Polymer 227 (2021) 123848

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

Microstructural insight on strain-induced crystallization of ethylene/

propylene(/diene) random copolymers
Finizia Auriemma a, *, Miriam Scoti a, **, Fabio De Stefano a, Giovanni Talarico a,
Odda Ruiz de Ballesteros a, Rocco Di Girolamo a, Anna Malafronte a, Claudio De Rosa a,
Roberta Cipullo a, Martin Van Duin b
a
Dipartimento di Scienze Chimiche, Università di Napoli “Federico II”, Complesso Monte Sant’Angelo, Via Cintia, 80126, Napoli, Italy
b
ARLANXEO Performance Elastomers, Innovation, P.O. Box 185, 6160AD Geleen the Netherlands

A R T I C L E I N F O A B S T R A C T

Keywords: The tensile properties and the structural transformations occurring by effect of deformation of un-vulcanized
Ethylene/propylene(/diene) copolymers ethylene/propylene(/diene) elastomers with ethylene contents ranging from 57 to 83 mol% are analyzed and
Chain microstructure interpreted in terms of the chain microstructure. It is shown that the samples with ethylene contents larger than
Mechanical properties
or equal to 73 mol% experience a slight but significant increase of crystallinity upon stretching and partial
Strain induced crystallization
Strain hardening
melting of the new oriented crystals formed by stretching after releasing the tension. The degree of crystallinity,
the tensile properties, the incremental crystallinity achieved upon stretching and the residual crystallinity left
upon release of the tension all show well-defined correlations with the average ethylene content and the ethylene
sequence length distribution. The tensile properties and the strain hardening behavior are correlated with the
incremental crystallinity achieved upon stretching at high strain.

1. Introduction
Ethylene/propylene (EPM) and ethylene/propylene/diene (EPDM)
random copolymers (EP(D)M) with ethylene contents in the range of
45–75 wt% are elastomers of high commercial relevance. They are
characterized by outstanding properties, such as long-term resistance to
oxygen, ozone, heat, UV irradiation, water and polar solvents in general,
even under extreme environmental conditions. As a result, EPDM rub­
bers find numerous applications, such as in the automotive and electrical
cable industries and for the production of building and construction
materials, and many others [1–9]. In EPDM copolymers, ethylene and
propylene are copolymerized in the presence of non-conjugated dienes
which are characterized by two C– – C unsaturations of different re­
activities towards insertion polymerization, such as 5-ethylidene-2-nor­
bornene (ENB), dicyclopentadiene (DCPD), or 5-vinyl-2-norbornene
(VNB). The easy incorporation of the strained unsaturations of the cyclic
norbornene units results in fully saturated polymer backbones bearing
the less reactive unsaturations in side groups. These pendant unsatura­
tions, in turn, enable subsequent sulfur vulcanization and facilitate
peroxide crosslinking reactions [1–9]. The outstanding properties of EP
(D)M elastomers are essentially due to the fully saturated and apolar
polymer backbones, the high chain flexibilities, the random distribu­
tions of comonomer units along the chains and the capability of the long
ethylene sequences to crystallize by cooling and deformation [10–22].
The industrial production of EP(D)M is based on insertion poly­
merization facilitated by coordinating catalyst systems, typically in a
solution process though an emulsion process is also possible [23,24].
The oldest and today still very important catalyst system consists of a
Ziegler-Natta vanadium-based pre-catalyst, such as VCl4, V(acac)3 (acac
= acetylacetonate), or VOCl3, and an organoaluminum co-catalyst, such
as AlEt3, AlEt2Cl or Al2Et3Cl3 [23–26]. The addition of a halogenated
ester as a so-called promoter (e.g. chloroacetate, n-butyl per­
chlorocrotonate, and trichlorotoluene) limits the deactivation tendency
of the catalytic center during polymerization, thus leading to products
(EP(D)M − V) of high molar mass, narrow molar mass distribution and
narrow chemical composition distribution [27,28]. However, the
V-based catalyst systems suffer from a number of drawbacks, including a
relatively low productivity, a relatively low affinity for the dienes and
the need of operating at low temperatures (below 60 ◦ C), thus requiring
deep-cooling of the monomer/solvent feed in order to obtain high molar

* Corresponding author.
** Corresponding author.
E-mail addresses: finizia.auriemma@unina.it (F. Auriemma), miriam.scoti@unina.it (M. Scoti).

