crystals

Review
A Review on Polymer Crystallization Theories
Michael C. Zhang, Bao-Hua Guo and Jun Xu *
Advanced Materials Laboratory of Ministry of Education, Department of Chemical Engineering,
Tsinghua University, Beijing 100084, China; mgtswtzc@126.com (M.C.Z.); bhguo@tsinghua.edu.cn (B.-H.G.)
* Correspondence: jun-xu@tsinghua.edu.cn; Tel.: +86-10-6278-4740; Fax: +86-10-6278-4550

Academic Editor: Bing Gao

Received: 24 November 2016; Accepted: 26 December 2016; Published: 29 December 2016

Abstract: It is the aim of this article to review the major theories of polymer crystallization since up to
now we still have not completely comprehended the underlying mechanism in a unified framework.
A lack of paradigm is an indicator of immaturity of the field itself; thus, the fundamental issue
of polymer crystallization remains unsolved. This paper provides an understanding of the basic
hypothesis, as well as relevant physical implications and consequences of each theory without too
much bias. We try to present the essential aspects of the major theories, and intuitive physical
arguments over rigorously mathematical calculations are highlighted. In addition, a detailed
comparison of various theories will be made in a logical and self-contained fashion. Our personal
view of the existing theories is presented as well, aiming to inspire further open discussions. We expect
that new theories based on the framework of kinetics with direct consideration of long-range multi-body
correlation will help solve the remaining problems in the field of polymer crystallization.

Keywords: polymer crystallization; theories; secondary nucleation; primary nucleation; crystal growth

1. Introduction
In recent decades, polymer crystallization has been extensively studied, which has contributed
to the development of polymer science. In fact, up to now, the subject of polymer crystallization still
receives considerable interest and consistently constitutes a fascinating and fruitful area of research.
This is mainly due to the commercial importance and rapid advance of the polymer industry, as well as
the inherent intriguing feature of long-chain molecules, which leads to a highly complex and divergent
hierarchy that is a rather challenging task for theorists and experimentalists. For instance, in 1957,
several groups [1–4] almost simultaneously obtained polyethylene single crystals, and, based on the
experimental observations, Keller subsequently proposed the celebrated “folded chain model” in a
reasonably self-consistent manner. “Folding” has never been seen in small molecular crystals, which
must be attributed to the unique properties of long-chain molecules. In the wake of the first theory
proposed by Hoffman and Lauritzen [5] in 1960 to explain the experimental crystallization results
of polymer chains, large-scale research projects have emerged. Many diverse opinions have been
presented, resulting in long-running controversies: many of these are unresolved, and discussions
continue to this day.
The aim of this article is to present an overview of polymer crystallization theories, which are
sometimes opaque and contradictory. Up to now, however, there have been several comprehensive
reviews focusing on the theoretical aspects of polymer crystallization [6–10]. What is the aim
of this article? From the authors’ perspective, two major features of this paper are highlighted:
(1) We believe that clear physical pictures are extremely important, especially for non-specialists;
therefore, an underlying principle of this paper is to provide an understanding of the basic hypothesis,
as well as the relevant physical implications and consequences of each theory. (2) Recent years have
seen the rapid advances of experiments and computer simulations, which constantly challenge the

Crystals 2017, 7, 4; doi:10.3390/cryst7010004 www.mdpi.com/journal/crystals

Crystals 2017, 7, 4 2 of 37

traditional understanding of the polymer crystallization process and stimulate various authors to
propose new theories. Therefore, comprehensive and detailed comparison of various theories should
be made in a logical and self-contained fashion, aiming to reflect the latest progress of the subject itself.
This is the main purpose of this article.
However, due to the complex nature of polymer crystallization, there are various schools and
different opinions. Therefore, it is impossible to cover all the developments, and we apologize in
advance for any omissions. Nevertheless, we try to present the essential aspects of the major theories
and compare them as objectively as possible. We also encourage readers to form their own perceptions,
recognizing that no review can be free of the personal preferences of the authors.
The structure of this article will be organized as follows: Section 2 provides the foundations of
polymer crystallization theories. We will discuss the concept of “chain folding” and its corresponding
physical implications, since chain folding is one of the most significant features different from
the crystallization of small molecules. Section 3 presents the basic thermodynamic considerations.
We especially focus on various defects and omissions behind the traditional treatment, which mainly
originates from the finite size effect because lamellar crystals can be roughly regarded as quasi-two
dimensional objects with one-dimensional confinement; however, the conventional thermodynamic
arguments always deal with infinitely large substances in all dimensions. Sections 4 and 5 are
the main parts of this paper, dealing with secondary and primary nucleation theories, respectively.
In Section 4, we follow the Hoffman–Lauritzen (HL) theory as the main line since it provides a
simple and analytical approach to deal with polymer crystallization, although the HL theory, to some
extent, is phenomenological and mean-field-type in nature. Therefore, inevitable oversimplifications
are essentially built in the HL model, which are subsequently critically argued and considerably
modified by several authors, who either remain within the HL framework and perform a more detailed
consideration or even completely renounce the original structure of HL treatment. We will present
the basic motivation for the introduction of various corrections; hence, based on the aforementioned
strategy, we try to incorporate the major secondary nucleation theories in such a logical manner.
In Section 5, we focus on primary nucleation theories, which share some similarities and, to some
extent, overlap with each other. We will compare the different theories in an explicit way. Finally,
in Section 6 we summarize and present a brief personal view on the remaining issues.

2. Foundations of Polymer Crystallization Theories

The early studies of crystalline polymers were mainly based on the X-ray diffraction technique.
Diffraction evidence gave information including unit cell parameters, the degree of crystallinity,
and crystal dimensions. The resulting picture of polymer crystals was several nanometers in size,
randomly oriented in space, and comprising about 30%–60% of the material. Since crystalline
polymers could bear loads and in many ways behaved like reinforced rubber, along with the fact that
macromolecules were generally much longer than the crystal dimensions, people at that time formed
the basic understanding that crystals might function as cross-linkers similar to those in cross-linked
rubbers. This is the well-known “fringed micelle” model (see Figure 1) proposed by Hermann et al. [11].
In 1938, Storks [12] observed very thin rhomboid-shaped polymer lamellar crystals. Considering
that a polymer chain is much longer than the lamellar thickness, Storks declared that the polymer chain
should fold back and forth in the crystals. Since the concept of the fringed micelle model prevailed
over the polymer community at that time, this article had not received much attention.
Crystals2017,
Crystals 7,44
2017,7, 33of
of36
37

Figure 1. Schematic picture of the fringed micelle model.

Figure 1. Schematic picture of the fringed micelle model.
Until 1957, several research groups [1–4] almost simultaneously obtained polyethylene single
crystals,1938,
In among Storks [12] observed
them Keller’s work was very thin rhomboid-shaped
of primary importance in that polymer
he alsolamellar
supplemented crystals.
an
Considering that a polymer chain is much longer than the lamellar
electron diffraction pattern, clearly indicating the molecular backbone oriented along the thinnest thickness, Storks declared that
the polymer
dimension of chain should
the crystal andfold
couldback and forth
be extended in aincontinuous
the crystals. Sincenothe
manner more concept
than 10 ofnm.
the Based
fringedon
micelle model prevailed
these experimental over the
facts, Keller [13]polymer
proposedcommunity
a reasonable at physical
that time, this article
picture had not received
of the organization of the
much
polymer attention.
chains in the lamellar crystals, which is known as the “folded chain model.” In the model,
Until
Keller assumed1957, several researchchain
that a polymer groups should[1–4]foldalmost
backsimultaneously
and forth on itself obtained polyethylene
in an adjacently single
re-entered
crystals, among them Keller’s work was of primary importance in that
manner, which is also frequently referred to as the tightly folded chain model or the adjacently folded he also supplemented an
electron
chain model.diffraction pattern, clearly indicating the molecular backbone oriented along the thinnest
dimension of the Flory
In addition, crystal[14] andcalculated
could be theextended in a continuous
free energy of the fringed manner
micelleno model,
more than and 10 he nm.
foundBased
that
on these experimental facts, Keller [13] proposed a reasonable physical
non-crystalline parts located at crystal surfaces were overcrowded, which limited the motion of these picture of the organization
of the polymer
amorphous chains
chains, in thetolamellar
leading a large crystals,
amount of which is known asentropy
conformational the “folded
loss. chain
Zachman model.” In also
[15,16] the
model,
estimated Keller
the assumed
optimal aspect that a ratio
polymerof the chain should
fringed fold and
micelle backidentified
and forththat on itself
it could in an
be adjacently
up to 56.8.
re-entered manner, which is also frequently referred to as the tightly
Apparently, in a disordered liquid state, the formation of such substantially asymmetrical fiber-like folded chain model or the
adjacently folded chain model.
structures is quite difficult to originate from spontaneous fluctuations. Therefore, the experimental
In addition,
results combinedFlory with[14] calculated
theoretical the free energy
calculations of the fringed
demonstrated that the micelle
fringed model,
micelle andmodel
he found
was
that non-crystalline parts located at crystal surfaces
inappropriate; hereafter, the folded chain model was widely accepted. were overcrowded, which limited the motion of
these Theamorphous
proposed chains,
folded leading
chain to a large
model amount of conformational
immediately entropy loss.
resulted in considerable Zachman [15,16]
controversy, among
also
which a substantial divergence lay in the mechanism of chain folding, which wascould
estimated the optimal aspect ratio of the fringed micelle and identified that it thoughtbe up
to to
be
56.8. Apparently, in a disordered liquid state, the formation of
energetically unfavorable since folding is accompanied by chain torsion. Here, we do not conduct such substantially asymmetrical
fiber-like structures quantitative
any mathematically is quite difficult to originate
calculation; however, fromwe spontaneous
do try to present fluctuations.
some intuitivelyTherefore, the
physical
experimental results combined with theoretical calculations demonstrated
arguments to demonstrate that the formation of folded chain crystals is actually a natural choice during that the fringed micelle
model
polymer was inappropriate;We
crystallization. hereafter, the folded
can consider two chain modelwhere
limit cases, was widely accepted. to the extremely
one corresponds
diluteThe proposed
polymer folded
solution, chain
which model
leads to the immediately resulted in considerable
so-called “single-molecule, controversy,
single crystals” [17–19], among
and the
which a substantial divergence lay in the mechanism of chain
other is relevant to an extremely concentrated solution, namely, the polymer bulk condition. folding, which was thought to be
energetically unfavorable since folding is accompanied by chain torsion. Here, we do not conduct
any mathematicallySingle
2.1. Solution-Grown quantitative
Crystals calculation; however, we do try to present some intuitively
physical arguments to demonstrate that the formation of folded chain crystals is actually a natural
In an extremely dilute solution, since polymer chains are separated from each other, we can focus
choice during polymer crystallization. We can consider two limit cases, where one corresponds to
on one single chain and regard it as an isolated system. In the following section, we will show that
the extremely dilute polymer solution, which leads to the so-called “single-molecule, single
the extended-chain crystals correspond to the most stable state in the context of thermodynamics.
crystals” [17–19], and the other is relevant to an extremely concentrated solution, namely, the
However, such extended configuration is the most energetically unfavorable state for the single-chain
polymer bulk condition.
crystal. The reason can be deduced from the following argument: Once a polymer chain is completely
extended
2.1. without other
Solution-Grown Single surrounding
Crystals chains, the extended single chain will gain the largest surface area
and the lowest conformational entropy, which is thermodynamically unstable. Only when the polymer
chain Infolds
an extremely
back and dilute
forth couldsolution,
it win since
the polymer
maximum chains
number are ofseparated
contacts fromand the each other, exposed
smallest we can
focus
surface area. Therefore, if we take account of the single-chain crystal formed from an extremely show
on one single chain and regard it as an isolated system. In the following section, we will dilute
that the extended-chain crystals
solution, folding is actually a natural tendency. correspond to the most stable state in the context of
thermodynamics. However, such extended configuration is the most energetically unfavorable state
for the single-chain crystal. The reason can be deduced from the following argument: Once a
Crystals 2017, 7, 4 4 of 37

Here, you may wonder whether the aforementioned thought experiment could be verified
experimentally. The answer is “Yes.” This challenging experiment was first realized by Bu et al. [17],
who sprayed an extremely dilute polymer solution, for instance, poly(ethylene oxide) (PEO) in benzene
with a concentration of about 2 × 10−4 wt %, onto the surface of hot water drop by drop. Only if one
drop of solution had spread on the surface and the solvent (benzene) had evaporated would another
drop be added, leading to the preparation of single-molecular particles. Moreover, they acquired the
morphology and the corresponding diffraction pattern of the single crystals under a transmission
electron microscope, both of which confirmed the formation of a folded chain structure. Subsequent
computer simulation [20–26] and experiments [27–30] also revealed that a single polymer chain would
spontaneously crystallize in a folded manner within an appropriate temperature range.

2.2. Melt-Grown Polymer Crystals

Since chain folding is inevitable in a dilute solution, is it possible to observe extended-chain
crystals when crystallized from the multi-chain system, namely, a concentrated solution or melt?
The answer is almost “No.” The natural trend of a polymer chain surrounded by other chain-like
objects is to penetrate with neighboring chains rather than individually collapse because the resulting
entangled configuration retains the maximal entropy [31,32] and thus eventually forms an intertwined
network structure, which is frequently referred to as “entanglement.” Entanglements lead to a certain
type of topological constraints, which force the polymer chain to move along its contour path [33].
This kind of confinement results in a dramatic slowing down of long-distance diffusion, with relaxation
time τrep approximately scaling as N3 , where N is the degree of polymerization. If several extended
chains randomly develop in bulk, they would tend to get close to each other, which would minimize
the free energy. The rearrangement of distant extended chains could be accomplished by the depletion
of intervening amorphous chains, which is largely determined by the reptation mechanism. However,
the relaxation time of an extended chain can be approximately estimated by Rouse dynamics [34],
whose relaxation time scales as N2 . Prior to any gain of effective interactions, an extended chain will
fluctuate back to its coiled state due to the mismatch of the two time scales because N is much larger
than 1. Hence, it is difficult to obtain extended-chain crystals of long flexible polymer chains when
crystallized from quiescent bulk.
A similar idea was recently proposed by Stepanow [35], who equated the average forming time
of stems of length L (described by a phenomenological expression) with the Rouse time of polymer
chains of the same arc length L, and yielded a lower bound for the thickness of stems. The competition
between the “formation of stems” and the “relaxation back to random coil shape” leads to a finite
lamellar thickness; therefore, chain folding is kinetic in nature. In addition, there are two remarkable
features in Stepanow’s theory. One is to introduce the unique properties of polymers, for instance,
the Rouse dynamics, which were apparently ignored in previous treatments. The other is to emphasize
the importance of repulsive force originated from stem packing. The repulsion between neighboring
stems forces them to align parallel to each other in order to minimize the excluded volume effect,
which results in the formation of bundles. This kind of repulsive interaction is analogous to the
isotropic–nematic transition in lyotropic liquid crystals [36]. Therefore, from a kinetic viewpoint,
an extended-chain crystal will also be difficult to develop from melt.
Furthermore, we can take account of this phenomenon in view of thermodynamics. The screening
of excluded volume in amorphous bulk state yields ideal Gaussian chain conformations [37], and the
probability of any state that deviates from Gaussian statistics will be exponentially small [38]; therefore,
an extended chain largely deviated from the equilibrium configuration will hardly occur in a statistical
sense. Based on the above analysis, either from kinetic considerations or from thermodynamic
perspectives, the same conclusion can be drawn: it is hardly possible to form an extended-chain crystal
under a quiescent condition. Once crystallized, a folded chain structure is most likely to appear.
Now we can safely accept the folded chain model. However, a subsequent long-standing debate
lies in the various mechanisms of chain folding. For instance, Hoffman [39] and his colleagues believed
debate lies in the various mechanisms of chain folding. For instance, Hoffman [39] and his
colleagues believed that crystals should be organized in an adjacent reentry fashion (also termed as
“tightly folded fashion”), while Flory [14] argued that, due to the slow dynamics of polymer
motion, a “switchboard model” might be responsible for the mechanism of polymer crystallization.
ThisCrystals 2017, 7, 4
signifies that polymer chains can only perform in-suit conformational alternation5 and of 37
that
large-scale modulations are statistically forbidden. A natural consequence of the switchboard
modelthatiscrystals
that one polymer
should chain canineither
be organized penetrate
an adjacent different
reentry fashionlamellae so as to
(also termed as form
“tightlytie folded
molecules,
or enter intowhile
fashion”), different positions
Flory [14] of one
argued that, due tolamella
the slowand resultofin
dynamics loops.motion,
polymer This concept was later
a “switchboard
model” might
generalized be responsible [40],
by Mandelkern for theand
mechanism
recently of polymer
revisited crystallization.
by Hu et al. This[41],
signifieswho thatproposed
polymer the
chains can only perform in-suit
so-called “intramolecular nucleation model.” conformational alternation and that large-scale modulations are
statistically forbidden. A natural consequence of the switchboard model
Here, we must emphasize that the adjacent reentry model originally proposed by Keller et al. is that one polymer chain
can either penetrate different lamellae so as to form tie molecules, or enter into different positions of
was mainly responsible for solution-grown single crystals, while Flory primarily took account of
one lamella and result in loops. This concept was later generalized by Mandelkern [40], and recently
the melt-grown condition. However, Keller extended his idea of tight folding to melt crystallization.
revisited by Hu et al. [41], who proposed the so-called “intramolecular nucleation model.”
The physical
Here, consideration
we must emphasize is largely dueadjacent
that the to the reentry
experimental observations
model originally that the
proposed dependence
by Keller et al. of
the crystal
was mainly responsible for solution-grown single crystals, while Flory primarily took account of as
growth rate and the lamellar thickness on supercooling in melt is in the same manner
in solution. Therefore,
the melt-grown the controlling
condition. factorextended
However, Keller should be his the
ideasame.
of tightItfolding
is generally
to meltaccepted that such
crystallization.
relations are determined
The physical considerationby the foldeddue
is largely surface
to theenergies
experimental (see following
observations section).
that theAccordingly,
dependence ofKeller
came to the conclusion that, in melt condition, an adjacent re-entry folding was also
the crystal growth rate and the lamellar thickness on supercooling in melt is in the same mannerpreferred,
as
whichin solution.
leads to aTherefore, the controlling
similar folded factor should be the same. It is generally accepted that such
surface energy.
relations
However, attention must be paid surface
are determined by the folded energies (see
since polymer following section).
crystallization in solution Accordingly,
and bulk Keller
may be
came to the conclusion that, in melt condition, an adjacent re-entry
sharply different. Various kinetic factors may be mutually cancelled, leading to similar folding was also preferred, which
leads to a similar folded surface energy.
experimental relations [42]. In addition, crystals obtained from melt usually present high
However, attention must be paid since polymer crystallization in solution and bulk may be
mechanical strength and toughness; therefore, various lamellar crystals must be connected by tie
sharply different. Various kinetic factors may be mutually cancelled, leading to similar experimental
molecules. Otherwise, they would resemble low molecular weight alkanes, such as paraffin, and
relations [42]. In addition, crystals obtained from melt usually present high mechanical strength
show andpoor mechanical
toughness; performance.
therefore, Therefore,
various lamellar formust
crystals crystallization
be connected from
by tiemelt, it is generally
molecules. Otherwise,realized
that they
the extent of chain folding will deviate from tightly folded conformation
would resemble low molecular weight alkanes, such as paraffin, and show poor mechanical and a certain amount
of tie molecules Therefore,
performance. will be generated. Nevertheless,
for crystallization from melt, since
it isthe vast majority
generally of nucleation
realized that the extent of theories
chain are
based on the
folding willsolution-grown
deviate from tightly single crystals.
folded In what
conformation and follows,
a certainwe still hypothesize
amount of tie molecules that
willpolymer
be
generated.
chains assumeNevertheless, since thewhen
tight chain folding vast majority of nucleation
they crystallize; theories are
however, webased
muston the solution-grown
keep in mind that loops
single
and/or tiecrystals.
molecules In what
mightfollows,
existwe still hypothesize
between differentthat polymer
nuclei. We chains
summarizeassumethe tightvarious
chain folding
models of
when they crystallize;
chain folding in Figure 2. however, we must keep in mind that loops and/or tie molecules might exist
between different nuclei. We summarize the various models of chain folding in Figure 2.

