J Mater Sci (2012) 47:6749–6767
DOI 10.1007/s10853-012-6620-y
REVIEW
Structural mechanics of semicrystalline polymers prior
to the yield point: a review
Stanislav Patlazhan • Yves Remond
Received: 3 April 2012 / Accepted: 26 May 2012 / Published online: 19 June 2012
 Springer Science+Business Media, LLC 2012
Abstract The review focuses on the current studies of the
deformation response and accompanying structural trans-
formations of thermoplastic semicrystalline polymers sub-
jected to uniaxial tension prior to the yield point. The
mechanisms of strain-induced cavitation of amorphous
layers and damages of crystalline lamellae are analyzed in
line with novel results on the deformation behavior of solid
polymers at temperatures exceeding the glass transition
point. The coupling of viscoelastic and plastic deformation
mechanisms with the small-strain structural transforma-
tions is critically discussed on the basis of the advanced
theoretical modeling of mechanical properties of semi-
crystalline polymers.
Introduction
Mechanical response of solid polymers cannot be generally
described in a framework of formal combination of elastic,
viscoelastic, and plastic deformation mechanisms. Such a
behavior has a direct bearing to structural transformations
induced by the imposed strain. With regard to semicrys-
talline polymers, structural changes and accompanying
mechanisms of plastic deformation are widely diverse. This
fact renders the analysis of the origin of the macroscopic
properties of such materials rather troublesome. Most of
experimental and theoretical papers are concentrated on
S. Patlazhan (&)
Semenov Institute of Chemical Physics of Russian Academy
of Sciences, 4, Kosygin Street, Moscow, Russia 119991
e-mail: sapat@yandex.ru
Y. Remond
Institute of Mechanics of Fluids and Solids, University of
Strasbourg/CNRS, 2 rue Boussingault, 67000 Strasbourg, France
large deformations followed by the massive rearrangement
of material morphology. Due to a complex structural
hierarchy, multiscale and multifunctional mechanical
reaction of semicrystalline polymers is implicated under
large plastic deformations which involve tie chains, crys-
talline lamellae, interphase, interlamellar entangled amor-
phous network, spherulites, etc. Their integrated self-
consistent response determines the macroscopic properties
of semicrystalline polymers. The larger are the strains, the
more intricate structural transformations are being involved
into the deformation process. Above glass transition
temperature such transformations include chain slip of
crystalline lamellae, their reorientation, fragmentation,
micro-fibrillation, local melting, recrystallization, mar-
tensitic phase transitions, stress-induced crystallization,
cavitation, microcrazing, shear banding, etc. The effect of
these transformations on the deformation behavior of
semicrystalline polymers is evident. However, full quanti-
tative description of these processes is still unachieved.
This is caused by a complex morphology of the materials
as well as strong correlation between different structural
elements under the given deformation conditions. Current
understanding of these phenomena is based on manifold
studies which were summarized in number of compre-
hensive reviews [1–7].
On the other hand, straining of semicrystalline polymers
prior to the yield point plays an important part in their
deformation history as a stage preceding dramatic changes
in polymer morphology beyond yielding. Structural trans-
formations induced by small deformations are not so pro-
nounced as at large strains. This hinders understanding their
relative contribution to viscoelastoplastic response of
semicrystalline polymers. Nevertheless, the consideration
of small-scale structural changes could make analysis of
deformation mechanisms more adequate than in the case of
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multiscale rearrangements activated at large strains. Thus,
the small-strain approach may be useful for deeper under-
standing of coupling between different structural transfor-
mations and local plastic and viscoelastic deformations.
The present survey is focused on the current state of
structural mechanics of semicrystalline polymers prior to
yielding. We restrict our attention to the uniaxial tension
above the glass transition temperature inherent to a given
polymer. Along with the well-established data, new find-
ings regarding structural defects occurring at small strains
as well as their role in the global deformation behavior of
semicrystalline polymers will be highlighted. At low strain
level, stretching favors the occurrence of different struc-
tural defects such as nanocavities in the interlamellar
amorphous layers [8–19] and damages of crystalline
lamellae [20–22]. These imperfections could lead either to
softening or modification of the plastic deformation
mechanisms of semicrystalline polymers. Answering to
this matter could be helpful in understanding grounds of
nonlinear deformation response at low strains as well as in
reexamination of the origin of yield point. Taken together,
these problems require a critical overview of the modern
state of experimental and theoretical studies of semicrys-
talline polymers focused on small-strain deformation
processes.
In the next section, the commonly accepted mechanisms
of plastic deformations are discussed. Recent studies of
structural transformations prior to the yield point will be
observed in the third section of the review. They concern:
(i) the generation and spatial distribution of nanovoids
registered by means of small-angle X-ray scattering and (ii)
the granular structure of crystalline lamellae revealed by
atomic force microscopy (AFM). Experimental results
concerning deformation behavior of semicrystalline poly-
mers under tensile drawing are analyzed in the fourth part.
Attention is focused on critical strains separating different
deformation mechanisms as well as evolution of quasi-
static (true) elastic modulus characterizing softening of the
materials prior to the yield point. Modern approaches to
micromechanical modeling of small-strain deformation
behavior of semicrystalline polymers are discussed in the
last section of the review.
Mechanisms of plastic deformation
At present we have rather fixed conceptions on the origins
of microstructure and deformation mechanisms of the melt-
crystallized thermoplastic polymers [1–7]. Such polymers
are composed of stacks of crystalline lamellae alternating
with amorphous layers. Generally, lamella aggregates are
radially arranged into spherulitic domains while lamellae
are twisted about their long axis [2, 3, 23] as it is depicted
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J Mater Sci (2012) 47:6749–6767
in Fig. 1 [24]. In terms of solid state mechanics of heter-
ogeneous materials, spherulites can be considered as a
representative volume element because they include most
of all configurations and orientations available for lamellar
bands. The imposed loading draws crystal lamellae and
amorphous parts into viscoelastic and plastic deformation.
Much attention was focused on large-deformation behavior
of semicrystalline polymers resulting in significant modi-
fication in material morphology. These structural rear-
rangements can be revealed with help of different
experimental techniques including wide- and small-angle
X-ray and neutron scattering (WAXS, SAXS, and SANS),
electron and atomic force microscopy, Raman, vibration,
and infrared spectroscopy, etc. [3]. Tensile drawing beyond
the yield point was found to involve manifold structural
transformations as cavitation, reorientation, and fragmen-
tation of crystal lamellae, micronecking, fibrillation, chain
unfolding, and disentanglement, etc. On the other hand,
coupling of the current morphology and deformation
response of semicrystalline polymers at small strains still
needs further investigations. Below we briefly recall the
recognized deformation mechanisms along with the
accompanying structural transformations which are rele-
vant prior to yielding.
The mechanical response of semicrystalline polymers to
an imposed loading involves both the intra- and interla-
mellar domains. The local deformation modes are deter-
mined by orientation of lamellae stacks with respect to the
main deformation axes. At small strains, deformation
manifests itself mainly through the soft amorphous layers.
In case of tensile drawing, three characteristic regions in a
spherulite are recognized as polar, equatorial, and diagonal
domains (see Fig. 1).
The polar domain reflects contribution of lamellae
stacks mostly aligned along the principal tensile axis. The
rigidity of crystallites leads to a strong deformation resis-
tance of this region which results in inhomogeneous
deformation of spherulites [2]. However, due to the almost
perpendicular orientation of crystal chains toward elonga-
tion, the resolved shear stress for the chain slip is low at
this domain. As a consequence, large strains could result in
a certain rotation of the twisted lamellae followed by their
defragmentation and micronecking [25]. Amorphous layers
are subjected to Poisson’s contraction and eventually may
cause partial squeezing of free chains between the neighbor
lamellae [26]. However, at small strains these mechanisms
of plastic deformation are inappropriate.
The equatorial domains are contributed by fans of
crystalline lamellae whose long axes are aligned across the
stretch direction. This assemblage favors lamella separa-
tion occurring at rather small strains due to the softness
of amorphous ligaments. This effect is enhanced with
temperature increase [27]. The interlamellar separation
J Mater Sci (2012) 47:6749–6767
Fig. 1 Forces acting in polar (P), diagonal (D), and equatorial
(E) domains of a spherulite. Depending on orientation, lamellae are
subjected to elongation (1), transverse compression (2), interlamellar
separation (3), interlamellar slip (4), and rotations (5). F denotes the
imposed load. Image adapted from [24]  1988 with permission from
Springer Science ? Business Media
enlarges the long period of the respective lamellar stacks
which is reproduced in contraction of SAXS ring pattern
along stretch direction. Small strains are almost reversible
due to the rubber-like recoiling of tie chains [28]. However,
continuous separation of lamellae in equatorial domain is
restricted by their lateral rigidity. It may cause violation of
continuity of amorphous phase resulting in the formation of
the interlamellar nanovoids [29–34]. The main question
arising from these observations concerns the onset of
cavitation. This was roughly estimated using equilibrium
condition between the Laplace pressure, exerted by the
polymer surface tension, and negative hydrostatic pressure
caused by the local stresses [11]. Comparing with the yield
stress, this approach provides a robust criterion for cavi-
tation prior the yield point. More precise ideas could be
derived from the time-resolved SAXS experiments con-
ducted during tensile testing.
The lamellae tilted with respect to elongation direction
belong to the diagonal domain. Depending on the angle
between lamellar bands and tensile axis, they are subjected
to both separation and shear deformations. Shear stress
6751
becomes larger when the tilt angle of lamellae approaches
45. Above the glass transition temperature, contribution of
the interlamellar shearing at small strains is dominant [35–
37]. This deformation mode is almost reversible. However,
certain irreversibility of the interlamellar shearing has been
found [27], which was attributed to breaking or pulling of
tie molecules out of the chain-folded crystals.
When tension of tie molecules exceeds certain thresh-
old, the irreversible plastic deformation of crystal lamellae
could be launched as a result of defrosting of the dislo-
cation mobility. This process is initiated at the critical
resolved shear stress exerted to the easiest slip system [1–
4]. The slip resistance is strongly dependent of crystallite
thickness [38–42]. In particular, in orthorhombic crystals
of high-density polyethylene (HDPE), the easiest slip
occurs in the plane (100) along the chain direction [001]
(c-axis). Among the other slip systems, this plane repre-
sents the most densely packed crystallographic plane
having the largest distance between similar planes. At
room temperature shear resistance of this slip system is of
g1 = 8 MPa while the resistance of the other slip systems
is substantially larger. For instance, shear resistance of
(100) [010] slip system is g2 = 13.3 MPa [43]. The
resolved shear stress sa of the ath slip system should be
larger than the respective shear resistance ga otherwise its
contribution to the plastic flow is negligible. The resolved
shear stress is defined as a projection sa ¼ rc : Ra of a
lamella stress tensor rc to the Schmid’s tensor Raik ¼
1 a a a a