https://doi.org/10.1016/j.polymer.2021.123848
Received 1 March 2021; Received in revised form 14 April 2021; Accepted 1 May 2021
Available online 12 May 2021
0032-3861/© 2021 Elsevier Ltd. All rights reserved.
F. Auriemma et al.
mass EP(D)M− V products and prevent catalyst deactivation. Finally, the
V-catalyst residues need to be removed from the rubber cement to obtain
high-quality EP(D)M− V rubber products [8,23–36].
The second relevant catalytic family for EP(D)M production is based
on (post-)metallocene or so-called advanced catalysts. Currently, all
major EPDM producers exploit (post-)metallocene catalysts, such as bis
(substituted cyclopentadienyl) zirconium dichloride and dimethylsilyl
tetramethylcyclopentadienyl titanium dichloride. ARLANXEO has
developed and exploits the so-called Keltan® Advanced Catalyst Elas­
tomer (ACE™) technology [23–25,36–39]. More than 50% of the global
EPDM production capacity consists of products from (post-)metallocene
catalysts (EPDM-M). A major advantage of (post-)metallocene catalysts
over the traditional V-based catalysts for the production of EPDM is the
much higher catalyst activity, resulting in the use of substantially lower
catalyst levels, thereby eliminating the need for deashing of the final
rubber product. Another advantage is the much higher
reaction-temperature operating window, thus requiring less energy for
the deep-cooling of the monomer/solvent reactor feed, the recycling of
unreacted monomers, and the solvent stripping.
EP(D)M rubbers are in general amorphous or low crystalline mate­
rials. Samples with an ethylene content larger than approximately 65 wt
% are crystalline at room temperature and may experience further
crystallization either at low temperatures or by stretching [10–22].The
bulky diene units are expelled from the crystals and reduce the length of
the crystallizable ethylene sequences. The methyl side groups derived
from the propylene monomers are instead partially included in the
crystals as defects and, thus, increase the effective length of the crys­
tallizable sequences [18,19,40–45]. The distribution of the ethylene
sequence lengths and the chain microstructure in general are established
in the polymerization step by the choice of the catalyst system and the
reaction conditions, including the temperature, the pressure, the
monomer feed ratio, and the chemical nature of the diene. In particular,
under given copolymerization conditions, the relative comonomer
conversion and the resultant chain microstructure depend on the reac­
tivity ratios of the ethylene, propylene and diene comonomers towards
the active metal centers [46–50]. The distribution of the ethylene
sequence lengths has a great influence on the crystallization and,
consequently, on the mechanical properties of EP(D)M and on their
rheological behavior during mixing and processing. Therefore, the un­
derstanding of the effects of the chain microstructure on the final per­
formance of EP(D)M products is a fundamental issue. As an example, it
has been shown that the EP(D)M-M samples often achieve the perfor­
mance shown by their EP(D)M− V counterparts at lower ethylene con­
tents, because of the greater tendency of (post-)metallocene catalysts
towards the incorporation of consecutive ethylene units rather than the
formation of hetero-sequences [23–25]. As a consequence, such EP(D)
M-M products show similar crystallinities and properties as EP(D)
M− V products at somewhat lower ethylene contents. Furthermore, EP
(D)M-M products with similar ethylene contents as their EP(D)M− V
counterparts show a higher crystallinity and, hence, also different
properties, namely higher hardness, higher tensile strengths, but also
higher permanent deformations in low-temperature compression set
tests [23–25].
In this paper the mechanical properties and the structural trans­
formations occurring by effect of deformation of EP(D)M samples with
ethylene contents in the range of 57–83 mol% (44–77 wt%) are inter­
preted in terms of the chain microstructure. The analysis is focused on
the evaluation of the tensile properties and the maximum degree of
crystallinity achieved by stretching at high deformations. The aim is to
establish a relationship between these properties and suitable micro­
structural parameters that describe the statistics of comonomer distri­
bution and the sequence length as established in the synthetic step.
The strain induced crystallization (SIC) behavior occurring at low/
moderate deformations of some V-based EP(D)M copolymers with
ethylene contents in the range of 64–78 wt% (57–83 mol%) was
analyzed in Ref. 16. It was shown that, for EP(D)M samples with
2
Polymer 227 (2021) 123848
ethylene contents larger than or equal to 71 wt%, stretched at low de­
formations, crystallinity starts increasing already at deformations close
to the yielding (20–40%). In contrast, for the samples with 64 wt%
ethylene, the crystallinity increase starts only at strains higher than
170%. In all cases, high degrees of orientation of the amorphous phases
are achieved already at low deformations. In particular, for samples with
high ethylene contents (>64 wt%), small, but significant amounts of
crystals are initially present at room temperature already in the unde­
formed state. These pre-existing crystals undergo fragmentation and/or
mechanical melting at low deformations and experience oriented
recrystallization at higher deformations. The crystallinity increases
upon stretching, already at low deformations, not only as the result of
the high degrees of orientation achieved by the chains in the amorphous
phase, but also because the fragments of the initial crystals act both as
physical crosslinks able to efficiently transmit the stress and as nuclei
able to trigger further crystallization. Because of the non-trivial role of
the pre-existing crystals, this behavior was coined “strain-induced post-
crystallization”.
For EP(D)M samples with 64 wt% ethylene the amount of initially
present crystals is very small though, making the crystallization
behavior upon stretching more similar to that of classic crystallizable
amorphous elastomers, such as natural rubber [51–55]. Indeed, the
crystallinity increase in these samples is “merely” induced by strain
(classic SIC), as it starts occurring only at high deformations, once the
amorphous phase has reached a high degree of orientation [51–55].
Regardless of the ethylene content and the role of the pre-existing
crystals, the crystallinity increases rather steeply after the onset. It
then reaches a quasi-plateau value at about 100% deformation for the
more crystalline samples undergoing strain-induced post-crystallization.
For the low crystalline samples experiencing classic SIC, instead, the
crystallinity increase reaches a quasi-plateau value at 200–300%
deformation, as the initial crystals do not play a role.
To date, the relationships between the initial degree of crystallinity,
the mechanical properties and the maximum degree of crystallinity
achieved by stretching of EP(D)M elastomers with the chain micro­
structure have been understood only in part, considering the sole role of
comonomer content. The relationships between the crystallization and
mechanical properties of EP(D)M with the average length of ethylene
sequence and the distributions of comonomers are only known quali­
tatively but have not been studied quantitatively. The work described in
this paper is aimed at filling this gap. In particular, the separate effects of
the ethylene content and the length of ethylene sequences on the crys­
tallization and tensile properties are outlined. Samples obtained with V-
based and (post-)metallocene catalysts, characterized by a large varia­
tion of the ethylene, propylene and diene contents, are analyzed to
unravel to which extent the properties of these products are controlled
by the average comonomer content and/or the differences in the
comonomer distribution.
2. Experimental section
Ethylene/propylene(/diene) copolymer samples with an ethylene
(E) content in the range of 44–77 wt% (57–83 mol%) have been
analyzed. They have been prepared at ARLANXEO, using a V-based
Ziegler-Natta catalyst system or Keltan ACE™ technology in a solution
polymerization process, except for the EPDM sample with 74 mol% E,
which has been obtained with a V-based catalyst in a slurry process.
Except for the EPM samples with ≈77 wt% ethylene content, all the
analyzed samples are commercially available in the ARLANXEO
portfolio.
The characteristics of the EP(D)M samples are shown in Table 1. First
the EPM samples and next the EPDM samples are listed in the sequence
of decreasing ethylene contents and, thus, decreasing crystallinities.
They are coded as EPM-Xn and EPDM-Xn-Ym, respectively. X = V or M
stands for samples prepared with vanadium- (EPM-V or EPDM-V) or
(post-)metallocene-based (EPDM-M) catalysts in solution
F. Auriemma et al. Polymer 227 (2021) 123848