Figure 2. Schematic diagram of molecular trajectory in various models: (A) Adjacent re-entry model.
Figure 2. Schematicmodel.
(B) Switchboard diagram
(C) of molecular trajectory
Intramolecular nucleationin various models: (A) Adjacent re-entry model.
model.
(B) Switchboard model. (C) Intramolecular nucleation model.
3. Thermodynamics of Polymer Crystallization
In the previous section, we discussed the chain trajectory in polymer crystals, the folded chain
model. In this section, we will mainly focus on the thermodynamic aspects of polymer lamellar crystals.
Thermodynamics is simple but powerful. On the one hand, thermodynamics is a phenomenological
theory directly connecting microscopic structure to macroscopic parameters, e.g., the variation of
lamellar thickness with supercooling. Such relations allow us to compare theoretical predictions with
experiments in an explicit manner. On the other hand, a set of fundamental principles established
Crystals 2017, 7, 4 6 of 37

by thermodynamics will rule out any theory that violates thermodynamic consideration. Therefore,
thermodynamic aspects of lamellar crystals should be taken into account first.
According to the classical thermodynamics, the total free energy change relevant to formation of
a crystal from amorphous phase can be expressed as

∆G = ∑ Alat σ + 2Aσe − ∆FAl. (1)

The first, second, and third term on right hand side (RHS) represent the total lateral surface energy,
the fold surface energy, and the bulk free energy change, respectively. Alat , A, and l correspond to
the lateral surface area, the folded surface area, and the lamellar thickness, respectively. The basic
assumption of Equation (1) is that the surface energy per area and the bulk energy per volume do
not vary with the crystal size. Since the folded surface area is much larger than that of lateral one for
sufficiently large crystals, namely A>>Alat , the first term on RHS can be ignored.

∆G = 2Aσe − ∆FAl. (2)

The bulk free energy change is defined as

∆F ( T ) = ∆H ( T ) − T∆S( T ) (3)

where ∆H(T) and ∆S(T) are enthalpy and entropy changes at temperature T, respectively.
Obviously, ∆G = 0 specifies the minimal lamellar thickness lmin for an infinitely large
lamellar crystal:
2σe
lmin = . (4)
∆F
Note that the minimal lamellar thickness obtained here is entirely based on thermodynamic
considerations, and the total free energy decreases with the increase in lamellar thickness, which
implies that extended-chain crystals correspond to the lowest free energy state. However, any lamella
with a thickness greater than lmin will also be thermodynamically accessible, namely, they could be
in metastable states. If a large free energy barrier needs to be overcome in the formation of a final
equilibrium state, metastable states with a finite lamellar thickness may occur.
The actual crystal thickness is always larger than lmin to assure crystal growth, and can be
expressed as
l = lmin + δl. (5)

If δl/lmin is much smaller than unity, the lamellar thickness approximately equals to lmin , then we
can replace l with lmin . Hence, correct estimations of ∆F and σe in Equation (4) will be crucial.
As a first-order approximation [43], we assume that both ∆H and ∆S are weakly dependent on
temperature near the equilibrium point, namely, ∆H and ∆S are almost constant in the vicinity of Tm
and can be replaced by ∆H[Tm (∞)] and ∆S[Tm (∞)]:

∆F ( T ) = ∆H [ Tm (∞)] − T∆S[ Tm (∞)] = ∆H [ Tm (∞)]( Tm (∞) − T )/Tm (∞) = ∆H [ Tm (∞)]∆T/Tm (∞). (6)

Immediately, we obtain a linear relation between ∆F and ∆T, which indicates that the driving
force for crystallization will linearly increase with supercooling.
However, we must point out that this approximation is valid only when the supercooling is
sufficient small. Once the system is in large supercooling, and once ∆H and ∆S are no longer constant
and remarkably change with temperature, the heat capacity contribution must be considered.

ZTm
∆H ( T ) = ∆H − ∆C p dT 0 (7)
T
Crystals 2017, 7, 4 7 of 37

ZTm
∆C p 0
∆S( T ) = ∆S − dT . (8)
T0
T

However, it is difficult in presenting the correct form of heat capacity in terms of temperature,
and such kind of formula has been argued for a long time [44,45].
An alternative approach may be employed by introducing an empirical correction function K(T),
which is directly multiplied on ∆F, leading to

∆F(T) = K(T)[∆H[Tm (∞)] ∆T/Tm (∞)]. (9)

K(T) is usually called the reduced Gibbs free energy change. Historically, K(T) has been endowed
with various forms by many researchers. However, this scheme also encounters difficulties; for example,
it was found that there was no universal formula of K(T) to match all polymer systems [46–48]. However,
Schawe [49] recently proposed a new approach and concluded that his method might be generally
valid for all polymers in the temperature range between the equilibrium melting temperature and the
glass transition temperature.
It is necessary to point out that, in traditional calculations of ∆F, heat capacity correction was
seldom taken into account. So far, most treatments still employ the simplest linear extrapolation
approximation form for the temperature dependence of ∆F. The well-known Gibbs–Thomson relation
for crystal size dependence is based on this simplified model as well [50]. However, for simplicity,
in what follows, we ignore such corrections, and resort to the simplified expression of ∆F. Even so,
the calculation of ∆F still has other potential problems.
Substituting the expression of ∆F into the formula of lamella thickness, lmin could be obtained

2σe Tm (∞)
lmin = . (10)
∆H [ Tm (∞)]∆T

It can be shown that the critical lamellar thickness is inversely proportional to supercooling, which
is in accordance with experimental results.
However, it must be noted that it could be a misunderstanding to regard ∆F as a bulk free energy
change within polymer crystals in that the crystals are not infinitely large [51]. Even though no folding
surfaces exist, all free ending groups will locate at crystal surfaces. Therefore, free ending surface
effects cannot be ignored even for extended-chain crystals [52]. However, Hoffman [53] ignored the
free ending effects and regarded the above equation as the definition of bulk free energy change and
assumed that σe had the same interpretation as that of the infinite chain length, namely, the surface
tension of the fold surface.
This issue was firstly recognized by Kovacs et al. [51], who argued that the aforementioned
expression of ∆F must subtract an appropriate term relevant to free ending effect, which corresponds
to the entropy of localization due to the pairing of chain ends and becomes important in the case of
closely stacked lamellar crystals. This amounts to −kB ln(CN) per molecule, where kB is the Boltzmann
constant, and C is a constant related to the flexibility of the chains in the melt [54].
The origin of this expression stems from the fact that each polymer chain has two ends, which
provides an excess of degree of freedom. For a polymer chain with N monomers, the portion of chain
ends equals 2/N. According to Boltzmann’s entropy formula S = kB lnW, the packing entropy should
be proportional to kB ln(2/N), which is exactly the same form as −kB ln(CN) apart from a constant
difference. Hence, if we consider the free ending correction, we will have

ln(CN )
∆F ( T ) = ∆H [ Tm (∞)] − T∆S[ Tm (∞)] − k B T (11)
Nυ
where υ represents the volume of one statistical unit since ∆F is defined as the free energy change
per unit volume. Recently, Crist [55] also proposed that the entropy resulting from chain folding and
Crystals 2017, 7, 4 8 of 37

cilium increases the effective surface energy, making crystals thicker than the previous estimation.
In addition, another consequence of the surface entropy is that the equilibrium amorphous fraction
increases with crystallization temperature.
So far, we have considered the finite size effect based on thermodynamic arguments. However,
recent experiments on semicrystalline polymers with ultrafast heating rates have inspired new insights
into how lamellar crystals rearrange themselves [56,57]. In particular, instrument developments, such
as ultrafast chip calorimetry, have allowed experiments with extremely fast heating rates of up to
100,000 K/s, much faster than those attainable in traditional calorimetric measurements with a typical
heating rate of about 10 K/min. Under this conventionally relative slow heating rate, the annealing
process simultaneously takes place, which leads to the spontaneous lamellar thickening. It is commonly
believed that, under a relatively high heating rate such as 1000 K/s, the annealing process can be
effectively prohibited due to the sluggish motion of long-chain polymers [58]. However, recent
experiments [56] have shown that, even at a heating rate of 100,000 K/s, the annealing process can still
be probed, which indicated that there may be a quite rapid process when heating polymer crystals,
and the difference between the melting temperatures measured at extremely fast heating rates and
those observed during normal calorimetric measurements at slower heating rates were caused by
changes in metastability during crystal heating [59].
It can be seen that there are many issues in traditional arguments of polymer crystals in the
context of thermodynamics as well as the kinetic process. The latest progress from experiments and
simulations presents increasing challenges to the commonly used concepts [60–62]. Therefore, a careful
interpretation of experimental data and an awareness of the defects of various theories are crucial.

4. Secondary Nucleation Theories

So far, people have realized that the vast majority of polymer crystals are in metastable states with
folded chain structures. It is now widely accepted that polymer crystallization process is determined
by kinetics rather than thermodynamics; thus, correspondingly, the so-called “kinetic theory” over the
equilibrium theory will be responsible for the description of polymer crystallization. Typical kinetic
theory usually includes two parts: one corresponds to the “driving force,” and the other is relevant to
some kind of “free energy barrier.” These two terms compete with each other and result in an optimal
growth rate associated with specific lamellar thickness.
That is to say, according to kinetic theory, lamellae with any thickness larger than lmin can be formed;
however, lamellae with various thicknesses will lead to different growth rates, and the experimental
observation corresponds to the fastest growth rate, which is the meaning of kinetic theory. The “driving
force” stems from the free energy difference between the crystalline and amorphous phases, which
would be the same for all kinetic theories, and the origin of “free energy barrier” differentiates various
kinds of kinetic theories. In fact, polymer crystallization is a very complicated process, involving
diffusion, adsorption, desorption, entanglement, exclusion of defects, and so on. Any factor that slows
down the growth of crystals could be regarded as some type of “barrier” [63]. Due to the complex
nature of polymer crystallization, it is difficult to specify a certain element acting as the universal
“barrier.” Instead, under certain conditions, a rate-limiting step will be phenomenologically regarded
as the “barrier.”
Early studies mainly focused on the theories of secondary nucleation, which is defined as the
nucleation and growth process on the well-defined crystal surfaces. Therefore, secondary nucleation
is frequently called the surface nucleation process. However, in recent decades, thanks to advances
in experimental techniques, particularly the application of scattering approaches in polymer science,
a deeper understanding of early stages of crystallization has been gained. Here, we still follow the
course of history, and divide nucleation theories into secondary nucleation (Section 4) and primary
nucleation (Section 5). Despite some kind of artificial division, we hope that a comparison of diverse
approaches relevant to the same issue will assist us in clarifying the differences and similarities
(Section 4) and primary nucleation (Section 5). Despite some kind of artificial division, we hope that
a comparison of diverse approaches relevant to the same issue will assist us in clarifying the
differences and similarities between various theories, and in appreciating why seemingly quite
distinct assumptions eventually yield similar predictions.
Crystals 2017, 7, 4 9 of 37

4.1. The Hoffman–Lauritzen Theory

between
Up to various
now, thetheories,
most and in appreciating
successful why seemingly
and widely accepted quite distinct
theory was assumptions
proposed byeventually
Hoffman and
yield similar predictions.
Lauritzen [5], now known as Hoffman–Lauritzen (HL) theory or the Lauritzen–Hoffman (LH)
theory.
4.1. TheOne of the advantages
Hoffman–Lauritzen Theoryof the HL theory is that it provides a simple analytical form to
connect microscopic parameters with macroscopic quantities. However, to be presented in a simple
Up to now, the most successful and widely accepted theory was proposed by Hoffman and
formalism, it is necessary to ignore numerous complicated details, namely, to sacrifice the
Lauritzen [5], now known as Hoffman–Lauritzen (HL) theory or the Lauritzen–Hoffman (LH) theory.
personality of each molecule and hold their common attribute, inevitably resulting in a
One of the advantages of the HL theory is that it provides a simple analytical form to connect
mean-field-type description.
microscopic parameters Such simplifications
with macroscopic were considered
quantities. However, to beinoversimplified
to be presented by many
a simple formalism,
researchers,
it is necessaryandtothe HL numerous
ignore theory hascomplicated
been constantly
details,challenged by experimentalists
namely, to sacrifice the personalityand theorists;
of each
correspondingly,
molecule and hold their common attribute, inevitably resulting in a mean-field-type description. and
the HL theory itself continuously underwent a series of extensions
modifications. Nonetheless,
Such simplifications the HL
were considered to betheory has become
oversimplified a “standard
by many researchers, model”
and the of has
HL theory polymer
crystallization,
been constantlythough some
challenged parameters are
by experimentalists andphenomenological and some
theorists; correspondingly, the HL assumptions
theory itself are
continuously underwent a series of extensions and modifications. Nonetheless, the HL theory has
oversimplified.
become
In theafollowing,
“standard model”
we will of outline
polymerthecrystallization, though some
basic assumptions parameters
of the HL theory,are phenomenological
as well as its physical
and some assumptions are oversimplified.
implications and consequences. In addition, we will compare its predictions with experiments and
In the following, we will outline the basic assumptions of the HL theory, as well as its physical
point out the successful and frustrated parts. Finally, we will present brief comments on the HL
implications and consequences. In addition, we will compare its predictions with experiments and
theory.
point out the successful and frustrated parts. Finally, we will present brief comments on the HL theory.
The HL theory assumes that the critical nucleus is a single stem created by random fluctuation,
The HL theory assumes that the critical nucleus is a single stem created by random fluctuation,
longer
longerthanthanthethe
minimum
minimumlamellar
lamellar thickness
thickness llmin
min. Other stems further deposit on the crystal front to
. Other stems further deposit on the crystal front
complete
to complete the growth process, which results in lateral
the growth process, which results in spreadingand
lateral spreading and
thethe formation
formation of a layer,
of a new new layer,
andand
then wait
then waitfor
forthe
thenext
nextnucleation event,which
nucleation event, which is is illustrated
illustrated in Figure
in Figure 3. 3.

Figure 3. The Hoffman–Lauritzen model with stems of width a, depth b, and height l. The surface free
Figure 3. The Hoffman–Lauritzen model with stems of width a, depth b, and height l. The surface
energy on fold and lateral surfaces are σe and σ, respectively. The lateral growth rate is g.
free energy on fold and lateral surfaces are σe and σ, respectively. The lateral growth rate is g.

Here, we need to further analyze its assumptions. These simplified assumptions were supplemented
Here, we need to further analyze its assumptions. These simplified assumptions were
or revised later, leading to a series of corrections and modifications by several authors.
supplemented or revised
(1) The critical nucleus later, leading
is considered as ato a series
single of corrections
stem. Obviously, this is aand modifications
coarse-graining by several
description
authors.
and undoubtedly leads to a mean field theory. In the light of the traditional nucleation process of
(1) The critical
non-polymeric nucleus
substances, smallismolecules
considered as atosingle
continue stem.
fluctuate in andObviously, this [64,65],
out of an embryo is a coarse-graining
up to the
description
formation and
of theundoubtedly leadscertain
critical nuclei with to a mean field theory.
characteristic In the
dimension andlight of the traditional
then stabilizes, indicatingnucleation
that
process of non-polymeric
nucleation is a sequential substances,
process per se.small
The molecules continue
nucleation process to fluctuate
of polymers in and
should out of an to
be analogous embryo
that ofup
[64,65], small
to molecules.
the formationUnits (or segments)
of the have
critical experienced
nuclei a coursecharacteristic
with certain of intricate steps and ultimately
dimension and then
form a stable stem with a dimension larger than the minimum lamellar thickness. Compared with
the coarse-graining model involved in the HL theory, the above description in terms of a sequential
process is generally referred to as the “fine grained model.” Frank and Tosi [66] proved that, when
 polymers indicating
stabilizes, should be analogous to thatisofa small
that nucleation molecules.
sequential processUnitsper(orse.segments) have experienced
The nucleation process ofa
course of intricate steps and ultimately form a stable stem with
polymers should be analogous to that of small molecules. Units (or segments) have experienceda dimension larger than the a
minimum lamellar thickness. Compared with the coarse-graining model
course of intricate steps and ultimately form a stable stem with a dimension larger than the involved in the HL theory,
the abovelamellar
minimum description in terms
thickness. of a sequential
Compared with theprocess is generally
coarse-graining referred
model to asinthe
involved the“fine grained
HL theory,
model.”
the above Frank and Tosi [66] proved that, when a detailed balance was satisfied, or roughly
Crystals 2017,description
7, 4 in terms of a sequential process is generally referred to as the “fine grained 10 of 37
speaking, when the
model.” Frank and Tosi [66] system was in equilibrium,
proved that, when these two approaches
a detailed balance were equivalent,
was satisfied, orleading
roughlyto
the same when
speaking, results.the system was in equilibrium, these two approaches were equivalent, leading to
However,
a detailed
the Frank
balance
same results. was and Tosi or
satisfied, assumed
roughlythat units could
speaking, when only fluctuate
the system wason and off along
in equilibrium, the
these
direction
two of theFrank
approaches
However, lamellar
were andthickness,
equivalent, and chain
leading
Tosi assumed thefolding
tothat same was inaccessible
units results.
could only fluctuate beforeontheandcumulative
off alonglength
the
of units
direction reached
However, the
of the Frank lamellar
lamellar thickness,
andthickness,
Tosi assumed as illustrated
that units
and chain in
could
folding wasFigure
only 4.
fluctuate before
inaccessible on andtheoff cumulative
along the direction
length
ofunits
of the lamellar
reachedthickness,
the lamellar and chain folding
thickness, was inaccessible
as illustrated in Figure 4.before the cumulative length of units
reached the lamellar thickness, as illustrated in Figure 4.

Figure 4. Schematic diagrams of the “fine grained model” proposed by Frank and Tosi. A series of
Figure Schematic
4. would
sub-steps take diagrams of the
place in order to “fine
form agrained model”
single stem; proposed
however, by Frank
fluctuation on and
and Tosi.
off by A series
subunits
Figure 4. Schematic diagrams of the “fine grained model” proposed by Frank and Tosi. A series of
of sub-steps would take place in order to form a single stem; however, fluctuation on and
can only occur along the vertical direction, and folding is inaccessible before it reaches the lamellaroff by
sub-steps would take place in order to form a single stem; however, fluctuation on and off by subunits
subunits
thickness.can only occur along the vertical direction, and folding is inaccessible before it reaches the
can only thickness.
lamellar occur along the vertical direction, and folding is inaccessible before it reaches the lamellar
thickness.
This hypothesis was subsequently modified by Point [67,68], who argued that, at each substep,
chain folding
This
This had a was
hypothesis
hypothesis certain probabilitymodified
wassubsequently
subsequently of occurring
modified (see Figure
byPoint
by Point 5).
[67,68],
[67,68], Such
who
who modifications
argued
argued considerably
that,atateach
that, each substep,
substep,
altered
chain the
foldingfinal
hadformalism,
a certain and the resulting
probability of consequences
occurring (see were
Figure 5). significant:
Such it effectively
modifications
chain folding had a certain probability of occurring (see Figure 5). Such modifications considerably excluded
considerably
the serious
altered
altered the problem
the final
final of “δl-catastrophe.”
formalism,
formalism, and
andthe Weconsequences
theresulting
resulting will return towere
consequences this
werepoint later. it effectively
significant:
significant: it effectivelyexcluded the
excluded
serious
the problem
serious problemof “δl-catastrophe.” We We
of “δl-catastrophe.” willwill
return to this
return point
to this later.
point later.