2 si mk þ mi sk [44], which states for the geometrical
characteristic of the ath slip system along unit vector ma
with normal sa to the slip plane. Taking into account that
local stresses in two-phase heterogeneous solids may
strongly exceed the imposed stress, it could be supposed
that plastic flow of crystal lamellae may appear locally at
fairly low strains [45].
Two general types of lamellar slip mechanisms were
recognized: the fine and coarse chain slips [1] (see Fig. 2).
The fine chain slip is characterized by multiple lattice
displacements along chain axis in the polymer crystallites.
These displacements cause tilting of the folded chains with
respect to lamellar surface [46]. However, they do not
considerably contribute to a specific reorientation of
crystalline lamellae. This is sustained by WAXS data
revealing changes in the angle between the lamellar chains
and easy slip planes in HDPE and polytetrafluoroethylene
(PTFE) without visible texturing of crystalline lamellae
[1, 2, 9].
The coarse chain slip occurs on a few parallel crystal-
lographic planes (hk0) [001] per lamella resulting in dis-
placement of its several pieces relative to each other
without tilting of the chain axes. This type of slip was
thought to be inherent mostly to the strains exceeding the
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Fig. 2 Schematic diagrams
illustrating fine (a) and coarse
(b) chain slip. Vectors n and
c represent the normal to the
crystal and chain axis,
respectively. Image adapted
from [1]  1974 with
permission from Springer
Science ? Business Media
yield point [47] while it was assumed negligible at small
strains [27]. However, recent AFM investigations of
structural transformation in polycaprolactone (PCL),
poly(1-butene) (PB), and polyamide-6 (PA6) disclosed
multiple coarse slip of crystalline lamellae in polar, diag-
onal, and equatorial domains of a spherulite below the
yield point [21, 22]. Physically, this may be motivated by
the mosaic blocks substructure of polymer crystallites [48].
This kind of substructure was first revealed by means of
WAXS [49–53] and then observed directly with the help of
transmission electron microscopy (TEM) [54, 55] and
AFM [56–58]. The average size of the lamella blocks was
found to be modified with temperature and draw ratio [53,
59]. The deformation behavior and the formation of
microfibril morphology in semi-crystalline polymers were
also explained in terms of crystal blocks composing mosaic
structure of crystalline lamellae [47, 60–64]. Most of these
studies were performed at large strains. The role of the
lamella blocky structure in the deformation response of
semicrystalline polymers prior to the yield point will be
discussed in ‘‘Blocky structure of crystalline lamellae’’.
The initiation of the coarse chain slip in crystalline
lamellae could be also associated with strong fluctuations
of stress and strain fields caused by heterogeneity of
semicrystalline polymers. In accordance with the solid
state mechanics of microheterogeneous materials, the
local strains may exceed considerably the macroscopic
deformation [65]. This was validated for PB with help of
AFM showing that the imposed strain e = 0.06, which is
well below the yield point, could lead to the significant
local deformation eloc ¼ 0:1 along the tensile axis [20].
Besides, a wide distribution of local strains within a
spherulite has been detected along with the intensive
cavitation processes. This fact should be taken into
account in modeling of deformation behavior of semi-
crystalline polymers.
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J Mater Sci (2012) 47:6749–6767
Structural transformations prior to the yield point
The morphological changes in semicrystalline polymers
occurring at small strains are much less marked than those
observed beyond yielding. Nonetheless, these transforma-
tions are of great importance since they could determine a
subsequent path of structural reorganization with the
elongation increase. The initial structural transformations
are intimately coupled with the original morphology
(crystallinity, texture, and thickness of crystalline lamellae,
spherulite size, etc.) of solid polymers. Variations in the
material structure occur due to the local overstress origi-
nated by the intrinsic heterogeneity of semicrystalline
polymers. At small uniaxial deformations this may lead to
nanocavitation and damage of crystalline lamellae.
Nanocavitation
The interlamellar strain-induced nanovoids can be easily
detected by SAXS due to their giant electron density
contrast as compared to crystalline and amorphous phases.
Considerable escalation of cavitation during cold tensile
drawing was reported for a number of semicrystalline
polymers as HDPE, isotactic polypropylene (i-PP), and
polymethylene oxide (POM) [8–19, 29, 30]. In particular,
cavity volume fraction beyond the yield point was found to
strongly depend on the initial crystallinity and polymer
morphology. According to the thermal history (quenching,
annealing, recrystallization), cavitation in HDPE may
become apparent in three different ways: (i) as a homo-
geneous cavitation along the sample, (ii) as a heteroge-
neous cavitation due to a localization in the neck, and (iii)
cavitation may not be present at all [17]. These scenarios
were shown to be strongly dependent on the lamella
thickness Lc: if Lc exceeds a certain critical value, cavita-
tion occurs. Otherwise, fragmentation of crystal lamellae is
J Mater Sci (2012) 47:6749–6767
preferred. This outcome is compatible with the independent
observations of Pawlak and Galeski [15]. In their former
work [11], it was found that cavities are formed readily in
HDPE, i-PP, and POM while they do not occur in low-
density polyethylene (LDPE), PA6, and ethylene–octene
copolymer. The origin of this difference is the same as in
the annealed or quenched HDPE: the first group of poly-
mers comprised of substantially thicker lamellae which
could maintain nanovoids opened due to the balance
between the local normal stresses and the Laplace pres-
sures exerted on the void interfaces.
Recently it was indicated for the stretched HDPE and
i-PP that nanovoids are generated at rather low strain level
[13, 18] (see Fig. 3). They could manifest themselves in the
SAXS patterns in the form of the small-angle strips along
the tensile axis. These strips are known as the butterfly
patterns. Similar scattering was recorded for different
semicrystalline polymers prior to the yield point [8, 9, 11,
66]. Further increase in tension leads to reversal of the
patterns into strips extended in perpendicular direction. To
explain these observations, it was suggested that at low
level of strain nanovoids become elongated across
stretching, while large deformations lengthen them along
this direction [8, 9, 11, 13]. The latter interpretation is
reasonable: voids tend to enlarge at large strains due to
multiplication and coalescence of the smaller voids, crystal
fragmentation, development of microfibrillar morphology,
etc. [47, 60, 61]. This favors to the void elongation along
the tensile axis which is in line with results obtained by
TEM for the thin HDPE films [67]. On the other hand, the
foregoing explanation of the origin of the small-strain
SAXS patterns should be clarified.
The alternative standpoint was proposed by Takenaka
et al. [68]. Using synchrotron radiation of wavelength
k = 0.05 nm and exceptionally long path length (150 m),
the ultra small-angle X-ray scattering (USAXS) patterns
were recorded in the extremely small window for scat-
tering vector q around the incident beam. The quenched
HDPE has been studied at room temperature at the fixed
elongation strain e = 0.05 which is below the yield point
eyield = 0.08. It was found that USAXS reveals the but-
terfly pattern as well (see Fig. 4b). However, in contrast
with the previous studies [8, 9, 11, 13], the scattering
patterns were measured in a much more narrow range of
scattering vector, 0.005 \ q \ 0.02 nm-1. It was sug-
gested [68] that the origin of the butterfly patterns is
similar to the ‘‘abnormal’’ small-angle neutron scattering
in stretched polymer gels [69, 70] and networks swollen in
the melt of short chains [71]. In the latter case the
‘‘abnormal’’ scattering was proved to be caused by the
strain-induced amplification of fluctuations of crosslink
density. In particular, an increase in elongation results in
an increase of local deformation of the less crosslinked
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Fig. 3 Evolution of SAXS pattern in injection-molded HDPE during
tensile drawing. Deformation direction is horizontal. Image adapted
from [13]  2007 with permission from Elsevier
(‘‘soft’’) domains. This leads to separation of the ‘‘hard’’
(more crosslinked) domains and eventually originates
structural anisotropy of the network [72]. In the case of
semicrystalline polymers, the revealed USAXS patterns
are attributed to scattering objects of the order of
1000 nm. This scale covers a large number of long periods
of crystalline lamellae that is enormously larger than voids
occurring at small strains. Taking that into account, the
observed SAXS and USAXS patterns could be interpreted
as an indication of large scattering domains of different
electron density which are extended across the tensile axis.
Modulation of the electron density contrast indicates var-
iation of nanovoid volume fractions in the domains. These
formations provide a basis for the crazes developing due
to the subsequent growing and coalescence of the strain-
induced nanocavities.
Blocky structure of crystalline lamellae
Intralamellar nanovoids reduce local stresses exerted to
lamellar crystals sited in the equatorial and diagonal
domains of a spherulite [11, 16]. However, this scenario
may be violated for polymers containing sufficiently thin
lamellae. Particularly, it was concluded that strain-induced
separation of lamellar crystals in PA6, LDPE, and ethyl-
ene-based copolymers may lead to their crumpling or
kinking which in turn prevent cavity formation [11] and
could modify deformation mechanisms of semicrystalline
polymers. To gain more insight about mechanical proper-
ties of these materials, the structure of lamellar crystals
should be reexamined.
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6754 J Mater Sci (2012) 47:6749–6767

