of short
chains adsorbs to a pointlike precursor. Dangling segments of adsorbed
chains become oriented due to shear. (b) Additional chains adsorb and
their dangling segments form streamers upstream and downstream of
the pointlike precursor. (c) Increased local orientation of the chain
segments increases the probability that long-lived ordered structures
will form. (d) More chains adsorb to these new nucleation sites, and the
process propagates a string of nuclei along the flow line. (e) The nuclei
along this thread lead to lateral lamellar growth. Reprinted with
permission from ref 95. Copyright 2002 American Chemical Society.
of crystallization in a different way. Working with extensional
rheology and in situ SAXS techniques, Cui et al.134 investigated
the FIC of bimodal PEO blends. As shown in Figure 12a, a
Figure 12. (a) 1D SAXS meridional integrations I(q) immediately after
cessation of extension (t = 0 s). (b) Orientation parameter of lamellar
crystals of PEO blends evolving with time under different strains at 52
°C. Reprinted with permission from ref 134. Copyright 2014 American
Chemical Society.
Figure 13. (a) SEM image of toluene-extracted UHMW PE crystallites with a shish-kebab structure having multiple shish. (b) Kebab growth rate G as a
function of time. Reprinted with permission from ref 59. Copyright 2005 American Physical Society.
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nonmonotonic change in the onset time of crystallization was
observed. For strain smaller than 1.5 or larger than 3.0, only
amorphous scattering is observed immediately after cessation of
flow, while with intermediate strain of 2.0 and 2.5, an obvious
lamellar scattering peak appears. On the other hand, with strain
of 3.5, the lamellar crystals have a relatively weak orientation in
the initial stage of crystallization but a higher orientation in the
late stage (Figure 12b), whereas an opposite evolution trend
appears for the sample with smaller strain of 1.5. Cui et al.134
attributed this unusual phenomenon to the destruction of
formed precursors by further increasing flow intensity. In the
fragmenting process, the precursors may be forced to fracture,
rotate, and tilt, leading to an increased onset time of
crystallization and low orientation of initial lamellar crystals
under large strains.
In addition to the onset of crystallization and lamellar
orientation, the growth process is also affected by the presence of
precursors. Hsiao et al.59 revealed an unexpected multiple shish
structure in a sheared PE blend containing 2 wt % crystalline
ultrahigh molecular weight (UHMW) component and 98 wt %
noncrystalline matrix. From the high-resolution scanning
electron microscopic (SEM) image shown in Figure 13a,
multiple shish with a diameter of several nanometers, rather than
single shish, are presented, different from the conventional view
of shish structure. With the presence of multiple shish, a time-
dependent growth rate of kebab is observed (Figure 13b), which
is demonstrated as diffusion-controlled growth. This result is
quite different from crystallization under quiescent conditions,
where diffusion is not a limiting step and causes a constant
growth rate. The results of Hsiao et al.59 are consistent with
AFM experiments conducted by Hobbs et al.,96,135,136 who
observed a similar diffusion-controlled growth process for
kebab.
More recently, Roozemond et al.137 proposed a self-regulation
mechanism in flow-induced structure formation of iPP.
Combining a slit flow device and in situ ultrafast WAXS
measurement (30 frame/s), they found that the kinetics of the
crystallization process in all shear layers are identical, regardless
of flow rate or flow time. The intensity of flow field only
influences the thickness of shear layer. They attributed this
abnormal phenomenon to the disturbance of local flow field by
the formed shish. Flow first promotes the formation of pointlike
precursors, which transform into shish in the same way as in the
model of Janeschitz-Kriegl and co-workers130−132 and Seki et
al.95 When the density of shish reaches a critical value, the
modulus of the shear layer is sufficient to hinder further
deformation and stop shish growth. Since the volume flow rate is
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Figure 14. Schematic of correlation between precursors and cylindrites at a local wall shear stress. (a) One-dimensional SAXS plots of structural melt
after annealing for 10 min at 180 °C (a-1; iPP was heated directly from room temperature to 180 °C) and supercooled melt at 180 °C (a-2; iPP was first
heated to 210 °C, kept at this temperature for 15 min to ensure thermal history, and finally cooled to 180 °C). (b) Schematic of shear stress distribution
in a slit shear cell. (c) Corresponding optical images obtained under crossed polarizers at wall shear stress of 20 kPa. The bright sections in optical
images represent β-form crystals of iPP. Reprinted with permission from ref 142. Copyright 2012 American Chemical Society.

constant, the material in the inner layer suffers the raised flow
rate, which facilitates the appearance of shish and formation of
shear layer.
3.4.3. Morphologies. The influence of FIP on crystal-
lization mainly depends on the density and orientation of
formed precursors. Mild flow gives rise to chain orientation and
promotes the formation of pointlike FIP, leading to a huge
number of spherulites that are small in size, while strong flow
results in chain stretch and favors the formation of shish
precursors, resulting in shish-kebab structure. Some intermedi-
ate structures have also been reported, depending on the density
and length of FIP. For example, oriented FIP with short length
lead to distorted spherulites,138 while those with long length but
low density give rise to sausagelike structures.139 Under strong
extensional flow, precursors with low and high densities can lead
to fibrillar structure and to homogeneous network structure
decorated by small highly oriented lamellar stacks, respec-
tively.134
Recently, Shen et al.140 performed an interesting work to
establish the relationship between initial precursors and final
fibrillar structure (the so-called cometlike shish-kebab morphol-
ogy in their definition). A combination of two-step shear
proposal and in situ optical microscopy was adopted in their
experiment. The aim of the first shear step is to generate
pointlike precursors. After the second shear step, they observed
that all fibrillar structures are initiated from pointlike precursors.
In addition to morphologies, crystal modifications are also
influenced by the presence of precursor. Zhang et al.141−143
obtained iPP precursors by melting a sample at a temperature
between the nominal melting point and the equilibrium melting
point. The formation of precursors can be demonstrated by the
periodic structure scattering in SAXS but no crystalline
1852
scattering in WAXS (Figure 14a). They found that, even with
low shear stress, the presence of precursor assists the formation
of β-cylindrites (Figure 14c). The density and content of β-
cylindrites increase with increasing precursor content. Their
further work142 indicated that, in a specific structural melt
containing precursors, the number of α-cylindrites increases
with shear stress at the expense of β-cylindrites. Moreover,
lamellar structure also depends on the type of precursor. Four
different types of precursornamely, pointlike, scaffold-net-
work, microshish, and shishwere observed sequentially by
increasing strain in a lightly cross-linked PE.144 The long period
of lamellar stacks resulted from the former three types of
precursor increasing in an orderly fashion, while the fourth type
of precursor decreased. This is due to the increase of
entanglement and cross-link densities in the former three
types of precursor, leading to a thick interlamellar amorphous
layer. In contrast, the chain conformation inside the fourth type
of precursor is almost extended, allowing lamellae to grow
without preservation.
4. FACTORS INFLUENCING THE FORMATION OF
FLOW-INDUCED PRECURSORS
FIP formation is influenced by many experimental parameters,
such as flow strength, temperature, polydispersity of materials,
and so on. Thus, study of the crucial factors determining FIP
formation is expected to improve our understanding of the
nature and formation mechanism of FIP.
4.1. Flow Parameters
Flow can disturb chain configuration from the initial equilibrium
random-coil state to oriented and aligned states and thus can
promote the formation of FIP as well as accelerate the
crystallization. However, promotion and acceleration happen
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only when flow is above a certain strength. In this sense, the
quantification of flow strength is essential to understand FIC.
The flow field can be assessed by several parameters such as
strain, strain rate, flow time, stress, and external work. The first
three parameters (strain rate, flow time, and stress) are intrinsic
flow properties, but the last parameter, mechanical work, is
associated with not only flow strength but also molecular
properties.
Recently, Peters and co-workers98,111,145 carried out some
elegant works to study the effects of strain rate on the formation
of FIP even during short-term flow. By combining a Linkam
shear cell and fast X-ray scattering, they investigated the early
stage of FIC from melt of iPP at 145 °C with a total strain ε = 180
but different strain rate ε̇ under strong flow.145 For ε̇ ≥ 90 s−1,
crystalline FIP containing 2% crystallinity were already
generated during flow, while for ε̇ ≤ 60 s−1, only metastable
FIP with no crystallinity were formed during flow, which
transform into crystals when flow stops. Later, combining the
characterizations of fast X-ray scattering, birefringence, and final
morphology, Ma et al.111 defined several types of FIP for iPP at
145 °C. For ε̇ ≥ 400 s−1, crystalline FIP can be generated during
flow, even when the flow duration is only 0.25 s. For ε̇ = 320 and
240 s−1, noncrystalline FIP formed during flow and quickly
transformed into crystalline shish after cessation of flow, which
are defined as precursor for shish. For ε̇ = 160 s−1, SAXS and
WAXS do not show characteristic structural signals, but the
birefringence signals, including a birefringence upturn during
flow and nonzero relaxation after flow, were observed. The
birefringence signals results demonstrate the formation of FIP,
which is termed as threadlike precursor. For ε̇ = 80 s−1, the
birefringence cannot capture a structural signal, but the
accelerated kinetics and orientation indirectly reveal the
generation of FIP, which is termed as needlelike precursor.
In addition to strain rate, strain also plays an important role in
FIP formation. For example, Liu et al.144 studied strain-induced
crystallization in lightly cross-linked PE and observed
uncorrelated oriented FIP when the applied strain is smaller
than 0.6; scaffold-network FIP when the applied strain is on the
order of 1.0; microshish-type FIP when the applied strain is up
to 1.3; and shish-type FIP when the applied strain is larger than
2.0.
Although the strain rate and strain provide useful ways to
assess flow strength, the flow time, that is, accumulation effect
for the whole flow period, is not fully considered. Many results
have shown that the strain rate ε̇ and flow time tflow together
influence FIP formation in a complex way. An empirical
relationship was constructed by Liedauer et al.90 that the
transition from spherulitic to fibrillar morphology (an indicator
of fibrillarlike FIP) is proportional to (ε̇)4tflow2. This conclusion
is qualitatively consistent with the results of Somani et al.146 in
the sense that a flow with large strain rate but short flow time has
more remarkable effects on the formation of FIP than a flow with
small strain rate but long flow time.
According to the work of Doi and Edwards,67 the anisotropy
in chain conformation can be directly related to the applied
stress. Thus, stress is also a key parameter to influence FIP
formation. Kornfield and co-workers95,139,147 carried out some
well-defined shear experiments with bimodal iPP blends by not
only fixing the stress but also employing similar flow time and
applied strain, aiming to control the same average chain
orientation at the molecular level. They found a critical shear
stress of 0.12 MPa at 137 °C, above which threadlike FIP forms
as evidenced by the anomalous stress upturn during flow and
1853
Review
shish-kebab structure in the final crystallized sample. For stress
below the critical value, flow induces the formation of pointlike
precursors, as confirmed by the accelerated kinetics and
increased number density of spherulites compared with the
quiescent conditions. These results of Kornfield and co-workers
are well consistent with that of Balzano et al.,148 who performed
shear experiments at temperatures around the nominal melting
point (163 °C for the iPP they used). Coincidentally, stable
threadlike FIP containing limited crystals form for stress larger
than 0.12 MPa, while short-length FIP with aspect ratios tending
to unity (pointlike FIP) are generated for stress smaller than
0.10 MPa and dissolve into the melt with time.
In contrast with the parameters describing flow field, such as
strain rate, strain, flow time, and stress, Janeschitz-Kriegl et al.149
proposed a concept of specific mechanical work, which is
defined as W = ∫ t0flowη[ε̇(t)]ε̇ 2(t) dt, where η is the strain-rate-
dependent viscosity. The specific mechanical work contains the
effects of stress and strain, which may be chosen as a decisive
parameter to characterize the effect of flow on FIP formation.
Janeschitz-Kriegl et al. found that the number of pointlike
precursor increases with the specific mechanical work applied,
but a sudden transformation from pointlike to threadlike FIP
happens when the specific mechanical work reaches a threshold.
Recently, the validity of specific mechanical work was
demonstrated by Mykhaylyk et al.150 by using a well-defined
model of linear−linear hydrogenated polybutadiene (h-PBD).
They found that, for an assigned sample, the specific mechanical
works for formation of threadlike FIP are almost the same and
independent of strain rate when the strain rate is larger than the
inverse Rouse time of long-chain molecules (Figure 15).
However, this specific work decreases with increasing fraction
of long-chain molecules in blends. Later, Mykhaylyk et
al.138,151,152 generalized this conclusion to polydisperse
materials and pointed out that the specific mechanical work
for threadlike FIP formation depends on the chemical structure
and molecular weight distribution of polymer as well as
experimental temperature.
4.2. Temperature
The effect of temperature is obvious in FIP formation, as in
nucleation and crystal growth. In this section, we mainly discuss
some unusual phenomena about the influence of temperature on
precursors with the presence of flow.
As already discussed in section 3.3, whether FIP are crystalline
or noncrystalline depends on temperature. Generally, in
polymer melt, for temperatures around and below the nominal
melting point, FIP stay in a crystalline state; for temperatures
slightly above the nominal melting temperature but still well
below the equilibrium melting temperature, FIP are in a
noncrystalline state; and for temperatures above the equilibrium
melting temperature, only amorphous melt is expected.
However, for PE at 142 °C, close to but above the equilibrium
melting temperature Tm0 (141.2 °C), FIP containing limited
crystallinity have been observed in blends of LMW (low
molecular weight) and HMW (high molecular weight)
components by Keum et al.153 and Balzano et al.27,120 Recently,
Liu et al.123 reported that, in lightly cross-linked PE, crystalline
FIP was observed under extensional flow at 184 °C, about 43 °C
higher than the equilibrium melting temperature.
Balzano et al.27 pointed out that, in polymer melt, precursors
could form if the HMW chains overcome a critical molecular
deformation at a time scale when those molecules cannot relax.
However, at such high temperatures, the crystalline FIP is not
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Figure 16. Crystallinity and SAXS intensity evolve with time after step
shear at 142 °C. The initial drop of SAXS intensity is fitted with Doi−
Edwards’ memory function; the fit is represented by the solid line.
Reprinted with permission from ref 120. Copyright 2008 American
Physical Society.

between the experimental dissolution process and the modified

memory function further indicated that the time scale for
dissolution of small FIP is related to the reputation time of
HMW chains, in line with the IR results of An et al.51
Intuitively, the threshold of FIP formation is expected to
increase with temperature because of the enhanced barrier. In
contrast, Kumaraswamy et al.154 found that the flow time for FIP
formation under strong shear flow decreases with increasing
temperature (Figure 17). However, after rescaling by the
rheological Williams−Landel−Ferry (WLF) time−temperature
shift factors, the values of the rescaled onset time for
birefringence upturn were approximately the same for various
temperatures ranging from 140 to 175 °C. This result implies

Figure 15. (a−f) Optical images of sheared blends of high and low
molar mass h-PBD (2 wt % 1700 kDa in a 15 kDa matrix). White dashed
circles mark a boundary between oriented and nonoriented lamellar
structures in samples. The plot superimposed on image d shows the
degree of orientation of lamellar structure along the flow direction,
measured across the diameter by SAXS. The color-coded scattering
patterns above were taken from the areas marked by the green and pink
squares. (g) Plot of specific mechanical work vs measured critical shear
rates, required for the formation of threadlike FIP. (Inset) Dependence
of shear rate required for orientation on shearing time. Reprinted with
permission from ref 150. Copyright 2008 American Chemical Society.

stable even though it could form. Balzano et al.120 studied the

structural evolution of FIP at 142 °C after cessation of flow,
using in situ SAXS and WAXS. At times before 600 s, some
interesting phenomena were observed; see Figure 16. After
cessation of flow, the SAXS intensity decreased exponentially,
while the corresponding crystallinity built up gradually. Balzano Figure 17. Temperature dependence of the time scale at quiescent
et al.120 speculated that the initially formed FIP show crystallization, tQ, and of the onset time of the abnormal upturn in
polydispersity in size. The FIP with sizes larger than the critical birefringence during flow, tu. The solid line presents WLF rheological
value transform into crystals, whereas those with sizes smaller shift factor with 190 °C as a reference temperature. Reprinted with
than the critical value dissolve into melt. The good correlation permission from ref 154. Copyright 2002 American Chemical Society.