Figure5.5.Illustration
Figure Illustrationofof
thethe
multi-path approach.
multi-path Chain
approach. folding
Chain is allowed
folding at eachatsubstep
is allowed and further
each substep and
growth relies on the removal of unfavorable configurations such as the third.
further growth relies on the removal of unfavorable configurations such as the third.
Figure 5. Illustration of the multi-path approach. Chain folding is allowed at each substep and
further growth relies on the removal of unfavorable configurations such as the third.
(2) After
(2) After thethe initial
initial deposition
deposition of of the
the nucleus
nucleus onto onto the
the crystal
crystal surface,
surface, the the remaining
remaining polymer
polymer
chain
chain will
(2)will be sequentially
be sequentially
After adsorbed
adsorbed of
the initial deposition to
to the the
the front
nucleusfront
withontowith
the the the
same same length
lengthsurface,
crystal as
as the original the original one. In
one. In principle,
the remaining polymer
principle,
the
chain stem the
willlength stem
may be
be sequentially length
subjectmayto abe
adsorbed subject
certain
to the to
degree aofcertain
front degree
fluctuation
with the (δl)of
same duefluctuation
to thermal
length as the (δl) due totherefore,
agitation;
original thermal
one. In
agitation;
a natural question
principle, therefore,
the stem arises: a natural
length To maywhatquestion
be extent
subjectwillarises:
to athe To what
fluctuation
certain extent
degreebe? will the fluctuation
If the fluctuation
of fluctuation (δl) due effectbe? If the
is weak,
to thermal
itfluctuation
can be regarded
agitation; effect is
therefore, asaweak,
some
natural it can
kind of be regarded
perturbation.
question arises: To asAs some kind ofwill
a zero-order
what extent perturbation.
approximation,
the fluctuation Asit acanzero-order
be?even
If the be
approximation,
neglected; thus, it
we can even
return to be neglected;
Hoffman’s thus,
treatment. we return
However, to
fluctuation effect is weak, it can be regarded as some kind of perturbation. As a zero-order Hoffman’s
if the influence treatment.
of However,
fluctuation cannot if the
be
influence of fluctuation
ignored, the HL ittheory
approximation, can even cannot
may fail. be ignored,
Here, we present
be neglected; the
thus, we HL theory
anreturn
intuitive may fail.
to estimation,
Hoffman’s and Here, we present
the detailed
treatment. However,an intuitive
quantitative
if the
estimation,
computation and
can the
be detailed
found in quantitative
relevant computation
papers [8,25,69]. can be found
influence of fluctuation cannot be ignored, the HL theory may fail. Here, we present an intuitive in relevant papers [8,25,69].
According
According
estimation, and the tothe
to the fluctuation–dissipation
fluctuation–dissipation
detailed quantitative computation theoremcan
theorem [70],
[70],bethethe fluctuation
fluctuation
found of of
in relevant thethe lamellar
lamellar
papers thickness
thickness
[8,25,69]. is
is associated
associated
According with
with to corresponding
corresponding dissipation
dissipation in that
the fluctuation–dissipation in that they
they share
theorem share
[70],the
thesame the same
driving of
fluctuation driving
force, force,
the namely, namely,
lamellarthe thermal
thickness the
thermal
random random
force
is associated with k T, force
where k
B correspondingBkT,
B where
is the kB is the Boltzmann
Boltzmann constant, constant,
and T is the and T
absoluteis the absolute
temperature.
dissipation in that they share the same driving force, namely, temperature.
The natural
the
The
thermal natural
consequence random consequence
of fluctuation
force kBT, whereof fluctuation
is to create is
more
kB is the to create more
lateral surfaces;
Boltzmann lateral
constant, surfaces;
therefore, therefore,
and T isdissipation
the absolute dissipation
is related to the
temperature. is
related
lateral
The to the
surface
natural lateral σ.
energy
consequence surface energy
Analogous
of fluctuationto σ. Analogous
classical
is to
Einstein’s
to create moreclassical
lateralEinstein’s
relation, relation,
we immediately
surfaces; therefore, wedissipation
have immediately is
have
related to the lateral surface energy σ. Analogous to classical Einstein’s relation, we immediately
σbδl ≈ k B T (12)
have σbδl ≈ k BT (12)
or σbδl ≈ k BT (12)
or δl ≈ k B T/σ (13)
or
where b is the width of the stem (see Figure 3 for more details). The physical consideration underlies
that, since the driving force relevant to fluctuation is of order kB T, the dissipation energy resulting
from the same origin must be of the same order of magnitude.
Although the lamellar thickness is allowed certain extent of fluctuation, here we merely deal with
lamellae with a constant thickness since the consideration of thickness fluctuation does not introduce
much difference. Interested readers can refer to the relevant literature [66,71].
Crystals 2017, 7, 4 11 of 37

(3) In addition, the HL theory also implicitly assumed that, once nuclei formed, the whole chain
must be consumed for lateral growth. Until a polymer chain was completely depleted, another chain
could be incorporated for further growth. This is a natural consequence of the tightly folding model.
The description may be true in a dilute solution; however, with an increase in concentration, or even
in the melt, other chains may inevitably be embodied before the initial chain is entirely consumed.
The resulting formation of the “cilium” structure originally proposed by Dimarzio [72] can bring in
at least two distinct effects: (a) Cilia facilitate secondary nucleation in that the cilium is close to the
crystal surface layer, which is much easier to deposit on the next crystal layer compared with a new
molecular chain; (b) cilia improve the mechanical properties of materials. Once a cilium is long enough,
it may transverse various lamellae, resulting in tie molecules. This is a kind of recurrence of Flory’s
switchboard model, as well as one of the starting points of subsequent theories such as Hoffman’s
variable cluster theory [73] and Hu’s intramolecular nucleation theory [41].
Furthermore, Dimarzio was able to estimate the fraction of ciliated material generated with
respect to molecular weight; thereafter, a series of generalizations was made [71,74]. However, in the
original treatment of the HL theory, these possibilities are ignored.
(4) Smooth surface nucleation. This may be the subtlest, yet the most critical assumption in the
HL theory. A smooth surface means that the preexisting surface is atomically smooth, which implies
that each step of deposition will create new surfaces. A smooth surface is almost planar with few
“steps“ or “vacancies”; however, at elevated temperatures, a smooth surface may become rough.
The transition between these two profiles is known as the roughening transition. This phenomenon
was first conjectured by Burton, Cabrera, and Frank [75]. This transition is expected to appear when either
the step free energy is of the order of kB T or the height correlation length becomes negligibly small [76,77].
The transition temperature TR can be considered as the temperature at which the entropic gain from a
fluctuation becomes greater than its associated loss in energy. Therefore, the smooth surface hypothesis
largely determines HL to be an “enthalpy barrier” model, which is in sharp contrast to the later
developed “entropy barrier” model.
From the aforementioned arguments, it can be seen that the elementary process involved in the
HL theory is rather simple. It only consists of two steps: one is to create a new nucleus; the other
is relevant to lateral growth. Consequently, two phenomenological parameters can be defined to
completely characterize the polymer crystallization process within the framework of the HL model.
Correspondingly, one is nucleation rate i, which is defined as the net deposition rate on the surface per
unit substrate length. The other is spreading rate g, which is expressed as the difference between the
rate of the arrival and departure of stems at the crystal surface.
However, deeper insight into these two quantities can be intuitively gained by considering their
asymptotic behaviors before introducing the specific expressions of i and g, which leads to the so-called
“regime phenomenon.”
(1) I << g. This corresponds to Regime I [78], usually at high temperatures, where the nucleation
rate is much smaller than the lateral spreading rate. Once a nucleation event occurs, subsequent lateral
growth will rapidly overspread a layer, and wait for the next nucleation event. Therefore, the crystal
growth rate is controlled by the nucleation rate. Since i is defined as the nucleation rate per unit
substrate length and, hence, if the crystal size is L, the nucleation rate is iL, and the crystal growth rate
is ibL, then
GI = biL. (14)

However, an immediate consequence derived from this equation is that GI is proportional to L,

namely, crystal growth rate is linearly dependent on the crystal width, implying that wider crystals
have faster growth rates. This is inconsistent with experimental results that the crystal growth rate is
almost constant, independent of the crystal size; therefore, L needs to be redefined. It is now generally
argued that L is an “effective length” much smaller than the width of the crystal growth face, and L is
usually represented by Lp , where the subscript p means “persistence” and Lp is called the “persistence
Crystals 2017, 7, 4 12 of 37

length” [79,80]. The introduction of persistence length effectively limits the spacing of continuous
crystal growth. Therefore, the above equation may be modified as

GI = biL p . (15)

However, the introduction of Lp may be one of the most serious issues in the HL theory and leads
to long-term controversy. In what follows, we will discuss this problem.
(2) I >> g. This case is usually called Regime III [73,81], in which nucleation rate is much faster
than the lateral spreading rate, corresponding to low temperatures. It is believed that, in this case,
nucleation events are so frequent that the averaged spacing between two adjacent nuclei again become
a constant, and the lateral spreading rate is thus physically irrelevant. Thus, the system will show
similar behaviors as in Regime I.
Instead, Lp needs to be considered as the average distance between two adjacent nuclei, which is
expected to be two to three lattice spacing.

GIII = biL p . (16)

(3) i approximately equals to g. This condition is referred to as Regime II, corresponding to a

moderate temperature range. In this case, the nucleation rate and lateral spreading rate are comparable,
leading to the competition between these two factors. The resulting expression involves the same
statistical weight of i and g [71].
p
GII = b ig. (17)

One of the remarkable features of the regime phenomenon is that it only depends on the relative
values of i and g; therefore, if we can effectively tune the magnitudes of i and g, for instance, by the
crosslinking method [82], regime transitions could be observed at the same temperature.
As mentioned earlier, the essential part of the HL theory is to present the analytic expressions of i
and g, which leads to explicit relations of macroscopic quantities in terms of microscopic parameters.
Thus, we can predict the lamellar thickness and crystal growth kinetics from a microscopic perspective.
Here, we briefly present the basic logic flow, and the detailed derivations can be referred to the original
work [5,46,69,81,83].
In the LH model a nucleus is formed and subsequently spreads by the addition and removal of
sequential stems, and the probabilities of addition and removal are related by the detailed balance in
steady state approximation.
For the nucleation process, according to the original assumption, the first step of deposition does
not create any folding surface, and only lateral surfaces are generated; for the lateral spreading process,
since lateral surfaces are no longer created, only folded surfaces are generated. Therefore, the free
energies relevant to each process are well specified.
However, such expressions only provide the ratio between different microscopic parameters.
In order to derive the expressions of i and g, the absolute values of the probabilities of addition and
removal must be given. Therefore, the total free energy must be partitioned to each microscopic
quantity, which is known as the “apportioning problem.”
Hoffman proposed the apportioning principle based on the fact that the free energy cost due to
the surfaces acts as a barrier to overcome in order to lay down a stem, and it should be embraced in the
forward rate constants, namely, the probabilities of adding a stem. However, a certain extent of bulk
free energy will be gained during the deposition process and therefore reduces this barrier; as a result,
the actual amount will be determined by the factor ψ.
Having the specific expressions of microscopic parameters, deriving the macroscopic quantities,
such as the lamellar thickness and the crystal growth rates in various regimes, is algebraically
straightforward. Here, we simply present some main results
Crystals 2017, 7, 4 13 of 37

(1) The averaged lamellar thickness:

2σe
< l > av = + δl (18)
∆F
where
kB T 2 + (1 − 2ψ) a∆F/2σ
δl = . (19)
2bσ (1 − a∆Fψ/2σ)[1 + a∆F (1 − ψ)/2σ ]
Obviously, δl is almost the same form (except for some prefactors) as our previous intuitive guess
in the light of fluctuation–dissipation theorem.
Notice that, for small ∆F, δl is approximately constant and the main temperature dependence
of <l>av is given by 2σe /∆F. Using the linear relationship between ∆F and ∆T, it can be immediately
found that <l>av is inversely proportional to ∆T as observed experimentally.
(2) Fluctuation of lamellar thickness:

( k B T )2 ( k B T )2 ∼ 1 kB T 2
< (l − < l > av )2 >= 2
+ 2 = ( ) . (20)
(2bσ − ab∆Fψ) [2bσ + (1 − ψ) ab∆F ] 2 bσ

(3) Growth rates in various regimes:

b 2abσe ψ −4bσσe
GI = βL p exp( ) exp( ) (21)
a kB T ∆Fk B T

abσe ψ − abσe (1 − ψ) −2bσσe

G I I = bβ exp( ) exp[ ] exp( ) (22)
kB T kB T ∆Fk B T
b 0 2abσe ψ −4bσσe
GI I I = βL p exp( ) exp( ) (23)
a kB T ∆Fk B T
where β is the kinetic prefactor. From the above results, we can find that, basically speaking, the HL
theory can quantitatively or semi-quantitatively reproduce the main experimental observations, which
demonstrates the success of the HL theory since, under such simple assumptions, it can correctly
predict most experimental results. Though the theory inevitably has many deficiencies, here we only
point out several of them. For more details, readers can refer to [8,67,84–86].

4.1.1. δl Catastrophe
From Equation (19), it is easy to see that once the denominator (1-a∆Fψ/2σ) equals to zero, δl
will diverge, which indicates that crystallization at this specific temperature has no energy barrier and
may generate crystals with infinite thickness. This has never been observed in experiments. Therefore,
the only way of eliminating the δl catastrophe is to set ψ as 0; however, this manipulation completely
violates the original intention of the introduction of ψ. In addition, it will lead to an unphysical result:
if stems are adsorbed on the crystal surface, all surface energy must be overcome first before any
gain of bulk free energy. Subsequently, Frank and Tosi [66], as well as Lauritzen and Passaglia [78],
developed corresponding theories that considered fluctuations. However, any theory based on the
framework of HL-type with non-zero ψ will eventually lead to δl catastrophe. After Point proposed
the multi-path approach, this problem could be fairly well solved.
Point [67] first assumed that, in each step, a unit or a segment rather than a complete stem
would deposit on the crystal surface, which is similar to fine-grained model of Frank and Tosi [66].
However, in Point’s approach, chain folding can occur at any stage, namely, when each unit deposits
on the crystal surface, in addition to the longitudinal growth, it can also have some probability to fold
(see Figure 5); in the Frank–Tosi treatment (see Figure 4), it is assumed that “the segments which join the
stem are allowed to fluctuate forwards and backwards, but only when they have reached the lamellar
thickness are they allowed to fold” [66]. Therefore, in Point’s model, even though the cumulative
length has not reached the assigned lamellar thickness, a folding event occurs, so the subsequent
Crystals 2017, 7, 4 14 of 37

growth process along the thickness is terminated. Further thickness growth must rely on the removal
of unfavorable folding configurations; therefore, the unfavorable configuration corresponds to some
kind of “pinning point,” and the removal of unfavorable configurations (pinning points) will cost time,
which is equivalent to slowing down the crystal growth rate. Hence, it can be regarded as some type
of “nucleation barrier.”
The introduction of unfavorable configurations is essentially some kind of “entropy effect,” which
is related to the number of configurations, namely, corresponds to entropy degeneracy. This concept
was subsequently extended by Sadler and Gilmer [85] and now known as the Sadler–Gilmer (SG)
model, which will be discussed in detail in the following section.
Once the concept of entropy barrier is introduced, the δl catastrophe is completely avoided.
Intuitively, it is easy to imagine that, when the lamellar thickness increases, the probability of the formation
of unfavorable configurations becomes higher before reaching the assigned lamellar thickness. Generally
speaking, it is not possible to grow lamellae with infinite thickness. Strict mathematical treatment can
be found in [87].

4.1.2. Curved Single Crystals

The HL theory was originally designed for facetted single crystals that have clear crystallographic
surfaces; however, it was experimentally found later that, at elevated temperatures, crystals with
curved edges can be observed in both solution and melt [88,89]. Obviously, this phenomenon is
inconsistent with the original prediction of the HL theory. In the HL theory, high temperatures
correspond to Regime I, which is controlled by the nucleation process; namely, once the first stem
deposits on the preexisting surface, the subsequent covering rate is rather rapid and a resulting regular
shape crystal can be obtained, which is, of course, in contrast to experimental results.
To reconcile the inconsistence between the HL theory and experimental observations, Hoffman
and Miller [90] modified the HL theory. They first noted the work of Patel and Farmer [91], who
studied the energetics of attaching a stem to (110) and (100) faces of polyethylene (PE) and found that
stems are energetically favorable when crystallized on (100) surfaces, while the mobility is much higher
when crystallized on (110) surfaces, leading to a higher lateral spreading rate. The slight difference
results in the so-called “lattice strain,” which occurs due to the “bulkiness” of the fold along one
growth face, and the interior of the crystal may expand. The resulting volume strain is translated into
a strain surface free energy. By introducing the concept of a lattice strain, Hoffman and Miller can
explain the curved edges of single crystals; however, Point [92] soon proved that this treatment leads
to another kind of δl catastrophe. Therefore, it might be difficult to interpret curved edges based on
the HL theory.

4.1.3. Lp Size Problem

The introduction of Lp , as mentioned previously, is to take into account the fact that the crystal
growth rate is irrelevant to the crystal size; therefore, the HL theory is only valid in a certain range
of length scale, referred to as persistence length Lp . The original estimation of Lp in the HL theory
was about a few microns; however, by means of the isochronous decoration method, Point [79]
subsequently proved that the Lp value should be much lower than that predicted by the HL theory and
concluded that the Lp value cannot exceed 1 micron. Later, Hoffman and Miller further modified Lp to
a few hundred nanometers by comparison with an X-ray diffraction experiment [93]. Until recently,
using the dark field TEM technique, Lotz et al. [94] directly probed this size and showed that it was
rather close to the prediction of Hoffman and Miller.
It can be readily seen that the development of the HL theory is accompanied by adjusting
parameters to be consistent with experimental results. On the one hand, the HL theory is quite general
and flexible to accommodate a series of modifications and extensions; on the other hand, the HL theory
actually omits some microscopic details of the nucleation process.
Crystals 2017, 7, 4 15 of 37

4.1.4. Phenomenon of Minimum Growth Rate

An integer folded phenomenon can usually be observed in the crystallization of n-alkanes [95] and
low molecular weight PEO [96–98], which is probably because integer fold can exclude all end defects
out of bulk crystals, and thereby reduce the free energy. In a certain temperature range, two adjacent
growth modes, for instance, an extended chain and a once-folded chain, can coexist, since they have
approximately the same growth rate. Within this temperature range, a minimal growth rate can often
be observed. Taking n-alkanes as an example, early studies [95,99] and subsequent, more sophisticated
experiments [100,101] found that, in a proper temperature window, a minimum growth rate would be
observed. This unexpected result cannot be explained by the HL theory.
One possible mechanism originates from the “entropy effect.” We can imagine that, if the chain
has been grown in an extended chain manner, when a specific temperature is chosen, the growth
rates of the “extended chain” and the “once-folded chain” are comparable. At this temperature,
it is possible to deposit a once-folded chain on an extended-chain crystal surface. Such a poisoning
point will stop further crystal growth unless either of the two following conditions is satisfied: either
the polymer chain undergoes conformation transition and transforms itself into the extended chain,
or the unfavorable folded chain configuration is removed. Both steps will cost additional time,
resulting in a minimal growth rate. Accordingly, this point is referred to as the “poisoning point” [99],
and this phenomenon is called the “self-poisoning phenomenon.” Since the origin of poisoning points
corresponds to the deposition of unfavorable configurations, it is actually related to a kind of entropy
effect. Hoffman [102] modified his theory by introducing the entropy contribution in lateral surface
free energy, namely, a transient layer of “kinetic ciliation”. Later, the characteristic ratio C∞ was also
taken into account [103], and the rate minimum phenomenon was successfully reproduced.
From previous analysis, it is not difficult to see that the HL theory succeeds in many aspects and
does not work in some facets. Nevertheless, the transparent assumptions as well as concise analytical
form still make the HL theory the most widely accepted model. Knowing “how to approximate” rather
than “how to be precise” resides in any good physical theory. From this viewpoint, the HL theory is
extremely successful.