Table 1
Concentrations of ethylene (E), propylene (P), diene (ENB or DCPD) comonomeric units, Mooney viscosity and used catalyst of EPM and EPDM samples.
Sample E (wt%)a E (mol%)a P (wt%)a P (mol%)a ENB (wt%)a,b ENB (mol%)a,b DCPD (wt%)a,b DCPD (mol%)a,b Mooney viscosity Catalyst
ML (1 + 4) 125 ◦ C
(MU)c

Ethylene/propylene copolymers
EPM-V83 77.2 83.5 22.8 16.5 35 V
EPM-V80 72.4 79.7 27.6 20.3 25 V
EPM-V58 48.4 58.5 51.6 41.5 51 V
Ethylene/propylene/diene copolymers
EPDM-V80-N1.2 70.5 80.0 24.9 18.8 4.6 1.2 55 V
EPDM-V78-N0.4 70.0 78.3 28.5 21.3 1.5 0.4 59 V
EPDM-M78-N1.2 68.1 77.9 27.3 20.8 4.6 1.2 55 M
EPDM-M78-N1.3 67.6 77.7 27.4 21.0 5.0 1.3 80 M
EPDM-Q74-N0.8 64.6 74.3 32.2 25.0 2.8 0.8 67 V, slurry
EPDM-V73-D0.3 64.0 73.2 34.8 26.5 1.2 0.3 63 V
EPDM-V62-N1.2 51.1 62.4 44.6 36.3 4.3 1.2 46 V
EPDM-M57-N2.7 44 56.8 47 40.5 9.0 2.7 60 M
a
Determined by high-resolution13C NMR solution spectroscopy (vide infra).
b
ENB = 5-ethylidene-2-norbornene; DCPD = dicyclopentadiene.
c
Mooney viscosity (in Mooney units MU) determined using a large rotor at 125 ◦ C, with 1 min preheating, using the final torque after 4 min of testing as a measure of
molar mass.

polymerization processes, respectively, whereas X = Q stands for the
sample prepared with a vanadium-based catalyst in slurry polymeriza­
tion process (EPDM-Q). The label “n” indicates the ethylene mole pre­
cent (mol%), whereas Y = N or D stands for ENB or DCPD diene
monomers, respectively, and “m” indicates the corresponding mol%
content.
The Mooney viscosities [ML (1 + 4) 125 ◦ C] of the EPM samples
range from 25 to 51 MU and of the EPDM samples between 46 and 80
MU, corresponding to mass average molar masses Mw between 150 and
175 kg/mol and between 200 and 300 kg/mol, respectively. The EPDM
samples contain about 1 mol% of ENB, except for the sample EPDM-
M57-N2.7 with the lowest ethylene content (56.8 mol%), which con­
tains 2.7 mol% of ENB, and the sample EPDM-V73-D0.3 with 73.2 mol%
ethylene, which contains 0.3 mol% DCPD.
Solution NMR spectra were recorded with a Bruker Avance III 400
spectrometer equipped with a 5 mm high-temperature cryoprobe. The
samples (~25 mg) are dissolved at 120 ◦ C in 1,2-dichlorobenzene-d4
(0.6 mL) with 0.40 mg mL− 1 of BHT stabilizer. Operating conditions for
1
H NMR spectroscopy are: 90◦ pulse; acquisition time, 2.7 s; relaxation
delay, 10.0 s; 1 to 16 transients. Operating conditions for 13C NMR
spectroscopy are: 45◦ pulse; acquisition time, 2.7 s; relaxation delay, 5 s;
2000 transients. Broad-band 1H decoupling was achieved with a modi­
fied WALTZ16 sequence (BI_WALTZ16_32 by Bruker). ENB or DCPD
contents have been determined by 1H NMR spectroscopy. Average
ethylene and propylene contents, and the ethylene sequence lenghts
have been determined by 13C NMR spectroscopy using the method
described in Ref. 56. The 13C NMR resonances have been assigned ac­
cording to Refs. [57, 58].
Films with a uniform thickness of approximatively 0.5 mm and
smooth surfaces were prepared by compression molding in a hydraulic
press by heating the samples, sandwiched between flat Teflon plates, at
temperatures of ≈30–40 ◦ C higher than the melting temperature (i.e.
100-150 ◦ C) for the crystalline samples, 100 ◦ C for the amorphous
samples, while applying only a small pressure (<1 bar) in order to not
induce any preferred chain orientation, according to the ASTM D-2292-
85 standard. After 5 min isotherm at 100–150 ◦ C, the films were slowly
cooled to 25 ◦ C at average rate of ≈15 ◦ C/min. All subsequent analyses
were performed on these films.
Melting thermograms were recorded with a differential scanning
calorimeter (DSC-1) by Mettler Toledo under a N2 atmosphere with a
scanning rate of 10 ◦ C/min. The degree of crystallinity xc(DSC) was
evaluated as xc(DSC) = 100 ΔHm/ΔH0m, with ΔHm the melting enthalpy
of the sample and ΔH0m = 293 J/g the thermodynamic melting enthalpy
of a 100% crystalline polyethylene (PE) [59].
Wide angle X-ray diffraction (WAXS) profiles were recorded with an
Empyrean diffractometer (Malvern Panalytical) using Ni-filtered CuKα
radiation (λ = 0.15418 nm). The degree of crystallinity xc(WAXS) was
evaluated from the area subtending the WAXS profiles of the sample (As)
and of the amorphous phase (Aa) as xc(WAXS) = 100 (As-Aa)/As. The
amorphous contribution was approximated by the diffraction profile of
the melt (at 120 ◦ C) after suitable scaling and translation along the x-
axis, up to make the position of the maximum coincident with the
maximum of the amorphous phase at 25 ◦ C.
Bidimensional (2D) WAXS patterns (Ni-filtered CuKα radiation) were
recorded on fibers obtained by stretching compression-molded films at
different degree of deformations, while keeping the sample in tension.
The 2D-WAXS images were recorded in a cylindrical camera (radius
57.30 mm) on BAS-MS imaging plates (FUJIFILM) and digitalized with a
reader PerkinElmer Cyclone Plus (storage phosphor system). Radial
profiles were extracted from the 2D WAXS images with the help of the
Fit2D and ImageJ softwares.
Mechanical tests were performed at room temperature by stretching
rectangular specimens having width, length and thickness equal to 5,
100 and 0.5 mm, respectively, cut from the compression molded films,
using an Instron 5566H1543 mechanical tester, following the ASTM
D882-83 standard. The deformation rate (v) was set at 10 and 0.1 times
the initial gauge length L0 (that is v = L0 10 and L0 0.1 mm min− 1,
respectively) for the determination of the tensile properties up to
breaking and of the Young modulus, respectively.
The recovered strain after breaking (elastic recovery) was measured,
according to the ASTM D412-87 standard, on compression molded
specimens stretched up to breaking (final deformation εb = 100(Lb-L0)/
L0, with Lb the final length achieved at break and L0 the initial gauge
length). Ten minutes after breaking, the lengths of the fully relaxed
specimens Lr were measured by moving the two broken pieces close to
each other till to fit them along the fracture line. The percentage of
recovered strain after breaking is calculated as R = 100(Lb-Lr)/(Lb-L0).
The values of L0, Lb and Lr were determined from the distances between
two marks, drawn on the samples with a pencil having a smooth tip, in
the transverse direction to the gauge length. The reported stress strain
curves and the values of the mechanical parameters are the result of the
average of a minimum of five independent reproducible experiments.
3. Results and discussion
Solution 13C NMR spectroscopy. All samples of EP(D)M copolymers
have been analyzed by 13C NMR spectroscopy to evaluate the chain
microstructure in terms of composition, comonomers distribution, and