1854 DOI: 10.1021/acs.chemrev.7b00500

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that the formation of FIP happens at a fixed strain. Thereby, they
proposed that the formation of FIP is determined by a critical
level of molecular orientation, consistent with the viewpoint of
Balzano et al.27 More recently, Cui et al.30 presented a similar
result in iPP under strong extensional flow. In their study, the
time resolution of SAXS/WAXS was down to 30 ms, and rather
short flow duration was adopted (less than 400 ms). By
combining SAXS/WAXS and rheological information, they
found that FIP already formed during flow and they discovered a
constant critical strain for FIP formation for temperatures
ranging from 130 to 170 °C. Cui et al.30 proposed a kinetic
pathway coupling flow-induced coil−helix transition and
isotropic−nematic transition, in which flow provides sufficient
concentration and alignment of helices for FIP formation,
exhibiting that the barrier is eliminated by flow.
4.3. Molecular Parameters
Most semicrystalline polymers have very broad molecular
weight distribution (i.e., polydispersity). Short and long chains
differ in their responses to imposed flow, which complicates the
explanation of FIP formation, especially the role of short and
long chains. From the rheological point of view, whether and
how much chains can be deformed by external flow depends on
the competition between molecular relaxation and flow strength.
This competition can be quantified by the Weissenberg number,
which is a product of strain rate ε̇ and relaxation time τ (Wi = ε̇τ,
which is named as Deborah number in the original reference155).
Two characteristic time constants, terminal relaxation time τrep
for chain orientation and Rouse relaxation time τRouse for chain
stretch, classify flow field in three regions: (i) Wirep < 1, where
flow is weak and has negligible influence on chain conformation;
(ii) Wirep > 1 and Wis < 1, where only chain orientation occurs
without segmental stretch; and (iii) Wirep > 1 and Wis > 1, where
flow is strong enough to ensure both chain orientation and chain
stretch. The two specific relaxation times follow the relationship
τrep = τRouseZ, where Z is the number of entanglements per
chain,145 meaning that Wirep is always larger than Wis. Also note
that the practical threshold of Weissenberg number may be
slightly larger than unity. According to the estimation of van
Meerveld et al.,155 the number density of spherulites can be
increased for Wis < 1−10, suggesting an enhancement of
pointlike FIP in this flow strength region. While shish-kebab
structure is generated for Wis > 1−10, implying the formation of
threadlike FIP. The validity of this Weissenberg number
approach has been further confirmed by Housmans et al.,156
Somani et al.,146 Zhao et al.,124 and many others.
According to this picture, it is obvious that molecular weight
and polydispersity play key roles in defining the flow regions and
in influencing FIP formation. At a given flow condition, long
chains are much more easily oriented or stretched than short
ones, as long chains have longer relaxation times. To assess the
effect of molecular weight and polydispersity on FIP formation,
bimodal blends composed of long and short chains in a matrix
were commonly used as a model system. Kornfield et al.128
studied the role of long chains in a bimodal blend of iPP under
shear flow. They found that the long chains are preferentially
involved in the formation of threadlike precursors. Chains
longer than about 4.7 times average are effective in promoting
threadlike precursor formation. Furthermore, the formation of
threadlike precursors is greatly enhanced by long chain−long
chain overlap, suggesting a cooperative effect of long chains. Seki
et al.95 reported a similar enhancement of threadlike precursor
formation by adding long chains in a short-chain matrix, in
1855
Review
agreement with the results of Kornfield et al.128 However, Seki et
al.95 pointed out that, at low stress, long chains have no priority
in accelerating the formation of pointlike precursors. They
speculated that the formation of pointlike precursors is
determined by the local stress or average orientation of chain
segments, which is independent of long chains.
The simulation results of Wang et al.157 showed that
polydispersity, together with orientational relaxation, deter-
mines precursor formation. They first studied athermal
relaxation in bulk extended chains and then investigated
isothermal crystallization of intermediately relaxed melt by
dynamic Monte Carlo simulation. Their results suggested a
longer orientational memory of long chains than short ones. For
isothermal crystallization, in the melt with uniform chain
lengths, the crystallization rate can be increased by the
orientational memory, but no precursors formed during
crystallization for either long- and short-chain systems.
However, in a bimodal blend with different chain lengths,
precursors were generated from the highly oriented long-chain
component. They argued that orientational relaxation leads to
selection of long chains, due to their long orientational memory,
and makes them the source for precursor formation.
5. CORRELATION BETWEEN DEFORMATION AT
WHOLE-CHAIN SCALE AND NUCLEATION
Ordering in FIP is not completely clear yet, but flow-induced
shish can be characterized much more easily due to their
sufficiently large density contrast with the surrounding melt. The
length of shish can reach micrometers, comparable with that of
extended chain, so shish have been recognized as extended-chain
crystals in early times. Hence, the formation of shish nuclei
seems correlated with the deformation of polymer at the whole-
chain scale. In this section, the formation mechanism of shish
nuclei is our primary concern. For this purpose, we will first
introduce the discovery and various formation mechanisms of
shish nuclei. Then some new understandings of shish-kebab
revealed by recent experimental investigations will be delivered,
which are essential but still under debate: (i) Is coil−stretch
transition (CST) or stretched network model (SNM)
responsible for shish formation in polymer melt (section
5.6.1)? (ii) How do polydispersity, long chain, and short chain
matrix influence shish formation (sections 5.6.2−5.6.4)? (iii)
How does shish evolve and grow under flow and thermal
conditions (section 5.6.5)? (iv) How does shish form under
near-equilibrium and far-from-equilibrium conditions (section
5.6.6)?(v) Is shish formation a single-stage or multistage process
(section 5.6.7)? (vi) Is shish a thermodynamic phase or a kinetic
state (section 5.6.8)?
5.1. Shish-Kebab Crystallite
The chain character of polymer molecules was recognized
around 80 years ago. Since then, many studies had been carried
out on extension and alignment of polymer chains to exploit the
intrinsically anisotropic properties of materials.158−171 First of
all, chain stretching in extensional flow benefits fiber spinning,
where a uniaxial flow from a spinneret dies and a subsequent
mechanical drawing are utilized to induce chain orientation.
Ziabicki et al.172,173 and Peterlin174 constructed a relationship
between extensional flow and processing parameters for
orientation phenomena in melt spinning. Early in 1963,
Mitsuhashi175 reported the generation of fibrous stringlike
structures in polyethylene solution upon stirring. In the same
year, Vanderheijde176 observed a similar crystal morphology in
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polyoxymethylene crystallized from stirred dilute solution. After
observing the stringlike structure (see Figure 18), Pennings and
Figure 18. Electron micrograph of shish-kebab in stirred PE solution.
Reprinted with permission from ref 177. Copyright 1965 Dr. Dietrich
Steinkopff Verlag.
Kiel177 demonstrated that it may consist of extended-chain
crystals in 1965. Moreover, similar stringlike structure was also
reported for several other polymers.178−180 In these cases, a
fibrillar core with diameter of about 10 nm was always found,
which acts as a nucleus for epitaxial growth of folded-chain
crystals. Such morphology was named shish-kebab.
For shish-kebab structure, Pennings and Kiel177 investigated
the melting behavior with polarized optical microscopy (POM).
It was found that the shish backbone shows strong birefringence
and can bear an unexpectedly high temperature up to 151 °C,
much larger than the melting point of common lamellar crystals.
They conjectured that the shish might be extended-chain
crystals. Later, in 1970, Pennings et al.181 studied extensional-
flow-induced crystallization in PE solutions with a Couette-type
apparatus. They found that shish-kebab could be observed only
with Taylor vortices, and they speculated that the extensional
Figure 19. Schematic of (a) difference between macro- and micro-shish-kebabs, (b) micro-shish-kebab, and (c) central core of micro-shish-kebab.
Adapted with permission from ref 189. Copyright 1985 Chapman and Hall Ltd.
1856
Review
flow component of Taylor vortices is responsible for shish-kebab
formation. Those essential experimental phenomena lead to the
genius idea of Frank182 about chain structure and end-use
properties of polymer products. Frank realized that the unit cell
of PE crystallites is similar to diamond in certain directions and
predicted that the Young’s modulus could be on the order of 285
GPa for the crystal consisting of fully extended chains. However,
in that era, the Young’s modulus was only on the order of 10
GPa, even for oriented PE. The potential of high-modulus PE, as
Frank conjectured, stimulated the polymer community greatly
and research on shish-kebab flourished, as shish have been
considered as extended-chain crystals.183−186
5.2. Hierarchical Structure of Shish-Kebab
Initially, it was thought that shish-kebab consists of parallel
extended long chains as shish or row nuclei, which nucleate the
epitaxial growth of folded-chain crystals as kebab.187,188 The
observations of shish-kebab at variant scales revealed that the
shish-kebab entity consists of two structural levels: micro- and
macro-shish-kebab. The macro-shish is constructed by micro-
shish-kebab, and the macro-kebab grows on the surface of
macro-shish. As shown in Figure 19a, Barham and Keller189
schematically showed the difference between macro- and micro-
shish-kebabs. Moreover, Pennings et al.180 gave the details of
micro-shish-kebab in Figure 19b. In the macro-shish-kebab
structure, the macro-kebab can be removed to reveal the central
micro-shish-kebab, while the micro-kebab is intrinsically
attached to the central micro-shish core. Figure 19c shows the
structure of the central core of a micro-shish-kebab. The core
was considered as continuous extended-chain crystals at first,
but later shrinkage measurements and dark-field electron
microscopic results suggested that the core may be elongated
bundlelike crystals connected by fringelike amorphous re-
gions.190 The chains originating from these regions may
crystallize later to form the platelets. The ends of the crystalline
region are tapered in order to satisfy the lower density of
amorphous regions.189
Such a hierarchical structure of shish-kebab has been
confirmed by monitoring the thermal and soluble behavior
with different techniques like scanning or transmission electron
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Figure 20. (a) Schematic of flow device consisting of two opposed jets. (b) Birefringent bright line under elongational flow in a PE dilute solution
above crystallization temperature. Adapted with permission from ref 207. Copyright 1993 Dr. Dietrich Steinkopff Verlag.
microscopy (SEM or TEM), providing real-space information,
and X-ray or neutron scattering, providing details in reciprocal
space.71,72,95,117,122,147,190−203 Keller and co-workers190,200 used
TEM to study shish-kebab structure before, during, and after the
melting process in PE. They observed smooth fibers with
diameters around 10−100 nm and small closely packed
plateletsthat is, micro-shish-kebabsand fibers with large
platelets with spacing distance about 0.4 μmthat is, macro-
shish-kebabs. The partial melting experiments in iPS of
Petermann and co-workers201 suggested that the entire shish-
kebab structure is composed of the following parts: extended-
chain micro-shish crystals, overgrown micro-kebabs that
nucleate and connect with micro-shish intrinsically, and
macro-kebabs generated by secondary crystallization with
micro-kebabs as nuclei. Different parts of shish-kebab structure
show different responses to external attack. It was found that
macro-kebab can be washed away by fuming nitric acid from
micro-shish-kebab.204 Moreover, micro-kebabs can be over-
heated and are more thermally stable than macro-kebabs, as
micro-kebabs are firmly attached to the micro-shish backbone.
Recently, Kanaya et al.205 investigated blends of low
molecular weight deuterated PE and high molecular weight
hydrogenated PE under shear flow by combining small-angle
neutron scattering (SANS), SAXS, and depolarized light
scattering (DPLS). They elucidated that a large oriented
structure, on the micrometer scale, contains some extended-
chain crystals with a diameter of approximately 10 nm, which
seems in accordance with the picture of macro-shish-kebab.
Their work also gave some structural details on both nanometer
and micrometer scales.
5.3. Coil−Stretch Transition in Polymer Solution
To generate extended-chain crystals, polymer chains have to be
stretched. Coil−stretch transition (CST) was used to account
for the formation of shish nuclei under flow. Historically, the
CST theory was first developed by De Gennes206 to study single-
chain dynamics in polymer dilute solution under external flow.
According to the CST theory, only outer segments are exposed
to the flow field when polymer is in random-coil conformation,
while all segments are subjected to flow when polymer is in
extended-chain conformation. Hence the hydrodynamic inter-
actions are decreased by chain stretching and a critical strain rate
exists, above which a solute polymer random coil will unwind
abruptly. That is to say, the steady flow generates dual
populations of chain conformations, random coil and fully
1857
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extended chains, where no stable intermediate chain con-
formation exists.
The elegant studies of Keller and Kolnaar207 and Mackley208
provided direct evidence of CST in polymer dilute solution
under extensional flow. They designed a flow cell that consists of
two opposed jets to create an elongational flow field, as depicted
in Figure 20a, and used birefringence to characterize chain
orientation. In a dilute solution of monodisperse PE, they found
that a sharp bright line appeared along the central line of the two
jet orifices, corresponding to full chain extension when the
imposed flow rate exceeded a critical value (Figure 20b).
Mackley and Keller209 later carried out experiments at lower
temperatures, where crystallization could happen, and found
that shish-kebab morphology was generated within the localized
regions only where birefringence appeared. On the basis of these
results, they constructed a nice correlation between initial chain
conformation and final morphology, that is, the CST model,
where extended chain is assigned to form shish and random coil
is assigned to form kebab.
Experimentally, the direct visualization of CST in individual
polymers was reported by Smith et al.,210,211 who observed
molecular extension as a function of strain rate through use of
fluorescently labeled DNA molecules in an extensional flow.
Their results gave the transient rather than the final steady-state
chain conformations, which indeed showed fully extended chain
conformations and are in line with the predictions of CST. The
simulation work conducted by Dukovski and Muthukumar212
also demonstrated the discontinuous CST of isolated chains
under extensional flow. Their calculated free-energy landscape
showed that chains may be in stretched or coil state depending
on the initial conformation under a specified flow field, even for a
monodisperse polymer. The stretched chains aggregate into
shish, while the coiled chains crystallize as kebabs subsequently.
5.4. Shish-Kebab Formation in Polymer Melt
In concentrated solutions and melts of polymer, chain overlap
and entanglements exist. The physical entanglements between
different chains can act as network junctions. With an opposed-
jets flow device and birefringence, Keller and Kolnaar207
demonstrated that, for concentrated solution under elongational
flow, there are two critical strain rates ε̇c and ε̇n, corresponding to
CST (Figure 21a) and network deformation of stretched
polymer chains (Figure 21b).
For an entangled polymer solution, it was demonstrated that
the chains become disentangled and stretched out individually
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Figure 21. Schematic of the response to an elongational flow field for
entangled polymer solution. (a) Chain stretch at strain rate window
ε̇c−ε̇n and (b) deformation of network of stretched polymer chains for
strain rate larger than ε̇n. Reprinted with permission from ref 207.
Copyright 1993 Dr. Dietrich Steinkopff Verlag.
when the strain rate reaches ε̇c. As the strain rate further
increases to ε̇n, the chains deform like a mechanically cross-
linked network and the viscosity of the polymer solution
increases drastically. That means, for entangled polymer
solution, there is a strain rate window between ε̇c and ε̇n
where stretch of individual chain occurs. Both ε̇c and ε̇n decrease
with increasing polymer concentration, while ε̇n decreases much
more steeply with concentration than ε̇c. The window ε̇c−ε̇n
narrows with increasing concentration, but it is not clear
whether there really exists a crossover at high concentrations,
due to the lack of well-defined materials. If there is no crossover,
as shown in Figure 22a, the CST holds true even in polymer melt
(C = 1); but if a crossover exists, as shown in Figure 22b, chains
cannot be extended individually but deform as a network in melt.
Keller and Kolnaar207 found that the oriented crystal
morphology observed in melt under flow displays the same
fiber-platelet duality as that in solution. Similar experimental
results have been widely obtained in polymer melt under
extensional flow.213−215 For example, Schultz and co-workers213
studied the structure development of PET during melt spinning
in the early stage of crystallization. They observed the diameter
of shish directly by TEM, which is about 5 nm, in accordance
Figure 22. Strain rate for CST and stretched network rate versus concentration plot in elongational flow. Two cases are shown: (a) CST exists up to
pure melt (C = 1); (b) no CST at high concentrations or pure melt. Adapted with permission from ref 207. Copyright 1993 Dr. Dietrich Steinkopff
Verlag.
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with the result of 3−4 nm obtained from X-ray radial
distribution function.214 Then the shish would be axially
punctuated with kebabs upon modest heat treatment. As
mentioned above, the correlation between CST in chain
conformation and the resulting crystal morphology of shish-
kebab has been firmly established for solution, while no
conclusive study on melt was conducted. On the basis of the
fact that fiber-platelet duality has been also widely observed in
melt, Keller et al.1,216 argued that the final morphology of shish-
kebab structure was a pointer to the preexistence of CST, and
thus they extended the application of CST model to polymer
melt, although there is no direct evidence for CST occurrence in
melt. Afterward, the CST model was widely accepted by the
community and recognized as a standard to explain shish-kebab
formation in both solution and melt.
However, it should be emphasized that the CST theory
proposed by De Gennes was originally deduced from polymer
dilute solution where hydrodynamic effect is an essential
ingredient. For polymer melt, this essential ingredient does
not exist. Thus, in polymer melt the argument for CST actually
lacks the strict physical fundamentals. Therefore, the above
experiments conducted by Keller and Kolnaar207 can provide
convincing evidence of CST only for dilute and semidilute
solutions. Polymer melt is a transient network constructed by a
large amount of entanglements, and the chains seem unlikely to
be extended individually. Experimental evidence on shish
composed of both short and long chains147 and the critical
strain for shish formation217 clearly revealed that CST is not a
necessary condition to induce shish in polymer melt. Those
works will be discussed in detail later.
5.5. Other Mechanisms for Shish-Kebab Formation
In addition to the dominant role of CST in explaining shish-
kebab formation, some other models and mechanisms were also
developed. In 1979, Hoffman218 proposed that the formation of
shish was a multiple nucleation event. In this model, long
molecules are more evident to be elongated by flow, which
provides a set of sites for the formation of bundlelike or fringed-
micellar nuclei. The nuclei are interlinked by short amorphous
ciliary bridges, and the interior of nuclei are partly of extended-
chain type crystals but with some chain-folding defects and chain
ends. Nucleation on the same aligned long chain leads to a set of
nuclei, which subsequently crystallize and transform into a very
long core fibril, shish. Then Hoffman219 combined continuum
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Figure 23. Engineering stress−strain curves of high-density polyethylene (HDPE) melt with (a) different strains at the same strain rate of 6.3 s−1 and
(b) different strain rates. Numbers at the largest stress indicate yield strain. (c) Extensional yield strain evolves with strain rate. Red dashed line
indicates the critical strain for shish formation. Reprinted with permission from ref 217. Copyright 2010 American Chemical Society.
mechanics and nucleation theory to describe this model
theoretically. The theory predicts several parameters, such as
shish diameter and mean characteristic length, that agree well
with experimental results.
In 1984, Smook and Pennings220 emphasized that elastic flow
instabilities play a key role in shish-kebab formation during gel
spinning of ultrahigh molecular weight PE. In the model
proposed by Smook and Pennings,220 the solution of ultrahigh
molecular weight PE can be considered as a highly entangled
network constructed by entanglements with different lifetimes.
The lifetime of entanglements is mainly dependent on the strand
length protruding from an entanglement. During extrusion flow,
the entangled network deforms inhomogeneously, since the
entanglements of short lifetime can be easily migrated and the
entanglements of long lifetime are more resistant to
deformation. In this process, parts of chains are stretched out
from the cluster of unoriented molecules. The stretched chains
are more likely to crystallize even at higher temperature, due to
the decrease in conformational entropy and the squeezing effect
on solvent. Further increasing flow strength, the large clusters
break into oriented chain bundles and small clusters. Finally, the
oriented chain bundles evolve into shish and the unoriented
cluster crystallize as kebab. This model was further supported by
SEM results, which provide a possible mechanism for shish-
kebab formation in gel spinning.
Janeschitz-Kriegl and co-workers130−132 proposed an explan-
ation for the nonlinear relationship between densities of nuclei
and mechanical loading times in flow-induced nucleation (FIN).
As mentioned in section 3, dormant nuclei exist even in
quiescent polymer melt at temperatures below the equilibrium
melting point. Those nuclei are local alignments or organized
aggregates with a shape of fringed micelle, and they can become
effective to induce crystal growth at low temperature or by the
action of flow. When the strength of flow field (called stress in
their work) is larger than a critical level, the dormant nuclei
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become active as point nuclei and are aligned along the flow
direction. With increasing stress, both the number and
longitudinal dimension of those nuclei are significantly enlarged.
At this stage, those nuclei have the ability to induce the growth of
lamellae and can be considered as precursors for shish. With
further increase in the intensity of flow field, the adjacent nuclei
merge into shish nuclei.
5.6. Advances in Understanding of Shish-Kebab
In the past 20 years, researchers have made great efforts with
time-resolved technologies including synchrotron radiation
SAXS and WAXS, AFM, and birefringence to unveil the features
of shish-kebab.11,93,95−97,131,150,156,205 New observations have
been obtained and are challenging the conventional models or
explanations for shish-kebab. In this section, we intend to
outline the current understanding of this subject.
5.6.1. Coil−Stretch Transition or Stretched Network
Model? Keller and Kolnaar207 reasoned the CST for shish-
kebab formation in polymer melt because similar morphologies
were observed in polymer solution and melt. Actually, no direct
evidence is available hitherto. Recent experiments on entangled
polymer melt and cross-linked network suggested that it is
unlikely for a long chain to disentangle and undergo CST at
typical flow conditions.59,116,217,221−223 On the other hand,
more and more researchers tend to accept that the primary
nucleus of shish comes from deformed network. Actually, early
in 1984, Smook and Pennings224 suggested that a stretched
network should be responsible for shish formation. Recent rheo-
optical experiments conducted by Zhang et al.116 showed that
shish can be generated at a very low shear rate, which cannot be
explained by CST. A report on shish composed of both short and
long chains in iPP melt by Kimata et al.147 is not reconciled with
the CST model either. Hsiao et al.59 found multiple shish with
SEM from a solvent-extracted sheared PE blend, where adjacent
kebabs are interconnected by several short shish instead of single
shish. They argued that CST occurs in the chain sections
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between kebabs or probably in adjacent entanglement points,