4.2. The Sadler–Gilmer Model

Having discussed the HL theory and its modifications, in what follows, we will present the
Sadler–Gilmer (SG) model. The two approaches are distinctly different: the HL theory corresponds
to the “enthalpic barrier,” while the SG model is relevant to the “entropic barrier.” Despite the
fundamental difference, both of them lead to similar predictions of lamellar thickness as well as crystal
growth kinetics.
The HL theory assumes that crystallization occurs on a “smooth surface,” namely, the crystal
surface is smooth at the atomic scale. Thus, the nucleation barrier originates from the formation
of new surfaces by the deposition of stems, leading to an increase in surface free energy. However,
as mentioned before, when temperatures are sufficiently high (T > TR ), crystal surfaces may be rough
at the atomic level, including many “steps” or “vacancies.” Therefore, when new stems deposit on the
surface, no more surface areas are created; therefore, it seems that no traditional nucleation barrier
exists. However, polymer crystallization at elevated temperatures also shows a tendency similar to
that at lower temperatures, indicating some kind of “nucleation” process. In order to explain the
experimental observations, the concept of an entropy barrier was introduced.
The earliest exploration of this new mechanism can be traced back to Binsbergen [104];
subsequently, Point proposed a similar idea, namely, the multi-path approach, and the essence of his
idea is to introduce conformation entropy degeneracy, that is, to incorporate a wider range of choices
available to the chain molecule during its attachment to the growth front. Therefore, an entropy part
was added to the traditional “nucleation barrier.” In 1983, Sadler and Gilmer [105] took this idea to
extremes and argued that the nucleation barrier is completely an “entropy barrier” without enthalpic
Crystals 2017, 7, 4 16 of 37

contribution. Meanwhile, they proposed that the regime transition from I to II corresponded to the
transition from rough surface nucleation to smooth surface nucleation [85,105,106].
The mechanism of the “entropy barrier” in the SG model is similar to that of Point’s approach.
Due to chain connectivity, if one segment adopts some kind of wrong configuration, the subsequent
deposition of stems will be blocked, and the resulting pinning point hinders further chain crystallization;
therefore, the “wrong” conformations must be removed to keep the crystallization process continuing.
Obviously, this is different from the traditional nucleation theory since the concept of “critical
nuclei” does not exist. However, under the generalized nucleation concept [63], any step limiting
crystal growth can be regarded as some type of “nucleation barrier.” In this general sense, the SG model
may also be considered as a type of “nucleation theory.” Now, we can employ a unified viewpoint to
examine all secondary nucleation theories.
In the SG theory, on the one hand, the driving force is still the free energy difference between the
crystalline phase and the liquid phase, which is proportional to the thickness of the lamellar thickness.
On the other hand, the barrier stems from the occurrence of “wrong configurations”; the thicker the
lamella is, the higher the probability of making mistakes will be. Therefore, the barrier is positively
correlated with l; hence, the competition of two factors leads to an optimal lamellar thickness; therefore,
the SG model is also kinetic in nature. From this point of view, this framework is quite analogous to
that of the HL theory, it is thus not surprising that the SG model will lead to predictions similar to
those of the HL theory.
However, the SG theory is not an analytical theory, and the relevant theoretical predictions can
only be realized by computer simulation. The lack of analytic treatment lies in that the SG model
involves conformational statistics, which corresponds to the arrangement of segments on the crystal
surface. Considering the enormous number of chain statistics, it will be hard for analytic methods to
deal with the conformational degeneracy. Here, we will make some comments on the SG theory.
(1) The significance of the SG theory, in the authors’ opinion, is to provide another way of
understanding the origin of nucleation barrier, though the conclusions derived from the SG model are
frequently qualitative. According to the traditional HL theory, the nucleation barrier is enthalpic in
nature. The SG model, however, points out another interpretation that the barrier can also originate
from entropic contribution. Based on the “entropic barrier,” the same conclusions as in the HL theory
can also be derived. In fact, this accordance originates from a plain idea: Since the free energy barrier
includes two parts (∆G* = ∆H* − T∆S*), consideration either from the enthalpic or the entropic aspect
will lead to some kind of free energy barrier. However, any concentration merely on enthalpy or
entropy is insufficient. Therefore, SG might be regarded as a complementary rather than contrary
approach in light of the HL theory. Comprehensive considerations of both enthalpy and entropy
contribution will eventually lead to a deeper understanding of the polymer crystallization process [63].
(2) Strictly speaking, the SG model was constructed with reference to small molecules. In small
molecular crystals, Kossel-type crystals are taken into account, i.e., the nearest neighboring interactions
are considered, and molecular adsorption or desorption can occur in any position on the crystal
surface [76]. However, a direct application to the polymer system will result in many problems.
For example, since a polymer chain is connected by chemical bonds, a strong correlation along the
chain direction exists, and the units within one chain cannot appear in any position on crystal surfaces.
Therefore, in the SG model, the connectivity of long-chain molecules has not been fully considered,
and the SG model is more appropriate for a short-chain system. Recently, one of the authors [107]
attempted to generalize the SG model to high polymers through the introduction of long-range
correlations. Interested readers can refer to the original literature.
(3) The SG model was originally proposed based on two experimental facts: the curved edges at
high temperatures and the rate minimum phenomenon. Both of these facts cannot be explained by the
traditional HL theory, which promoted Sadler and Gilmer for the so-called “rough surface nucleation.”
However, both of these two points are not necessarily attributed to a rough surface, and this has been
a point of contention for a long time.
Crystals 2017, 7, 4 17 of 37

(a) Firstly, curved edges cannot always be seen at high temperatures. For instance, during the
growth of PE crystals, curved lamellar growth only occurs on the (200) surface and does not show up
at the rapid grown (110) surface; therefore, it seems arbitrary to consider rough surface crystallization
as a general explanation. In addition, the strict definition of TR is associated with the thermodynamic
limit, while the polymer crystals are usually in metastable folded states; hence, whether such a
transition exists will be questionable. At least for metastable lamellar crystals, there may no longer be
a sharp transition.
Moreover, in addition to the “lattice strain” proposed by Hoffman and the “rough surface”
introduced by Sadler, other explanations also exist. For example, Toda [89] attributed the curved edges
to the influence of impurities. Furthermore, the solvent effects, the segregation of short-chain molecules,
and the lattice mismatching are all likely to result in curved edges. Hence, surface roughening
cannot necessarily be responsible for curved edges; on the contrary, a rough surface only serves as a
possible explanation.
(b) On the other hand, considering the rate minimal phenomenon, Sadler argued that it was the
pinning points that prevented the subsequent crystal growth. Later, Ungar and Keller [99] generalized
this idea, and the so-called “self-poisoning” mechanism was introduced. Recent experiments and
simulations, however, preferred the interpretation of the occurrence of a self-poisoning phenomenon
from the perspective of the driving force rather than the energy barrier [108].
Based on the above arguments, it is better to consider the SG theory as an alternative rather than
an inevitable approach. However, the unfortunate leave of David Sadler in 1989 terminated the further
development of the SG model, which is far from satisfaction to everyone.
Previously, we mainly focus on two representative models: the HL and SG models, based on
the enthalpic and the entropic barrier, respectively. In the following, we will further introduce other
secondary nucleation theories. Compared to the HL theory, most of them remain in a conceptual level;
therefore, we will concentrate on the essential concepts and physical origin of these ideas.

4.3. Hikosaka’s Sliding Diffusion Model

As aforementioned, the starting point of polymer crystallization is the folded chain model;
however, under certain conditions, for instance, at elevated pressures, extended-chain crystals of
some polymers can be obtained. Early studies can be traced back to Wunderlich and Arakawa [109],
who found that, at 5 K bar and 220 ◦ C, PE could form extended-chain crystals. However, at that time,
it was known that PE crystals are orthogonal and closely packed; therefore, large-scale thickening
behavior, in principle, is inaccessible. This led Wunderlich [110] to conjecture that, under high
pressures, PE crystals will form a new phase with high mobility along the chain direction. This new
phase, later known as the hexagonal phase, was originally observed by Bassett and Turner [111,112]
and Yasuniwa [113,114]. It is a columnar phase, which has a two-dimensional long-range order and a
one-dimensional short-range order. Along the thickness direction, the chain mobility is rather high;
therefore, polymer chains can grow into extended-chain crystals.
Hikosaka [115–117] subsequently proposed the sliding diffusion model to account for this
phenomenon. The terminology of “chain sliding diffusion” can be defined as the self-diffusion
of a polymer chain along its chain axis direction, probably surrounded by anisotropic potential field.
The essence of this model is to introduce a two-dimensional growth mechanism and to take account
of the topological nature of polymers. In addition to the traditional HL theory assuming the lateral
growth, the diffusion motion can also occur along the chain direction, and the activated free energy of
motion ∆Es along the chain direction is proportional to the thickness of lamellar thickness l, namely,
∆Es ~Kl, where K is a constant. In the orthogonal phase, chain slippage is quite difficult because ∆Es is
much greater than kB T, while in the hexagonal phase, high mobility along the chain direction leads to
a small value of K.
Crystals 2017, 7, 4 18 of 37

Hikosaka’s sliding diffusion model provides a theoretical explanation of extended-chain crystals.

In addition, the free energy barrier of sliding diffusion is proportional to the lamellar thickness, which
effectively prevents the occurrence of δl-catastrophe.
Later detailed studies showed that, in PE crystals, at low pressures, the orthogonal phase is
the stable phase; at high pressures, the hexagonal phase becomes the stable phase. Subsequently,
Hikosaka et al. [117] proposed that the crystallization process of PE usually had two distinct regimes.
In one regime, lamellae can only grow with a specific thickness; in the other regime, the crystal
firstly formed a hexagonal phase, then kept growing along both the lateral and chain directions
until the hexagonal phase transformed into the orthogonal phase, or crystal impingement occurred.
The transformation from the hexagonal phase to the orthogonal phase indicated that phase stability is
related to phase dimension, which is quite interesting, but is beyond the scope of this article. Interested
readers can resort to the original paper of Cheng and Keller [118].
The concept of the hexagonal phase that is similar to the liquid crystalline phase with high
mobility was subsequently generalized by Strobl [119], who argued that it was a common intermediate
state during polymer crystallization. This is the so-called “multi-stage model,” and we will discuss it
in the following section.
In addition to PE crystals, there are a few systems that can also obtain extended-chain crystals. For
instance, polyvinylidene difluoride [120,121], polytetrafluoroethylene [122], polychlorotrifluoroethylene [123],
trans-1,4-polybutadiene [124–127], and polyethylene terephthalate [128–130].
Finally, we make some personal comments on the Hikosaka’s model: it should be said that
sliding diffusion mechanism is an important supplement to the traditional folding chain model, which
provides a theoretical explanation for lamellar thickening. Moreover, the topological nature and chain
entanglement effect are taken into account in an explicit manner. Recently, Hikosaka [131] found that
both primary nucleation and lateral growth rates showed power-law dependence on molecular weight,
which confirmed that the topological nature of polymer chains assumes the most important role during
polymer crystallization. Therefore, chain sliding diffusion motion may play a significant role both in
primary and secondary nucleation processes.

4.4. Wunderlich’s Molecular Nucleation Theory

This concept was originally derived from the molecular segregation phenomenon. If two chemically
identical components with different molecular weights (termed as “bimodal”) are mixed together,
a question may arise: How to separate them? An immediate answer is as follows: Since the different
molecular weights correspond to different equilibrium melting points, if we fixed the crystallization
temperature between two equilibrium melting points, the component with high molecular weight
would crystallize, while the low molecular one would not. Obviously, this separation method is based
on the concept of thermodynamics and frequently referred to as fractionation [132].
However, it was observed that, even when the crystallization temperature was several centigrade
degrees lower than the equilibrium melting point of the small molecular weight sample, crystallization
stopped. Therefore, this separation approach is irrelevant to thermodynamics; instead, it is attributed to
the kinetic effect, which is usually called segregation. Compared with short-chain molecules, long-chain
molecules appear to crystallize more easily. Therefore, from the experimental results, it looks as if each
chain has to undergo its own process of nucleation. This conjecture is called the “molecular nucleation”
mechanism [133].
Another well-known example relevant to molecular segregation is the formation of
spherulites [134–136]. It has been observed that, for polydisperse polymers, the long-chain fractions
are enriched in the early stage, leading to thicker lamellae termed as the “dominant lamellae”;
in the later-grown crystals, short-chain fractions are enriched, resulting in thinner lamellar crystals
called subsidiary lamellae. According to Keith-Padden’s phenomenological theory, the occurrence of
branching is attributed to the fractionation of polymers, together with the segregation of impurities
during the formation of spherulites [137].
Crystals 2017, 7, 4 19 of 37

The phenomena of fractionation as well as segregation may be quite unique in polymer

crystallization distinguished from those of small molecules [58]. Obviously, these observations violate
the HL theory since, in the HL model, there is no explicit molecular weight dependence except the
kinetic prefactor β [83], which is, however, physically irrelevant to the present argument.
Furthermore, the “critical molecular length” can be defined for the PE samples with wide
distribution of molecular weight [135]. Beyond the critical molecular weight, components can
crystallize, while samples cannot crystallize below the critical molecular weight, which is inconsistent
with the theoretical calculation of the HL theory.
Molecular nucleation theory provides a theoretical explanation of the molecular segregation
phenomenon, or, more generally, of molecular weight dependence during the polymer crystallization
process. Meanwhile, it revises the opinion of the LH theory; a polymer chain rather than partial
segments must form a stable nucleus, which was later supported by computer simulations [138].
Another alternative interpretation may also be responsible for the phenomenon of molecular
weight segregation. It can be estimated that the typical growth rates corresponding to polymer
crystallization (10−3 –10 µm/h) [139,140] are orders of magnitude lower than that expected in the
diffusion-controlled crystal growth (10–105 µm/h) [141,142]. This implies that a polymer chain
has to “wait” a sufficiently long time in front of the crystal facet before it can be incorporated into
the crystal. This is exactly the idea of nucleation theories! Therefore, many instances of surface
attachment/detachment will be conducted, and the most stable configuration will eventually be
chosen. This immediately leads to the competition between two components with different molecular
weights on the surface [143–145]. The low molecular weight fraction will be kinetically equilibrated
first; however, the long-chain fraction will be thermodynamically more stable since it can obtain more
contact energy. Hence, the higher molecular component continues to replace the lower one; as a result,
segregation occurs. Therefore, it must be noted that the nucleation theory is only a possible explanation;
any kinetic process depending on molecular weight may lead to a similar result.

4.5. Hu’s Intra-Molecular Nucleation Theory

Despite the early treatment of molecular segregation proposed by Wunderlich, the molecular
weight dependence within polymer crystallization was still poorly understood. For example, there was
no quantitative calculation to support the mechanism of chain segregation until Hu et al. [41] proposed
a simplified single-chain model to take this issue into account. They assumed that the molecular chain
is arranged in a three-dimensional lattice. The degree of polymerization of the chain is N, and the
number of uncrystalline units is n. The free energy difference can thus be explicitly calculated in the
following way.
Assuming that the system is originally in crystalline phase and the energy required for each
formation of an amorphous unit is Ep , the energy cost will be (q−2)nEp /2, where q is the coordination
number. However, once the amorphous unit forms, its orientation can be arbitrary, resulting in a
certain amount of entropy compensation. The entropy gain corresponding to one monomer entropy
should be ln(q−1); for n amorphous monomers, the resulting free energy gain will be kTnln(q−1).
Therefore, the bulk free energy change can be estimated as

∆f = (q−2)nEp /2 + kTnln(q−1). (24)

In addition, surfaces will be created between the crystalline and amorphous phases. For primary
nucleation, due to the three-dimensional shape of the nucleus, the corresponding surface free energy
scales as (N −n)2/3 , whereas, for secondary nucleation, the relevant surface free energy is proportional
to (N −n)1/2 since a two-dimensional nucleus is concerned.
Therefore, the total energy difference for primary nucleus can be estimated as

q−2
F (n) = nE p + σ( N − n)2/3 − k B Tn ln(q − 1) = n∆ f + σ ( N − n)2/3 . (25)
2
Crystals 2017, 7, 4 20 of 37

This simplified model gives an explicit expression of the free energy difference, which can be
directly calculated by numerical methods. Hu et al. note that, at a fixed temperature, the nucleation
barrier (∆Fc ) is independent of the molecular weight, while the melting barrier (∆Fm ) depends on the
molecular weight.

4σ3
∆Fc = (26)
27∆ f 2
4σ3
∆Fm = ∆ f N − σN 2/3 + . (27)
27∆ f 2
It is obvious that the melting barrier will be higher when the molecular weight increases. Therefore,
only when the molecular weight exceeds a critical molecular weight, the nucleus will not dissolve into
the melt and the crystalline segments can survive. Therefore, the above arguments have explained the
molecular weight dependence during polymer crystallization.
Now we can return to the issue of secondary nucleation (the previous arguments are related to
primary nucleation). This simplified model allows us to make an explicit estimation of the “critical
chain length” proposed by Wunderlich [135]. It is obvious that the critical chain length corresponds to
the situation when the crystallization barrier and the melting barrier are equal to each other:

σ2
∆Fc2D = (28)
4∆ f 2D

2
σ2D
∆Fm2D = N∆ f 2D − σ2D N 1/2 + (29)
4∆ f 2D
 2
σ2D
Nc = (30)
∆ f e2D
where ∆Fc2D and ∆Fm2D correspond to the energy barrier of formation and the melting of the secondary
nucleus, respectively. The critical molecular weight Nc is inversely proportional to the square of the
free energy difference, which is, equivalently, inversely proportional to the square of supercooling,
in agreement with the experimental data of PE reported by Wunderlich.
In addition, Mehta and Wunderlich [135] also proposed an upper bound of molecular weight
during the molecular segregation process, namely, once the short-chain fraction exceeded the upper
limit, the segregation phenomenon would no longer occur. This limit was subsequently confirmed
by Glaser and Mandelkern [146]. It is now easy to understand by using this simplified model. If the
free energy of the melting barrier increases with the increase of N, when N exceeds a certain value,
the melting barrier will be much larger than the crystallization barrier, indicating that the melting
process will not occur.
In addition, Hu et al. noticed a significant defect in the molecular nucleation theory, namely,
when the chain is long enough, the crystal growth front with a finite size is unlikely to feel the
existence of the whole chain. One possible mechanism may lie in the fact that, as long as the sequential
segments (rather than the whole chain) are sufficient, they can grow into the crystal, and the remaining
amorphous part can further crystallize if its chain length is larger than the critical molecular length
(see Figure 2). There may be multiples reason for the formation of the partial amorphous chain, namely,
by the impingement of other crystallites or by the constraint imposed through long-range topological
entanglements. Crystallization in the same or different lamellae will lead to loops or tie molecules,
respectively. Furthermore, when the crystallization temperature is lower, the corresponding critical
chain length becomes shorter; therefore, at low temperatures, the polymer crystallization process will
be rapid, and each polymer chain may pass through multiple lamellae or through the same lamella
many times. This image is similar to the variable cluster model [73], as well as to the widely spaced
stem cluster model [147,148].
Crystals 2017, 7, 4 21 of 37

Compared to the HL theory, the intramolecular nucleation model does not need to introduce the
hypothesis that the first deposited stem assumes the total nucleation barrier. Moreover, it also does
not require the assumption of smooth crystal fronts in large scale, as long as the growth fronts can be
relatively smooth locally.
On the basis of the intramolecular nucleation model, Hu et al. have successfully explained various
well-known phenomena in polymer crystallization, such as chain folding, molecular segregation,
and regime phenomenon, and computer simulation results support their conclusions [149].
From a theoretical viewpoint, the intramolecular model combines reasonable aspects of various
theories together and presents a more appropriate description. It provides a quantitative explanation of
molecular segregation phenomenon and agrees with experiments quite well. In addition, the intramolecular
model takes the topological structure of polymers into account and derives explicitly analytic expression
of the minimum molecular weight dependence on supercooling based on a simplified model. Obviously,
the intramolecular nucleation model takes a significant step in understanding the crystallization
behavior of long-chain molecules.