3
F. Auriemma et al.
lengths of ethylene sequences. 13CNMR spectra of representative sam­
ples are reported in the Supporting Information (Fig. S1). The statistical
analysis of comonomers distribution has been performed using a five-
parameter model, considering all samples as terpolymers constituted
by three monomers (viz. ethylene, primary 1,2-propylene and secondary
2,1-propylene units), following the procedure of Ref. 56. Furthermore,
in the statistical analysis, the contribution of the diene has been
neglected in a first approximation, since its content is by far much lower
than that of the other comonomers and the available fifteen independent
experimental data are not sufficient to handle a more complex statistical
model. Therefore, the statistical analysis has been performed only for
the EP(D)M copolymers with diene contents below or around 1 mol%.
The mole fraction of ethylene units sequences of length n (p(E ≥ n))
with respect to ethylene sequences of all lengths has been calculated
according to the following general equation:
p(E≥n) = E pn11 + P pn−11 1 p21 + P* pn−11 1 p31
where pij are the conditional probabilities of insertion of a monomer j
after a monomer i, (with 1 = ethylene, 2 = 1,2-propylene, 3 = 2,1-
propylene), and E, P, P* are the mole fractions of ethylene, 1,2-propyl­
ene and 2,1-propylene, respectively.
The conditional probabilities pij have been determined by best-fit
calculations on sequence distribution, determined by 13C NMR
spectra, according to the method reported in ref. 56. In all cases the
statistical analysis ended up with a χ2r close to 1, proving the goodness of
fit testing. The conditional probabilities values for all samples are re­
ported in Table S1 of the Supplementary Data file, while the relevant
microstructural characterization results are summarized in Table 2.
From the conditional probabilities values the apparent reactivity
ratios product “rE rP” reported in Table 2 have been calculated by Eq. (2),
including in rp the presence of both 1,2 and 2,1-propylene units [56]:
˝rE rP ˝ =p11 [NP (p22 +p23 )+NP∗ (p32 +p33 )]/[(p12 +p13 )+(NP p21 +NP∗ p31 )]
In Eq. (2), NP and NP* are given by Eqs. (3) and (4) as it follows:
NP = K(p32 p12 + p32 p13 + p31 p12 )
NP∗ = K(p13 p23 + p13 p21 + p12 p23 )
where K is an arbitrary proportionality constant.
It should be recalled that, since the V-based Ziegler-Natta catalysts
are considered multi-site systems [23–29], the values of the apparent
reactivity ratios product (“rE rP”) are average values over different cat­
alytic species producing macromolecules with different composition.
In all cases, the “rE rP” values are lower than 1.0, indicating the
tendency to alternation (Table 2). However, the EP(D)M-M samples
exhibit slightly higher apparent reactivity ratios product values
(0.66–0.69) compared with EP(D)M− V copolymers (0.45–0.60), prob­
ably reflecting the major propensity of the adopted (post-)metallocene
catalysts towards the incorporation of consecutive ethylene units rather
than the formation of hetero-sequences with respect to the V-based
counterparts [23].
In all EP(D)M− V samples from V-based catalyst about 20 mol% of
the total propylene content consists of 2,1-propylene units P*, whereas
in EPDM-M samples from (post-)metallocene catalyst the P* content is
“only” about 2–3 mol% (Table 2). This difference may have relevant
effects on the microstructure of the chains, since the presence of P* units
is known to favor ethylene insertion (p31 > p33 and p32 for all samples in
Table S1). Contrary to (post-)metallocene catalyst systems, for V-based
systems, after an ethylene insertion, the propylene insertion can be both
1,2 and 2,1 (p12 and p13 > 0 in Table S1) [60]. As a result, the presence of
a high fraction of secondary 2,1 propylene units in EP(D)M− V samples
produces sequences of 2,1 propylene units followed by ethylene and
both primary 1,2- or secondary 2,1-propylene units [60–63], which are
absent in EPDM-M.
Polymer 227 (2021) 123848
It is worth noting that the results of solution 13C NMR analysis of
Table 2 are in agreement with literature data, indicating that in the
copolymerization of propylene with ethylene the conventional V-based
catalyts [60–63] and the less-conventional (“constrained geometry”)
(post-)metallocene catalysts [64] are both non regiospecific, even
though for the copolymers synthesized with the latter systems the con­
centration of regiodefects (viz. 2,1 propylene units, P*) is lower.
Furthermore, both classes of catalysts systems are poorly stereospecific
[60–64].
For EP(D)M samples with ethylene content in the range 73–83 mol%,
the average length of ethylene sequences LM1 determined using a first
order Markov statistics of comonomer addition [57] is comprised in the
range 3–6 (Table 2). The so obtained values of LM1 are slightly smaller
than those calculated using a Bernoulli type statistics LBe as the inverse
of the sum of the contents of propylene (P) and diene (D) units (LBe =
100/(P + D)), in agreement with the tendency to alternation denoted by
(1)
the values of the apparent reactivity ratios product smaller than 1.0.
Using both statistics, no great differences have been found in the values
of the average length of ethylene sequences for the samples EP(D)M− V
and EP(D)M-M having similar ethylene concentration of 78–80 mol%
(LM1 = 4.2–4.5 and LBe = 4.5–4.6 for the samples EPDM-V78-E0.4,
EPDM-M78-N1.2 and EPDM-M78-N1.3 in Table 2), which confirms
the fact that the differences between V-based and (post-)metallocene
samples are more related to the effective sequence distribution of
comonomeric units.
Thermal and structural analysis. The WAXS profiles of the
compression molded films and the corresponding DSC thermograms
recorded starting from 25 ◦ C are shown in Fig. 1.
The WAXS profiles of the EP(D)M samples of Fig. 1A are typical of
such polymers. The diffraction peak at 2θ ≈ 21◦ corresponds to the
(110)o and/or (100)h reflections of the orthorhombic or pseudohex­
agonal forms of PE, respectively (curve a in Fig. 1A) [16,40,45].1 Only
for the sample EPM-V83 with 83 mol% ethylene, this reflection appears
(2) as a sharp peak at 2θ ≈ 21◦ , overlaying the amorphous halo (curve a in
Fig. 1A) [16]. With a decrease of the ethylene content, the (110)o/(100)h
reflection is hardly distinguishable, as it appears as a faint shoulder (at
(3) 2θ ≈ 21◦ ) of the amorphous halo in the WAXS profiles of the samples
with ethylene contents in the range 80 to 73 mol% (curves b and d to i in
(4) Fig. 1A). It is completely absent for the samples with ethylene contents
in the range 57–62 mol%, for which only an amorphous halo is apparent
(curves c, j and k in Fig. 1A).
The presence of crystals is better revealed in the DSC thermograms
shown in Fig. 1B. The samples with ethylene contents in the range
73–83 mol% show broad melting peaks at temperatures in the range
40–50 ◦ C. The peak areas tend to decrease with a decrease of the
ethylene content (curves a, b and d to i in Fig. 1B). The absence of
endothermic peaks in the DSC thermograms of the samples with
ethylene contents in the range 57–62 mol% confirms that the samples
are amorphous (curves c, j and k in Fig. 1B). Therefore, for the EP(D)M
samples with ethylene content in the range 83 to 77 mol%, whereas the
Bragg peak at 2θ ≈ 21◦ in the WAXS profiles becomes increasingly
weaker and broader with decreasing the ethylene content, up to become
barely detectable, the corresponding melting endotherms remain better
defined. The decrease of the intensity and the increase of the width of
the Bragg reflections with decreasing ethylene content are due to the
easy inclusion of the propylene methyl groups in the unit cells of the
orthorhombic and/or pseudo-hexagonal forms of PE on the one hand
and to the decrease of the crystallizable ethylene sequence fractions on
1
The crystallization of the pseudo-hexagonal form in EP(D)M rubbers is
driven by the easy inclusion of propylene units in the orthorhombic unit cell of
PE. In fact, as the concentration of propylene units increases, the size of the a-
axis of the orthorhombic unit cell of PE increases, while the size of the b- and c-
axes remains almost constant. The pseudo-hexagonal form corresponds to a
length of the a-axis approaching the value of 31 ⁄ 2 times the b-axis.
4
F. Auriemma et al. Polymer 227 (2021) 123848