leading to extended chain sections. Furthermore, the rheo-
optical experiments on iPP melt conducted by Seki et al.95
showed that the effect of long chain on shish formation becomes
remarkable after exceeding a critical concentration, which is
about half the overlap concentration of long chain. Ogino et
al.225 reported that, in PE melt, shish was generated when the
long chain is above a certain concentration, about 2.5−3 times
larger than the overlap concentration. Later, they further
pointed out that the critical concentration of long chain is
independent of temperature below 125 °C, while it increases
Figure 24. Critical extension ratio to induce shish formation as a
with temperature above 125 °C.197 One may argue that the function of chain concentration at 131 °C. The red line presents the
materials used in the above studies were broadly dispersed in fitting with the stretched network model (inset equation). Reprinted
matrix or long chain or both. However, the blends of well- with permission from ref 227. Copyright 2015 American Chemical
defined monodisperse samples of h-PBD in the work of Heeley Society.
et al.226 also gave the same conclusion, that is, the formation of
shish at a concentration of long chain around the overlap
concentration. These results imply that long chains should be
deformed as an entangled network rather than individual chain
behavior.
On the basis of results measured by in situ synchrotron
radiation X-ray scattering and homemade extensional rheom-
eter, Yan et al.217 argued that the occurrence of CST does not
need chains to undergo a disentanglement process in PE melt.
This argument can be justified by a combination of rheological
and structural information (Figure 23). On one hand, the
disentanglement can be judged by yielding strain. On the other
hand, the appearance of shish structure can be detected by streak
scatting in SAXS. As exhibited in Figure 23c, the yield strain
increases with increasing strain rate. However, the critical strain
for shish formation is constant when the strain rate is sufficiently
large to overcome the Rouse relaxation of chains. Meanwhile, Figure 25. Correlation between flow-induced nucleation morphologies
the critical strain for shish formation was found to be smaller and strain in polyethylene. Reprinted with permission from ref 144.
than the yield strain, which demonstrates that shish have already Copyright 2013 American Chemical Society.
been generated before CST occurs. These results excluded CST
for shish formation, and the stretched network is proved to be shish formation should be attributed to network stretching
the contributor in PE melt. instead of CST. Yang et al.228 further detected real chain
More recently, Cui et al.227 prepared a series of bimodal PE conformation in a similar lightly cross-linked system, composed
blends with various long-chain concentrations. In all bimodal of deuterated PE/hydrogenated PE blend, with real time SANS;
blends, only the long-chain component meets the requirement see Figure 26. Their results demonstrated an expectedly small
of chain stretch to induce shish formation. They utilized the chain deformation of about 1.3 for shish formation, which does
scaling law between entanglement molecular weight and not support CST. Yang et al.228 pointed out that the coupling
concentration of long-chain component to justify whether between chain conformation and density, rather than intrachain
CST or stretched network is responsible for shish formation. If conformation alone, is the key factor for shish formation.
the stretched network model holds true, the critical strain to While in iPP, Cui et al.97 revealed that shish is generated after
induce shish formation should follow this scaling law. As the collapse of entangled network during flow. They studied the
depicted in Figure 24, the critical extension ratio (strain) for rheological and crystallization behaviors in a wide flow
shish formation decrease with increasing long-chain concen- parameter space and found that at each strain rate a fracture
tration, which is fitted with the stretched network model well. strain exists. Unexpectedly, a sample can maintain integrity
With a unique PE system consisting of cross-linked network without fracture if a strain larger than the fracture strain is
and free chains, Liu et al.144 revealed four types of nucleation imposed on the sample directly. Before and beyond fracture
morphology in strain space, which coincides nicely with the four strain zones were defined, with the fracture strain as boundary.
regions defined by stress−strain curve. From rheological and SAXS results indicated that the before and beyond fracture strain
structural information, they established a correlation between zones correspond to weak and strong acceleration in
flow-induced conformations of chains and morphologies of crystallization kinetics, respectively, accompanying the tran-
nuclei, as shown in Figure 25. The uncorrelated oriented point sition from point nuclei to shish nuclei. They proposed a ghost
nuclei in region I result from the orientation of cross-linked nucleation model, in which whether a sample fractures or not
network and free chains, while the formation of scaffold-network depends on the interplay between the initial entangled chain
nuclei in region II is due to the disentanglement of free chain. network and the physical cross-linked network constructed by
Not only orientation but also stretch of chain segments is the ordering structure or point nuclei induced by flow. As
required to induce the micro-shish in region III, and finally, exhibited in Figure 27, the formation of point nuclei has two
nearly extended-chain segments give rise to shish nuclei in effects. On one hand, the chain segments between point nuclei
region IV. As the sample they used is permanently cross-linked, are more easily oriented or stretched. On the other hand, the
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Figure 26. Stress−draw ratio curve and in situ 2D SANS patterns of lightly cross-linked PE with different draw ratios (number in the upper left corner
of each pattern) of the extension processes at 170 °C. Reprinted with permission from ref 228. Copyright 2016 American Chemical Society.
Figure 27. Ghost nucleation model. Path I indicates the chain segments
between nuclei are easily deformed to induce new nuclei, and path II
indicates that the initial nuclei N0 move to Nt during flow, which
induces daughter nuclei along their trails. Reprinted with permission
from ref 97. Copyright 2012 American Chemical Society.
movement of initial nuclei provides a dynamic template for
surface nucleation. This model explains their experimental
results well and provides a new explanation for shish-kebab
formation. Wang et al.229 studied the effect of formed ordering
structure on nucleation and crystallization in more detail. They
utilized a two-step flow protocol and revealed a transition from
chain to crystal network in extension-induced crystallization of
iPP. During the interval between two extensional operations, the
structures induced by the first strain evolve into different stages
before application of the second strain. As the interval time
increases, large-scale lamellar crystallites are formed, and during
the second flow, the resultant concentration of stress on the
crystal network increased, leading to an unusual increase of
crystallization half-time. However, if the crystal network is
continuously perfected, the dynamic symmetry of the system
can be rebuilt, and crystallization kinetics is accelerated again.
5.6.2. Is Long Chain the Only Contributor for Shish
Formation? As mentioned earlier, whether in the CST
model207,209 or from the rheological point of view,155 only
chains above a critical molecular weight undergo stretch at a
specific flow strength. Thereby, long chains were thought to be
mainly responsible for shish formation. Using a crystalline
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HMW PE in noncrystalline LMW PE copolymer with rheo-
SAXS and rheo-WAXS, Yang et al.230 demonstrated that the
HMW component dominates the formation of FIP. Balzano et
al.120 studied a specially synthesized HDPE bimodal blend at
temperatures slightly above the equilibrium melting point and
concluded that long chains construct the backbone of shish. In
addition, Ogino et al.225 combined SAXS and SANS as well as
DPLS to investigate the blends of LMW deuterated PE and
HMW hydrogenated PE under shear flow. Their results implied
that shish were mainly generated from the HMW component.
Moreover, the simulation results of Wang et al.157 from a melt of
short- and long-chain blend concluded that the crystallization of
oriented long chains forms shish, which induces the subsequent
crystallization. However, a contrary conclusion was drawn by
Kimata et al.147 with deuterium labeling to distinguish different
chain lengths in iPP. Their results highlighted the presence of
LMW component in shish; that is, shish consist of both short
and long chains. They suggested that the long chain may play a
catalytic role, recruiting short chains into the formation of shish.
Those contradictory viewpoints about shish were recently
unified by Zhao et al.231 Two simplified mixtures of free and end-
linked PEO were designed to mimic the blends of short and long
chains. Their results indicated that, without the entanglement−
disentanglement transition (EDT) in end-linked network, the
formation of shish is a synergetic effect between the stretch of
network and the fast diffusion of free chains. In other words,
short chains are involved in the formation of shish, consistent
with the report of Kimata et al.147 This situation may be the
general case in the polymer melt, where highly entangled chains
are unlikely to disentangle themselves, while with the
appearance of EDT in end-linked network, the long chains are
the main contributors for shish formation, in line with the results
of Yang et al.,230 Balzano et al.,120 Ogino et al.,225 and Wang et
al.157 This situation may be the general case in polymer solution.
Actually, the noncrystalline PE in the work of Yang et al.230 and
short chains at temperatures above the equilibrium melting
point in the work of Balzano et al.120 can be considered as
solvent from a general point of view.
5.6.3. How Does Polydispersity Influence the Thresh-
old for Shish Formation? Polydispersity seems to be a
prerequisite for shish formation.207 Here we focus on the
influence of polydispersity on the threshold for shish formation,
in which the effects of concentration and length of long chain are
mainly discussed. Mykhaylyk et al.150 reported that the critical
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Figure 28. AFM amplitude images of the growth process of lamellae from the oriented backbone at various temperatures: (a) 132.5, (b) 132.3, (c) 132,
and (d) 131 °C. Scale bars represent 300 nm. Reprinted with permission from ref 136. Copyright 2001 American Chemical Society.
specific mechanical work for shish formation is inversely
proportional to the long-chain concentration, which stems
from the change in Rouse relaxation time of long chain due to
polydispersity. With a molecular weight ratio between HMW
and LMW components of about 5, Seki et al.95 demonstrated an
almost constant critical stress of 0.12 MPa for shish formation,
which is independent of HMW concentration. while with use of
the same LMW component but an increase of this ratio to 20,
the critical stress decreases significantly with HMW concen-
tration.139 Fernandez-Ballester et al.139 ascribed that the
differences correlate to the onset of chain stretch during flow.
Recently, Cui et al.227 found that the critical strain for shish
formation decreases with increasing long-chain concentration,
which agrees pretty well with the stretched network model.
Their quantitative analysis further demonstrated that the
formation of shish is determined by the deformation degree of
long-chain entangled network, but not by a sole parameter such
as strain or long chain concentration.
5.6.4. How Does Short-Chain Matrix Influence Shish
Formation? As discussed above, the role of long chains in shish
formation was investigated quite extensively. However, less
attention has been paid to the effect of matrix, that is, short
chains. The length and concentration of long chain have a strong
influence on shish formation. Similarly, the matrix is also
expected to have an influence. Using blends of long chains of
crystalline PE with two different short chains of noncrystalline
PE copolymer, Yang et al.230 studied shear-induced shish
formation by in situ rheo-SAXS and rheo-WAXS. Their results
suggested that the matrix viscosity influences the formation of
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shish in a cooperative manner. When matrix viscosity is low, the
long chains have low orientation under flow but a fast diffusion
rate. On the contrary, when matrix viscosity is high, the long
chains have high orientation but slow diffusion rate. The
interplay between those two factors influences the arrangement
of shish. Recently, Okura et al.232 gave some quantitative results
for the effect of matrix on shish formation. By studying
bidisperse blends of HMW h-PBD in LMW polymer matrices
under shear flow, they found that the critical specific mechanical
work for shish formation (revealed by an oriented morphology)
has a power law dependence on the molecular weight of matrix,
in which the index is 2.59 ± 0.27. They speculated that the
matrix influences the viscosity of blends, which opposes flow and
makes the long chain difficult to stretch. Thereby, the critical
specific mechanical work increases with increasing molecular
weight of matrix.
5.6.5. In Situ Observation of Evolution of Shish-Kebab.
With the help of in situ characterization techniques, in both real
space (i.e., POM, AFM) and reciprocal space (i.e., SAXS and
WAXS), the detailed evolution process of shish-kebab can be
traced. Here we take AFM and X-ray scattering as examples to
illustrate in situ studies of shish-kebab.
AFM is now becoming a standard method to provide real-
space information on the nanometer scale. Hobbs and co-
workers96,233,234 developed a novel rapid AFM technique
(video-AFM) with the capability to detect crystal growth on
the millisecond time scale and applied this technique to study
FIC for the first time. Their AFM works on shish-kebab
formation are especially interesting, as structure evolution on the
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Figure 29. Critical strain for nucleation from (a) SAXS and (b) WAXD as a function of temperature. Reprinted with permission from ref 123.
Copyright 2014 American Chemical Society.
Figure 30. Schematic of morphologies and structures of four regions in the strain−temperature space, deduced from both WAXD and SAXS.
Reprinted with permission from ref 123. Copyright 2014 American Chemical Society.
lamellar scale was revealed in real time and in real
space.96,135,136,235 Oriented PE melt was obtained by dragging
a razor blade across the melt on glass coverslip. It should be
noted that the direct observation of shish growth was not
realized. However, the subsequent overgrowth of kebab could be
monitored, which exhibits a number of interesting features. As
shown in Figure 28a, when the melt was cooled from 133 to
132.5 °C, a new nucleation event of one lamella occurs on the
shish (marked A). When the neighboring shish-kebabs meet
each other, interdigitations may happen (marked B in Figure
28b). The kebabs change their directions to avoid joining,
implying that the advancing lamella has a strong influence on the
melt. In some case, lamellae can even join together to form a
single long crystal (marked C in Figure 28d). Hobbs and
Miles136 further measured the growth rate of lamella and found
different lamellar growth rates. Even for individual lamellae, the
growth rate was not constant with time, different from the
constant growth rate of spherulites observed by POM.
In this AFM study, flow field is difficult to define and only
qualitative results were obtained. Quantitative information can
be obtained through X-ray scattering techniques. Keum et al.153
investigated the formation and stability of shish-kebab with in
situ rheo-SAXS and rheo-WAXS. In their experiment, PE blends
with long-chain concentrations of 2 and 5 wt % were used, which
were named 2/98 and 5/95 blends, respectively. They chose a
high shear temperature (142 °C), to allow the sole formation of
shish without kebab, and performed isothermal measurements
at this temperature. In both blends, shish scattering intensity
decreases within the initial 400 s and afterward increases with
time. They reasoned the initial intensity decrease was due to the
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decrease in volume fraction of shish due to internal stress and
relaxation of stretched chains, in line with the viewpoint of
Gutierrez et al.117 and Balzano et al.120 that defective or small-
size shish are unstable and may relax into melt. Interestingly, in
2/98 blend, the length of shish was found to increase after 400 s,
which can be explained by the autocatalytic growth mechanism
proposed by Petermann et al.236 For 5/95 blend, the length of
shish decreased monotonously during isothermal process,
consistent with the recent report of Cui et al.,227 who argued
that if only defective and short shish melted during isothermal
process, the average length of shish should increase rather than
decrease. Cui et al.227 pointed out a new relaxation process by
which some defective sections in a long shish may relax and give
rise to several short shish, hence decreasing the average length of
shish. Note that Ma et al.237 recently found that, during
relaxation, the disappearance of SAXS signal does not mean the
complete relaxation of shish into ideal random coil, since the
partially ordered intermediate structures that are below SAXS
detection limit may be formed, which can crystallize into shish
again upon further cooling.
5.6.6. Shish Formation under Near-Equilibrium and
Far-from-Equilibrium Conditions. From the thermodynam-
ic point of view, entropy-reduction model (ERM) is the most
recognized mechanism for FIN, which is based on the idea of
flow-induced reduction of conformational entropy.238−240 In
ERM, the entropic reduction or external work is directly added
to the driving force of nucleation in classical nucleation theory,
which lowers nucleation barrier and enhances nucleation rate.
The ERM predicts a strain−temperature equivalence; that is,
lowering temperature and increasing strain have the same effect
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for nucleation. However, it should be noted that in ERM the appearance of streak scattering in SAXS, crystalline scattering in
external work is treated as a perturbation, restricting itself to an WAXS, and stress-upturn in the stress−strain curve in Figure 31.
equilibrium thermodynamic framework, which may be not Unexpectedly, they discovered that the critical strain for shish
applicable to far-from-equilibrium conditions. Recently, Liu et formation remains almost constant in the temperature range
al.123 and Cui et al.30 designed two model experiments to study
nucleation under near-equilibrium and far-from-equilibrium
conditions. In the near-equilibrium experiment, Liu et al.123
verified the validity of ERM and found that free energy
determines the transition from point nucleus to shish, while in
the far-from-equilibrium experiment, Cui et al.30 invalidated the
prediction of strain−temperature equivalence in classical ERM
but demonstrated a constant critical strain for nucleation in a
wide temperature range, which reveals the nonequilibrium
nature of nucleation under strong flow.
5.6.6.1. Near-Equilibrium Experiments. With a series of
lightly cross-linked HDPE, step extension with a strain rate of
0.02 s−1 and a total strain of 2.8 were imposed to induce
nucleation. A slow strain rate was selected in order to approach a
near-equilibrium experimental condition. By a combination of
SAXS, wide-angle X-ray diffraction (WAXD), and stress−strain
results, the incipient strain (εi) for nucleation can be obtained by
the first appearance of shish scattering in SAXS or crystalline
scattering in WAXD. As shown in Figure 29, for each sample εi
increases with temperature, while at the same temperature εi
decreases with increasing irradiation dose or cross-link density.
S15, S30, and S50 represent the absorbed doses of 15, 30, and 50
kGy, respectively. Meanwhile, four regions can be defined in
strain−temperature space according to the formed crystal
morphology and structure (Figure 30): orthorhombic lamellar
crystal (OLC), orthorhombic shish crystal (OSC), hexagonal
shish crystal (HSC), and oriented shish precursor (OSP). Figure 31. (a) Engineering stress (σengr) and corresponding 2D (b)
This work indicates that flow not only reduces the entropy of SAXS and (c) WAXS patterns evolve during flow at 140 °C. The flow
direction is horizontal. Reprinted with permission from ref 30.
initial melt but also modifies the free energies of final states,
Copyright 2015 American Chemical Society.
which were often overlooked in classical ERM in FIN. They
incorporated the free energies of various final states in ERM, from 130 to 170 °C (Figure 32), which breaks the strain−
which agrees with their results pretty well. With this modified temperature equivalence predicted by ERM but unveils the
ERM, the estimated critical thicknesses for OLC, OSC, and nonequilibrium nature of FIN. To account for this temperature
HSC nuclei are on the order of 10, 100, and 500 nm,
respectively, implying that the critical thickness of nuclei
determines the transition from point nuclei to shish nuclei.
This work demonstrates the validity of classical nucleation
theory for FIC under near-equilibrium conditions, provided that
the entropy reduction of initial melt and the free-energy changes
of final states induced by flow are taken into consideration.
5.6.6.2. Far-from-Equilibrium Experiments. Nucleation
under strong flow is a typical kinetics-controlled process,
where the equilibrium ERM may not be applicable. Validation of
the equilibrium ERM theory under strong flow condition
requires simultaneous acquisition of nucleation and stress−
strain information during flow, which is rather challenging. As Figure 32. Critical strain for shish formation at different temperatures.
FIN is extremely fast (on the order of tens of milliseconds) Dashed red line indicates the average critical strain measured from 130
under strong flow, a structural detection technique with high to 170 °C. Reprinted with permission from ref 30. Copyright 2015
time resolution is a precondition, which restricts most studies on American Chemical Society.
FIC that can only detect crystallization after the cessation of flow
rather than during flow.98,124 To construct a strain−temperature independence of FIN, Cui et al.30 proposed a tentative kinetic
diagram for nucleation, the capability to collect stress−strain pathway of nucleation containing stretch-induced coil−helix
during flow is another precondition. and isotropic−nematic transitions, in which flow provides both
Cui et al.30 combined extensional rheological and ultrafast X- the concentration and the compatible alignment of helixes for
ray scattering measurements to reveal the nucleation in iPP melt nucleation. These two transitions are dictated by strong flow
under strong flow, with a strain rate of 12.6 s−1, flow duration less rather than thermal fluctuation, manifesting that FIC is a strong
than 400 ms, and time resolution of X-ray scattering up to 30 ms. external-field-driven nonequilibrium phase transition.
By combining SAXS/WAXS and rheological information, the 5.6.7. Is Shish Formation a Single-Stage or Multistage
critical strain for nucleation can be defined precisely by the Process? Early mechanisms for shish-kebab formation, such as
1864 DOI: 10.1021/acs.chemrev.7b00500
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Figure 33. Schematic illustration of shish-kebab formation during (A) spinning and (B−D) shear flow. B and D are optical and birefringent results,
respectively. Reprinted with permission from ref 222. Copyright 2011 American Chemical Society.