4.6. Muthukumar’s Continuum Theory

Generally speaking, polymer crystallization can be classified into two categories: one is valid for
melt-grown crystals and solution-grown crystals with relative high molecular weight, in which the
crystal growth rate G is nucleation-controlled and exponentially depends on 1/T∆T; the other is valid
for solution-grown crystals with relative low molecular weight (Mw), in which the growth rate G is
diffusion-controlled and linearly proportional to supercooling ∆T [150,151].
Another remarkable feature of polymer crystallization is the significant dependence of the
crystallization rate on Mw. It can be expected that, in a concentrated solution or even in a melt,
the entanglement effect must be crucial for high polymers, which strongly depend on molecular
weight as well as concentration; however, for solution-grown crystals with a low molecular weight,
the transport effect may dominate. Therefore, to some extent, these two variables are unique
to macromolecules, which distinctively separate polymer crystallization from small molecular
crystallization. However, the mechanism of dependence on Mw and concentration is still partially
understood and various explanations coexist.
Muthukumar et al. [152] developed a unified formalism to take the two kinetic regimes into
account. The key element of this continuum theory is to invoke an entropic barrier that originates from
the accumulation of polymer chains near the crystal front. Experiments and simulations demonstrate
the congestion of chain-like objects, even for rather dilute solutions, which leads to an entropic pressure,
together with the influence of an excluded volume effect. Due to the higher concentration at the crystal
front, the un-crystalline chains are subject to mutual penetration, and accessible configurations will
hence be reduced. Therefore, these polymer chains must negotiate the entropic barrier before their
incorporation into crystals. Based on this simple physical picture, two distinct regions can be identified.
One is termed as the “inner layer” or the “boundary layer” near the crystal front, while the other
is termed as the “outer layer.” Polymer chains are subject to free diffusion only in the outer layer,
whereas in the boundary layer they are exerted to entropic force. Therefore, the dense inner layer
enforces different dynamics from the outer layer, and, as a natural consequence, the effects of Mw and
concentration are involved.
In addition, due to the arbitrary division of these two regions, the boundary condition must match
the common interface. Under the steady-state condition, a continuum coarse-grained model of polymer
crystallization focusing on detailed dynamics can be constructed. The specific free energy profile will
significantly depend on how polymer chains organize within the boundary layer, corresponding to the
detailed dynamics of polymers. Obviously, this description is in contrast to the case only considering
energy contribution. Here, we must note, however, that the concept of “surface free energy” still
holds in this barrier layer theory. The degeneracy due to possibility and energetic equivalence for
stems to organize themselves on the crystal front gives rise to the surface free energy at the very first
Crystals 2017, 7, 4 22 of 37

place. In this model, the stems are still subject to this kind of degeneracy at the growth front after they
reconcile the entropic barrier layer adjacent to the front.
The conclusive analytical result can be summarized as the following expression:

G ∼ C0 Din exp(− P/Tc ∆T ) × [1 − exp(∆H∆T/κB Tm Tc )] (31)

where G is the linear growth rate, C0 is the initial concentration, Din is the diffusion coefficient inside the
boundary layer, ∆H is the enthalpy of fusion, ∆T is the under-cooling, Tm is the melting temperature
at the finite molecular weight, Tc is the crystallization temperature, and P is a parameter that depends
on the details of the entropic barrier as well as on ∆H, Tm , and Tc . The above expression captures the
two kinetic regimes both for nucleation-controlled (G ~exp(−1/∆T)) and diffusion-controlled (G ~∆T).
The concentration and molecular weight dependences have been assumed to obey different
dynamics in the dense boundary zone compared with the outer layer. Based on this hypothesis,
the growth rates can be evaluated to be weakly or marginally dependent on concentration (the exponent
γ in G ~Cγ is smaller or much smaller than 1). This is not surprising since the enrichment of
polymer chains near the front considerably eliminates the sensitivity to the overall macromolecular
concentration. These predictions agreed with the experimental results and implied a barrier control
near the growth front. Therefore, based on the novel concept of entropic barrier within the boundary
layer, a unified theory with reaction-diffusion type has been established. This model explicitly takes
the characteristics of long-chain polymers into account and reveals the effects of concentration and
molecular weight in a quantitative manner. The topological structure of chain-like objects is one of
the most significant features of polymers, and the incorporation of the detailed dynamics of polymer
motion inevitably deepens our understanding of polymer crystallization.
In summary, in this section, we mainly focus on the surface nucleation theories, namely, the secondary
nucleation theories. The basic assumptions in various theories are highlighted since different theories
will, to some extent, lead to the same experimental conclusions. Therefore, understanding the validity of
their assumptions will be crucial. So far, most of the theories are kinetic in nature. The construction of
them can be roughly divided into two competitive factors, one is the driving force and the other is the
nucleation barrier. Different kinetic theories assume the same driving force, which originates from
the Gibbs free energy change between the crystalline and amorphous phases. The divergence results
from the definition of the nucleation barrier. Diverse factors are believed to be the rate-determining
process in various theories. The various ingredients built in the kinetic model leads to complete
distinct formalism. Here, we put some typical microscopic models in Figure 6 together and hope
that the similarities and differences between various models are self-evident. In fact, any theory
that reasonably includes the driving force and the nucleation barrier will certainly result in similar
conclusions. From this perspective, the kinetic theory is rather powerful since it can accommodate
different elements. However, it should be noted that the nucleation barrier cannot be controlled by
a single factor of enthalpy or entropy, comprehensive considerations will eventually lead to a more
clear figure.
 Crystals 2017, 7, 4 23 of 36
Crystals 2017, 7, 4 23 of 37

Figure 6. Schematic diagram of some typical microscopic models: (A) The fine-grained model proposed
Figure
by Frank6. andSchematic diagram
Tosi. At each step, aofunit
some typical rather
or segment microscopic models:
than a stem (A)added
will be The fine-grained
on the crystal model
front,
proposed
and by can
the units Frank and
only Tosi. Aton
fluctuate each
andstep, a unitthe
off along or direction
segment rather than athickness.
of lamellar stem willChain
be added on the
folding is
crystal front, and the units can only fluctuate on and off along the direction of lamellar
inaccessible before the cumulative length of units reaches the lamellar thickness. (B) Point’s multi-path thickness.
Chain folding
approach allowsischain
inaccessible
folding before
at eachthe cumulative
step. length
In addition, of unitspoint
the pinning reaches the lamellar
is adjacent to thethickness.
pre-existing(B)
Point’s
units, multi-path
which approachfavorable.
is energetically allows chain
(C) Thefolding at each step.
Sadler–Gilmer In addition,
model. The shadow the area
pinning
means point
thatis
adjacent
the crystaltofront
the is
pre-existing
atomicallyunits,
rough,which
whileistheenergetically favorable.
crystal fronts of (A) and(C) (B)
Theare
Sadler–Gilmer model.
atomically smooth;
The shadow
therefore, area meansofthat
the deposition unitstheoncrystal frontsurface
the rough is atomically rough, while
is not necessarily the crystal
adjacent to eachfronts
otherof(in(A) and
order
(B) are atomically smooth; therefore, the deposition
to minimize the exposed areas) and the barrier is entropic origin.of units on the rough surface is not necessarily
adjacent to each other (in order to minimize the exposed areas) and the barrier is entropic origin.
5. Primary Nucleation
5. Primary Nucleation
In the previous section, we mainly discussed the surface nucleation theories, in which we assume
In system
that the the previous section, wepreexisting
has well-defined mainly discussed the surface
crystal fronts, eithernucleation
flat or rough theories,
at the in which we
microscopic
assume that the system has well-defined preexisting crystal
level. However, in recent decades, with the development of experimental techniques, especially fronts, either flat or rough at the
the
microscopic level. However, in recent decades, with the development
application of scattering approaches in polymer science, dramatic advances in the understanding of experimental techniques,
especially
of the earlythe stagesapplication of scattering
of crystallization (usuallyapproaches
termed as in “primary
polymer science,
nucleation”) dramatic
have advances
been achieved, in the
understanding of the early stages of crystallization (usually termed
and a great amount of models have been proposed. In this section, we will introduce and present as “primary nucleation”) have
been achieved,
comparisons and a great
of various amount
primary of models
nucleation haveHowever,
theories. been proposed. it mustIn bethis section, we
emphasized thatwill
theintroduce
theories
mentioned here address both primary and secondary nucleation processes. Nevertheless,emphasized
and present comparisons of various primary nucleation theories. However, it must be in order to
that the these
highlight theories mentioned
theories in the same herecontext
address both primary
to compare and secondary
their similarities nucleation
and differences, processes.
we hope that
Nevertheless, in order to highlight
such an arrangement will not lead to confusion. these theories in the same context to compare their similarities
and Asdifferences,
is known,we hope that such
crystallization an arrangement
is a first-order will not
transition. Here,leadweto confusion.
first present some general physical
As is known, crystallization is a first-order transition.
pictures of phase transitions and show the main streams of current investigation. Here, we first present somethat
It is hoped general
the
establishment of an “overall picture” will help us to gain a deep insight into the phase transitionsis
physical pictures of phase transitions and show the main streams of current investigation. It
hoped that
involved the establishment
in polymer crystallization.of an “overall picture” will help us to gain a deep insight into the
phase transitions
Generally involved
speaking, in are
there polymer crystallization.
two different mechanisms in phase separation. One is the nucleation
Generally speaking,
and growth process (NG) and the other isthere are two different mechanisms
the spinodal in phase(SD).
decomposition separation.
The twoOne kindsis the
of
nucleation and growth process (NG) and the other is the spinodal
mechanisms deserve some comments here. Although both of them lead to phase separation, there decomposition (SD). The two
kinds
are of mechanisms
remarkable distinctions deserve
between some them:comments
(I) They here.
occur Although
at differentboth of them
regions. NG takesleadeffect
to phase
in a
separation, there are remarkable distinctions between them: (I) They
metastable region, while SD dominates in an unstable region. (II) Since they occur in different regions,occur at different regions. NG
takes effect in a metastable region, while SD dominates in an unstable
the corresponding kinetic process are different. In the unstable region, the second derivative of free region. (II) Since they occur
in different
energy regions,tothe
with respect the corresponding
order parameter kinetic process
is negative, soare
anydifferent.
tiny localIn the unstablefluctuations
concentration region, the
second derivative of free energy with respect to the order parameter
will decrease the free energy. Hence, SD is a spontaneous process without any “barrier.” On the is negative, so any tinyother
local
concentration
hand, the secondfluctuations
derivative ofwill free decrease
energy with therespect
free energy.
to the orderHence, SD is isa positive
parameter spontaneous process
in metastable
without any “barrier.” On the other hand, the second derivative
regions. An energy barrier must be overcome by random thermal fluctuation leading to the stable of free energy with respect to the
order parameter is positive in metastable regions. An energy barrier
“critical nuclei.” Thus, NG is responsible for this kind of phase separation. (III) The morphology will must be overcome by random
thermal
be fluctuation
different. leading to
SD corresponds to the stable
a zero “critical
“barrier” nuclei.”and
process, Thus, NG is responsible
spontaneous fluctuation forcanthishappen
kind of
phase separation. (III) The morphology will be different. SD
at any location of the system, which results in a bicontinuous texture. However, NG rests on local corresponds to a zero “barrier”
process,
large and spontaneous
concentration fluctuationsfluctuation can happen
to nucleation; at any
therefore, location of the
it sporadically system,
occurs in thewhich
system, results in a
leading
bicontinuous
to a sea-island texture.
structure. However,
Of course, NG in rests
the lateon stage,
local due
largetoconcentration
surface tension, fluctuations
bicontinuous to nucleation;
structure
therefore, it sporadically occurs in the system, leading to a sea-island structure. Of course, in the
Crystals 2017, 7, 4 24 of 37

breaks up and eventually coarsens into the sea-island structure. Nonetheless, in the early stage of
phase separation, there are sharp differences between the morphologies of the two mechanisms.
In summary, for nucleation and growth (NG), relevant perturbation is small in extent but large
in amplitude; therefore, the metastable state relaxes by the activated growth of localized density
fluctuations of large amplitude. For SD, however, relevant perturbation is large in extent but small
in amplitude; therefore, an unstable state relaxes by the spontaneous growth of long-wavelength
fluctuations of small amplitude [153].
Studies on the early stage of crystallization mainly rest on two distinct approaches. One is from a
“solid” perspective, i.e., we can extrapolate the crystallization process from the final crystal structures,
since it is believed that the final crystal morphology and structure actually reflect the true crystallization
process. The other is from a “liquid” view, i.e., we need to examine the correlation function of the
system, since, in the early stage, there are no crystallographic crystals. The system, to a large extent,
is still in an undercooled amorphous state. For liquid states, the most direct approach is to explore the
correlation function by means of a scattering technique.
From the “solid” perspective, a typical approach is to employ the “droplet” method. For instance,
Vonnegat [154] broke liquid film into tiny droplets of a few microns. The droplet was so small that
most of them did not include heterogeneous nuclei; therefore, it was an ideal system to examine
homogeneous nucleation, which could be directly observed under an optical microscope. Subsequent
studies showed that the dimension of primary nucleus was about 10 nm3 , which is much smaller than
the volume size of a whole macromolecule (about 100–1000 nm3 ). It was concluded that the primary
nucleus is only part of the macromolecular chain. Therefore, it is possible to prepare the so-called
“single-chain, single crystals” to study the primary nucleation process [155]. Bu et al. successfully
prepared the single-chain crystals of PEO [17]. In addition, similar results can also be obtained from
other polymer systems, such as i-PS [156] and PTFE [157]. These evidences indicate that the primary
nucleation follows the classical NG mechanism.
On the other hand, from the “liquid” perspective, a scattering technique has been applied to
study the correlation function, and the situation is completely different. The scattering experiment will
eventually give a time-averaged scattering curve. Meanwhile, the interpretation of the curve depends
on the mathematical model employed. Early studies of the undercooled polymeric liquid found that,
in addition to the expected correlation length around 2~3 nm, a large-scale correlation up to 300 nm
can also be observed [158]. In small molecules, a similar result could be found as well [159]. Further
studies [160–162] showed that the two length scales were decoupled with respect to the long-range
fluctuation correlation, which indicated that there should be some certain large-scale structure within
the super-cooled liquid, since correlation is exactly equivalent to structure.
In addition to the large-scale correlation length, more sophisticated scattering experiments
demonstrated that the system has the following kinetic features [163–167]:
(1) Before any signals could be detected from wide angle X-ray diffraction, i.e., no crystallographic
crystals formed, the plotted scattering curve of the integrated intensity I(q,t) versus q showed a peak
qmax , which scaled as qmax ~(∆T)1/2 , where ∆T represents supercooling.
(2) I(q) exponentially grew with time, and the growth rate Ωq /q2 presented a linear relation with
respect to q2 for intermediate values of q.
These observations are very similar to the kinetics of spinodal decomposition, and several
researchers have proposed that the early crystallization process was dominated by the mechanism
of SD rather than NG. However, from previous analyses, it can be seen that NG and SD are quite
different—to some extent, they are incompatible.
Taking the SD mechanism to explain the formation of primary nuclei was firstly proposed by
Imai et al. [167], and later discussed by Olmsted et al. [164]. According to the experimental scattering
curves, they found that these curves were similar to the kinetics of the phase separation of the
traditional polymer blends, which inspired them to propose that the formation of primary nuclei was
a spinodal-assisted process. However, SD here is not relevant to the traditional phase separation of
Crystals 2017, 7, 4 25 of 37

polymer blends; instead, it refers to the so-called “conformational separation.” They argued that, in the
PE melt, since the temperature was high, the occurrence of various conformations was equally probable.
According to the assumption of the rotational isomeric state, at high temperatures, the probability
of trans- and gauche- (g+, g−) conformations was 1/3 and 2/3, respectively. When the temperature
is below the melting point, the trans-conformation will aggregate and form the primary nuclei.
In addition, they calculated the difference of the free energy barrier before and after phase separation
and found that, due to phase separation, the nucleation barrier of crystallization would be considerably
reduced. Therefore, they concluded that primary nuclei could form by a spinodal-assisted mechanism.
Subsequently, a similar mechanism termed as the “conformation-assisted fluctuation of density”
was proposed by Yan et al. [168]. They argued that, when the temperature was lower than the melting
point, in addition to the density fluctuation, conformational fluctuation should also be taken into
account. The starting point of this theory was to construct an appropriate free energy function of the
Ginzburg–Landau-type and substitute it into the Cahn–Hilliard equation, and the evolution of the
system could thus be obtained.
One of the essential parts of the aforementioned theories lies in that these authors realized that
the undercooled liquid may be heterogeneous rather than homogeneous. However, attention must be
paid to the following aspects: (1) If the formation of primary nuclei stemmed from conformational
separation, the corresponding time scales would probably mismatch. The dynamic transition of trans-
and gauch-conformations is in the range of 10−11 ~10−13 s, while the experimental detection of nuclei
may occur at the time scale of seconds to minutes. The difference of several orders of magnitude
and why the completion of conformational separation must wait several orders of magnitude before
nucleation occurs are difficult to explain. (2) Some computer simulation results [25,84,169,170] and
later scattering experiments [171,172] revealed that nucleation and growth mechanism still dominated
primary nucleation, while other simulation results reported that spinodal decomposition preceded
polymer crystallization [173].
Muthukumar [25,84,169,170] employed Langevin dynamics to study the single-chain crystallization
process, and they found that the snapshots demonstrated the following characteristics:
(i) Several regions of segmental aggregation with some visibly apparent local orientational orders
are formed. Connected by the same chain, these regions are referred as “baby nuclei.”
(ii) As time evolves, the monomers in the flexible strands are reeled into the baby nuclei, and the
orientational order in each nuclei increases.
(iii) Simultaneously, the competition between nuclei for further growth dissolves some nuclei.
It can be clearly seen that this process is exactly an NG process; the only difference is that, at this
time, a polymer chain can participate in the formation of several nuclei since the polymer chain is
very long.
In addition, it was also found that, during the simulation time, the spacing between baby nuclei
remained unchanged, which was inversely proportional to the qmax . In the late stage of crystallization,
the number of monomers involved in connectors gradually decreased, and the strands were reeled
into baby nuclei, leading to the merge of some baby nuclei. This was followed by a cooperative
reorganization, by which nuclei merged to form a single lamella. The mechanism of the merging was
not via sequentially placing stems, but via a highly cooperative process, involving all stems of the
lamella. Obviously, it is in contrast to the HL theory.
Later, Muthukumar [25] considered the density fluctuation in an early stage. The starting point
was still based on the Cahn–Hilliard equation and the considerable improvement was to introduce
the new form of free energy. In the classical Cahn–Hilliard equation, the free energy obeys the
Ginzburg–Landau functional form. Due to the non-local gradient term, the Fourier transform is
frequently performed to decouple the non-local term into a local one. In Fourier space, one is the
bulk term proportional to ψ2 , where ψ is the order parameter in inverse space; the other corresponds
to the interface term scaling as q2 ψ2 , while Muthukumar added the third term q−2 ψ2 , taking chain
connectivity into account. It should be noted that the form of q−2 ψ2 is similar to the Debye structure
Crystals 2017, 7, 4 26 of 37

factor within a distance less than the radius of gyration, which reflects the statistical properties of
different monomers. Therefore, the constructed free energy reads