Fig. 4 The reversed images of

2D USAXS patterns of HDPE at
undeformed state e = 0 (a) and
deformed up to e = 0.05 (b).
Image adapted from [68] 
2007 by the American Physical
Society

Long ago the quantitative analysis of WAXS patterns of

oriented semicrystalline polymers made it possible to
reveal heterogeneous mosaic block structure of crystalline
lamellae [49–53]. This information was extracted from the
broadening of Bragg reflections from (hk0) crystallo-
graphic planes. WAXS provides records on lateral coher-
ence lengths Dhk0 corresponding to average block size. It
was found that D110 and D200 are of order of lamellar
thickness [53, 58]. However, the direct observation of the
intralamellar blocks was implemented by means of TEM
[54, 55] and AFM [56, 57, 73, 74]. These experimental
techniques are based on different physical principles of
visualization of lamellar substructure: TEM micrographs
use capability of the staining agent to infiltrate into the
interfaces between the adjusted blocks while AFM employs
mechanical probes. Nevertheless, the mean size of the
crystal blocks giving by these tools is consistent with
the corresponding data extracted from WAXS patterns.
Figure 5 presents an example of granular structure of
crystalline lamellae revealed by AFM tapping mode for
Fig. 5 Small-scale tapping mode AFM images of surface morphol-
HDPE [56]. This kind of substructure reflects the intimate ogy of HDPE (1 lm in each side). Image adapted from [56]  1999
essence of polymer crystallization processes which are with permission from the American Chemical Society
believed to include an intermediate mesomorphic domain
at the front of growing crystallites [45].
Nowadays, AFM was broadly used for testing structural The structural changes in PB, PCL, and PA6 under
transformations under shear and uniaxial deformation uniaxial stretching prior to yielding were examined
modes in different semicrystalline polymers as different recently [21, 22]. In situ AFM measurements made it
polyethylenes and related copolymers, i-PP and s-PP, PCL, possible to provide a direct view of microstructural chan-
PB, PA6, polyvinylidene fluoride (PVDF), polyethylene ges occurring in the early stages of deformation. Among
oxide (PEO), poly(propene-co-octene), etc. [20–22, 73– the other things, it was shown that these transformations
77]. Most of the papers focused on the effects of large depend on the initial morphology of semicrystalline poly-
deformations. They demonstrated that AFM is able to mers. For instance, different crystallization conditions of
detect different structural transformations such as kinking PB admit attaining spherulites of different sizes and dif-
of crystal lamellae along the compression axis, nanocracks ferent lamella thicknesses. The thinner are crystalline
across the lamellae parallel to the tensile axis, fragmenta- lamellae, the smaller are spherulites. Specifically, PB with
tion of lamellae along shear axis, etc. [73]. spherulites of 5 and 200 lm in diameter acquire lamellae