Table 2
Mole percent of ethylene (E), 1,2-propylene (P), diene (D) comonomeric units and mole percent of 2,1-propylene units (P*) relative to the total propylene content,
apparent reactivity ratios product (“rE rP”), mole fractions of ethylene sequences of length n (p(E ≥ n)) relative to sequences of ethylene units of all lengths, and average
length of consecutive ethylene sequences (LM1 and LBe) for EP(D)M copolymers.a
Sample E (mol%) P (mol%) Diene (mol%) P* (%)b “rE rP” p(E ≥ 6) p(E ≥ 7) p(E ≥ 8) p(E ≥ 9) p(E ≥ 10) p(E ≥ 11) p(E ≥ 12) p(E ≥ 13) p(E ≥ 14) p(E ≥ 15) LM1c LdBe

EPM-V83 83.5 16.5 18 0.60 0.32 0.26 0.22 0.18 0.15 0.12 0.10 0.08 0.07 0.06 5.7 6.1
EPM-V80 79.7 20.3 20 0.45 0.22 0.17 0.13 0.10 0.08 0.06 0.05 0.04 0.03 0.02 4.5 4.9
EPM-V58 58.8 41.5 24 0.47 0.02 0.01 <0.01 <0.01 <0.01 <0.01 0.00 0.00 0.00 0.00 2.0 2.4
EPDM-V80-N1.2 80.0 18.8 1.2 22 0.46 0.25 0.20 0.16 0.12 0.10 0.08 0.06 0.05 0.04 0.03 4.8 5.0
EPDM-V78-N0.4 78.3 21.3 0.4 22 0.45 0.20 0.15 0.12 0.09 0.07 0.05 0.04 0.03 0.02 0.02 4.2 4.6
EPDM-M78- 77.9 20.8 1.2 3 0.66 0.22 0.17 0.13 0.10 0.08 0.06 0.05 0.04 0.03 0.02 4.5 4.5
N1.2
EPDM-M78- 77.7 21.0 1.3 2 0.69 0.22 0.17 0.13 0.10 0.08 0.06 0.05 0.04 0.03 0.02 4.4 4.5
N1.3
EPDM-Q74-N0.8 74.3 25.0 0.8 20 0.58 0.15 0.11 0.08 0.06 0.04 0.03 0.02 0.02 0.01 <0.01 3.6 3.9
EPDM-V73-D0.3 73.2 26.6 0.3 20 0.59 0.13 0.09 0.06 0.05 0.03 0.02 0.02 0.01 <0.01 <0.01 3.4 3.7
EPDM-V62-N1.2 62.4 36.3 1.2 21 0.46 0.04 0.02 0.01 <0.01 <0.01 <0.01 <0.01 <0.01 0.00 0.00 2.3 2.7
a
The calculations of “rE rP” and p(E ≥ n) values were performed only for EP(D)M copolymers with diene contents below or around 1 mol%.
b
Relative value calculated with respect to propylene units only.
c
Calculated using a first-order Markov statistics of comonomer addition.d)Calculated as LBe = 100/(P + Diene).