1
F ∼ ∑ (−∆T + q2 + q2 )ψq2 . (32)
q

Substituting it into the Cahn–Hilliard equation, the following is obtained:

∂ψq (t) 1
= −q2 (−∆T + q2 + 2 )ψq (t) (33)
∂t q

1
Ωq = q2 (∆T − q2 − ). (34)
q2
It should be noted that at this stage that both small and large q-values are cut off. Therefore, for a
large q, it has the same predictions as the spinodal decomposition, namely, the plot of Ωq /q2 versus q2
presents a straight line with a negative slope. However, for small q regimes, the term q–2 dominates
and Ωq /q2 versus q2 rapidly increases up to qmax , which is consistent with experiments.
To summarize, despite controversies over different mechanisms of primary nucleation, all theories
have tried to clarify the origin of experimentally observed heterogeneous structures in the supercooled
melt. Some kind of ordered structure, frequently referred to as a “preordered structure,” may exist.
Various authors, in addition to the above-mentioned ones, including Hoffman [69], who proposed this
concept in his last review article, have stated a similar idea.
The “preordered structure” idea may be traced back to Allegra [174,175], who proposed that,
prior to the formation of crystals, some kind of intra-molecular cluster (or bundles) with metastable
equilibrium distributions first occurred in a liquid state. Furthermore, these clusters aggregated by van
der Waals force and finally formed the crystal. This idea was generalized by Allegra and Meille [176,177],
and the so-called “bundle theory” was proposed. The bundle is an aggregate of a few parallel polymer
segments or stems connected by folds and stabilized by attractive crystal-like interactions.
From this point of view, the concept of a “bundle” is analogous to the idea of “baby nuclei”
proposed by Muthukumar. However, Allegra and Meille argued that stems involved in one bundle
originates from the same polymer chain in the context of a polymer solution, and these stems are
connected by chain folds, while in bulk or concentrated solution, one bundle may include stems from
distant chain portions, or even from different chains.
According to the original concept of the bundle theory, it may only apply to the case of a dilution
solution. For melt crystallization, due to topological constraints, the mobility of polymer chains
dramatic slowed down, resulting in the relaxation time of chain motion even longer than that of bundle
stems. The mismatch of two time scales leads to a non-equilibrium process and cannot be treated in
classical statistical thermodynamics.
Another key point of the bundle theory lies in that the lamellar crystal is formed by the transfer
of stems from bundles to the lateral lamellar surface. Therefore, the lamellar thickness is largely
determined by the statistical characteristics of stems in the bundle. However, it must be pointed out
that the bundle theory is mainly a secondary nucleation theory, namely, it is assumed that crystal
fronts are first formed by an aggregation of different bundles; hence, the subsequent growth process
on the preexisting crystal fronts can be examined.
Dealing with the secondary nucleation theory is beyond the scope of this section. Interested
readers can refer to the original papers [176].
The starting point of the theoretical treatment of the bundle stem is to calculate the partition
function. Here, only the case of polymer crystallization in a dilute solution will be introduced. When the
polymer chain is in a liquid state, its partition function is assumed to be Z0 . When the temperature is
Crystals 2017, 7, 4 27 of 37

below its melting temperature, T0 , the bundles will form and correspond to the following expression
of the partition function:

Z ( T ) = Z0 + ∑ Ωi [exp(− Ei /k B T ) − exp(− Ei /k B T0 )] ∼
= Z0 − ∑ (Ωi Ei /k B T02 )( T0 − T ) (35)
i i

where Ωi is the multiplicity function, and Ei is the attractive energy involved in the i-th conformation.
The subtracted term in the square brackets results from the fact that it has already been calculated in
the reference state. Therefore, in order to avoid repeated computations, it must be subtracted. It should
also be noted that the above formula employs the assumption that the temperature is in the vicinity
of the equilibrium temperature T0 , namely, under small supercoolings. Once we have the partition
function, the free energy can be readily obtained:

ΩE
∆G ( T ) = G ( T ) − G ( T0 ) = −k B T [ln( Z ( T ))] − ln( Z0 ) ∼
= ∑ T0iZ0i (T0 − T ) (36)
i

Compared with the thermodynamics derivations in Section 2, it is not difficult to find that
they both have the same expression, i.e., the free energy difference is proportional to supercooling.
However, it should be noted that ∆G corresponds to the bundle state rather than the crystalline state,
which indicates that the same dependence is valid for both the intermediate metastable state and the
equilibrium state. Therefore, we can infer that the statistical properties of bundles will determine the
subsequent growth kinetics, which inevitably leads to similar results as mentioned previously.
In addition, in order to explain the difference between the re-crystallization line and the melting line
observed in experiments, Strobl [119,178–180] also proposed the concept of the “mesomorphic phase.”
He argued that there was a mesomorphic inner structure between the crystalline and amorphous
phase, which was stabilized by epitaxial force. In addition, all stereo defects and noncrystalline
co-units will be rejected on its fronts by the lateral growth. In this model, the mesomorphic phase
requires a minimal dimension to maintain its stability in the melt condition. High inner mobility allows
for the spontaneous thickening of a long-chain direction, which is similar to the sliding diffusion
motion proposed by Hikosaka. However, the inner mobility will be reduced by lamellar thickening,
which effectively prevents the occurrence of extended-chain crystals and leads to a limited lamellar
thickness. In addition, the outside layer has a higher mobility than the inside layers, which leads
to the “solidification” of inner parts and transforms to more perfectly ordered structures, frequently
called “granular blocks.” These blocks then collide and combine with each other to form larger
aggregates. Such transformation does not need much energy to overcome the free energy barrier.
These aggregates further undergo “perfection” and eventually form the crystals with specific lamellar
thickness. This process is usually termed as the “multi-stage model.”
From the above description, we can see that the multi-stage model proposed by Strobl is quite
different from the traditional nucleation theory. Strobl introduces the third phase, i.e., the mesomorphic
phase, and the traditional thermodynamic theories of crystallization merely take two phases into
account, that is, they only consider the crystalline phase and the amorphous phase. This is the origin
of introduction of the third phase by Strobl, who argued that the traditional treatment was insufficient.
From experiments, it can be clearly seen that melting and crystallization follow two distinct pathways,
which may be, in principle, irreversible. Obviously, it violates the classical nucleation theory and
cannot be explained by the two-phase model.
Moreover, the introduction of the mesomorphic phase may also be inspired by the hexagonal
phase proposed by Hikosaka. The most prominent merit of Strobl’s multistage model is that the
thermodynamic parameters, such as the surface and bulk free energies of the intermediate state
(mesophase) is different from those of the final crystals. The future theory for polymer crystallization
should take the size effect into account. However, some authors have argued that the introduction of
the mesomorphic phase would affect the correct formation of crystals by the random incorporation of
blocks [181,182].
 Crystals 2017, 7, 4 28 of 37

Crystals 2017, 7, 4 28 of 36
The concept of the “mesomorphic phase” is similar to that of the “bundle” proposed by Allegra.
andIneventually
Strobl’s model,form the crystals.
preordered Instructures
accordancewith with the mobility
high inner bundle will theory, Allegra
undergo employed the
a self-perfection
traditional process, i.e., stems involved in the bundle diffuse and adsorb onto
process and form granular blocks, and these blocks will then merge with each other and eventually the crystal fronts.
Furthermore,
form crystals.in Muthukumar’s
In accordance with simulation
the bundleresults,
theory,crystal
Allegragrowth
employed is controlled by process,
the traditional diffusioni.e.,rather
stems involved in the bundle diffuse and adsorb onto the crystal fronts. Furthermore,
than surface nucleation, i.e., once a few segments contact the crystal fronts, the remaining parts of in Muthukumar’s
simulation
the chain quicklyresults,
add crystal growth surfaces,
to the crystal is controlled
whichby indicates
diffusion rather
that thethan surfaceofnucleation,
addition i.e., the
segments onto
once a few segments contact the crystal fronts, the remaining parts of the
crystal fronts corresponds to small energy barriers. On the contrary, in order to commensurate chain quickly add to with
the crystal surfaces, which indicates that the addition of segments onto the crystal fronts corresponds
the growth crystals, subsequent molecular rearrangement on the crystal surface is the
to small energy barriers. On the contrary, in order to commensurate with the growth crystals,
rate-determining process. Moreover, the arrangement is a highly cooperative process involving
subsequent molecular rearrangement on the crystal surface is the rate-determining process. Moreover,
participation of many molecular chains, and subsequent experiments and simulations clarify the
the arrangement is a highly cooperative process involving participation of many molecular chains,
“precursor” state more
and subsequent clearly and
experiments [183–187]. All these
simulations clarifyaspects are in contrast
the “precursor” to traditional
state more nucleation
clearly [183–187].
theories [61].aspects are in contrast to traditional nucleation theories [61].
All these
Finally, wewe
Finally, present
presentthree
threedifferent typicalroutes
different typical routesrelevant
relevant to to
thethe polymer
polymer crystallization
crystallization process
process
andand
the the
corresponding
corresponding free
freeenergy
energy landscapes
landscapes in inFigure
Figure7. 7.

Figure
Figure Schematic diagrams
7. 7.Schematic diagrams of three
of typical
three routes
typical in polymer
routes crystallization
in polymer and the corresponding
crystallization and the
free energy landscapes. (A) Representative of fine-grained microscopic
corresponding free energy landscapes. (A) Representative of fine-grained microscopic process during crystallization,
process
either proposed by Frank and Tosi, or modified by Point, for more details, see Figure 6. The corresponding
during crystallization, either proposed by Frank and Tosi, or modified by Point, for more details, see
free energy diagram shows the formation of only one stem (composed of various substeps). Attachment
Figure 6. The corresponding free energy diagram shows the formation of only one stem (composed
of the first chain stem is the rate determining step. (B) The Hoffman–Lauritzen model, which can be
of various
regardedsubsteps). Attachment
as a coarse-grained modelof the first
compared withchain stem
(A). The isenergy
free the rate determining
landscape step. (B)
corresponding to The
Hoffman–Lauritzen
the formation of various model,stems
which can be
shows thatregarded
initiation as
of athe
coarse-grained
first stem is themodel compared step.
rate determining with (A).
The(C)free energy landscape corresponding to the formation of various stems
Strobl’s multistage model, in which the mesomorphic phase (which is a thermodynamic phase) is shows that initiation of
the highlighted
first stem isand thetherate determining
corresponding step. (C) Strobl’s
thermodynamic multistage
quantities model,
different in initial
from the whichand thefinal
mesomorphic
states
phasecan (which
be derived.is aThe relevant free energy
thermodynamic phase)landscape shows that and
is highlighted the mesomorphic phase is athermodynamic
the corresponding metastable
phase and
quantities the rate determining
different step is and
from the initial the formation of thecan
final states mesomorphic
be derived. phase.
The relevant free energy
landscape shows that the mesomorphic phase is a metastable phase and the rate determining step is
6.the
Conclusions
formation of the mesomorphic phase.
It is the aim of this article to review the major theories relevant to polymer crystallization.
6. Conclusions
Basic assumptions of various theories are highlighted, and detailed discussions are performed in a
physically intuitive way. We hope that such treatments will help readers to appreciate the beauty of
It is the aim of this article to review the major theories relevant to polymer crystallization. Basic
each theory and recognize their successful and unsuccessful parts. Polymer crystallization features in
assumptions
the development of various
of polymertheories areand
science highlighted,
the corresponding and detailed
theories havediscussions are performed
been put forward for more in a
physically
than fifty intuitive way. We
years; however, newhope thatorsuch
models treatments
theories will help
are still being readers
proposed to appreciate
nowadays, the beauty of
which indicates
eachthat
theory anditself
the field recognize their successful
is essentially complex and and unsuccessful
robustly parts. Polymer
vital. Nevertheless, crystallization
open questions remainfeatures
in
in the
thisdevelopment of polymer
field, and controversial science
opinions and thecoexist.
sometimes corresponding
Here we give theories
a shorthave been and
summary put present
forward for
moresomethan fifty years;
personal viewshowever, new models
on the potential problemsorintheories
polymer are still beingtheories.
crystallization proposed nowadays, which
indicates that the field itself is essentially complex and robustly vital. Nevertheless, open questions
remain in this field, and controversial opinions sometimes coexist. Here we give a short summary
and present some personal views on the potential problems in polymer crystallization theories.
We firstly discuss the concept of chain folding in Section 2, since it is one of the most
significant features different from the crystallization of small molecules, as well as its physical
implications, such as why a polymer chain needs to fold during crystallization. In Section 3, we
Crystals 2017, 7, 4 29 of 37

We firstly discuss the concept of chain folding in Section 2, since it is one of the most significant
features different from the crystallization of small molecules, as well as its physical implications,
such as why a polymer chain needs to fold during crystallization. In Section 3, we present the basic
thermodynamic considerations, in which we especially focus on various defects and omissions behind
the conventional treatment, which mainly stems from the finite size effect. Sections 4 and 5 are the main
parts of this paper, dealing with secondary and primary nucleation theories, respectively. In Section 4,
we firstly introduce the Hoffman–Lauritzen (HL) theory as the main line within this section because it
provides a simple and analytical formalism to deal with polymer crystallization, as well as a reference
model that was subsequently modified by other theories and models. In Section 5, we mainly focus
on primary nucleation theories, which share some similarities and, to some extent, overlap with each
other, and we compare the different theories in an explicit way.
In the following, we will present some personal views on potential issues remaining in polymer
crystallization theories.
(1) A topological long-chain nature is one of the most significant features of polymers, and should
certainly be taken into account in any theory. So far, various authors have addressed this issue from
apparently distinct perspectives. The most common approach is to invoke an entropic barrier, which
may originate either from wrong configurations or from entropic pressure. In addition, the topological
structure can also be implicitly treated by addressing the effects of entanglement, diffusion, and so on.
Therefore, a natural question may be raised: Some treatments are rather microscopic while others,
to some extent, are phenomenological. Are these descriptions equivalent or not? We can also
further ask whether these descriptions are complete or not. Apparently, no theory can interpret
all experimental results, and a fortiori make predictions about unknown phenomena of polymer
crystallization. Therefore, we have to resort to the paradigm of how to appropriately describe the
polymer crystallization process by compromising microscopic details and its physical nature; however,
we do not know the answer at present.
(2) Polymer crystal is, in essence, a strong correlated system far from equilibrium. At equilibrium,
statistical analysis can be employed to associate macroscopic quantities with microscopic parameters.
Based on the self-similar property of polymers, scaling analysis could be successfully performed
and lead to remarkable physical consequences. Nevertheless, for non-equilibrium systems along
with strong correlations, it is uncertain whether scaling arguments could be valid. Recent studies on
non-equilibrium systems [188] found that, even under far from equilibrium conditions, unexpected
long-range correlations may appear. Power-law behaviors indicate the potential application of scaling
analysis; such a treatment, however, has seldom appeared in the literature.
(3) Recent studies on the early stage of crystallization reveal new phenomena that undercooled liquid
may have a heterogeneous structure [187]. Traditional crystallization theories are well established based
on homogeneous primary nucleation; if the system is heterogeneous rather than homogeneous, many
aspects relevant to polymer crystallization process should be reconsidered, and the pre-crystalline
ordered state also presents a challenging issue against the conventional treatments.
(4) All the theories and models established for polymer crystallization can be divided into the
subcategories according to the number of microscopic states and the treatment of the long-range
multi-body interactions. Here, various microscopic states possess different sets of thermodynamic or
kinetic parameters. For instance, HL theory is a two-state theory, where the interface free energy per
area and bulk free energy per volume of polymer lamellae are independent of crystal size. In contrast,
Strobl’s new model is a three-state model, in which the meso-phase and the stabilized crystal have
different thermodynamic parameters. The treatment of long-range multi-body interaction in polymer
lamellar crystals is tricky, which lies in the core of any crystallization theory. For the classical
thermodynamic description, the long-range multi-body interaction enters the interfacial free energy
term. In fact, the interfacial free energy may vary with crystal size when the crystal is very small,
e.g., of nanometer scale. On the contrary, in some kinetics models, only the interaction between the
nearest neighbors are considered, which is analogous to the treatment of phase separation and may
Crystals 2017, 7, 4 30 of 37

have a limited value of energy barrier around several kB T if the interfacial free energy is not taken into
account. As a result, this would lead to spinodal-like behavior. Consequently, the future new theory on
polymer crystallization (or more generally on crystallization) should bear the ability to describe various
intermediate states with long-range multi-body interaction. Microscopic kinetics model independent
of the thermodynamics frame may be a potential candidate of the new crystallization theory.
(5) What is the relationship between polymer crystallization and other subjects such as glass
transition? Both of them are strongly correlated with many body systems. Is there a unified framework
to understand them? Glass transition also relates to physical aging, which is an important issue
both in scientific research and industrial application. Besides, the phenomena relevant to lamellar
thickening, melting, and/or recrystallization are frequently encountered. All of them are the physical
consequences of the evolution from non-equilibrium to equilibrium. Unfortunately, we do not know
exactly the rules controlling evolution except the Ostwald ripening principle. In addition, the final
mechanical properties are largely determined by the structure, namely, the morphology of the crystals,
which is further tightly connected with nucleation. Up to now, polymer crystallization theories mainly
correspond to the nucleation process, and, of course, we need to develop more detailed theories
relevant to superstructures, such as spherulites and oriented crystal structures formed in external
force fields.