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J Mater Sci (2012) 47:6749–6767
of 8 and 15 nm thick, respectively [21]. The gradual
fragmentation of the crystallites into smaller pieces was
found in the small spherulites while the large ones exhibit
intensive cavitation prior to the yield point [20]. Multiple
fragmentations of crystal lamellae without visible accu-
mulation of nanovoids were also revealed in PCL and PA6
well below the yield point [22]. These results are in good
agreement with SAXS data showing that cavitation is
negligible in polymers composed of reasonably thin
lamellae [11]. However, direct observation of the small-
strain fragmentation of polymer crystallites provides dee-
per insight about the origin of plasticity mechanisms. The
clearly visible granular structure of crystalline lamellae
shown in the AFM images [20, 21] sets one to think that
fragmentation occurs through sliding of lamella parts along
interfaces between the crystalline blocks. The slip mecha-
nism appears to be obscure because of deficiency of reli-
able data on structure of the block lateral interfaces. We
could just suppose that block sliding may occur either due
to the coarse chain slip, twinning, or particular disorder of
the block interfaces.
Another important AFM observation prior to the yield-
ing is the revealing of short cracks across the stretch
direction in three semicrystalline polymers as PB, PCL,
and PA6 [21, 22]. These cracks cause fragmentation of a
number of neighbor lamellar crystals along with their
subsequent separation. The ordering of the cracks across
lamellae bands in the polar domain might contribute to the
‘‘abnormal’’ SAXS discussed in the previous section. On
the other side, cracking or fragmentation of crystalline
lamellae may lead to macroscopic softening of the crys-
talline skeleton which in turn could result in the nonlinear
behavior of stress–strain diagrams observed in the early
stage of deformation of semicrystalline polymers. To
include this effect into theoretical models, the coupling of
structural transformation with particular mechanisms of
plastic deformation should be taken into consideration.
This problem is discussed in the next section.
Deformation behavior of semicrystalline polymers
at small-strain tensile drawing
Critical strains and block structure of crystalline
lamellae
In a series of papers, Strobl and co-authors presented
number of important results regarding the origin of
mechanical behavior of semicrystalline polymers under
tensile drawing. Using video-controlled tests [78, 79], it
was found that variations of true stress with true strain
follow certain regularities. Experiments were carried out
for different thermoplastic polymers as HDPE, LDPE,
6755
ethylene-vinylacetate copolymers (PEVA) [80–86], HDPE/
LDPE blends [87], s-PP [88], PB [89], PCL and its blends
with poly(vinyl methyl ether) and poly(styrene-co-acrylo-
nitrile) [90]. All these materials exhibit a similar behavior:
deformation mechanisms of semicrystalline polymers
change in four critical points, A, B, C, and D corresponding
to the certain strains. These strains were found to be
invariant while stresses may change significantly with
crystallinity and temperature. It was also reported that
the critical points are independent on the imposed strain
rate [81].
Point A indicates the initial deviation of the true stress–
true strain diagrams from the linear form. It was detected
with a reasonable accuracy from the deformation behavior
of the residual (basic) eH,b and recovered (cyclic)
eH,c = eH - eH,b parts of the total true strain eH. These
strain components can be extracted from the step-cycle test
conducted at a constant strain rate. When the imposed
deformation is small, the basic eH,b and cyclic strains eH,c
are very close to the pure plastic eH,p and elastic
eH,e = eH - eH,p parts of deformation, respectively, which
could be obtained after the complete strain recovery.
Figure 6 shows that the basic part of strain in PEVA12
(polyethylene copolymer containing 12 wt % of vinyl
acetate co-units) is almost invisible up to eA & 0.03 and
the deformation is practically elastic in this strain range.
This deformation is almost the same for all polyethylenes
and the related copolymers [80, 81]. However, other
polymers may show different positions of point A: for s-PP,
poly(e-caprolactone) and its blends with PVME and PSAN
eA & 0.04 [88, 90] while for PB eA & 0.05 [89]. Violation
of linear dependence of true stress versus true strain at
point A may be originated by sliding of the lamella block or
nanocavitation (see ‘‘Structural transformations prior to the
yield point’’).
Point B is associated with the yield point which is
located roughly at the point of maximum curvature in the
true stress–true strain diagram [80, 88]. In the case of
HDPE and the related copolymers eB & 0.1 [80, 81], while
for s-PP eB & 0.12 [88], for PB eB & 0.1 [89], and for
PCL eB & 0.11 [90]. It is worth noting that the elastic part
eH,c of the imposed strain keeps growing above point B (see
Fig. 6). This indicates that this point is not associated with
the onset of total plastic flow. The physical origin of the
yield point is still discussed. Along with the generally
accepted mechanisms based on ideas of nucleation, grow-
ing, and collective motion of the screw dislocation along
the easy crystallographic planes [1–3, 38, 41], recent
studies brought new conjectures. Specifically, the observed
independence of eB on polymer crystallinity and tempera-
ture enforces to associate this point with a cooperative
motion of blocks of crystalline lamellae [83, 84] (see the
next section).
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6756
Fig. 6 True strain–true stress diagrams of PEVA12 at low deforma-
tions. Arrows indicate location of the critical points A and B. Image
adapted from [80]  1999 with permission from the American
Chemical Society
The strains corresponding to points C and D are far
above yielding and thus beyond the scope of this survey.
Nonetheless, it is worthwhile to mention that stress in point
C runs to a critical value causing fragmentation of crys-
talline lamellae into separate blocks and microfibril for-
mation. This is confirmed by the fact that above this point
the elastic part of total deformation is flattened while
plastic strain rate grows appreciably [83]. Point C was
found to be shifted toward lower strains when molecular
weight M of the polymer is below a certain value Mt [82]
(for PE it corresponds to Mt ffi 1:5  105 g mol1 :). This
effect is associated with the occurrence of clusters of chain
entanglements in the amorphous phase [91]. The last crit-
ical point D corresponds to a disentanglement of polymer
chains at large strains. It is undergone the appreciable shift
in the vicinity of the critical molecular weight M * Mt
[82]. In contrast, points A and B are independent of poly-
mer molecular weight. This result underlines that transi-
tions between different deformation mechanisms at small
strains are determined solely by the crystalline phase [92].
Notice that plastic and elastic parts of the total defor-
mation depend strongly on polymer crystallinity. In par-
ticular, in the case of HDPE plastic strain is of the same
order or exceeds elastic strain near critical points A, B, and
C whereas in polymers with lower crystallinity, as in
PEVA, s-PP, PCL, elastic strain predominates for both
tension and plane-strain compression [80, 86, 87, 93].
123
J Mater Sci (2012) 47:6749–6767
Bartczak [93] has found that the discovered deformation
scheme is also suitable for the plane-strain compression of
semicrystalline polymers. It was revealed that stress–strain
diagrams of HDPE, LDPE, and their relative copolymers,
corresponding to this deformation mode, obey similar
deformation mechanisms separated by four critical points A,
B, C, and D as in tension. These mechanisms were distin-
guished by the specific behavior of residual and elastic parts
of the total strain along the flow direction. In particular, it
was shown that low strain behavior of the polyethylenes up
to the yield point B obeys similar regularities. However,
structural transformations at point C are different: in con-
trast to the tensile drawing resulting in fragmentation of
crystal lamellae and formation of the fibrillar morphology,
the strong constraints intrinsic to plane-strain compression
result mostly in the lamella cooperative kinking [93].
It is worth noting that the observed independence of
characteristic strains at points A, B, C, and D on polymer
crystallinity, temperature, and strain rate was asserted to
indicate homogeneity of strain field through the semicrys-
talline polymers [80–90]. Such a property was suggested to
be sustained due to the mobility granular substructure of
crystal lamellae: the sliding of the neighboring crystal
blocks combined with the interlamellar shearing could
accommodate lamellae and amorphous layers to the
imposed strain. This statement needs an elucidation since it
is at variance with a broad distribution of local strains
within a spherulite observed for PB by AFM [20]. The
contradiction could be removed by the fact that strain
measured in macroscopic experiment represent the average
value of local deformations integrated over a spherulite.
Nonetheless, the microscopic origin of the observed strain
invariance of the critical points remains open. It is apparent
that at small strains (points A and B) the readjustment of
lamellae stacks to the macroscopic strain due to sliding of
the lamella blocks depends on their orientation with regard
to the tensile axis. This mechanism could be best realized
in the diagonal domains of a spherulite where the devia-
toric part of stress tensor prevails. In contrast, shearing of
crystal blocks in the polar and equatorial domains could
meet restrictions resulting in the significant deviation of the
local strains from the imposed one [20]. However, this
inference cannot be applied to points C and D.
It seems that the observed invariance of strains corre-
sponding to the critical points A, B, C, and D is associated
with the specific distribution of local strains caused by
(i) sliding of crystal domains in the equatorial domains, (ii)
lamellar separation accompanied by the interlamellar cav-
itation in the equatorial domains, and (iii) damage of
crystalline lamellae in the polar domains of a spherulite. To
justify this assumption, closer examination of the spatial
distribution of the local strains within the deformed
spherulites should be carried out.
J Mater Sci (2012) 47:6749–6767 6757