Figure 34. Schematic illustration of kinetic process for shish formation. (A) Stretched network, (B) type I shish without lamellar structure, (C) type II
shish with sporadic lamellae, and (D) type III shish containing periodic lamellae. The flow direction is horizontal. Reprinted with permission from ref
227. Copyright 2015 American Chemical Society.

CST or SNM, only propose the correspondence between initial
chain conformation and final crystal morphology. However, it is
unclear how extended chains or stretched networks transform
into shish. Massive studies on FIN imply that shish may nucleate
via a precursor or metastable stage rather than a direct
transformation.72,120,124,241−243 On the basis of X-ray scattering
results, Balzano et al.145 and Zhao et al.124 argued that precursors
first generated during flow, which may transform to shish
crystals or dissolve gradually. Works by Kanaya and co-
workers68,70,71,121 provided more details on the nature of shish
precursors. Their results showed that large stringlike precursors,
on the micrometer scale, form above the melting point, which
are able to induce shish when cooled. Microbeam WAXS
1865
measurements indicated that the crystallinity of inner structure
of the stringlike precursors is rather low, about 0.15%.
By studying the structure evolution in solution of UHMW PE
under shear flow and along spinning line, Hashimoto and co-
workers194,222,244 proposed a new scenario, in which flow-
induced phase separation, mediated by the dynamic asymmetry
and the stress−diffusion coupling245−247 preceding nucleation,
was taken into account. As shown in Figure 33, the nucleation
process can be divided into four regions. In the t1 region, PE
entangled network is swollen homogeneously in solvent, as
evidenced by no feature in the optical image. In the t2 region,
plane-wave-type concentration fluctuations with wave vectors
oriented along the flow direction appear. In the t3 region,
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Figure 35. (a) True stress−time curve during extension of cross-linked PE with strain rate of 3 s−1 at 172 °C, and corresponding SAXS and WAXD
images. (b) Nonequilibrium phase diagram of cross-linked PE in stress−temperature space. L, δ, H and O are melt, noncrystalline shish, H-crystal and
O-crystal, respectively. Reprinted with permission from ref 248. Copyright 2016 Springer Nature.