Acknowledgments: The authors are deeply grateful to the financial support from the National Natural Science
Foundation of China (Grant No. 21374054) and the Sino-German Center for Research Promotion (Grant No. GZ 833).
Author Contributions: Michael C. Zhang and Jun Xu designed the outlines of the review. Michael C. Zhang
wrote the paper and Bao-Hua Guo and Jun Xu revised the paper considerably.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Fischer, E.W. Notizen: Stufen-und spiralförmiges Kristallwachstum bei Hochpolymeren. Z. Naturforsch. A
1957, 12, 753–754. [CrossRef]
2. Keller, A. A note on single crystals in polymers—Evidence for a folded chain configuration. Philos. Mag.
1957, 2, 1171–1175. [CrossRef]
3. Till, P.H. The growth of single crystals of linear polyethylene. J. Polym. Sci. 1957, 24, 301–306. [CrossRef]
4. Jaccodine, R. Observations of spiral growth steps in ethylene polymer. Nature 1955, 176, 305–306. [CrossRef]
5. Lauritzen, J.; Hoffman, J.D. Theory of formation of polymer crystals with folded chains in dilute solution.
J. Res. Natl. Bur. Stand. A 1960, 64, 73–102. [CrossRef]
6. Sommer, J.-U. Theoretical Aspects of the Equilibrium State of Chain Crystals. In Progress in Understanding of
Polymer Crystallization; Springer: Berlin/Heidelberg, Germany, 2007; pp. 19–45.
7. Phillips, P.J. Polymer crystals. Rep. Prog. Phys. 1990, 53, 549–604. [CrossRef]
8. Armitstead, K.; Goldbeck-Wood, G.; Keller, A. Polymer Crystallization Theories. In Macromolecules: Synthesis,
Order and Advanced Properties; Springer: Berlin/Heidelberg, Germany, 1992; pp. 219–312.
9. Keller, A. Polymer crystals. Rep. Prog. Phys. 1968, 31, 623–704. [CrossRef]
10. Muthukumar, M. Nucleation in polymer crystallization. Adv. Chem. Phys. 2004, 128, 1–64.
11. Herrmann, K.; Gerngross, O.; Abitz, W. Zur rontgenographischen Strukturforschung des gelatinemicells.
Z. Phys. Chem. B 1930, 10, 371–394.
12. Storks, K. An electron diffraction examination of some linear high polymers. J. Am. Chem. Soc. 1938, 60,
1753–1761. [CrossRef]
13. Keller, A.; O’Connor, A. Large periods in polyethylene: The origin of low-angle X-ray scattering. Nature
1957, 180, 1289–1290. [CrossRef]
14. Flory, P.J. On the morphology of the crystalline state in polymers. J. Am. Chem. Soc. 1962, 84, 2857–2867.
[CrossRef]
15. Zachmann, H. Der Einfluß der Konfigurationsentropie auf das Kristallisations-und Schmelzverhalten von
hochpolymeren Stoffen. Kolloid-Zeitschrift und Zeitschrift für Polymere 1967, 216, 180–191. [CrossRef]
16. Zachmann, H. Statistische Thermodynamik des Kristallisierens und Schmelzens von hochpolymeren Stoffen.
Colloid Polym. Sci. 1969, 231, 504–534. [CrossRef]
Crystals 2017, 7, 4 31 of 37

17. Bu, H.S.; Pang, Y.W.; Song, D.D.; Yu, T.Y.; Voll, T.; Czornyj, G.; Wunderlich, B. Single-molecule single crystals.
J. Polym. Sci. Part B Polym. Phys. 1991, 29, 139–152. [CrossRef]
18. Liu, L.Z.; Su, F.Y.; Zhu, H.S.; Li, H.; Zhou, E.L.; Yan, R.F.; Qian, R.Y. Single-chain single crystals of gutta-percha.
J. Macromol. Sci. Part B Phys. 1997, 36, 195–203. [CrossRef]
19. Shi, S.H.; Chen, E.Q.; Hu, H.J.; Bu, H.S.; Zhang, Z. Morphology of single-chain single crystals of poly
(ethylene oxide). Macromol. Rapid Commun. 1995, 16, 77–80. [CrossRef]
20. Yamamoto, T. Computer modeling of polymer crystallization—Toward computer-assisted materials’ design.
Polymer 2009, 50, 1975–1985. [CrossRef]
21. Hu, W.B.; Frenkel, D.; Mathot, V.B. Free energy barrier to melting of single-chain polymer crystallite.
J. Chem. Phys. 2003, 118, 3455–3457. [CrossRef]
22. Fujiwara, S.; Sato, T. Molecular dynamics simulations of structural formation of a single polymer chain:
Bond-orientational order and conformational defects. J. Chem. Phys. 1997, 107, 613–622. [CrossRef]
23. Yang, X.Z.; Qian, R.Y. Molecular dynamics simulation of the crystal nucleation behavior of a single chain
touching a substrate surface. Macromol. Theory Simul. 1996, 5, 75–80. [CrossRef]
24. Kavassalis, T.; Sundararajan, P. A molecular-dynamics study of polyethylene crystallization. Macromolecules
1993, 26, 4144–4150. [CrossRef]
25. Muthukumar, M. Molecular modelling of nucleation in polymers. Philos. Trans. R. Soc. Lond. Ser. A 2003, 361,
539–556. [CrossRef] [PubMed]
26. Yang, X.Z.; Mao, X. Molecular dynamics simulation on crystalline nucleation behaviour of a single chain
touching a substrate surface II. Temperature dependence. Comput. Theor. Polym. Sci. 1997, 7, 81–84.
[CrossRef]
27. Hong, Y.L.; Koga, T.; Miyoshi, T. Chain trajectory and crystallization mechanism of a semicrystalline polymer
in melt-and solution-grown crystals as studied using 13 C–13 C double-quantum NMR. Macromolecules 2015,
48, 3282–3293. [CrossRef]
28. Hong, Y.L.; Yuan, S.C.; Li, Z.; Ke, Y.T.; Nozaki, K.; Miyoshi, T. Three-dimensional conformation of folded
polymers in single crystals. Phys. Rev. Lett. 2015, 115, 168301. [CrossRef] [PubMed]
29. Hong, Y.L.; Chen, W.; Yuan, S.C.; Kang, J.; Miyoshi, T. Chain trajectory of semicrystalline polymers as
revealed by solid-state nmr spectroscopy. ACS Macro Lett. 2016, 5, 355–358. [CrossRef]
30. Kumaki, J. Observation of polymer chain structures in two-dimensional films by atomic force microscopy.
Polym. J. 2016, 48, 3–14. [CrossRef]
31. De Gennes, P.-G. Reptation of a polymer chain in the presence of fixed obstacles. J. Chem. Phys. 1971, 55,
572–579. [CrossRef]
32. Flory, P.J. The configuration of real polymer chains. J. Chem. Phys. 1949, 17, 303–310. [CrossRef]
33. De Gennes, P.-G. Scaling Concepts in Polymer Physics; Cornell University Press: Ithaca, NY, USA, 1979.
34. Rouse, P.E., Jr. A theory of the linear viscoelastic properties of dilute solutions of coiling polymers.
J. Chem. Phys. 1953, 21, 1272–1280. [CrossRef]
35. Stepanow, S. Kinetic mechanism of chain folding in polymer crystallization. Phys. Rev. E 2014, 90, 032601.
[CrossRef] [PubMed]
36. Onsager, L. The effects of shape on the interaction of colloidal particles. Ann. N. Y. Acad. Sci. 1949, 51,
627–659. [CrossRef]
37. Edwards, S. The theory of polymer solutions at intermediate concentration. Proc. Phys. Soc. 1966, 88, 265–280.
[CrossRef]
38. Willard, G.J. Elementary Principles in Statistical Mechanics. In The Rational Foundation of Thermodynamics;
Charles Scribner’s Sons: New York, NY, USA; Edward Arnold: London, UK, 1902.
39. Hoffman, J.D.; Guttman, C.M.; DiMarzio, E.A. On the problem of crystallization of polymers from the melt
with chain folding. Faraday Discuss. Chem. Soc. 1979, 68, 177–197. [CrossRef]
40. Mandelkern, L. Crystallization of Polymers; McGraw-Hill: New York, NY, USA, 1964; Volume 38.
41. Hu, W.B.; Frenkel, D.; Mathot, V.B. Intramolecular nucleation model for polymer crystallization. Macromolecules
2003, 36, 8178–8183. [CrossRef]
42. Yoon, D.; Flory, P. Small-angle neutron scattering by semicrystalline polyethylene. Polymer 1977, 18, 509–513.
[CrossRef]
43. Meissner, F. Mitteilungen aus dem Institut für phys. Chemie der Universität Göttingen. Nr. 8. Über den
Einfluß der Zerteilung auf die Schmelztemperatur. Z. Anorg. Allg. Chem. 1920, 110, 169–186. [CrossRef]
Crystals 2017, 7, 4 32 of 37

44. Hoffman, J.D. Thermodynamic driving force in nucleation and growth processes. J. Chem. Phys. 1958, 29,
1192–1193. [CrossRef]
45. Jones, D.; Chadwick, G. An expression for the free energy of fusion in the homogeneous nucleation of solid
from pure melts. Philos. Mag. 1971, 24, 995–998. [CrossRef]
46. Hoffman, J.D.; Davis, G.T.; Lauritzen, J.I., Jr. The Rate of Crystallization of Linear Polymers with Chain
Folding. In Treatise on Solid State Chemistry; Springer: New York, NY, USA, 1976; pp. 497–614.
47. Hoffman, J.D.; Weeks, J.J. Rate of spherulitic crystallization with chain folds in polychlorotrifluoroethylene.
J. Chem. Phys. 1962, 37, 1723–1741. [CrossRef]
48. Thompson, C.V.; Spaepen, F. On the approximation of the free energy change on crystallization. Acta Metall.
1979, 27, 1855–1859. [CrossRef]
49. Schawe, J.E. The gibbs free energy difference between a supercooled melt and the crystalline phase of
polymers. J. Therm. Anal. Calorim. 2015, 120, 1417–1425. [CrossRef]
50. Wunderlich, B. Thermodynamic description of condensed phases. J. Therm. Anal. Calorim. 2010, 102, 413–424.
[CrossRef]
51. Buckley, C.; Kovacs, A.J. Melting behaviour of low molecular weight poly (ethylene-oxide) fractions.
Colloid Polym. Sci. 1976, 254, 695–715. [CrossRef]
52. Point, J.J.; Kovacs, A.J. A critical look at some conceptual aspects of kinetic theories of polymer crystal
growth. Macromolecules 1980, 13, 399–409. [CrossRef]
53. Hoffman, J.D.; Frolen, L.J.; Ross, G.S.; Lauritzen, J.I., Jr. Growth-rate of spherulites and axialites from melt in
polyethylene fractions-regime-I and regime-II crystallization. J. Res. Natl. Bur. Stand. Sect. A 1975, 79, 671.
[CrossRef]
54. Flory, P.; Vrij, A. Melting points of linear-chain homologs. The normal paraffin hydrocarbons. J. Am. Chem. Soc.
1963, 85, 3548–3553. [CrossRef]
55. Crist, B. Equilibrium aspects of folded chain polymer crystals. Macromolecules 2006, 39, 1971–1980. [CrossRef]
56. Adamovsky, S.; Schick, C. Ultra-fast isothermal calorimetry using thin film sensors. Thermochim. Acta 2004,
415, 1–7. [CrossRef]
57. Adamovsky, S.; Minakov, A.; Schick, C. Scanning microcalorimetry at high cooling rate. Thermochim. Acta
2003, 403, 55–63. [CrossRef]
58. Wunderlich, B. Macromolecules Physics; Elsevier: Amsterdam, The Netherlands, 2012; Volume 2.
59. Cheng, S.Z.D. Phase Transitions in Polymers: The Role of Metastable States; Elsevier: Amsterdam,
The Netherlands, 2008.
60. Reiter, G.; Sommer, J.-U. Polymer Crystallization: Obervations, Concepts and Interpretations; Springer Science &
Business Media: Berlin/Heidelberg, Germany, 2003; Volume 606.
61. Reiter, G.; Strobl, G.R. Progress in Understanding of Polymer Crystallization; Springer: Berlin/Heidelberg,
Germany, 2007; Volume 714.
62. Xu, J.; Heck, B.; Ye, H.M.; Jiang, J.; Tang, Y.R.; Liu, J.; Guo, B.H.; Reiter, R.; Zhou, D.S.; Reiter, G. Stabilization
of nuclei of lamellar polymer crystals: Insights from a comparison of the Hoffman-Weeks line with the
crystallization line. Macromolecules 2016, 49, 2206–2215. [CrossRef]
63. Cheng, S.Z.D.; Lotz, B. Enthalpic and entropic origins of nucleation barriers during polymer crystallization:
The Hoffman-Lauritzen theory and beyond. Polymer 2005, 46, 8662–8681. [CrossRef]
64. Lupi, L.; Hudait, A.; Molinero, V. Heterogeneous nucleation of ice on carbon surfaces. J. Am. Chem. Soc. 2014,
136, 3156–3164. [CrossRef] [PubMed]
65. Cox, S.J.; Kathmann, S.M.; Slater, B.; Michaelides, A. Molecular simulations of heterogeneous ice nucleation.
II. Peeling back the layers. J. Chem. Phys. 2015, 142, 184705. [CrossRef] [PubMed]
66. Frank, F.; Tosi, M. On the theory of polymer crystallization. Proc. R. Soc. Lond. Ser. A 1961, 263, 323–339.
[CrossRef]
67. Point, J.J. A new theoretical approach of the secondary nucleation at high supercooling. Macromolecules 1979,
12, 770–775. [CrossRef]
68. Point, J.-J. Reconsideration of kinetic theories of polymer crystal growth with chain folding. Faraday Discuss.
Chem. Soc. 1979, 68, 167–176. [CrossRef]
69. Hoffman, J.D.; Miller, R.L. Kinetic of crystallization from the melt and chain folding in polyethylene fractions
revisited: Theory and experiment. Polymer 1997, 38, 3151–3212. [CrossRef]
70. Kubo, R. The fluctuation-dissipation theorem. Rep. Prog. Phys. 1966, 29, 255–284. [CrossRef]
Crystals 2017, 7, 4 33 of 37

71. Sanchez, I.C.; DiMarzio, E.A. Dilute solution theory of polymer crystal growth: A kinetic theory of chain
folding. J. Chem. Phys. 1971, 55, 893–908. [CrossRef]
72. DiMarzio, E.A. Some contributions to the kinetics of growth of multicomponent chains with application to
the problems of ciliation and fractionation in polymer crystallization. J. Chem. Phys. 1967, 47, 3451–3469.
[CrossRef]
73. Hoffman, J.D. Regime III crystallization in melt-crystallized polymers: The variable cluster model of chain
folding. Polymer 1983, 24, 3–26. [CrossRef]
74. Sanchez, I.C.; DiMarzio, E.A. Dilute-solution theory of polymer crystal growth. Some thermodynamic and
predictive aspects for polyethylene. Macromolecules 1971, 4, 677–687. [CrossRef]
75. Burton, W.K.; Cabrera, N.; Frank, F.C. The growth of crystals and the equilibrium structure of their surfaces.
Philos. Trans. R. Soc. Lond. Ser. A 1951, 243, 299–358. [CrossRef]
76. Van Beijeren, H.; Nolden, I.; Schommers, W.; von Blanckenhagen, P. Structure and dynamics of surfaces II.
Top. Curr. Phys. 1987, 43, 259.
77. Riste, T. Ordering in Strongly Fluctuating Condensed Matter Systems; Springer Science & Business Media:
Berlin/Heidelberg, Germany, 2012; Volume 50.
78. Lauritzen, J.; Passaglia, E. Kinetics of crystallization in multicomponent systems: II. Chain-folded polymer
crystals. J. Res. Natl. Bur. Stand. 1967, 71, 261–275. [CrossRef]
79. Point, J.J.; Colet, M.C.; Dosiere, M. Experimental criterion for the crystallization regime in polymer crystals
grown from dilute solution: Possible limitation due to fractionation. J. Polym. Sci. Part B Polym. Phys. 1986,
24, 357–388. [CrossRef]
80. Dosiere, M.; Colet, M.C.; Point, J.J. An isochronous decoration method for measuring linear growth rates in
polymer crystals. J. Polym. Sci. Part B Polym. Phys. 1986, 24, 345–356. [CrossRef]
81. Lauritzen, J.I., Jr.; Hoffman, J.D. Extension of theory of growth of chain-folded polymer crystals to large
undercoolings. J. Appl. Phys. 1973, 44, 4340–4352. [CrossRef]
82. Phillips, P.; Lambert, W. Regime transitions in a non-reptating polymer: Crosslinked linear polyethylene.
Macromolecules 1990, 23, 2075–2081. [CrossRef]
83. Hoffman, J.D. Role of reptation in the rate of crystallization of polyethylene fractions from the melt. Polymer
1982, 23, 656–670. [CrossRef]
84. Muthukumar, M.; Welch, P. Modeling polymer crystallization from solutions. Polymer 2000, 41, 8833–8837.
[CrossRef]
85. Sadler, D.; Gilmer, G. A model for chain folding in polymer crystals: Rough growth faces are consistent with
the observed growth rates. Polymer 1984, 25, 1446–1452. [CrossRef]
86. Point, J.J.; Dosiere, M. On the self-consistency of the Hoffman-Miller theory of polymer crystallization.
Macromolecules 1989, 22, 3501–3502. [CrossRef]
87. DiMarzio, E.; Guttman, C. Polymer crystallization: Proper accounting of a wider class of paths to
crystallization-variations on a theme of Point. J. Appl. Phys. 1982, 53, 6581–6590. [CrossRef]
88. Toda, A. Growth mode and curved lateral habits of polyethylene single crystals. Faraday Discuss. 1993, 95,
129–143. [CrossRef]
89. Toda, A. Growth of polyethylene single crystals from the melt: Change in lateral habit and regime I–II
transition. Colloid Polym. Sci. 1992, 270, 667–681. [CrossRef]
90. Hoffman, J.D.; Miller, R.L. Surface nucleation theory for chain-folded systems with lattice strain: Curved
edges. Macromolecules 1989, 22, 3038–3054. [CrossRef]
91. Patel, A.; Farmer, B. Energetics analysis of polyethylene crystallization: Single crystal growth surfaces.
Polymer 1980, 21, 153–163. [CrossRef]
92. Point, J.J.; Villers, D. Nucleation-controlled growth and normal growth: A unified view. J. Cryst. Growth
1991, 114, 228–238. [CrossRef]
93. Hoffman, J.D.; Miller, R.L. Response to criticism of nucleation theory as applied to crystallization of lamellar
polymers. Macromolecules 1989, 22, 3502–3505. [CrossRef]
94. Alcazar, D.; Thierry, A.; Schultz, P.; Kawaguchi, A.; Cheng, S.Z.; Lotz, B. Determination of the extent of
lateral spread and density of secondary nucleation in polymer single crystal growth. Macromolecules 2006, 39,
9120–9131. [CrossRef]
95. Organ, S.; Ungar, G.; Keller, A. Rate minimum in solution crystallization of long paraffins. Macromolecules
1989, 22, 1995–2000. [CrossRef]
Crystals 2017, 7, 4 34 of 37