Quasi-static stress–strain state and elastic moduli

It was long aware that strain rate of linear PE subjected to

plane-strain compression affects the deformation recovery
after the complete unloading [94, 95]. This means that in
addition to the elastic and elastoplastic response of amor-
phous and crystalline phases, deformation of semicrystal-
line polymers is also controlled by the strain rate dependent
viscous forces. These forces could be revealed from the
stress relaxation tests. The strain rate dependence is
reflected in peculiarities of nonlinear deformation behavior
of semicrystalline polymers through a gradual variation of
differential elastic moduli along the stress–strain curves.
This makes interpretation of experimental data more
complicated. To extract influence of the evolution of Fig. 7 True stress–true strain curve for PEVA12 (solid line), quasi-
material structure to the deformation processes, the strain static stress–strain diagram (dotted line), and stress transmitted
through the crystal skeleton (dashed line). Image adapted from [84] 
rate independent elastic moduli should be revealed.
2004 with permission from the American Chemical Society
This was done by the evaluation of the quasi-static
stress–strain diagram via the subtraction of the viscous
stresses from the true stress–true strain curves for PEVA12
[83, 84, 86]. One of the obtained diagrams is depicted in
Fig. 7 [84]. It is attributed to the elastic forces stored in the
crystalline skeleton and amorphous layers and is indepen-
dent of strain rate. Stress /crc transmitted through the
crystal skeleton of crystallinity /c was derived by the
subtraction of the elastic stress (1 - /c)rn, stored in the
amorphous phase, from the obtained quasi-static stress. In
so doing, it was supposed that amorphous layers respond as
the Gaussian network of the entangled tie chains at any
imposed strain [84]. In consequence, flattening of rc(eH)
function above point C has been revealed indicating the
limitation of crystal skeleton to keep elastic forces.
Having in mind the derived quasi-static stress–strain
relation and elastic component of the total strain eH,e(eH),
the true elastic modulus Ecn of semicrystalline polymers
were estimated [84, 86]. The comparative study of different
PE-based copolymers shows that this modulus decreases
with reduction of crystallinity [86]. This implies that Ecn is Fig. 8 Variation of true elastic modulus of PEVA12 with true strain:
strongly dependent on the elastic modulus Ec of the crys- T = 25 C (1), 42 C (2), 58 C (3), and 71 C (4). Image adapted
talline skeleton and its changes with deformation reflect the from [86]  1988 with permission from Springer Science ? Business
Media
strain-induced variations of material structure.
Figure 8 represents the evolution of the true elastic imposed strain increases above the yield point [80] (see
modulus with the imposed true strain eH at different tem- Fig. 6), it can be concluded that point B is not associated
peratures [86], where dashed lines indicate position of the with the onset of total plastic flow [84, 86].
critical points A, B, and C. This plot reveals two specific Taking into account that stiffness of the crystalline
features of the elastic modulus: (i) tensile drawing leads to skeleton is provided by coupling of blocks constituting
the reduction of true elastic modulus Ecn up to the onset of crystalline lamellae, the latter results can be explained in
fibrillation at point C and (ii) Ecn decreases with temper- terms of the strain-induced weakening of links between the
ature. The first feature provides an original view to the neighbor crystal blocks leading to a significant softening of
yield point B. Being located in the maximum curvature of a material. This inference is in line with the observed
the stress–strain diagram, this point is also associated with fragmentation of lamellar blocks in the stretched semi-
the pronounced softening of the crystalline skeleton (star- crystalline polymers [20–22] discussed in ‘‘Blocky struc-
ted at point A). Remembering that the elastic part of the ture of crystalline lamellae’’.

123
6758
The temperature dependence of the true elastic modulus,
shown in Fig. 8, may also be interpreted as an indication of
weakening of links between the lamella blocks with ele-
vation of temperature. The supporting evidence comes
from the flattening of Ecn(eH) curve which becomes visible
at high temperatures. This result implies reduction of
sensitivity of the true elastic modulus to the imposed strain
which confirms that material softening is originated by the
decoupling of the lamella crystal blocks with increase in
temperature and strain.
The instructive studies of semicrystalline polymers at
very small strain rates were carried out in [96, 97]. The high
temperature tensile drawing of different polymers, as PA11,
HDPE, PVDF, and i-PP, showed that the loading stages of
stress–strain curves are insensitive to strain rate at very
small strain rates, ranging between 10-5 and 10-6 s-1. It
might be thought that this ‘‘relaxed’’ state should be free of
viscous stresses and similar to the quasi-static state which
was discussed above. However, stress relaxation, creep, and
considerable residual strains were recorded after loading.
These observations indicate viscoelastoplastic character of
the mechanical response of semicrystalline polymers even
at the extremely small strain rates. This means that viscous
stresses, which are accumulated at very low strain rates, are
still relevant. The observed effect may be explained by the
increase of the local strain rates in the soft amorphous
layers needed to adapt the macroscopic strain rate. Hence,
the ‘‘relaxed’’ state, recorded at the extremely low strain
rates [96, 97], do not represent the quasi-static stress–strain
diagrams considered above [83, 84, 86].
Modeling of small-strain deformation behavior
of semicrystalline polymers
The multiscale and multifunctional response of semicrys-
talline polymers adds difficulties in the quantitative
description of experimental results. Theoretical modeling
should basically take into relevant deformation mechanisms
of the constituent elements, self-consistent interaction
between them, and accompanying structural transforma-
tions. As a result, it should provide a reasonable fitting of
stress–strain and time-dependent diagrams obtained at dif-
ferent experimental conditions as cyclic loading and
unloading, stress relaxation, strain recovering, creep, etc.
Capability of the modeling to describe correctly both
loading and unloading stages of stress–strain diagrams at
different strain rates under the same set of material char-
acteristics is one of the challenging issues.
Semicrystalline polymers are often considered as struc-
tureless homogeneous continuum with different phenome-
nological assumptions on the mechanisms and kinetics of
plastic deformation [98–107]. However, structural
123
J Mater Sci (2012) 47:6749–6767
properties are treated implicitly in this approach. Another
group of papers [108–121] uses conception of two-phase
continuum containing rigid and soft components (crystal-
line and amorphous phases) with essentially different
mechanical properties. The main distinction of semicrys-
talline polymers from the particulate composites is their
peculiar self-organized structure containing stacks of crys-
tal lamellae alternating with thin amorphous layers. For this
reason a formal use of classical homogenization schemes
predicting macroscopic mechanical behavior is inefficient.
Instead, theoretical description demands accounting not
only for specific plastic properties of crystalline and
amorphous phases but also the possibility of rearrangements
of polymer morphology. In contrast to the homogenization
schemes, a second group of models is capable to describe
coupling between mechanical properties and evolution of
material structure. The basic part of these papers aims at
describing behavior of semicrystalline polymers at large
deformations. Among them, the two-layer composite
inclusion model should be mentioned as one of the most
prominent approach [114–116].
A number of questions arise around the physical origin
of small-strain behavior of semicrystalline polymers. This
particularly concerns the origin of temperature and strain
rate dependences of the initial Young’s modulus as a
parameter sensitive to the variations of material structure.
Another query refers to an origin of nonlinear character of
stress–strain diagrams prior to the yield point. It is not
entirely clear whether this behavior reflects constitutive
properties of crystalline and amorphous phases or if it is
originated by tiny structural transformations or micro-
scopic damages occurring in the beginning of deformation
processes. Both of these problems require physically based
models covering the relevant deformation mechanisms
coupled with the accompanying structural transformations.
Temperature dependence of Young’s modulus
The temperature dependence of the true (quasi-static)
elastic moduli of semicrystalline polymers [84, 86] dis-
cussed in previous paragraph is consistent with the corre-
sponding dependence of the initial Young’s modulus (cf.
Fig. 8). In this connection it is worth recalling the thorough
examination of elastic properties of ultra drawn polyeth-
ylene films reported by Matsuo and Sawatari [122, 123].
Investigation of X-ray diffraction from the stretched films
showed that elastic moduli of polyethylene crystals are
practically independent of temperature up to 145 C while
Young’s modulus of the films decreased with temperature.
Using the composite model under the assumption of serial
connection of crystal lamellae and amorphous layers along
the tension axis, the authors concluded that temperature
dependence of initial Young’s modulus of semicrystalline
J Mater Sci (2012) 47:6749–6767
polymers is governed by changes in the specific volume of
the amorphous phase induced by thermal expansion.
However, in view of the current knowledge about granular
structure of crystalline lamellae it seems to be reasonable
to reexamine these conclusions in terms of temperature
dependence of lamella block bonding [86]. Similar idea of
thermal dissociation of secondary (physical) bonds
between polymer chains has been elaborated in series of
theoretical studies of variations of the Young’s modulus in
a broad range of temperatures [124–127]. According to this
concept, the elevation of temperature leads to rupturing of
physical bonds due to Van der Waals, hydrogen or dipole-
dipole interactions which restrict molecular motions and
define the initial stiffness.
Strain rate effect on Young’s modulus
An increase in strain rate results in increasing the stress
[78, 128–130] and the initial Young’s modulus [131] of
semicrystalline polymers. Long ago, it was suggested to
represent the total stress r as a sum of the internal stress
ri(eH), depending on the imposed strain, and viscous stress
rr ðe_ H Þ attributed to strain rate [78, 129]. The first term
corresponds to the quasi-static stress [83, 84] discussed in
‘‘Quasi-static stress–strain state and elastic moduli’’. This
approach enables to describe time dependent behavior of
stress decay Dr(t) = r(0) - r(t) during stress relaxation
and strain recovery De(t). For PEVA12 it was shown that
Dr(t) * ln(t) and DeH * ln(t) if the observation period is
less than the corresponding relaxation times [83, 84].
The large variations of strain rate lead to the relatively
small changes in the total stress. This reflects the funda-
mental fact that in semicrystalline polymers viscous stres-
ses are thermally activated and obey the Eyring law
rr  lnða_eH Þ [78, 80, 132, 133] where a is the temperature
dependent parameter.
There are a few papers trying to explain the microscopic
origin of the strain rate dependence of the initial Young’s
modulus of semicrystalline polymers. One of them is based
on the assumption that above glass transition temperature
structure of interlamellar amorphous layers is noticeably
different from polymer melt in bulk [108, 109]. This was
argued by the fact that persistent length of flexible mac-
romolecules lp * 1 nm is comparable with a typical
thickness of amorphous layers La ranged from 10 to 30 nm,
which leads to shortening of subchains between the
neighboring entanglements as opposed to the unconstrained
polymer melt. Therefore, the subchains could be treated as
nematogene semiflexible liquid-crystalline units [134]. As
a result, structure of the thin layers could be represented as
collection of microdomains of average size R0 separated by
the topological defects [135, 136]. The accumulated stress
6759
is defined by the elastic distortion of macromolecules
rather than their stretching and reptation as it is considered
for the unconstrained polymer melts [109]. This results in
distortion of the liquid-crystalline microdomains to a lower
size R [135, 137]. The balance of the distortion energy and
viscous stress defines dependence of the current domain
size R on shear rate c_ a . The resulting elastic modulus of the
 