Figure 36. (a) Nonequilibrium phase diagram of cross-linked iPP in strain rate−temperature space. M, S, α, and β are melt, noncrystalline shish, α
crystals, and β crystals, respectively. (b) Relative content of β crystals in strain rate−temperature space. Reprinted with permission from ref 249.
Copyright 2016 Wiley−VCH.

demixed domains are generated and distributed in space
randomly. In the t4 region, the domains are aligned into strings
by flow to create bundles of stretched chains. The stretched-
chain bundles and the nearly isotropic demixed domains
transform into shish and kebab, respectively. This model is
further supported by the transient structures revealed by TEM
along spinning line with a special fixation method, which is
rational and may be general for dynamically asymmetric polymer
systems.
Very recently, Cui et al.227 revealed a kinetic process for shish
formation from initial chain conformation to final stable nuclei.
They first demonstrated that the stretched entangled chain
network is responsible for shish formation. Then, with a
delicately designed thermal history and real-time SAXS method,
they further observed three types of shish with different
stabilities by increasing strain, which can be considered as
three stages in the formation of stable shish nuclei; see Figure 34.
When the deformation of entangled network reaches a critical
degree, the stretched chains couple with each other to transform
into fibrillar type I shish, which is similar to nematic phase. Type
I shish has density contrast to surrounding matrix but no
embedded lamellar structure. Type I shish further transforms
into type II shish, containing sporadic lamellar structure, and
type III shish, containing lamellar stacks with well-defined
periodicity. The barriers for those transformations can be
overcome by flow. It should be noted that the lamellar structure
mentioned here is within shish, which is different from the kebab
that grows on the surface of shish.
5.6.8. Is Shish a Thermodynamic Phase or a Kinetic
State? Noncrystalline shish has been observed at temperatures
near or above the melting temperature of lamellar crystals.
1866
However, whether the noncrystalline shish is a thermodynamic
phase or a kinetic state remains unclear. Wang et al.248 studied
flow-induced phase behaviors of a cross-linked PE (with gel
fraction 43.5%) in a wide temperature range up to 240 °C with
ultrafast X-ray scattering. By combining SAXS, WAXD, and
extensional rheology, they could determine the onset or critical
stress for various structure formations, such as shish structure
(named δ-phase in their work), hexagonal crystal (H-crystal),
and orthorhombic crystal (O-crystal). Figure 35a is an example
to show structural evolution during extension at 172 °C, where
melt, noncrystalline shish, and H-crystal appear sequentially. On
the basis of critical stress for the structures formed at various
temperatures, they constructed a nonequilibrium thermody-
namic phase diagram for FIC of PE in stress−temperature space.
This phase diagram has four regions: melt (L), noncrystalline
shish (δ), H-crystal (H), and O-crystal (O) (Figure 35b).
Increasing stress (σ) leads to a sharp increase of L → δ transition
temperature, a moderate increase of δ → H transition
temperature, and a decrease of O → H transition temperature.
Wang et al.248 verified the reversibility of flow-induced phase
transitions by conducting a stress reduction experiment. The
structure evolution follows a pathway L → δ → H with
increasing stress, while a reversed transition H → δ→ L occurs
with decreasing stress. Interestingly, the critical stresses for H →
δ and δ → L transitions during stress reduction are smaller than
their reversed δ → H and L → δ transitions during stress
increase, indicating that δ ↔ H and L ↔ δ are two pairs of
nonequilibrium phase transitions with stress hysteresis.
Considering the facts that shish (δ) can be observed solely
without crystalline diffraction even at temperatures above 200
°C and that Figure 35b shows a clear direction and pathway for
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Chemical Reviews
Figure 37. Strain rate−temperature flow structural (a) and morphological (b) diagrams of poly(1-butene). Reprinted with permission from ref 250.
Copyright 2017 Royal Society of Chemistry.
shish (δ) structure transition in stress−temperature spaces,
Wang et al.248 claimed that shish is a thermodynamic phase and
can be stable or metastable depending on the stress and
temperature.
Ju et al.249 constructed a similar flow diagram of iPP in strain
rate−temperature space, which is composed of melt (M),
noncrystalline shish (S in their work), α crystals, and an α/β
crystal coexistence regions (Figure 36). What needs to be
emphasized here is that the noncrystalline shish presents alone
in a small region at temperatures above the melting point of α
crystals. This region is located at the most violent competition
zone in the strain rate−temperature phase diagram, where
dynamic competitions happen among four involved phases. Ju et
al.249 attributed the formation of noncrystalline shish to the
kinetic competitiveness of shish over α and β crystals but not to
thermodynamic stability. The frustration effect due to the
violent competitions among four phases leaves the noncrystal-
line shish winning out. For poly(1-butene),250 the constructed
structural and morphological diagram (Figure 37), the same in
strain rate−temperature space, revealed that metastable form III
can be crystallized from the melt, which may further transform
into form II during flow. Concerning the crystallite morphology,
a transition from flow-induced network to the shish structure
was also observed upon elevating flow temperature from below
to above the melting temperature for form II.
A recent work of Liu et al.251 even gave a quantitative
estimation of the thermodynamic parameter of noncrystalline
shish in cross-linked PE. They calculated the critical external
works for melt−noncrystalline shish and noncrystalline shish−
crystal transitions based on rheology and X-ray scattering
methods. The critical external work of melt−noncrystalline
shish transition is larger than that of noncrystalline shish−crystal
transition at low temperature, but the situation is reversed at
high temperature. Thermodynamic parameters such as the
enthalpy and surface energy of noncrystalline shish were
analyzed by incorporating the critical external work into a
modified stretch network model.123 Their results help to
illustrate the following two issues: (1) the energy barrier of
noncrystalline shish formation increases with increasing temper-
ature, and (2) the surface free energy and bulk free energy of
noncrystalline shish are much smaller than those of correspond-
ing crystals.
6. THEORIES AND MODELS OF FLOW-INDUCED
NUCLEATION
6.1. Molecular Theory of Flow-Induced Nucleation
Nucleation of polymer can be greatly influenced by flow, from
kinetics to crystal morphology. From the prediction point of
1867
Review
view, it is necessary to understand experimental phenomena on a
molecular level.
Conformational entropy reduction is commonly considered
as the origin of FIC. Polymer crystallization is different from the
crystallization of small molecules because of the long-chain
feature. The covalent connection of polymer not only restricts
the diffusion of chain segments but also leads to a huge amount
of conformational entropy. For a single chain with a fixed end-to-
end distance, the position of segments varies with time and a
great number of conformations can be obtained. The freedom to
form a large number of possible conformations corresponds to
large entropy. Evidently, when a coiled polymer chain is
deformed, the number of possible conformations is reduced. If
equilibrium phase transition is still assumed with no change of
free energy, the reduction of entropy directly leads to the
increase of equilibrium melting temperature. Equivalently, the
undercooling becomes larger, and thus the crystallization is
facilitated. This is the widely accepted molecular mechanism for
flow-induced polymer nucleation.
The quantitative description of FIC needs a specified chain
model to calculate the conformational entropy. At the very
beginning, it is worth pointing out that crystallization of polymer
mostly happens under a large undercooling, while for the sake of
simplification, the equilibrium thermodynamics of crystalliza-
tion is used to describe the phase transition. Furthermore, the
enthalpy of crystallization is considered as a constant at different
crystallization temperatures, and the entropy of undercooled
melt is considered the same as that at equilibrium temperature.
With these assumptions, the conformational entropy change is
the only parameter that needs to be calculated. Various models
will give different expressions of this entropy change. With the
quantified entropy change, a predictable model for crystal-
lization can be obtained.
In the following subsections, we will discuss some molecular
theories to describe the crystallization of polymer under either
strain or flow. This section dates back to the independent works
focusing on cross-linked network and melt. Although the
external field is macroscopically imposed by extensional or/and
shear flow, it is believed that molecular deformation, rather than
macroscopic flow, is the substantial reason for changes in
crystallization behavior, so strain-induced crystallization in
cross-linked network and FIC in melt will not be distinguished.
However, crystal morphology and chain relaxation behavior
differ in the two conditions, which make these models slightly
different.
6.1.1. Crystallization Induced by Stretching of Cross-
Linked Network. A cross-linked network like vulcanized
natural rubber can sustain strain without significant relaxation,
which provides a model system to link chain deformation with
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the resulting crystallization. Flory developed a thermodynamic where

theory to describe the strain-induced crystallization in cross-
linked natural rubber, which hardly crystallizes at ordinary β′ = β[n/(n − ξ)]1/2 (6)
temperatures. The segments between cross-link points are and z′ is the algebraic sum of the z displacement lengths of
defined as an individual chain, of which the end-to-end distance amorphous sections of the chain.
increases with strain. During stretch, chains are elongated and To calculate the conformation entropy change with respect to
the number of possible conformations gradually decreases, the fully crystallized state, two hypothetical steps are considered
which reduces the entropy. Gaussian distribution is still used to by Flory: (a) n − ξ segments per chain are first melted and the
describe the conformation distribution. It is assumed that chain ends are assumed to be free, and (b) the free chain ends are
crystallization does not happen before chains are stretched to the reassigned to the cross-link points, which leads to a trans-
final length, so the entropy change coming from deformation formation of conformation distribution from ν′(x, y, z′) to ν(x ,y
can be calculated from the strain. When crystallization begins, ,z):
the conformational entropy change is further divided into two
parts. The first part comes from the transition from oriented Sa = σ(n − ξ)sf (7)
amorphous segments to crystals, where the involved segments where sf is the entropy of fusion per segment and is obtained by
are completely frozen by crystallization. This reduction in the lattice model.
entropy is monotonic. The second part originates in the (partial) Sb is calculated by employing the Boltzmann relationship:
release of chain stretching of the residual amorphous segments.
Since crystals in natural rubber are found to orient well along the S = k ∑ ν ln W (8)
stretch direction, the crystals in this theory are assumed to align
along the stretch direction. Segments in the crystals have a more S b = k ∑ ν(x , y , z) ln W ′(x , y , z′)
extended conformation than that in the amorphous phase; thus, xyz
for the same end-to-end distance, the stretching of amorphous
segments will release partially. When crystallinity is low, the − k ∑ ν′(x , y , z′) ln W ′(x , y , z′)
second part of entropy change is positive. With increasing xyz′ (9)
crystallinity, the segment number may become so small that the
The obtained entropy change is given in eq 10:
entropy decreases again. This decrease in entropy will prevent
full crystallization of the segments between cross-link points. S = σk[(n − ξ)sf /k − (ξβl)2 n/(n − ξ)
Obviously, calculation of the entropy change of the
amorphous part under stretch is a major problem. Fully + (2αξβl /π 1/2)n/(n − ξ)]
crystallized state is chosen as the reference state, and partial − (α 2/2 + 1/α)n/(n − ξ) + 3/2 (10)
melting of crystals is considered to give the equilibrium
crystallinity. The detailed theory is briefly described as follows. The free energy of the system, with perfectly ordered and totally
The number of probable conformations of an amorphous crystalline chains as the standard state, becomes
chain is assumed to be dependent on their end-to-end distance r F = σ(n − ξ)hf − TS (11)
by Gaussian function:
If we define λ = (n − ξ)/n and θ = sf/k − hf/kT, the equilibrium
r = (x 2 + y 2 + z 2)1/2 (1) state can be obtained by eq 12 and the result is given by eq 13:

Ä ÉÑ ÄÅ ÉÑ|1/2
∂F/∂λ = 0 (12)

oÅÅÅÅ 3
l
W (x , y , z) = (β /π 1/2)3 exp[−β 2(x 2 + y 2 + z 2)]
ÑÑ ÅÅ 3 Ño
ÅÅ 2 − θ ÑÑÑÑ}
(2)

λ=m
oÅÅÇ 2 ÑÑ
n ÑÖ ÅÇ ÑÖo
~
where x, y, and z represent the coordinates of one end of the − ϕ( α )
chain with respect to the other end and 1/β equals the most (13)
probable value of chain displacement length, r. After stretching
along the z-axis, the distribution of chain coordinates becomes where
ϕ(α) = (6/π )1/2 α /n1/2 − (α 2/2 + 1/α)/n (14)
ν(x , y , z) = σ(β /π 1/2)3 exp[−β 2(αx 2 + αy 2 + z 2/α 2)]
(3) The incipient crystallization temperature Tm, at which
crystallization just happens, can be obtained by assigning λ =
where σ is the total number of chains under consideration and α
1 in eq 13:
is the stretch ratio. The freely jointed chain model with
independently oriented rigid segments is used. For such chains, 1/Tm = 1/Tm 0 − (R /hf )ϕ(α) (15)
the reciprocal most probable displacement length is given by
The force can be obtained by
i ∂F y i ∂F y
f = jjj zzz = jjj zzz
β = (3/2n)1/2 /l (4)
where l is the length of each segment and n is the number of k ∂α {e k ∂α { λ
segments per chain. The product nl is taken to equal the
maximum extension L of the actual chain. = σRT[(α − 1/α 2) − (2nβl /π 1/2)(1 − λ)] /λ (16)
When ξ of the n segments of the chain participate in
crystallization, the relative number of configurations available to When no crystal forms, λ equals 1 and f becomes
the remaining n − ξ segments becomes f = σRT(α − 1/α 2) (17)
1/2 3 2 2 2 2
W ′(x , y , z′) = (β′/π ) exp[−(β′) (x + y + z′ )] Force is an easily measurable parameter; thus, for an
(5) approximation, the integration of force with strain can be used
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Figure 38. Schematic illustration of the free energies of different morphologies and structures: (a) under quiescent conditions, (b) classical stretched
network only involves the effect of flow on the entropic reduction of melt, and (c) modified stretched network considers different crystal morphologies
and structures in the final stage of nucleation as well. G is free energy, where subscripts L and N represent melt and nuclei, respectively; ΔG* is the
nucleation barrier of critical nucleus; ΔGfN is the free-energy change of nuclei induced by flow. Reprinted with permission from ref 19. Copyright 2016
American Chemical Society.