96. Kovacs, A.J.; Straupe, C. Isothermal growth, thickening and melting of poly(ethylene-oxide) single crystals
in the bulk: III. Bilayer crystals and the effect of chain ends. J. Cryst. Growth 1980, 48, 210–226. [CrossRef]
97. Kovacs, A.J.; Straupe, C.; Gonthier, A. Isothermal growth, thickening, and melting of (polyethylene oxide)
single crystals in the bulk. II. J. Polym. Sci. Polym. Symp. 1977, 59, 31–54. [CrossRef]
98. Kovacs, A.J.; Gonthier, A.; Straupe, C. Isothermal growth, thickening, and melting of poly(ethylene oxide)
single crystals in the bulk. J. Polym. Sci. Polym. Symp. 1975, 50, 283–325. [CrossRef]
99. Ungar, G.; Keller, A. Time-resolved synchrotron X-ray study of chain-folded crystallization of long paraffins.
Polymer 1986, 27, 1835–1844. [CrossRef]
100. Putra, E.G.; Ungar, G. In situ solution crystallization study of n-C246 H494 : Self-poisoning and morphology of
polymethylene crystals. Macromolecules 2003, 36, 5214–5225. [CrossRef]
101. Ungar, G.; Putra, E.; De Silva, D.; Shcherbina, M.; Waddon, A. The Effect of Self-Poisoning on Crystal
Morphology and Growth Rates. In Interphases and Mesophases in Polymer Crystallization I; Springer:
Berlin/Heidelberg, Germany, 2005; pp. 45–87.
102. Hoffman, J.D. Transition from extended-chain to once-folded behaviour in pure n-paraffins crystallized from
the melt. Polymer 1991, 32, 2828–2841. [CrossRef]
103. Hoffman, J.D. The relationship of C∞ to the lateral surface free energy σ: Estimation of C∞ for the melt from
rate of crystallization data. Polymer 1992, 33, 2643–2644. [CrossRef]
104. Binsbergen, F. Computer simulation of nucleation and crystal growth. J. Cryst. Growth 1972, 16, 249–258.
[CrossRef]
105. Sadler, D.M. Roughness of growth faces of polymer crystals: Evidence from morphology and implications
for growth mechanisms and types of folding. Polymer 1983, 24, 1401–1409. [CrossRef]
106. Sadler, D.M.; Gilmer, G. Rate-theory model of polymer crystallization. Phys. Rev. Lett. 1986, 56, 2708.
[CrossRef] [PubMed]
107. Xu, K.L.; Guo, B.H.; Reiter, R.; Reiter, G.; Xu, J. Simulation of secondary nucleation of polymer crystallization
via a model of microscopic kinetics. Chin. Chem. Lett. 2015, 26, 1105–1108. [CrossRef]
108. Ma, Y.; Qi, B.; Ren, Y.J.; Ungar, G.; Hobbs, J.K.; Hu, W.B. Understanding self-poisoning phenomenon in
crystal growth of short-chain polymers. J. Chem. Phys. B 2009, 113, 13485–13490. [CrossRef] [PubMed]
109. Geil, P.H.; Anderson, F.R.; Wunderlich, B.; Arakawa, T. Morphology of polyethylene crystallized from the
melt under pressure. J. Polym. Sci. Part A 1964, 2, 3707–3720. [CrossRef]
110. Wunderlich, B.; Mielillo, L. Morphology and growth of extended chain crystals of polyethylene.
Die Makromol. Chem. 1968, 118, 250–264. [CrossRef]
111. Bassett, D.; Turner, B. On chain-extended and chainfolded crystallization of polyethylene. Philos. Mag. 1974,
29, 285–307. [CrossRef]
112. Bassett, D.; Turner, B. New high-pressure phase in chain-extended crystallization of polythene. Nat. Phys. Sci.
1972, 240, 146–148. [CrossRef]
113. Yasuniwa, M.; Enoshita, R.; Takemura, T. X-ray studies of polyethylene under high pressure. Jpn. J. Appl. Phys.
1976, 15, 1421. [CrossRef]
114. Yasuniwa, M.; Nakafuku, C.; Takemura, T. Melting and crystallization process of polyethylene under high
pressure. Polym. J. 1973, 4, 526–533. [CrossRef]
115. Hikosaka, M. Unified theory of nucleation of folded-chain crystals (FCCs) and extended-chain crystals
(ECCs) of linear-chain polymers: 2. Origin of FCC and ECC. Polymer 1990, 31, 458–468. [CrossRef]
116. Hikosaka, M. Unified theory of nucleation of folded-chain crystals and extended-chain crystals of linear-chain
polymers. Polymer 1987, 28, 1257–1264. [CrossRef]
117. Hikosaka, M.; Amano, K.; Rastogi, S.; Keller, A. Crystallization of Polymers; Dosiere, M., Ed.; Kluwer Academic
Publishers: Dordrecht, The Netherlands, 1993; p. 331.
118. Cheng, S.Z.D.; Keller, A. The role of metastable states in polymer phase transitions: Concepts, principles,
and experimental observations. Annu. Rev. Mater. Sci. 1998, 28, 533–562. [CrossRef]
119. Strobl, G. From the melt via mesomorphic and granular crystalline layers to lamellar crystallites: A major
route followed in polymer crystallization? Eur. Phys. J. E 2000, 3, 165–183. [CrossRef]
120. Hasegawa, R.; Kobayashi, M.; Tadokoro, H. Molecular conformation and packing of poly(vinylidene
fluoride). Stability of three crystalline forms and the effect of high pressure. Polym. J. 1972, 3, 591–599.
[CrossRef]
Crystals 2017, 7, 4 35 of 37

121. Hasegawa, R.; Tanabe, Y.; Kobayashi, M.; Tadokoro, H.; Sawaoka, A.; Kawai, N. Structural studies of
pressure-crystallized polymers. I. Heat treatment of oriented polymers under high pressure. J. Polym. Sci.
Part B Polym. Phys. 1970, 8, 1073–1087. [CrossRef]
122. Melillo, L.; Wunderlich, B. Extended-chain crystals. Kolloid-Zeitschrift und Zeitschrift für Polymere 1972, 250,
417–425. [CrossRef]
123. Miyamoto, Y.; Nakafuku, C.; Takemura, T. Crystallization of poly (chlorotrifluoroethylene). Polym. J. 1972,
3, 122–128. [CrossRef]
124. Natta, G.; Corradini, P.; Bassi, I. Crystal structure of poly-ortho-fluorostyrene. Il Nuovo Cimento (1955–1965)
1960, 15, 83–95. [CrossRef]
125. Natta, G.; Corradini, P.; Bassi, I.W. Crystal structure of isotactic poly-alpha-butene. Stereoregul. Polym.
Stereospecif. Polym. 1967, 2, 747–749. [CrossRef]
126. Suehiro, K.; Takayanagi, M. Structural studies of the high temperature form of trans-1, 4-polybutadiene
crystal. J. Macromol. Sci. B 1970, 4, 39–46. [CrossRef]
127. Finter, J.; Wegner, G. The relation between phase transition and crystallization behavior of 1, 4-trans-poly
(butadiene). Die Makromol. Chem. 1981, 182, 1859–1874. [CrossRef]
128. Lu, J.; Huang, R.; Li, L.B.; Luo, J.B. Growth of large polymer extended-chain single crystals in a poly(ethylene
terephthalate)/bisphenol a polycarbonate blend under high pressure. Macromol. Rapid Commun. 2005, 26,
1478–1482. [CrossRef]
129. Li, L.B.; Huang, R.; Lu, A.; Fan, W.Y.; Hong, S.M.; Fu, Q. Electron microscopy of high-pressure crystallized
poly(ethylene terephthalate). J. Polym. Sci. Part B Polym. Phys. 2000, 38, 1612–1616.
130. Li, L.B.; Huang, R.; Lu, A.; Fan, W.Y.; Hong, S.M.; Fu, Q. Stereo-open spherulites in high-pressure crystallized
poly(ethylene terephthalate). J. Cryst. Growth 2000, 216, 538–541. [CrossRef]
131. Hikosaka, M.; Watanabe, K.; Okada, K.; Yamazaki, S. Topological Mechanism of Polymer Nucleation and
Growth—The Role of Chain Sliding Diffusion and Entanglement. In Interphases and Mesophases in Polymer
Crystallization III; Springer: Berlin/Heidelberg, Germany, 2005; pp. 137–186.
132. Dlugosz, J.; Fraser, G.; Grubb, D.; Keller, A.; Odell, J.; Goggin, P. Study of crystallization and isothermal
thickening in polyethylene using saxd, low frequency raman spectroscopy and electron microscopy. Polymer
1976, 17, 471–480. [CrossRef]
133. Wunderlich, B.; Mehta, A. Macromolecular nucleation. J. Polym. Sci. Part B Polym. Phys. 1974, 12, 255–263.
[CrossRef]
134. Keith, H.D.; Padden, F.J., Jr. A phenomenological theory of spherulitic crystallization. J. Appl. Phys. 1963, 34,
2409–2421. [CrossRef]
135. Mehta, A.; Wunderlich, B. A study of molecular fractionation during the crystallization of polymers.
Colloid Polym. Sci. 1975, 253, 193–205. [CrossRef]
136. Keith, H.D.; Padden, F.J., Jr. Spherulitic crystallization from the melt. I. Fractionation and impurity
segregation and their influence on crystalline morphology. J. Appl. Phys. 1964, 35, 1270–1285. [CrossRef]
137. Bassett, D.C. Principles of Polymer Morphology; Cambridge University Press: Cambridge, UK, 1981.
138. Cheng, S.Z.D.; Noid, D.W.; Wunderlich, B. Molecular segregation and nucleation of poly(ethylene oxide)
crystallized from the melt. IV. Computer modeling. J. Polym. Sci. Part B Polym. Phys. 1989, 27, 1149–1160.
[CrossRef]
139. Toda, A. Growth kinetics of polyethylene single crystals from dilute solution at low supercoolings. Polymer
1987, 28, 1645–1651. [CrossRef]
140. Keller, A.; Pedemonte, E. A study of growth rates of polyethylene single crystals. J. Cryst. Growth 1973, 18,
111–123. [CrossRef]
141. Malkin, A.; Land, T.; Kuznetsov, Y.G.; McPherson, A.; DeYoreo, J. Investigation of virus crystal growth
mechanisms by in situ atomic force microscopy. Phys. Rev. Lett. 1995, 75, 2778. [CrossRef] [PubMed]
142. Langer, J. Instabilities and pattern formation in crystal growth. Rev. Mod. Phys. 1980, 52, 1–28. [CrossRef]
143. Frantz, P.; Granick, S. Kinetics of polymer adsorption and desorption. Phys. Rev. Lett. 1991, 66, 899.
[CrossRef] [PubMed]
144. Hlady, V.; Buijs, J. Protein adsorption on solid surfaces. Curr. Opin. Biotechnol. 1996, 7, 72–77. [CrossRef]
145. Frantz, P.; Granick, S. Exchange kinetics of adsorbed polymer and the achievement of conformational
equilibrium. Macromolecules 1994, 27, 2553–2558. [CrossRef]
Crystals 2017, 7, 4 36 of 37

146. Glaser, R.H.; Mandelkern, L. On the fractionation of homopolymers during crystallization from the pure
melt. J. Polym. Sci. Part B Polym. Phys. 1988, 26, 221–234. [CrossRef]
147. Fischer, E. The conformation of polymer chains in the semicrystalline state. Makromol. Chem. Macromol. Symp.
1988, 20/21, 277–291. [CrossRef]
148. Fischer, E.; Hahn, K.; Kugler, J.; Struth, U.; Born, R.; Stamm, M. An estimation of the number of tie molecules
in semicrystalline polymers by means of neutron scattering. J. Polym. Sci. Part B Polym. Phys. 1984, 22,
1491–1513. [CrossRef]
149. Hu, W.B.; Cai, T. Regime transitions of polymer crystal growth rates: Molecular simulations and interpretation
beyond Lauritzen-Hoffman model. Macromolecules 2008, 41, 2049–2061. [CrossRef]
150. Leung, W.M.; St. John Manley, R.; Panaras, A. Isothermal growth of low molecular weight polyethylene
single crystals from solution. 3. Kinetic studies. Macromolecules 1985, 18, 760–771. [CrossRef]
151. Cheng, S.Z.D.; Chen, J.H.; Heberer, D.P. Extended chain crystal growth of low molecular mass poly(ethylene
oxide) and α, ω-methoxy poly(ethylene oxide) fractions near their melting temperatures. Polymer 1992, 33,
1429–1436. [CrossRef]
152. Kundagrami, A.; Muthukumar, M. Continuum theory of polymer crystallization. J. Chem. Phys. 2007,
126, 144901. [CrossRef] [PubMed]
153. Debenedetti, P.G. Metastable Liquids: Concepts and Principles; Princeton University Press: Princeton, NJ, USA, 1996.
154. Vonnegut, B. Variation with temperature of the nucleation rate of supercooled liquid tin and water drops.
J. Colloid Sci. 1948, 3, 563–569. [CrossRef]
155. Wunderlich, B. Macromolecular Physics: Crystal nucleation, Growth, Annealing; Academic Press: New York, NY,
USA, 1976; Volume 2.
156. Bu, H.S.; Cao, J.; Zhang, Z.; Zhang, Z.S.; Festag, R.; Joy, D.C.; Kwon, Y.K.; Wunderlich, B. Structure of
single-molecule single crystals of isotactic polystyrene and their radiation resistance. J. Polym. Sci. Part B
Polym. Phys. 1998, 36, 105–112. [CrossRef]
157. Geil, P.; Yang, J.; Williams, R.; Petersen, K.; Long, T.C.; Xu, P. Effect of Molecular Weight and Melt Time
and Temperature on the Morphologyof Poly (Tetrafluorethylene). In Interphases and Mesophases in Polymer
Crystallization I; Springer: Berlin/Heidelberg, Germany, 2005; pp. 89–159.
158. Debye, P.; Bueche, A. Scattering by an inhomogeneous solid. J. Appl. Phys. 1949, 20, 518–525. [CrossRef]
159. Fischer, E.W. Light scattering and dielectric studies on glass forming liquids. Phys. A 1993, 201, 183–206.
[CrossRef]
160. Murry, R.L.; Fourkas, J.T.; Li, W.-X.; Keyes, T. Mechanisms of light scattering in supercooled liquids.
Phys. Rev. Lett. 1999, 83, 3550. [CrossRef]
161. Ediger, M.D. Spatially heterogeneous dynamics in supercooled liquids. Annu. Rev. Phys. Chem. 2000,
51, 99–128. [CrossRef] [PubMed]
162. Ngai, K.; Rendell, R. Supercooled Liquids, Advances and Novel Applications; ACS Publications: Washington, DC,
USA, 1997; p. 45.
163. Ryan, A.; Terrill, N.; Olmsted, P.; Poon, W.K. A scattering study of nucleation phenomena in polymer
crystallisation. Faraday Discuss. 1999, 112, 13–29. [CrossRef]
164. Olmsted, P.D.; Poon, W.C.; McLeish, T.; Terrill, N.; Ryan, A. Spinodal-assisted crystallization in polymer
melts. Phys. Rev. Lett. 1998, 81, 373. [CrossRef]
165. Terrill, N.J.; Fairclough, P.A.; Towns-Andrews, E.; Komanschek, B.U.; Young, R.J.; Ryan, A.J. Density
fluctuations: The nucleation event in isotactic polypropylene crystallization. Polymer 1998, 39, 2381–2385.
[CrossRef]
166. Ezquerra, T.; López-Cabarcos, E.; Hsiao, B.; Balta-Calleja, F. Precursors of crystallization via density
fluctuations in stiff-chain polymers. Phys. Rev. E 1996, 54, 989–992. [CrossRef]
167. Imai, M.; Kaji, K.; Kanaya, T. Structural formation of poly(ethylene terephthalate) during the induction
period of crystallization. 3. Evolution of density fluctuations to lamellar crystal. Macromolecules 1994, 27,
7103–7108. [CrossRef]
168. Tan, H.G.; Miao, B.; Yan, D.D. Conformation-assisted fluctuation of density and kinetics of nucleation in
polymer melts. J. Chem. Phys. 2003, 119, 2886–2891. [CrossRef]
169. Welch, P.; Muthukumar, M. Molecular mechanisms of polymer crystallization from solution. Phys. Rev. Lett.
2001, 87, 218302. [CrossRef] [PubMed]
Crystals 2017, 7, 4 37 of 37

170. Liu, C.; Muthukumar, M. Langevin dynamics simulations of early-stage polymer nucleation and
crystallization. J. Chem. Phys. 1998, 109, 2536–2542. [CrossRef]
171. Li, J.Y.; Li, W.; Cheng, H.; Zhang, L.N.; Li, Y.; Han, C.C. Early stages of nucleation and growth in melt
crystallized polyethylene. Polymer 2012, 53, 2315–2319. [CrossRef]
172. Panine, P.; Di Cola, E.; Sztucki, M.; Narayanan, T. Early stages of polymer melt crystallization. Polymer 2008,
49, 676–680. [CrossRef]
173. Gee, R.H.; Lacevic, N.; Fried, L.E. Atomistic simulations of spinodal phase separation preceding polymer
crystallization. Nat. Mater. 2006, 5, 39–43. [CrossRef] [PubMed]
174. Allegra, G. Polymer crystallization: The bundle model. Ferroelectrics 1980, 30, 195–211. [CrossRef]
175. Allegra, G. Chain folding and polymer crystallization: A statistical–mechanical approach. J. Chem. Phys.
1977, 66, 5453–5463. [CrossRef]
176. Allegra, G.; Meille, S.V. Pre-Crystalline, High-Entropy Aggregates: A Role in Polymer Crystallization?
In Interphases and Mesophases in Polymer Crystallization III; Springer: Berlin/Heidelberg, Germany, 2005;
pp. 87–135.
177. Allegra, G.; Meille, S.V. The bundle theory for polymer crystallisation. Phys. Chem. Chem. Phys. 1999, 1,
5179–5188. [CrossRef]
178. Strobl, G. Crystallization and melting of bulk polymers: New observations, conclusions and a thermodynamic
scheme. Prog. Polym. Sci. 2006, 31, 398–442. [CrossRef]
179. Strobl, G. A thermodynamic multiphase scheme treating polymer crystallization and melting. Eur. Phys. J. E
2005, 18, 295–309. [CrossRef] [PubMed]
180. Strobl, G. Colloquium: Laws controlling crystallization and melting in bulk polymers. Rev. Mod. Phys. 2009,
81, 1287. [CrossRef]
181. Lotz, B. What can polymer crystal structure tell about polymer crystallization processes? Eur. Phys. J. E 2000,
3, 185–194. [CrossRef]
182. Cheng, S.Z.D.; Li, C.Y.; Zhu, L. Commentary on polymer crystallization: Selection rules in different length
scales of a nucleation process. Eur. Phys. J. E 2000, 3, 195–197. [CrossRef]
183. Luo, C.F.; Sommer, J.-U. Growth pathway and precursor states in single lamellar crystallization: MD
simulations. Macromolecules 2011, 44, 1523–1529. [CrossRef]
184. Sommer, J.U.; Luo, C.F. Molecular dynamics simulations of semicrystalline polymers: Crystallization,
melting, and reorganization. J. Polym. Sci. Part B Polym. Phys. 2010, 48, 2222–2232. [CrossRef]
185. Luo, C.F.; Sommer, J.-U. Coexistence of melting and growth during heating of a semicrystalline polymer.
Phys. Rev. Lett. 2009, 102, 147801. [CrossRef] [PubMed]
186. Meyer, H. Structure Formation and Chain-Folding in Supercooled Polymer Melts. Some Ideas from MD
Simulations with a Coarse-Grained Model. In Polymer Crystallization: Observations, Concepts and Interpretations;
Springer: Berlin/Heidelberg, Germany, 2003; pp. 177–195.
187. Yan, C.; Li, H.H.; Zhang, J.M.; Ozaki, Y.; Shen, D.; Yan, D.D.; Shi, A.-C.; Yan, S.K. Surface-induced
anisotropic chain ordering of polycarprolactone on oriented polyethylene substrate: Epitaxy and soft
epitaxy. Macromolecules 2006, 39, 8041–8048. [CrossRef]
188. Aminov, A.; Kafri, Y.; Kardar, M. Fluctuation-induced forces in nonequilibrium diffusive dynamics.
Phys. Rev. Lett. 2015, 114, 230602. [CrossRef] [PubMed]

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