the other hand [13]. This leads to an increase of the structural disorder
in the crystals, to a decrease of the crystal size and to the consequent loss
of the long-range order in the chain conformation and packing [12–15,
22].
The glass transition temperatures of the EP(D)M samples (deter­
mined from independent DSC scans recorded starting from − 100 ◦ C) are
in between − 35 ◦ C for the sample EPM-V83 and -59 ◦ C for the sample
EPDM-V62-N1.2 (Table 3). The main melting peaks of the EP(D)M
samples occur in the temperature range from 40 to 44 ◦ C regardless of
ethylene content, except for the EPM sample with the highest ethylene
content EPM-V83 (83.5 mol% ethylene) which shows a main endotherm
at approximately 50 ◦ C and a small endotherm at around 112 ◦ C, the
latter due to the presence of a small fraction of PE crystals formed by
long ethylene sequences (Table 3). It is worth noting that the melting
temperature of V-based EP(D)M samples with ethylene content of 78–80
mol% of about 41 ◦ C, is lower than that of the samples EPDM-M78-N1.2
and EPDM-M78-N1.3 of similar ethylene content, synthesized with
(post-)metallocene catalysts that melt at about 44 ◦ C (Table 3). These
differences may be due to the lower tendency of the (post-)metallocene
catalysts toward alternation and/or to the lower concentration of
regiomistakes (viz. 2,1-propylene units P*) in the resultant copolymers
(Table 2).

Fig. 1. WAXS profiles (A) and DSC thermograms (B) of compression-molded EP(D)M samples. In A, the (110)o and/or (100)h reflection of the orthorhombic or
pseudo-hexagonal forms of PE, at 2θ ≈ 21◦ , respectively, is indicated with arrows, whereas the narrow diffraction peaks at 2θ ≈ 6, 9, 12, 19, 25, 28 and 31◦ observed
for several samples (curves b, and d to i) and indicated by an asterisk for EPM-V80 (curve b) are due to talc added to the samples to prevent sticking. The dashed lines
in B indicate the baselines adopted for the calculation of the melting enthalpies, drawn by extrapolating the high-temperature DSC tails.

5
F. Auriemma et al. Polymer 227 (2021) 123848

It is worth noting that the effect of regio- (and stereo)irregularities of
propylene insertion on the crystallization behavior of ethylene/propyl­
ene copolymers has been investigated in Ref. [65]. It has been shown
that the presence of both regio- and stereoirregular propylene counits
induces disturbance on crystallization, but regioirregularities of pro­
pylene insertion induce higher disturbance than stereoirregularities. As
the analyzed EP(D)M copolymers are both stereo- and regioirregular,
the differences in the crystallization behavior are small. Therefore, the
slightly higher melting temperature of the samples EPDM-M78-N1.2 and
EPDM-M78-N1.3 of similar ethylene content, synthesized with (post-)
metallocene catalysts, than the melting temperature of the V-based co­
polymers EPDM-V80-N1.2, EPDM-V78-N0.4, with 80 and 78 mol%
ethylene content, respectively, should be ascribed not only to the
different concentration of 2,1 counits (P*), but also to the small differ­
ences in the co-monomer sequence distribution, associated with the
lower tendency of the (post-)metallocene catalysts toward propagation
of alternating ethylene/propylene sequences. The occurrence of these
small microstructural differences probably accounts also for the fact that
the melting endotherms of the samples EPDM-M (curves f and g of
Fig. 2B) appear slightly narrower than those of the EPDM-V systems
(curves d and e of Fig. 2B).
The values of the crystallinity index extracted from WAXS data
(xc(WAXS)) and DSC analysis (xc(DSC)) (Table 3) are reported in Fig. 2
as a function of the ethylene content (A) and of the mole fraction of
ethylene sequences of length 7 (p(E ≥ 7)) relative to the ethylene se­
quences of all lengths (B). The parameter p(E ≥ 7) is selected based on the
consideration that the minimum length of crystallizable ethylene se­
quences in ethylene/α-olefin copolymers is reported to correspond to a
number of consecutive ethylene units in the range 4–18 [49,66–70]. It is
apparent that the values of xc(WAXS) and xc(DSC) increase with
increasing ethylene content (Fig. 2A) and the mole fraction of ethylene
sequences of length 7 (p(E ≥ 7)) relative to the ethylene sequences of all
lengths (Fig. 2B). However, the plot of Fig. 2B allows highlighting the
effect of the presence of diene units because it shows that the values of
xc(WAXS) and xc(DSC) of EPM copolymers are larger than those of the
corresponding EPDM samples with identical p(E ≥ 7) values. This in­
dicates that even a small amount of diene co-units may induce a large
disturbance in the crystallization properties of EPDMs.
To an indepth insight, the distribution function of ethytlene sequence
lengths in the samples EPDM-V80-N1.2, EPDM-V78-N0.4, EPDM-M78-
N1.2 and EPDM-M78-N1.3 are compared in Fig. S2. It is apparent that
the samples EPDM-M78-N1.2 and EPDM-M78-N1.3 with 78 mol%
ethylene content and synthesized with (post-)metallocene catalysts
show nearly coincident distribution functions of ethylene sequence
lengths that are intermediate between those of the samples EPDM-V78-
N0.4, with identical ethylene content, and EPDM-V80-N1.2, with 80 mol
% ethylene content, both synthesized with V-based catalysts. The length
weighed fractions of ethylene sequences of length higher than 7 (cor­
responding to the integrated area of the distribution function of ethyt­
lene sequence lengths for sequence lengths higher than or equal to 7) are
51% for the sample EPDM-V80-N1.2, 43% for the sample EPDM-V78-
N0.4 and 48–49% for the samples EPDM-M78-N1.2 and EPDM-M78-
N1.3. These small differences reflect only in part the small differences
in the values of the crystallinity index xc(WAXS) equal to 10, 8, 8 and
8%, respectively, indicating that for regio- and stereoirregular random
EPDM copolymers, the leading parameter controlling the crystallinity
index achieved by melt-crystallization is the ethylene content.
Tensile properties. The results of the tensile testing of the EP(D)M
samples are shown in Fig. 3. The corresponding values of the Young
modulus, strain at break and stress at break are reported in Fig. 4 and
Table S2.
All the samples show uniform deformation up to breaking. The EP(D)
M samples with ethylene contents larger than 62 mol% show diffuse
yielding and strain at break larger than ≈1000% (Fig. 3A and B). The
samples with ethylene contents larger than 73 mol% show remarkable
strain hardening (Fig. 3A and B). The amorphous and sticky samples
with ethylene contents smaller than or equal to 62 mol% show no
yielding, no strain hardening and strain at break smaller than 200%
(Fig. 3C).
The mechanical parameters extracted from Fig. 3 are reported in
Fig. 4 as a function of the ethylene content and the mole fraction of
ethylene sequences of length 7 (p(E ≥ 7)) relative to the ethylene se­
quences of all lengths. It is apparent that the values of the Young
modulus (Fig. 4A and A′ ) increase and the values of strain at yield
decrease (Fig. 4D and D’) with increasing both ethylene content and the
fraction p(E ≥ 7), according to single trends regardless of the catalyst
system used for the preparation of the samples. This indicates that these
properties are not sensitive to the details of the chain microstructure for
the analyzed EP(D)M systems but are only dependent on the ethylene
content.
It is also apparent that with increasing of the ethylene content and of
the p(E ≥ 7) fraction, the values of the strain at break (Fig. 4B and B′ )
increase for the EPM copolymers, whereas for the EPDM copolymers
they first increase and then they decrease. The values of the stress at
break, instead (Fig. 4C and C′ ), increase monotonically with increasing
the ethylene content and the fraction p(E ≥ 7) for both EPM and EPDM
copolymers, following two distinct trends. In particular, for identical
values of ethylene content and p(E ≥ 7) values, the values of stress at