amorphous phase is equal to Ga ðc_ a Þ ¼ K= lp Rðc_ a Þ . Use of
this relationship in the two-layer composite inclusion
model for semicrystalline polymers [115–117] gives a
strain rate dependence of the initial Young modulus [108,
109]. Note that the described deformation mechanism may
be pertinent for high-crystalline polymers.
Another line of studies uses molecular dynamics (MD)
numerical simulation of deformation behavior based on
the two-layer model of semicrystalline polymer [138]. The
origin of the strain rate dependence of the deformation
response has been investigated for the systems with dif-
ferent molecular weights, crystallinity, and thickness of
the crystalline lamella with help of the standard coarse-
grained MD modeling [139]. An amorphization of the
crystalline lamella has been revealed at very small strain
rates e_ while this effect vanishes at higher strain rates. The
coarse-grained MD simulation made it possible to derive
dependence of the effective elastic modulus of the system
on the ratio of the imposed strain rate to relaxation rate. If
the strain rate does not exceed the relaxation rates of both
crystalline and amorphous phases, the elastic modulus
grows slowly with strain rate due to tiny structural
transformations of the deformed system. However, after a
certain threshold e_ cr a considerable increase in the effec-
tive elastic modulus sets in. This indicates an augmenta-
tion of the deformation resistance due to the incomplete
relaxation of the amorphous layer under the faster
stretching. Further increase in the strain rate results in a
stronger growing of the elastic modulus. This is consistent
qualitatively with experimental observations [131]. The
elastic modulus was shown to be independent on molec-
ular weight of the model system in a broad range of strain
rates. The same conclusion was obtained for the role of
lamella thickness at a fixed level of crystallinity [138]. By
contrast, increase in the polymer crystallinity /c leads to
faster augmentation of the effective modulus with strain
rate. This effect was shown to depend on the increase in
the local strain rate of the amorphous phase according to
expression e_ a  e_ =ð1  /c Þ. At large crystallinity /c the
local strain rate e_ a may exceed rate of relaxation of the
amorphous layer. The MD simulations made it possible to
reveal the strain-induced nanocavities [138]. These for-
mations may lead to the self-consistent increase in
relaxation times of the amorphous phase and eventually
shift the threshold e_ cr toward smaller strain rates.
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6760
Thereby, strain rate behavior of the initial Young’s
modulus could be governed by both deformation mecha-
nisms of thin amorphous layers confined between crystal
lamellae as well as ratio of the imposed strain rate to
relaxation rates of crystalline and amorphous phases. To
gain a closer idea on molecular origin of the initial Young’s
modulus of semicrystalline polymers, the corresponding
physical theory should be adapted.
Global deformation behavior of semicrystalline
polymers
Approaches based on concept of pseudoelasticity
Several interesting ideas in the theory of small-strain
deformation of semicrystalline polymers were proposed by
Drozdov [98–103, 111, 140]. These approaches represent
important piece of theoretical work and deserve to be
considered in more details. In the early version, uniaxial
tension and retraction of i-PP has been analyzed in terms of
equivalent isotropic heterogeneous network comprised of
elastoplastic meso-domains [99]. Links between meso-
domains were supposed to be associated with crystallites.
The proposed model used an idea that only the amorphous
phase is distorted during the small-strain loading while the
crystalline phase is unaffected [141]. According to this
approach, plastic strain was considered as a sum of two
parts, ep = ep1 ? ep2. The first term is attributed to chain
sliding of tie molecules while the second one was supposed
to be caused by the relative motion of meso-domains and
characterizes implicitly the coarse chain slip or disinte-
gration of crystalline lamellae. It was suggested that the
rate of the first part of plastic strain is a linear function of
the imposed strain rate, e_ p1 ¼ /1 e_ , where the coefficient /1
was taken to be dependent on the elastic fraction ee of the
total deformation e. Simultaneously, the rate of plastic
strain caused by the relative sliding of meso-domains was
supposed to vanish, e_ p2 ¼ 0 during active loading (_e  0)
because small tension does not affect the crystalline
lamellae prior to the yield point [142, 143]. However, the
fragmentation of lamellae was admitted for the unloading
stage (_e\0) of the stress–strain diagram. In this case, rate
of plastic strain e_ p2 was suggested to be proportional to the
strain power. This approximation is based on the concept of
pseudoelasticity [144] presuming that certain material
characteristics may be considered as step-wise functions of
the applied strain rate. Accordingly, the evolution rate of
the meso-domains was suggested to be governed by dif-
ferent rules at loading and unloading: N_ ¼ 0 at e_  0 and
N_   N e_ p2 at e_ \0, respectively. This difference is argued
by the assumption of fragmentation of crystalline lamellae
occurring only during unloading. This model enabled to
123
J Mater Sci (2012) 47:6749–6767
describe the observed softening of semicrystalline poly-
mers during unloading and provided a good fitting of
stress–strain diagrams measured at a given strain rate and
different backtracking points prior to the yield point.
This approach was generalized to the case of equivalent
network containing heterogeneous meso-domains of active
and passive strands [98, 102]. Passive strands were thought
to have permanent links and contribute to the elastic
response while the active strands were supposed to be
connected to the network by temporary junctions repre-
senting entanglements of polymer chains or physical
crosslinks on lamellar surfaces in accordance with concept
of transient networks [145, 146]. The rearrangement of
these junctions was considered as a thermally activated
process contributing to a viscoelastic response of the
material but plastic deformation due to the relative sliding
of meso-domains was disregarded. By this reason this
approach was only used for the modeling of a tensile
loading at constant strain rates and stress relaxation tests
conducted at different temperatures.
Application of these ideas for modeling of multicycle
deformation behavior of semicrystalline polymers reques-
ted to adapt parameters governing intensity of intra- and
inter-lamellae plastic flow [100, 103, 111, 140]. To this
end, plastic deformation rate of crystalline lamellae e_ p2 was
suggested to be considered as a linear function e_ p2 ¼ wr0 of
the deviatoric component r0 of the macroscopic stress
tensor [103, 111]. In contrast with previous approaches
[99], rate of plastic deformation, attributable to the chain
sliding, was considered as a linear function e_ p1 ¼ /2 e_ of
the imposed strain rate, where the coefficient /2 obeys the
second order kinetic equation. In Ref. [140] e_ p2 was even
neglected in comparison with plastic strain rate e_ p1 of the
amorphous phase. However, in all the cases, both the
coefficients w and /2 were supplied by different values
along loading and unloading branches of stress–strain
diagram as it was done in the early modeling [99].
Thus, the concept of pseudoelasticity [144] used in the
referred works provides excellent fitting of multicycle
tensile deformations at a constant strain rate and differ-
ent temperatures. However, the step-wise changes of
mechanical and structural characteristics of semicrystalline
polymers at the backtracking points lack support from any
known factual evidence. This requires development of the
physically based models, which are able to predict cor-
rectly not only mechanical response but also strain-induced
structural transformations.
Structure-sensitive mechanics of semicrystalline polymers
Physically, it would naturally appear that material and
structural characteristics have no singularities at the
J Mater Sci (2012) 47:6749–6767
backtracking points between loading and unloading paths
of deforming solid polymers. This statement was used in a
series of papers devoted to structural mechanics of semi-
crystalline polymers prior to the yield point [147–152]. The
central idea of the proposed approach is based on the
experimental evidence of stiffness decrease of semicrys-
talline polymers under small-strain tensile drawing (see
‘‘Quasi-static stress–strain state and elastic moduli’’). This
fact could be imagined in terms of local softening of the
overstressed domains of rigid crystalline skeleton along the
tensile axis. As a result, the skeleton connectivity will be
violated leading to the total softening of the material. It is
important that this effect could be achieved through a
certain structural transformations (cavitation, local frag-
mentation of crystal blocks, etc.) while the novel soft
component occupies a small fraction of the skeleton. The
formal scheme of this process is depicted in Fig. 9.
This assumption was integrated into the simple Zener-like
model named as basic structural-mechanical element
(BSME) and shown in Fig. 10. The minimal amount of
structural units is taken there into consideration. These units
represent the crystalline skeleton and the amorphous phases.
They are named as hard (H) and soft (S) components due to
the significant difference in stiffness of crystalline and
amorphous phases. The hard component is placed in parallel
with the basic soft one representing the initial amorphous
phase. This reflects homogeneity of macroscopic strain field
being consistent with experimental observations [80–90].
Parallel connection implies that the total stress is provided by
weight average of stresses stored in the hard and soft com-
ponents, r ¼ /ðtÞrH þ ½1  /ðtÞrS , where /(t), a current
volume fraction of the hard component, is introduced.
At small strains, the basic and new soft components could
be represented by elastic element while the hard component
is described by viscoelastic element. Its viscous strain rate
was taken to obey the Eyring law e_ p ¼ a sinhðarH Þ, where