to indicate the entropy change. Particularly, there should be no 6.1.2.1. Microrheological Model. The Doi−Edwards theory,
crystallization during stretch. Crystallization is the most- based on the tube model proposed by De Gennes, is widely used
encountered reason for deviation from Flory’s theory. Based as a rheological theory of polymer melt. This theory gives an
on this approach, several recent works have been reported.123 analytical expression of the constitutive equation in orientation
In addition to the aforementioned entropic reduction of initial or even strong chain-stretch conditions. With this theory,
melt, Liu et al.123 also considered the flow-induced free-energy Coppola et al.252 have calculated chain deformation and the
change of the final nuclei, which was quantitatively expressed as corresponding entropy change during flow. For the sake of
simplification of mathematical analysis, the independent align-
1
=
1
−
(
vk αi2 + α − 3
i
2
) ment approximationthat the segments are still of the same
length and number as at equilibrium and that deformation has
4σ only changed their orientation in spaceis introduced.253 Note
Tc(αi) Tc(1) (
2ΔH 1 − ΔHle * ) that this approximation excludes chain stretch, which is actually
important in crystal morphology change.
where Tc(αi) and Tc(1) are the crystallization temperatures at
As described by the Lauritzen and Hoffman theory,
elongation ratios of αi and 1, respectively, and v is the network-
ÄÅ É
K n ÑÑÑÑ
nucleation rate can be expressed as

jij Ea zyz ÅÅ
chain density. Concerning the final nuclei, melting entropy ΔH

z expÅÅÅ−Å
N = CkBT ΔG expjj−
j kBT zz ÑÑ
ÅÅÇ T (ΔG)n ÑÑÑÖ
depends on their specific crystal modification formed, while

surface free energy σe and critical nucleus thickness l* both are
determined by the crystallite morphology. For instance, the
surface free energy σe can be varied from folded-chain to fringe
micellar structures, due to the morphological transition from
folded-chain lamellae to shish. In this way, the flow-induced
change of free energy is also considered for the final nuclei, as
shown by Figure 38.19
6.1.2. Flow-Induced Nucleation in Free Melt. Different
from the permanent constraint on chain mobility in cross-linked
networks, the constraint from entanglements is temporary in
melt and the chain can relax via chain movement; for instance,
the terminal time for a single chain to move out the original tube
is on the order of seconds or less. Two effects must be
considered due to the occurrence of relaxation in melt: (i)
during flow, the deviation between macroscopic strain and
molecular deformation is probably significant, which hinders a
direct correlation between chain deformation and crystalliza-
tion; and (ii) after flow cessation, the continuous decay of chain
k {
̇
(18)
where C includes energetic and geometrical constants, kB is
Boltzmann’s constant, T is crystallization temperature, ΔG is
thermodynamic driving force (the volumetric free-energy
difference between melt and crystal), and Ea is diffusion
activation energy across the liquid−nucleus interface. Kn is a
constant containing energetic and geometrical factors of nuclei.
For primary nucleation, n equals 2, and for secondary nucleation,
n is 1.
When flow is imposed, the volumetric free energy of melt is
raised and ΔG changes into
ΔG = ΔGq + ΔGf
(19)
Here ΔGq is the thermodynamic driving force under quiescent
conditions and can be written as

ij T yz
ΔGq = ΔH0jjj1 − 0 zzz
deformation may make crystallization also dependent on time
j Tm z{
k
after flow. A more comprehensive model is needed to include
strain rate and time-dependent chain deformation, in addition to (20)
the thermodynamic model of crystallization.
Rheological theory of polymer melt is a good candidate to where ΔH0 is the latent heat of fusion and Tm0 is the equilibrium
describe chain deformation during and after flow. From the melting point. ΔGf is the driving force contributed by external
rheological point of view, the stress response due to flow is field, as the step strain in this work. If ΔGf is known, nucleation
determined by chain deformation, which is commonly described rate under flow can be predicted. The Doi−Edwards theory with
by the constitutive equation. The correspondence between independent alignment approximation (IAA) was proposed to
macroscopic stress and microscopic chain deformation makes describe the effect of flow in the linear region. The general form
the theory verifiable and gives abundant information about the given by Marrucci and Grizzuti253 is
strain rate and time-dependent chain deformation. Two models t
have been proposed: the microrheological model (section
6.1.2.1) and the dumbbell model (section 6.1.2.2).
ΔGf = 3ckBT ∫−∞ μ(̇ t , t′)A[E(t , t′)] dt′ (21)

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where c is the primitive chain-segment concentration, equivalent This deduction assumes a monodisperse sample, while in
to entanglement density. It can be expressed as practice a polydisperse sample is commonly used. To
ρ demonstrate the validity of the theory, Acierno et al.254 also
c= NA use this model to describe a long- and short-chain blend of
Me (22) polybutene. The only change is the form of the memory
where ρ is the density of melt, Me is molecule weight between function, which is modified as
entanglements, and NA is Avogadro’s number.
The Doi−Edwards memory function μ(t,t′) gives the memory μDR (t , t ′, τdH , τdL)
of flow at time t when flow was imposed at time t′. It can be = [ϕHμSR (t , t ′, τdH) + ϕLμSR (t , t ′, τdL)]2
ÄÅ ÉÑ
(32)

ÅÅÅ (t − t ′)p2 ÑÑÑ

written as

μ(t , t ′) = 2 ∑ 2 expÅÅÅ− ÑÑ
where ϕH and τdH are the volume fraction and relaxation time of

ÅÅÅ ÑÑ
ÑÑÖ
8 1
Ç
long chain and ϕL and τdL are the volume fraction and relaxation
π p p τd time of short chain, respectively.
odd (23)
The effects of crystallization temperature were also inves-
where τd is the terminal relaxation time. tigated.255 Qualitatively, as temperature increases, chain
For steady-state flow, ΔGf can be rewritten as relaxation becomes faster. To quantitatively capture this change,
+∞ the time−temperature equivalence principle was used, which is a
ΔGf = 3ckBT ∫0 μ(̇ z)A[Wiz ] dz
(24)
standard approach in rheology. The Weissenberg number is
modified by a shift factor α, and other parts of the theory remain
Wi is the Weissenberg number (named as Deborah number in the same. Good agreement was obtained on the experimental
the original reference252), that is, deformation rate multiplied by and modeling induction time.
polymer relaxation time. z is a dimensionless value defined as In summary, the microrheological model developed by
time divided by relaxation time τd. Coppola et al.252 gives the free-energy change induced by flow
For uniaxial elongation deformation with an elongation ratio in steady state and correlates it with the acceleration of
λ, we have crystallization kinetics. The introduction of independent
alignment approximation intrinsically neglects chain stretch
tan−1(λ 3 − 1)1/2 and only accounts for the effect of orientation. The use of
A(λ) = ln λ + −1
(λ 3 − 1)1/2 (25) memory function clearly shows the importance of chain
relaxation in melt.
ÄÅ É
and for shear deformation with strain γ, we can write
ÅÅ 1 + γ 2x 2 + [x 4(γ 4 + 4γ 2) − 2γ 2x 2 + 1]0.5 ÑÑÑ
6.1.2.2. Dumbbell Model. The dumbbell model considers the

ln ÅÅÅÅ ÑÑ dx
ÑÑ
polymer chain as two rigid beads linked by a flexible spring. The
ÅÅÅ ÑÑÑ
1

Ç Ö
1
A(γ ) =
2
∫0 2
vector R, giving the relative position of the two beads, is the only
parameter to describe chain deformation. Evidently, this model
(26) is simpler than the Doi−Edwards theory. Several works have
In the small Wi limit, the integration in eq 24 has the form shown been reported to describe the crystallization of polymer based on
in eqs 27 and 28 for shear and extension: this model.
The configurational distribution function of the end-to-end
ΔGf π4
Wi 2 vector R can be written as

jij[κ·R]ψ − 2kBT ∂ ψ − 2 F ψ zyz

=

jj e z
3ckBT 600 (27)

z
k {
∂ψ ∂
=−
ΔGf π4 ∂t ∂R ζ ∂R ζ (33)
= Wi 2
3ckBT 200 (28)
where κ is the velocity gradient tensor, kB is Boltzmann’s
In the large Wi limit, the form for shear and extension will be constant, ζ is bead friction coefficient, and Fe is elastic force of
expressed as shown in eqs 29 and 30: the spring. For a Hookean spring, the force is
ΔGf Fe = K R (34)
= ln Wi − 2.41
3ckBT (29) where K is the spring elastic constant. For a finite extendable
2 nonlinear elastic dumbbell, the force will be
ΔGf π
= Wi − 1 KR
3ckBT 12 (30) Fe =
1 − ⟨(R /R 0)2 ⟩ (35)
Clearly, the microrheological model only describes steady-state
flow, which is not valid after crystallization happens. The authors where R0 is the maximum length of the dumbbell.
thus compared the predicted induction period with exper- The free energy of the system A, for the deformed chain under
imental value, where the crystallinity is rather low. flow, is
Nq̇ A = nkBT ln⟨ψ /ψ0⟩ (36)

ÅÄÅ É
Θ=

yzÑÑÑÑ
Nḟ
ÅÅ K ij
where ψ0 is the equilibrium distribution and n is the number

expÅÅÅ Å j
j z
− 1zzÑÑÑÑ
z
j
ÅÅ T (ΔGq )n jj (1 + ΔGf /ΔGq )n zÑÑ
1 1 density of molecules. In entangled melt, n is equivalent to the

ÅÇ k {ÑÖ
n
= entanglement density.
1 + ΔGf /ΔGq
With eqs 33−35, when flow field is assigned by the tensor κ,
(31) the distribution function ψ can be obtained by eq 33. When ψ is
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Chemical Reviews Review

known, the free-energy change after flow can be calculated by eq When the expression for the Hamiltonian is substituted, the
36. rate of crystallization is
ij T yzz
Z ΔHujjjj1 − zz
In the work of Coppola et al.,252 the free-energy change by

Tm 0 z{
∂ϕc ρ
k
dumbbell model is also used as a comparison. The free-energy =
ÄÅ ÉÑ
nkTZ ÅÅÅÅ Ñ
change obtained by eq 36 is assigned directly as ΔGf. The ∂t Mu
ij 24Nc11 yz 2Ñ ÑÑ
Å
Å j
j z
z c Ñ ÑÑ
formula describing crystallization kinetics follows the Laur-
2(1 − ϕc)2 ÅÅÅÇ
1/2

k π { ÑÑÖ
itzen−Hoffman theory. It is found that the simplification of − tr c − + 6N ϕ − 3Nϕ
ÄÅ ÉÑ
̅ c

ÅÅ ÑÑ
chain conformation gives a larger free-energy change than that in
ÅÅ ÑÑ
nkTZ ÅÅÅ ÑÑ
ÑÑ
the Doi−Edwards theory. 1/2

ÅÅ
2 ÅÅÅ c c c + 3ϕ 2Nc c − ϕ 24Nc11̅ 1/2 c c ÑÑÑÑ
24Nc11
Bushman and McHugh256 further use the Hamiltonian to 6ϕ c
Nc c
̅ 33
22 ̅ − ( π
̅
)
c c
̅ 33
22 ̅

ÅÅ 11 ̅ ÑÑÑÖ
+
ÅÇ ̅ 22
derive the time evolution of crystallinity. When crystallization is
taken into account, the free-energy change of the remaining ̅ 33 ̅ c ̅ 33
22 ̅ c (
π )
̅ 33
22

ÅÄÅ ÑÉÑ
amorphous part by the dumbbell model becomes (41)

nkBT ÅÅÅ ijjj 3⟨R cR c⟩ yzzzÑÑÑ

ln ÅÅÅdetjj 2 zÑÑ
The conformational tensor during crystallization can be

ÅÅ j ⟨R N ⟩(1 − ϕ ) zzÑÑÑ ÄÅ ÉÑ
obtained as
ÅÇ k c {Ñ ÅÅ ÑÑ
Ö ÅÅ c11c 22 c33 − ϕ 6Nc11̅ Ñ
A=−

ÄÅ ÉÑ ̅ = 2ε ̇c + 1 ÅÅÅÅ ̅ ̅ ̅ ̅ ÑÑÑ
2
Å Ñ ÑÑ
1/2

Å Ñ λ ÅÅÅÅ c11 ÑÑ
( )
3nkBT ÅÅ Ñ
0
c c

− 1ÑÑÑÑ
ÑÑ
∂ c11 ̅ 33

ÅÅ
c π 22

ÅÅ ÑÑ
Å
Å ÑÑ ÅÇ ÑÖ
2 ̅
11

2 Å ⟨R N0 ⟩(1 − ϕc)
⟨R c ⟩ ∂t ̅ c 22
̅ c33
2
̅ + 3ϕc Nc 22̅ c33
ÅÇ ÑÖ Ä É
̅
ÅÅ 1/2 Ñ
+

i 24Nc11 y Å i 6Nc11 y ÑÑÑÑ

2

j z ÅÅ j z
− ϕcjj zz c 22 ̅ − λ(1 − ϕ ) ÅÅÅÅ c11 ̅ − ϕcjj π zz ÑÑÑÑ
(37) 1/2

k π { c Å k { ÑÖ
1
Ç
̅ ̅
Upon conversion of Rc to the end-to-end distance of whole ̅ c33
molecules, RN, the free-energy change in extension becomes

nk T ij ⟨RN ⟩(1 − ϕc) yzz

(42a)

A = B ln jjjj zz
zz
3

j
2 ∂ c 22 c 22
̅ = − 1 ε(1 1 ̅
k {
̇ + p) c 22
̅ + −

ÅÄÅ ÑÉÑ
2 3 ∂t 2 λ λ(1 − ϕc) (42b)

nkBT ÅÅÅ ij 8c11 yz ÑÑ

ln ÅÅdet c + c 22c33l − j
ÅÅ
j z lc 22c33ÑÑÑÑ
z
1/2 ∂ c33 c33
k { ÑÑÖ
̅ = − 1 ε(1 1 ̅
ÅÇ
2 ̇ − p) c33 + −
− ̅
ÄÅ ÉÑ
∂t 2 λ λ(1 − ϕc)
ÅÅ Ñ
2 π (42c)