Table 3
Ethylene content (E), glass transition temperatures (Tg), melting temperature (Tm) and enthalpy (ΔHm) and crystallinity indices determined from
WAXS profiles (xc(WAXS)) and DSC thermograms (xc(DSC)) of compression molded samples of EP(D)M copolymers, corresponding increment of crystallinity achieved
by stretching at maximum deformation (Δxcs) and residual crystallinity achieved after releasing the tension (Δxcr) evaluated from X-ray fiber diffraction
patterns of EP(D)M samples (Fig. 5).
Sample E (mol%) xc(WAXS) (%) Tg (◦ C)a Tm (◦ C) ΔHm (J/g) xc(DSC)b (%) Δxcs (%) Δxcr (%)

EPM-V83 83.5 16 − 35 50.2; 112c − 43 14 13 10

EPM-V80 79.7 10 − 46 41.2 − 19 6 16 10
EPM-V58 58.5 – − 53 – – – – –
EPDM-V80-N1.2 80.0 10 − 40 41.5 − 20 7 17 6
EPDM-V78-N0.4 78.3 8 − 45 40.4 − 12 4 15 5
EPDM-M78-N1.2 77.9 8 − 40 43.9 − 13 4 16 5
EPDM-M78-N1.3 77.7 8 − 40 43.7 − 13 4 16 4
EPDM-Q74-N0.8 74.3 5 − 46 40.1 − 3 1 12 3
EPDM-V73-D0.3 73.2 3 − 50 41.6 − 2 1 10 1
EPDM-V62-N1.2d 62.4 – − 59 – – – – –
EPDM-M57-N2.7d 56.8 – − 43 – – – – –
a)
Determined from independent DSC scans recorded starting from − 100 ◦ C.
b)
Calculated as xc(DSC) = 100 ΔHm/ΔH0m, with ΔHm the melting enthalpy of the sample and ΔH0m = 293 J/g the thermodynamic melting enthalpy of a 100%
crystalline polyethylene (PE) [59].
c)
The main endothermic peak is accompanied by a small endotherm at 112 ◦ C, due to melting of very long ethylene sequences in thicker PE crystals.
d)
The samples EPM-V58, EPDM-V62-N1.2 and EPDM-M57-N2.7 are amorphous, so that there exist no crystallinity data.