a ¼ e_ 0p exp Up =kT , Up is the activation energy, and
a = cp/kT is the plastic flow intensity parameter. Note that at
low values of a or stress, the Eyring equation is approxi-
mated by the linear relationship e_ p ffi aarH corresponding to
a Newtonian viscous flow.
Fig. 9 Schematic
representation of the violation
of rigid skeleton connectivity. It
is due to the local structural
transformations caused by the
uniaxial tension. Hard
component is represented by the
dark domains. Image adapted
from [147]  2004 with
permission from Springer
Science ? Business Media
6761
The proposed model accounts for the strain-induced
transformation of the overstressed domains of crystalline
skeleton along the tensile axis resulting in growing of the
new soft component. At small strains this component
matches different structural elements as nanovoids, dam-
ages of crystalline lamellae, etc. [8, 9, 11, 20–22]. In the
model, new soft component is connected in series to the
hard component resulting in softening of BSME. The
inverse transformation of the soft to hard component is
permitted by the model which reflects partial structure
healing during unloading or strain recovery. The evolution
of the volume fraction of rigid component is taken to obey
the first order kinetic equation:
/_ ¼ kHS / þ kSH ð1  /Þ ð1Þ
where kHS and kSH correspond to the structural
transformation rates H ? S and S ? H, respectively.
They were assumed to depend on the stresses applied to
the hard and soft components in accordance with ther-
mofluctuation mechanism
kHS ¼ bHS expðbrH Þ and kSH ¼ bSH expðbrS Þ ð2Þ
where b = c/kT is the measure of structural transformation
intensity under the applied stresses [149, 151, 152]. The
constitutive equations corresponding to the BSME pre-
sented in Fig. 10 along with Eqs. (1) and (2) describe the
stress–strain relation and accompanying evolution of
material structure in terms of volume fractions of hard
component.
The BSME model provides a good fitting of the cyclic
loading–unloading behavior of semicrystalline polymers at
small-strain tensile drawing for a fixed strain rate. It was
particularly demonstrated that small values of the residual
strains observed after the complete unloading are explained
by partial healing of material structure [147, 148, 150].
However, a single BSME cannot describe properly loading
and unloading carried out at different strain rates. The
reason of this inconsistency is that this model possesses a
single relaxation time. At small stress or a values, the
BSME relaxation time corresponds to s = (aaEH)-1 where
EH is the elastic modulus of crystalline lamellae.
123
6762
Hard New soft
component component
σ σ
Basic soft
component
Fig. 10 Basic structural-mechanical element
This problem has been bypassed by combination of
different viscoelastic elements connected into the entire
model: instead of a single structural-mechanical element, a
number of BSME connected to one another in parallel were
introduced [149]. Different BSME included to the model
are characterized by different relaxation times as
si = (aiaiEHi)-1 where index i = 1, …, m represents
number of an element. Such an approach takes into account
complexity of semicrystalline polymer morphology. The
material structure was expressed in terms of relative vol-
ume fraction of the hard component n = /(e)//eq, where
/eq = bSH/(bHS ? bSH) corresponds to the equilibrium
volume fraction. Figure 11a shows that the model consid-
ered is able to give correct fitting of stress–strain diagrams
corresponding to different unloading strain rates. It is seen
that the nonlinear behavior of the deformation curve upon
loading couples with a small reduction in volume fraction
of the hard phase which is depicted in Fig. 11b. These
structural transformations could occur due to the formation
of strain-induced nanocavities or damages of crystalline
lamellae. On the other hand, the observed decrease in the
residual strain with diminution of the unloading strain rate
is caused by the gradual restructuring of the hard
component.
The generalized BSME model showed oneself the
advantage in the prediction of multiple cyclic tests corre-
sponding to the small-strain tensile drawing of HDPE for
Fig. 11 Stress–strain (a) and structure evolution (b) diagrams of
HDPE at small-strain tension with strain rate e_ ¼ 103 s1 (0) and
subsequent unloading with different strain rates: e_ ¼ 101 s1 (1),
123
J Mater Sci (2012) 47:6749–6767
different deformation programs [152]. Figure 12a gives an
example of the multicycle stress–strain diagram corre-
sponding to the stress-controlled deformation program at
the fixed value of strain rate. It was found that the best
fitting could be attained if an effect of nanovoids to the
rates of plastic deformations and cavitation is taken into
account. These assumptions are admissible if we accept
that the plastic flow of semicrystalline polymers is attrib-
uted to the interlamellar sliding prior to the yield point. It
was found that volume fraction of nanovoids accumulated
during the tests, tends to saturate with the number of cycles
(see Fig. 12b). It is worth noting that proper fitting of
stress–strain diagrams measured at different experimental
conditions has been obtained for the same set of material
characteristics [152].
Another application of the idea of the strain-induced
material softening in modeling of cyclic deformations was
proposed in Refs. [112, 113]. According to this model, the
amorphous phase of semicrystalline polymers was regarded
as a heterogeneous network composed of the high- and
low-density components having larger and smaller rigidity,
respectively. The high-density zone was associated to the
interphase whereas the low-density zone was suggested to
be formed by the reversible sliding of the mobile chains.
The chain sliding results in increase of the fraction of the
low-density zone and leads to the material softening. This
effect was shown to originate the nonlinear stress–strain
dependence prior to the yield point [113]. The proposed
model provides a good fitting of loading–unloading
behavior of PP under uniaxial tension and torsion without
alteration of the material parameters at the backtracking
point.
The alternative theory taking into account the strain-
induced softening of semicrystalline polymer was devel-
oped in Ref. [153]. This approach uses the idea of coupling
between the local damages and plasticity of crystalline
e_ ¼ 103 s1 (2), and e_ ¼ 105 s1 (3). The solid lines correspond
to the theoretical calculations. Image adapted from [151]  2008 with
permission from Springer Science ? Business Media
J Mater Sci (2012) 47:6749–6767
Fig. 12 Uniaxial cyclic stress–
Stress, MPa
strain diagram of HDPE (a) and 20
the accompanied evolution of
nanovoid volume fractions (b) 16
Stress, MPa
corresponding to the stress-
controlled program at the fixed
12
strain rate je_ j ¼ 5  104 s1 .
Symbols and solid lines 8 0.04
represent experimental data and
calculation results, respectively. 4
The inset shows fitting of the
last cycle. Image adapted from 0 0.02
[152]  2011 with permission 0 0.01
from American Society of
Mechanical Engineers
lamellae which is in line with the recent AFM observations
of lamella fragmentations under the tensile drawing [20–
22] (‘‘Blocky structure of crystalline lamellae’’ section).
The model describes deformation behavior of semicrys-
talline polymers considering contribution of the intrala-
mellar cohesive forces along with the interlamellar
viscoelastic response of the amorphous phase. The cohe-
sive forces are associated with a bonding strength between
blocks of crystalline lamellae. The key idea of the model
[153] is based on the physically justified assumption that
lamellae fragmentation reduces contribution of the cohe-
sive forces. The authors called this phenomenon as an
unbridled effect and formalized it by means of introduction
of the damage internal variable D coupled with the plastic
strain ep: the larger the plastic strain is, the larger is D. The
proposed approach was able to give a good fitting of
multicycle tensile tests carried out at constant strain rate for
three different polymers, PCL, PB, and PA6 [22].
So, the common attribute of the described theoretical
approaches is the understanding that small-strain defor-
mation behavior can be described properly if and only if
the local softening of semicrystalline polymers would be
taken into consideration. This effect may be caused due to
cavitation of amorphous phase or damages in crystalline
lamellae and was justified in the numerous experimental
works.
Numerical modeling of structural transformation
The one-dimensional approach [147–152] has been gen-
eralized to a 2D structure-sensitive model [154]. Its initial
structure is defined as a random distribution of elastic hard
and soft domains. In Fig. 13a these domains are colored in
black and gray, respectively. The stress-induced transfor-
mations of the hard domains into the soft ones and inver-
sely were allowed with probabilities governed by the
Eyring law [147, 149]. The activation energy of the
structural transformations was supposed to be reduced with
6763
20
16
12
Void volume fraction
8
4 0.06
0
0.02 0.04
Strain
0.02 0.03 0.04 0.05 0 0.02 0.04
Strain Strain
(a) (b)
increase of bulk component of the local stress tensor at any
point of the heterogeneous structure (cf. Eq. 2).
The local stresses were calculated at any time by means
of finite element method on the square periodicity domain.
Elastic moduli of the hard and soft components as well as
parameters of Eyring equation, governing rates of struc-
tural transformations, correspond to similar characteristics
of one-dimensional model considered above [149]. The
obtained results are depicted in Fig. 13. It shows that
uniaxial stretching results in the transformation of the ini-
tially random isotropic structure into an anisotropic one
due to the stress-induced transitions of the hard to soft
domains. For the sake of simplicity, the novel soft domains
were considered to acquire the same properties as the basic
soft component and were colored in gray. It is seen that at
the small strain e = 0.05, clusters of hard domains become
discontinuous and extended across the stretch direction.
This confirms the original idea suggesting that uniaxial
tension leads to the softening of semicrystalline polymers
due to the violation of the crystalline skeleton connectivity
[147].
Similar anisotropic distribution of cavities, appeared
between crystalline lamellae, has been revealed by means
of TEM in the oriented HDPE thin films stretched to a
certain strain along the chain direction in crystalline
lamellae [67]. This is demonstrated by Fig. 14a. The
observed cavities are quite large due to the coalescence of
smaller ones. However, it may be guessed that at lower
strain level the interlamellar voids should be much smaller
while their spatial distribution keeps the same peculiarities
as exposed in Fig. 14a. Figure 14b shows that further
elongation could produce larger voids which prefer to be
stretched along the tension axis [67].
The Fourier transformation of the model structures
given in Fig. 13 results in scattering patterns presented in
Fig. 15. It can be seen in Fig. 15a that the nondeformed
model leads to an ordinary diffusive halo expectable for
the random isotropic systems. However, the stretched
structure results in the butterfly-like pattern depicted in
123
6764 J Mater Sci (2012) 47:6749–6767