ÅÅtr c + l 2 − jij 8c11 zyz l ÑÑÑ − 3nkBT

ÅÅ j z ÑÑ
where λ is the characteristic relaxation time of the medium,
2⟨RN ⟩(1 − ϕc) ÅÅÅÇ k π { ÑÑÑÖ
1/2
3nkBT
+ 2 which is chosen to reproduce the known result for a
2 noncrystalline system.
(38) The dumbbell model used above has two interesting points
where c is the conformation tensor of the whole molecule and l is making it different from other models, as the authors pointed
the length of crystal. out. First, it can simultaneously account for the dynamics of flow
The Hamiltonian can be expressed as follows: and the crystallization that is occurring. Second, the finite

l
extensibility of molecules is taken into consideration in the finite
o
∫Ω omooo 21ρ M·M + σem
extendable nonlinear elastic dumbbell. These two characters are

n
H= clearly different from the model of Marrucci and Grizzuti,253 in

ij T yzz 3nkT
which only induction time under orientation conditions can be
ϕcΔHujjjj1 − zz +
Tm 0 z{
ρ obtained.
k
− ln (1 − ϕc)
ÄÅ ÉÑ
Titomanlio and co-workers focus on the modeling of

nkT ÅÅÅÅ ÑÑ
Mu 2
ij 24Nc11 yz ÑÑ
crystallization during real polymer processing, for example,
ln ÅÅ c11 − ϕcjj zz c 22 ÑÑ
ÅÅ ÑÑ
1/2
film casting257,258 and injection molding.259 In their works, both
ÅÇ k π { ÑÖ
− c 22 c33 2
+ 3ϕc Nc 22 c33 ̅ c33
ÄÅ É
̅ ̅ ̅ ̅ ̅ ̅ ̅ the evolution of crystallinity and crystal morphology under
1/2 Ñ |
2

nkT ÅÅÅ Å Ñ o 3
i 24Nc11
ÅÅtr c̅ + 3ϕc 2 − ϕcjjj ̅ yzz ÑÑÑÑ − 3nkT o
nonisothermal crystallization processes are modeled. The
z ÑÑ }
odx
2(1 − ϕc) ÅÅÇ Å k π { ÑÑÖ 2 o o
dumbbell model is used in their model to describe chain
~
+
extension, which is transformed to entropy change and further to
elevation of the melting temperature of crystals. The complete
(39)
model is rather complicated, since many factors affecting the
Here M = ρv is the momentum density, Mu is the molecular crystallization have to be considered. Introduction of the details
weight of a single chain, σem is the interface energy between is beyond the aim of this review.
crystal and amorphous melt, and c̅ = 3c/Nb2 is the non- 6.1.3. Quantitative Description of Extension-Induced
dimensionalized conformation tensor. Nucleation. 6.1.3.1. Relaxation-Related Long Period Evolu-
Upon introduction of a parameter Z describing crystallization tion. It is widely accepted that, during flow, molecular
kinetics, the time evolution of crystallinity can be given by deformation depends on the competition between flow strength
and chain relaxation. However, whether chain relaxation plays a
∂ϕc δH role in FIC after flow is a question that is paid little attention.
= −νβ∇β ϕc − Z
∂t δϕc (40) Optical microscopic results show that all spherulites have the
same dimension, which indicates all nuclei form at the same
where νβ is a component of the velocity tensor and Z is a fitting time. Besides, the rate of lamellar growth is mainly determined
parameter. by the crystallization temperature. Then, it seems that chain
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relaxation does not affect the FIC after flow. Intuitively, just after
flow, the chain relaxation affects chain conformation, which
leads to a time-dependent entropy loss. According to nucleation
theory, the nucleation rate should correspondingly change with
time. It is convincing to us that the apparent discrepancy is
rooted in the length scale covered by the experiments, which is
spherulite scale for microscopic experiments but lamellar details
for X-ray methods.
It was found that at high extensional rate the long period of
PEO first increases just after flow; see Figure 39.260 The
abnormal increase upon flow cessation is different from the
increase of long period induced by lamellar thickening; the latter
takes a long time for chain segments in crystals and amorphous
phase sliding collectively. A model based on relaxation is
proposed to explain the increase in the distance between two
lamellae, as shown in Figure 40.
After cessation of the step strain at time t0, the highly oriented
molecular chains tend to gradually relax back to equilibrium Figure 40. Schematic illustration of nucleation model after step strain.
The nucleation density decreases (long period increases) with
random-coil state, during which FIN takes place. In the situation nucleation time, due to relaxation of polymer chains. Reprinted with
permission from ref 260. Copyright 2011 American Chemical Society.

happens during stretch. The free-energy change at time t after

cessation of deformation (t = 0 s) is the product of the memory
function and a constant, A0, which is the free-energy change in
the absence of relaxation:
ΔGf = 3ckBTA(t ) = 3ckBTA 0μ(t ) (45)
The nucleation rate of unit volume can be written as eq 46,

ÄÅ ÉÑ
ÅÅÅ ÑÑ
following the microrheological model:
ij Ea yz ÑÑ
Ṅ = CkBT ΔG expjjj− zz expÅÅ− Ñ
j kBT zz Å
ÅÅ T (ΔGq + ΔGf ) ÑÑÑ
K
k { ÅÇ ÑÖ
n
n