Fig. 13 2D heterogeneous ε =0 ε = 0.05

structures before (a) and after
(b) tensile strain e = 0.05.
Arrows indicate the tension axis.
Image adapted from [154]

(a) (b)

(a) (b)
Fig. 14 TEM images of HDPE film uniaxially stretched along the tension axis. Image adapted from [67]  1989 with permission
lamellar chain direction: cavitations between lamellae (a) and from Springer Science ? Business Media
coalescence of cavities into longitudinal voids (b). Arrows indicate

Fig. 15 Theoretical scattering

patterns corresponding to 2D
heterogeneous structures shown
in Fig. 13: e = 0 (a) and
e = 0.05 (b)

Fig. 15b [155]. This pattern is similar to the small-angle
X-ray scattering patterns reported in number of experi-
mental works [8, 9, 11–15, 17–19, 68] and presented in
Figs. 3 and 4. The obtained result counts in favor of
understanding the origin of the small strains SAXS and
USAXS of semicrystalline polymers discussed in ‘‘Nan-
ocavitation’’: at uniaxial deformation prior to the yield
point, the ‘‘abnormal’’ small-angles scattering patterns
oriented along the tensile axis are originated by an
anisotropic heterogeneous distribution of density

123
J Mater Sci (2012) 47:6749–6767
fluctuations or strain-induced nanovoids rather the void
form-factor.
Conclusions
The current studies of the deformation behavior of semi-
crystalline polymers prior to the yield point indicate a
strong correlation between mechanical response and the
accompanying structural transformations. For the small-
strain uniaxial tension, these transformations include
mostly the interlamellar nanovoids and damages of crys-
talline lamellae which can be revealed by means of SAXS
and AFM well below the yield point [9, 11, 13, 20–22].
Structural changes, occurring initially in the equatorial and
polar regions of spherulites, give rise to the material soft-
ening and local plastic deformations, which define the
global mechanical properties of the materials. The relative
contribution of these defects depends on the initial polymer
morphology and thickness of the crystalline lamellae. An
increase in the lamellar thickness intensifies the cavitation
processes [11, 17]. The small-strain butterfly USAXS and
SAXS patterns disclose heterogeneous distribution of the
interlamellar nanovoids which are collected into domains
of different density and extended across the tensile axis
[68]. These structural transformations are supposed to
forego crazing occurring at larger deformation.
Uniaxial tension of different semicrystalline polymers
reveals common behavior of the true stress–true strain
diagrams indicating five deformation mechanisms which
are separated by four critical points A, B, C, and D [80–90].
Two of them, A and B, embrace mechanisms inherent to
strain range prior to the yield point, while points C and
D reflect the large deformation processes. Specifically,
point A indicates the transition from elastic to the vis-
coelastoplastic deformation response, B is associated with
the yield point corresponding to maximum curvature of the
true stress–true strain diagram, C specifies the onset of
fibrillation, and D corresponds to the chain disentangle-
ment process.
The granular structure of the crystal lamellae and
interaction of the lamellar blocks are responsible for the
strain and temperature behavior of the true elastic modulus
of semicrystalline polymers. This parameter can be derived
from the quasi-static true stress–true strain diagrams
obtained after the subtraction of viscous forces. An
important finding is that the true elastic modulus is
decreased considerably starting from the critical point A up
to the point C. This provides an insight about the origin of
the yield point B which is attributed to softening of the
crystalline skeleton rather than an onset of global plastic
flow [86]. The discovered importance of granular structure
of crystalline lamellae in the deformation behavior of
6765
semicrystalline polymers appeals to the reexamination of
the basic mechanisms of plastic deformations including the
coarse chain slip and resolved stresses on interfaces
between the lamella blocks.
In theoretical consideration, it was recognized that the
strain-induced softening plays an essential part in the
small-strain nonlinear mechanical response of semicrys-
talline polymers. The correct description of the cyclic
stress–strain diagrams at different strain rates during
loading and unloading can be done only in the case of
relevant conceptions of evolution of polymer structure and
deformation mechanisms of the constituent elements. Some
of the approaches explain strain-induced softening as
appearance of the novel soft component (nanovoids,
damages in crystal lamellae, etc.) in series with rigid
crystalline skeleton. The volume fraction of the strain-
induced defects depends on the imposed strain and can be
recovered at small strains under the internal elastic stresses.
Generalization of this concept to the 2D model confirms an
idea of heterogeneous anisotropic distribution of the novel
soft domains. This leads to (i) the violation of connectivity
of the rigid skeleton accompanied by the material softening
and (ii) the butterfly scattering patterns inherent to some
semicrystalline polymers at small-strain tensile drawing.
Further modeling of mechanical response of semicrystal-
line polymers requires development of 3D approaches
taking into account coupling between deformation behav-
ior and the observed structural transformations.
Acknowledgements The authors are grateful to Prof. Eduard
Oleinik, Dr. Frederic Addiego, and Dr. Daniel George for the helpful
advises and comments. S.P. appreciates the University of Strasbourg
for the hospitality and financial support during work on this review at
the Institute of Fluid and Solid Mechanics of Strasbourg.
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