Figure 39. Abnormal increase of long period during extension-induced
crystallization of PEO. (a) Two-dimensional scattering patterns. (b)
Lorentz-corrected one-dimensional intensity profiles. (c) Time
evolution of the long period. Reprinted with permission from ref 260.
Copyright 2011 American Chemical Society.
of high orientation, the long period is assumed to be
proportional to the inverse of linear density of nuclei, as
shown in eq 43:
V (t )
L (t ) ∼
N (t )
Here the symbol ∼ means the coefficient is omitted. The density
of nuclei decreases with time due to relaxation of the oriented
polymer network. Correspondingly, the long period increases
with nucleation time; namely, Lt 1< Lt 2, with t1< t2 as
schematically illustrated in Figure 40. The long period obtained
with SAXS is the inverse of nucleation density averaged over
total nucleation time, which also increases with time.
The original microrheological theory is extended to the step
strain case to interpret the evolution of long period
quantitatively. Generally, when a deformation with finite time
is considered, the free-energy change can be calculated as
t One drawback of this model is the exclusion of chain stretch,
A(t ) = A[E(t , 0)] − ∫0 A[E(t ′, 0)] μ(̇ t − t ′) dt ′
When step strain with a strain rate much higher than is
considered, it is a good approximation that no relaxation
(46)
The volume is estimated by assuming that the filling rate has a
linear relationship with the unoccupied volume, as eq 47 shows:
d V (t )
= B[V0 − V (t )]
dt (47)
where V(t) is the volume occupied by nuclei and V0 is the total
volume. B is a constant with units of reciprocal seconds and
reflects the speed of nucleation. B will be referred as the volume
filling rate hereafter. Solving eq 47, we get
V (t ) = V0[1 − exp( −Bt )] (48)
(43)
The total nucleation rate depends on the remaining volume;
hence eq 46 has to be multiplied by exp(−Bt). Subsequently the
number of nuclei N(t) can be obtained:
t
N (t ) ∼ ∫0 Ṅ (t ′) exp( −Bt ′) dt ′
(49)
With the time-dependent number of nuclei and the occupied
volume, the long period obtained from SAXS is numerically
fitted. The fitted curves of the long period are presented in
Figure 41. The volume filling rate B, reflecting the speed of
nucleation, is given in Figure 42, which shows good agreement
with the time of onset of a distinct scattering peak.
(44)
which is rooted in the microrheological model by Coppola et
al.252 Nevertheless, chain stretch is definitely very important in
τd−1 FIC of polymer. Besides the abrupt morphology change, some
interesting changes in long period evolution have been
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found.261,262 How to describe these transient changes is still an
open question in modeling.
6.1.3.2. Crystallization under Single Molecular Stretching.
Crystallization theories, particularly those based on rheological
Figure 41. Comparison of calculated and observed long period.
Reprinted with permission from ref 260. Copyright 2011 American
Chemical Society.
Figure 42. Comparison of 1/B and the time of onset of scattering peak.
Reprinted with permission from ref 260. Copyright 2011 American
Chemical Society.
models, often assume that material system studied is
monodisperse. The assumption simplifies the derivation of
theory but impedes its comparison with experimental results. As
the material practically used is polydisperse, sometimes the
response to flow is dominated by the long-chain portion, which
composes only a minority of the material.221,230,263 Even with a
monodisperse sample, the inhomogeneous flow in strong flow
field may also disrupt the comparison between experimental and
theoretical results.264,265 How to stretch a polymer chain in a
controllable way and how to correlate deformation with
subsequent crystallization are still unsolved issues.
Stretching a single chain directly is a promising way to solve
the above problem. A poly(L-lactic acid) (PLLA)−poly-
(ethylene oxide) (PEO) diblock copolymer was designed and
synthesized.266 PLLA has a relatively higher melting temper-
ature and crystallizes first at 90−130 °C. The different variations
of crystallization temperature will cause different lamellar
thicknesses. After crystallization, the contraction of PLLA
makes the PEO chains deviate from random-coil state. An
1873
Review
equivalent chain stretch, which originates in the surface
crowding of PEO, can be obtained. The thickness of PLLA
lamellae determines the strength of stretch imposed on PEO. By
use of this block copolymer, a single molecular stretch was
achieved, as presented in Figure 43.
The crystallization kinetics can also be described by classical
nucleation theory (CNT) incorporating free-energy change
induced by stretch. The free-energy change by stretch can be
given through surface crowding theory, as shown in eq 50:
π 2kBTcNA
ΔGf = lPEO2
16NMb2 (50)
where N is the number of segments with Kuhn length b, M is the
molecular weight of PEO block, NA is Avogadro’s number, and
Figure 43. Illustration of single molecular stretch and the effect of
temperature. Reprinted with permission from ref 266. Copyright 2011
American Chemical Society.
lPEO is the length of PEO block and is calculated from the density
of crystals and amorphous region.
The induction time is obtained by the decrease of SAXS
intensity, since after PEO crystallizes the density contrast begins
to decrease. The fitted induction time is presented in Figure 44.
The good agreement indicates a well-controlled single molecular
stretch.
6.2. Macroscale Continuum Modeling
Modeling provides a very powerful tool to understand FIN.
Focusing on different length and time scales of polymer
crystallization, there are various classes of modeling methods,
including full molecular dynamics simulations,267−269 lattice
Monte Carlo,270,271 coarse-grained kinetic Monte Carlo,272,273
and macroscopic continuum models.274,275 The bottom-up
strategy is to develop detailed models by resolving the motion of
individual atoms. However, the corresponding high computa-
tional cost hinders its wide application to the crystallization of
polymers on practical length and time scales, especially under
the mutual influence of severe processing-relevant (flow,
temperature, and pressure) conditions.
Alternatively, the top-down investigation starts with deriva-
tion of macroscopic continuum models from the empirical
relationships obtained from abundant experimental observa-
tions. Unlike molecular models, which are capable of presenting
many details of nucleation, macroscopic models are disadvan-
taged by the absence of molecular details, and consequently, the
macroscale continuum model requires initial assumptions as
input to build the quantitative relationship between flow
strength and resultant nucleation features like density and
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Figure 44. (a) SAXS intensity during crystallization of PEO. The temperature indicates the crystallization temperature of PLLA. (b) Fitted induction
time. Reprinted with permission from ref 266. Copyright 2011 American Chemical Society.
Figure 45. Model for growth of nuclei. Reprinted with permission from ref 275. Copyright 2009 Wiley−VCH.
orientation. A detailed comparison between different model
methods and recent progress of coarse-grain kinetic Monte
Carlo and molecular dynamics models can be found in the
recent reviews of Graham13 and Rutledge.276
In this section, macroscale continuum models will be mainly
discussed. Besides the potential application to practical
processes, the macroscopic model can directly use experimental
results to test and to improve mechanism understanding, in the
form of assumptions. Also note that only modeling of FIN is
introduced; other models describing the subsequent crystal-
lization process, including crystallite growth, are outside the
scope of this work, and readers are referred to ref 277.
Under severe flow strength, the formed nuclei have a fibrillar
geometry, where the length is much larger than the lateral
diameter. It was suggested that formation of fibrillar nuclei may
start with pointlike objects and subsequently grow in the
longitudinal direction to form the ultimate fibrillar shape.
The first model aspect concerns what determines the
appearance of fibrillar nuclei in a quantitative manner. The
quantity of formed fibrillar nuclei is often macroscopically
indicated by the sharp morphology transition from fine-grained
layer to oriented layer observed with a polarized microscope.
Janeschitz-Kriegl and co-workers90,278 found that a parameter
(the product of the fourth power of shear rate and the square of
shear time) remains approximately constant at the boundary
between fine-grained layer and oriented skin layer in a
rectangular shear slit. This parameter was linked to the density
of flow-induced fibrillar nuclei, and the developed model
interpreted such dependence as meaning the creation rate of
nuclei and their longitudinal growth rate are both proportional
to the square of shear rate. However, this empirical correlation is
restricted to specific material (molecular weight and molecular
weight distribution). The model needs to relate nucleation with
deformation on the molecular level in order to be more generally
applicable to other materials and flow conditions, as McHugh et
al.279 suggested that molecular strain due to flow may be the
dominant process in FIN.
Systematic work has been done by Peters and co-workers on
macroscale continuum models to describe the onset of
1874
Review
formation of fibrillar nuclei, the detailed longitudinal growth
rate, and the influence of generated nuclei on rheology. Zuidema
et al.274 first proposed that the recoverable strain, that is, elastic
deformation, dominates FIN. Later, Steenbakkers and Peters280
replaced the recoverable strain by molecular stretch, and
Custodio et al.275 applied it on injection molding processes. It
has been demonstrated that the high molecular weight (HMW)
tail dominates FIN; the part controlling molecular stretch
should be the HWM tail. Thus, flow-enhanced nucleation rate
was modeled to be fourth-order-dependent on the molecular
stretch ΛHMW of the slowest relaxation mode, Ṅ f = gn(ΛHMW4 −
1), with a scaling parameter gn dependent on temperature. Next,
when the molecular stretch of HMW tail surpasses a threshold,
the formed nuclei change from pointlike to fibrillar, resulting in
the morphology transition from spherulite to oriented
crystallites, as shown in Figure 45.
After formation, the fibrillar nuclei grow longitudinally. The
HMW tail plays a crucial role in triggering the formation of
fibrillar nuclei, but Kimata et al.147 found that shish structure has
a comparable concentration of HMW parts as the rest of
polymer melt. This implies that the development of fibrillar
nucleithat is, L̇ , the growth along longitudinal direction
should be participated in by all chains in the melt. Thus, the
longitudinal growth rate of fibrillar nuclei was determined by the
average stretch of all chains and written as L̇ = gLJ2(Be,avgd),
where J2(Be,avgd) is the second invariant of the deviatoric elastic
Finger tensor of a mode representing whole-chain-length
distribution of the melt, indicating the combined effect of
molecular stretch and orientation, and gL is a scaling factor. In
addition, the fibrillar nuclei and the caps can grow in the radial
direction at a lamellar growth rate G; see schematic illustration
in Figure 46.
Another important aspect of this model is inclusion of the link
between flow-induced nuclei and rheological properties of the
corresponding melt, which often was not considered by the
simulation of the length and time scales of individual molecules.
FIP or nuclei are usually envisioned as clusters of chain
segments, in which the mobility of chain segments is lower than
that of free chains in the melt due to dense packing effects; as a
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Chemical Reviews
consequence, the flow-induced nuclei can act as physical cross-
linking points. Zuidema et al.274 proposed that the relaxation
times of HMW chains in the flow melt depend on the number of
flow-induced nuclei in a linear function.
Figure 46. Growth of isotropic and oriented crystalline structures.
Reprinted with permission from ref 275. Copyright 2009 Wiley−VCH.
This model was then applied to two sets of well-defined
injection molding experiments employing isothermal and
Figure 47. Distribution across half the normalized slit thickness of (i) total length of fibrillar nuclei, (ii) number of flow-induced nuclei per volume, and
(iii) average length of fibrillar nuclei for flow conditions MPR1 and MPR 2. Reprinted with permission from ref 275. Copyright 2009 Wiley−VCH.
1875
Review
nonisothermal protocols, respectively. A finite element code
was utilized to implement the model, and a decoupled approach
was employed to compute the flow kinematics. From the growth
rate of fibrillar nuclei, Eder rate equations278 were employed to
calculate the total undisturbed length, surface, and volume of
oriented crystallites per unit volume. Figure 47 compared the
modeling and experimental results for isothermal crystalliza-
tions. The features of flow-induced fibrillar nuclei, in terms of (i)
total length per volume, (ii) total number density, and (iii)
average length, are predicted along the slit thickness direction,
where various locations along the thickness direction experi-
enced distinct flow strengths. Experiment MPR1 serves as the
reference experiment, and its microscopic images show three
distinct regions of spherulitic core layer, fine-grained layer, and
oriented layer, moving from the slit center to the wall. These two
transition locations along the thickness direction are used in the
predicted curves to determine critical points modeled for flow
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Figure 48. Distribution across half the normalized slit thickness of (i) total length of fibrillar nuclei, (ii) number of flow-induced nuclei per volume, and
(iii) average length of fibrillar nuclei for flow conditions MPR3 and MPR4. Reprinted with permission from ref 275. Copyright 2009 Wiley−VCH.
condition MPR1 (shown by ●, which change to ○ under other
conditions). These critical values obtained from experimental
condition MPR1 are further compared with those values of
transitions under other flow conditions, to test whether MPR1
modeled criteria are applicable to other flow conditions. Figure
47 right column (MPR2) clearly shows that the critical values
predicted from MPR1 (○) are almost on top of the prediction
curve for flow condition MPR2, indicating that the morpho-
logical criteria modeled are applicable to both MPR1 and MPR2
conditions.
Further applied to conditions MPR3 and MPR4, the model
predicted a lower value of total length per volume of fibrillar
nuclei than the MPR1 criteria; see Figure 48. This agrees well
with the fact that no oriented layer is observed under these two
flow conditions, implying that a critical total length of fibrillar
nuclei is required to cause a detectable oriented layer. In
addition, the relative volume fraction of oriented crystals can be
obtained as Vori = ψ0/(ϕ0 + ψ0), as shown in Figure 49, which
1876
Review
interestingly shows that the values of Vori at the transition from
fine-grained layer to oriented layer for MPR1 and MPR2 are
both around 0.025.
The model was also applied to nonisothermal experiments,
where the criterion based on the relative volume of oriented
crystals shows good agreement between predictions and
experimental observations (see Figure 22 in ref 275). The
agreement between modeling predictions and experimental
results shows that the molecular assumptions about criteria for
the formation of fibrillar nuclei, longitudinal growth rate, and
correlation between nuclei and melt viscosity, are reasonable for
these flow conditions. However, the authors also point out that
the predicted critical average length of fibrillar nuclei is up to 1
mm, which seems too high and needs more experiments to
calibrate the model parameters.275
Meanwhile, alternative insights are given into the formation
mechanism of FIN. Van Erp et al.281 studied the combined effect
of shear and pressure on FIN in iPP. Among flow conditions,
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Chemical Reviews
Figure 49. Distribution of relative volume of oriented material, Vori = ψ0/(ϕ0 + ψ0), across half the normalized slit thickness under flow conditions (a)
MPR1, (b) MPR2, (c) MPR3, and (d) MPR4. Reprinted with permission from ref 275. Copyright 2009 Wiley−VCH.
Figure 50. (a) Molecular and (b) cumulative molecular stretch over time (shear time ts = 1 s). Reprinted with permission from ref 281. Copyright 2013
Wiley−VCH.
two typical cases are 180 s−1 at 500 bar and 100 s−1 at 1200 bar,
respectively causing distinct isotropic and oriented morpholo-
gies. Again the molecular stretch during flow is calculated and
presented in Figure 50a, which shows a relatively larger ultimate
molecular stretch for 100 s−1 at 1200 bar than for 180 s−1 at 500
bar. According to the aforementioned model using the critical
molecular stretch as a criterion, fibrillar nuclei are more likely to
be generated in 100 s−1 at 1200 bar. However, the experimental
result displayed that fibrillar nuclei appear in 180 s−1 at 500 bar.
To understand this deviation, van Erp et al.281 compared the
time integrals over the stretch history during the shear time
∫ t0sΛHMW dt between these two conditions (see Figure 50b).
Interestingly, it was found that the accumulative molecular
stretch of 180 s−1 at 500 bar is always larger than that of 100 s−1
at 1200 bar, which is consistent with experimental results that
fibrillar nuclei are observed under the former flow conditions.
This indicates that, different from the critical value of the
transient molecular stretch, the accumulative molecular
stretchthat is, the integral of transient molecular stretch
over flow timeseems to be the controlling parameter to
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Review
determine the formation of fibrillar nuclei under the combined
influences of flow and pressure.
The experimental results used to compare with modeling
results are the final crystallite morphologies ex situ examined
after complete solidification. Recently, Ma et al.98 utilized a
modified multipass rheometer and an advanced ultrafast
synchrotron X-ray method to successfully track time evolution
of rheological properties during severe flows close to the
processing strength and lasting only 0.2−0.25 s. A significant rise
in melt viscosity was found during the severe flow pluses, instead
of the steady-state plateau. On the basis of these experimental
results, Roozemond et al.282 modeled the FIN at such high shear
rates and found that, when describing the dependence of
nucleation rate on molecular stretch of the HMW tail, an
exponential relationship works better than the power law used
before by Zuidema et al.274 and van Erp et al.;281 see the
comparison of various models in Figure 51.
Actually, Pantani et al.283 also proposed a molecular stretch
model to describe the transition from spherulitic to fibrillar
morphology. By employing the elastic dumbbell model, the
constitutive equation was written as
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Chemical Reviews
Figure 51. (a) Pressure drop and (b) apparent crystallinity during and after flow with piston of 100 mm/s for 0.2 s. Symbols show experimental data;
solid lines show the model of Roozemond et al.282 (indicated as current model); and dashed lines show the model of Zuidema et al.274 Reprinted with
permission from ref 282. Copyright 2015 AIP Publishing LLC.
D 1
A̿ − (∇ν ̅ )T A̿ − A̿ (∇ν ̅ ) = − A̿ + (∇ν ̅ ) + (∇ν ̅ )T
Dt λ intermediates.
(51)
where A̿ is the deformation tensor with respect to equilibrium
state, ν̅ is the velocity field, and λ is the relaxation time. If a flow
at the constant shear rate (γ̇) is applied to melt at the reference
time and the relaxation time λ is considered as constant during
flow, then the deformation tensor A̿ at time t can be written as
ÄÅ É
t yÑÑÑ
follows:
ÅÅ
i t yi
A11 = 2λ 2γ 2̇ ÅÅÅ1 − expjjj− zzzjjj1 + zzzÑÑÑ
ÅÅÇ k λ {k λ {ÑÑÖ
(52)
ÄÅ É
ÅÅ i t yÑÑÑ
A12 = λγÅÅÅ̇ 1 − expjjj− zzzÑÑÑ
ÅÅÇ k λ {ÑÑÖ
(53)
The difference between the two main eigenvalues of the
deformation tensor can be taken as a measurement of the
elongation of the system. For simple shear, the system
elongation becomes Δ = (A112 + 4A12 2 )1/2 . When the Debor-
ah number (defined as the ratio between relaxation time and
shear time) is much larger than 1, the molecular stretch reaches
its maximum value, Δ = 2Wi[(1 + Wi 2)1/2 ], where Wi = λγ̇.
Then, to form fibrillar morphology, molecular stretch Δ needs to
reach a certain critical value of Δc. Thus, the relaxation time (λ)
is considered as a fitting parameter to reproduce the measured
boundary of shish formation in shear rate−shear time space.
7. FINAL REMARKS
After decades of effort, a wealth of phenomenological
accumulations and substantial progress in theory and modeling
have been achieved in FIN. However, there are still many
challenges in unveiling the multiscale and multistep process of
FIN, which are summarized as follows.
(1) Molecular mechanism of FIN: The long-chain nature of
polymers endows them with multiscale structure and relaxation
time. During nucleation induced by flow, the anisotropic long
chain assembles into hierarchical structures, where the multi-
scale ordering involves via both intra- and interchain ordering.
As discussed in section 3, those ordering processes may occur
sequentially, leading to appearance of structural intermediates
like precursors. The occurrence of precursor challenges the
traditional two-phase nucleation model, and the future
1878
Review
molecular mechanism of FIN should incorporate structural
(2) Ordering parameter of precursors: Fast X-ray scattering
studies have demonstrated the formation of precursors during
flow, which have a large influence on nucleation, crystallization
kinetics, and final crystal morphology. However, the definition
of precursors is still obscure due to the lack of a precise ordering
parameter. Although relaxation time was proposed as an
ordering parameter of precursors, this parameter lacks structural
information and depends on temperature. Finding a suitable
ordering parameter of precursors is essential to construct the
molecular mechanism of FIN and to understand how precursors
influence the nucleation process.
(3) Nonequilibrium nature of FIN: Current theoretical
considerations of FIN are based on the framework of classical
two-phase nucleation model. The effect of flow is incorporated
into nucleation driving force through a simple add-up method.
However, nucleation under strong flow is a typical non-
equilibrium phase transition, which is not a simple extension
of equilibrium phase transition and cannot be described by small
modifications of the equilibrium case. On the other hand, the
intrinsic nature of multiple lengths and multiple relaxation
modes makes polymers a rather suitable model system to study
nonequilibrium phase transition. Meanwhile, flow is an effective
trigger to reveal the nonequilibrium nature of nucleation.
Therefore, exploring the nonequilibrium nature of flow-induced
polymer nucleation not only helps to underscore the molecular
mechanism of FIN but also enriches the study of nonequilibrium
science.
(4) Diversity in mechanism of FIN: Concerning FIN, the
general effects revealed for all polymers include raised
nucleation density, oriented nuclei, and even altered crystallite
modifications. However, the mechanism of FIN may vary greatly
in different polymers, or even for the identical polymer with
changes in experimental conditions like temperature and flow
strength. It seems difficult, at least presently, to build one
universal mechanism to describe FIN for all polymers.
Therefore, molecular structures and flow conditions should be
studied in a systematic manner, rather than under a single
condition, to identify all similarities and differences to
comprehensively understand the FIN mechanism. Moreover,
experimental conditions should be well-defined to precisely
specify the mechanism under certain limited molecular and
experimental conditions as well as to avoid occurrence of
unintended effects like inhomogeneous flow and melt fracture.
DOI: 10.1021/acs.chemrev.7b00500
Chem. Rev. 2018, 118, 1840−1886
Chemical Reviews
(5) Developing new and powerful experimental and modeling
approaches: Nucleation of polymer under flow is a multiscale
and multistep process. The spatial uniformity and fast dynamics
of this process require robust detection techniques with
sufficiently high space and time resolution. As the development
of synchrotron radiation-based X-ray scattering benefits the
understanding of structural evolution during crystallization,
innovative techniques with ultrahigh time and space resolution
can shed light on the complex nucleation process and help to
construct the molecular mechanism. Meanwhile, multiscale
modeling approaches are also expected to give verification and
new understanding of nucleation at the molecular level and
bridge gaps between different detection techniques in both time
and length scales.
(6) FIN in real polymer processing: Different from most FIN
studies that were performed under relatively mild conditions in
the lab, real polymer processes have much stronger flow strength
and more complex flow conditions. For instance, in film blowing
and casting, flow gradients are two-dimensional and exist along
both stretching and lateral directions. More attention should be
paid to FIN events under complex real processing conditions. In
the meantime, based on these obtained experimental results, the
mesoscale simulation and modeling need to be developed to
gain understanding of mechanism and to also validate/modify
the current mechanism.
In summary, FIN is a very fundamental and industrially core
subject. The intrinsic multiscale features of polymer chain lead
to multiscale ordered structures and multistep ordering process
for nucleation. The multiscale structures include segmental
conformation, packing of conformational ordering, deformation
on the whole-chain scale, and macroscopic aggregation of
crystallites. The multistep process involves conformation
transition, isotropic−nematic transition, density fluctuation
(or phase separation), formation of precursors, and shish-
kebab crystallites. The molecular mechanism of FIN, incorpo-
rating both multiscale and multistep considerations, is in urgent
demand. A full understanding of nucleation under flow will
ultimately benefit the precise control of polymer products and
the understanding of nonequilibrium phase transition.
AUTHOR INFORMATION
Corresponding Authors
*E-mail zhe.ma@tju.edu.cn (Z.M.).
*E-mail lbli@ustc.edu.cn (L.L.).
ORCID
Nan Tian: 0000-0003-1822-876X
Liangbin Li: 0000-0002-1887-9856
Notes
The authors declare no competing financial interest.
Biographies
Kunpeng Cui received a B.S. in material science and engineering from
Zhengzhou University in 2010. Then he joined the research group of
Professor Liangbin Li at the University of Science and Technology of
China, where he investigated flow-induced polymer crystallization and
received a Ph.D. in 2015. He is currently working as a JSPS (Japan
Society for the Promotion of Science) research fellow at Hokkaido
University. His research interests include polymer crystallization,
toughening mechanism of hydrogels, and synchrotron-based X-ray
scattering techniques.
1879
Review
Zhe Ma received a B.S. in polymer science and technology from
Zhejiang University of Technology in 2005 and obtained his M.S. in
polymer material processing from Sichuan University in 2008. Later, he
joined Eindhoven University of Technology, where he received a Ph.D.
in polymer materials in 2012 and worked as a postdoctoral researcher
from 2012 to 2015. He is currently working as an associate professor of
polymer science and engineering at Tianjin University. His research
focuses on the crystallization behaviors of polyolefins and their
correlations with molecular structures.
Nan Tian received a B.S. in polymer materials and engineering from the
University of Science and Technology of China in 2009 and obtained a
Ph.D. in nuclear science and technology from the University of Science
and Technology of China in 2014. Since then, he has worked as an
associate professor of polymer chemistry and physics at Northwestern
Polytechnical University. His research focuses on the relation between
entanglement, chain dynamics, and crystallization of polymers.
Dong Liu received a B.S. in chemistry from the University of Science
and Technology of China in 2009. Later, he joined Professor Liangbin
Li’s Soft Matter Group at National Synchrotron Radiation Laboratory,
University of Science and Technology of China, where he received a
Ph.D. in nuclear science and technology in 2015. He is currently
working as a research assistant in neutron scattering, based at the China
Mianyang Research Reactor (CMRR) at Key Laboratory of Neutron
Physics and Institute of Nuclear Physics and Chemistry, China
Academy of Engineering Physics (CAEP). His research focuses on
structure analysis in polymer science with the help of neutron and X-ray
scattering.
Fengmei Su received a B.S. (2011) in polymer material and engineering
from Sichuan University and obtained a Ph.D. (2016) in nuclear
science and technology from the University of Science and Technology
of China. She is currently a postdoctoral fellow in the Synchrotron
Radiation Laboratory, University of Science and Technology of China.
Her primary research interest is flow-induced polymer crystallization,
such as conformation ordering and flow-induced precursors, etc.
Liangbin Li received a B.S. (1994) from Sichuan Normal University and
M.S. (1997) from Sichuan University in physics and a Ph.D. (2000) in
polymer material processing from Sichuan University. From 2000 to
2004, he was a postdoctoral fellow in FOM-Institute for Atomic and
Molecular Physics and Technology University of Delft, The Nether-
lands. From 2004 to 2006, he worked as a materials scientist at Unilever
Food and Health Research Institute. Since 2006, under the One-
Hundred Talent Program of Chinese Academy of Science, Dr. Li joined
National Synchrotron Radiation Laboratory, University of Science and
Technology of China as a full professor and started the Soft Matter
Group. His primary research interests are polymer physics relevant to
processing, such as flow-induced crystallization of polymer and stress-
induced deformation and phase transitions of crystalline polymers.
ACKNOWLEDGMENTS
This work was supported by the National Natural Science
Foundation of China (51325301, 51633009, 51573132, and
51227801) and the key research and development tasks of
MOST (2016YFB0302501).
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