6
F. Auriemma et al.
Fig. 2. Crystallinity indices determined from WAXS profiles (xc(WAXS)) and DSC thermograms (xc(DSC)) of EP(D)M samples as a function of the ethylene content
(A) and the mole fraction of ethylene sequences of length 7 (p(E ≥ 7)) relative to the ethylene sequences of all lengths (B).
Fig. 3. Stress-strain curves of EP(D)M samples. Dots mark the approximate
beginning of strain hardening. A: EP(D)M samples with high ethylene contents,
strong strain hardening and high stress at break; B: EP(D)M samples with in­
termediate ethylene contents, some strain hardening and intermediate stress at
break; C: EP(D)M samples with low ethylene contents without any strain
hardening and low stress at break.
break of EPM copolymers are smaller than those of EPDM terpolymers.
For EP(D)M samples with ethylene content larger than 70 mol%
(Fig. 4C) and p(E ≥ 7) values larger than 0.09–0.1 (Fig. 4C’), the increase
of the stress at break with ethylene content reflects the increase of initial
crystallinity of the samples (Fig. 2), but the different values of stress at
7
Polymer 227 (2021) 123848
break is somehow related to the fact that samples with ethylene content
larger than 73 mol% display remarkable strain hardening the amount of
which is different depending on the occurrence of further crystallization
during deformation (vide infra). The low values of the stresses and
strains at break of the amorphous samples are due to the absence of any
crystallinity. This indicates that in absence of crystals acting as the
physical cross-links of the amorphous network and as efficient stress
transmitters, the entanglement density is not sufficiently high to prevent
the viscous flow of the chains and/or the breaking already at low de­
formations (Fig. 4B, B′ , C and C’).
The values of the stress at yield of the EPM and EPDM samples tend
to increase according to a single trend with increasing the ethylene
content (Fig. 4E) and according to two different trends with increasing
the values of the fraction p(E ≥ 7) (Fig. 4E’). In particular, it is apparent
that for identical values of p(E ≥ 7), the values of the yield stress of the
EPM copolymers are larger than those of EPDM samples. This indicates
that the presence of about 1 mol% of diene co-units induces a small but
significant decrease of the stress at yield, even though the values of
strain at yield of the samples are identical (Fig. 4D’). The values of the
ultimate tensile strength of EPDM samples, instead, are larger than those
of EPM copolymers (Fig. 4C,C’), due to occurrence of strong strain
hardening, which is related to the possible occurrence of further crys­
tallization during deformation (vide infra).
Finally, the percentage of recovered strain after breaking R (Fig. 4F
and F’) are in all cases larger than 70%. In particular, the crystalline
EPDM copolymers with ethylene content from 75 to 80 mol% and values
of the fraction p(E ≥ 7) larger than 0.09–0.1 show the best elastic per­
formances with R values larger than 90%. The remarkable elastic per­
formances of the crystalline un-crosslinked EP(D)M copolymers suggest
that the initial crystals present in the undeformed samples play a key
role. Indeed, not only they act as efficient physical knots of the elasto­
meric network, preventing the viscous flow of the chains during defor­
mation, but they may also play a role, after fragmentation, as nuclei in
triggering further crystallization of the samples during deformation
(vide infra) [16].
In the next section, it is shown that the amount of the new crystals
that are formed by stretching at deformations close to the break, that is
up to reach the maximum increment of crystallinity, depends on the
initial level of crystallinity in the undeformed state.
Fiber diffraction analysis and strain-induced crystallization. The X-
ray fiber diffraction patterns and the corresponding radial profiles of
selected EP(D)M samples are presented in Fig. 5. For the sake of
simplicity, and without loss of generality, only the patterns recorded for
the undeformed samples and for specimens stretched up to a
F. Auriemma et al. Polymer 227 (2021) 123848

Fig. 4. Tensile properties of EP(D)M samples as a function of the ethylene content (A to F) and the mole fraction of ethylene sequences of length 7 (p(E ≥ 7)) relative to
the ethylene sequences of all lengths (A′ to F′ ). Young modulus (A and A′ ), strain (B and B′ ) and stress (C and C′ ) at break, strain (D and D′ ) and stress (E and E′ ) at
yield, and elastic recovery (F and F′ ).

deformation close to breaking, and after the release of the tension are
reported in Fig. 5. It is worth noting that the maximum deformation
achieved before breaking is higher than or equal to 0.95 εb, for all the
samples. It has been checked that, at these deformations, the samples
have well-reached the maximum increment of crystallinity by effect of
strain. Indeed, the maximum increment of crystallinity is already
reached at much lower deformations, close to 0.4–0.5 times the defor­
mation at break (data not shown).
As already visualized in the X-ray powder diffraction profiles of
Fig. 1A, the radial WAXS profiles of the undeformed samples show only
amorphous halos centered at 2θ ≈ 19◦ (Fig. 5D’, G′ and J′ ). Only the
diffraction patterns of the sample EPM-V83 with the highest ethylene
content shows the presence of a sharp peak at 2θ ≈ 21◦ , corresponding to
the (110)o/(100)h reflection of the orthorhombic/pseudo-hexagonal
forms of PE (Fig. 5A,A’). At high deformations, the samples achieve
high degrees of orientation, with the chain axes parallel to the stretching
direction, as indicated by the polarization of the reflection at 2θ ≈ 21◦ on
the equator (Fig. 5B, E, H and K). As shown in Ref. [16], a high degree of
orientation is achieved by the chains belonging not only to the crystals,
but also to the amorphous phase, already at low deformations.
In particular, in the radial WAXS profiles of the samples stretched at
high deformations, the (110)o/(100)h reflection appears well-

8
F. Auriemma et al.
Fig. 5. X-ray fiber diffraction patterns (A to L) and corresponding radial profiles (A′ to L′ ) of the samples EPM-V83 (A to C and A′ to C′ ), EPDM-V78-N0.4 (D to F and
D′ to F′ ), EPDM-M78-N1.2 (G to I and G′ to I′ ) and EPDM-V73-D0.3 (J to L and J′ to L′ ). The radial profiles are corrected for the background contributions,
approximated by straight lines.
pronounced for the sample EPM-V83 (Fig. 5B’), less intense, but as a still
distinguishable reflection overlaying the amorphous halo for the sam­
ples EPDM-V78-N0.4 (Fig. 5E’) and EPDM-M78-N1.2 (Fig. 5H’), and is
completely concealed by the amorphous halo for the sample EPDM-V73-
D0.3 (Fig. 5K’). Indeed, for the latter sample, the (110)o/(100)h reflec­
tion appears distinguishable only in the two-dimensional WAXS image
(Fig. 5K) and in the corresponding equatorial profile (Fig. S3).
Upon release of the tension, the samples recover their initial di­
mensions almost completely (Fig. 4F and F’), while the high degree of
orientation achieved in the stretched states by the chains in the amor­
phous [16] and crystalline phases is lost at least in part (Fig. 5C, F, I and
L). The structural and textural changes observed for the samples shown
in Fig. 5 is common to all the EP(D)M samples of Table 1 with ethylene
contents larger than or equal to 73 mol%. The samples with ethylene
contents smaller than or equal to 62 mol%, instead, remain amorphous
even upon stretching.
The EP(D)M samples show small tendencies to crystallize upon
stretching.16 In particular, it was shown that for samples with ethylene
contents larger than or equal to 78 mol% the crystallinity starts to in­
crease already at low deformations by effect of stretching [16]. For less
crystalline samples (ethylene content ≈ 73 mol%), the onset of further
crystallization occurs at strains higher than 170%. In both cases, the
crystallinity increment tends to level off at deformations of 100–300%
[16]. Using the fiber diffraction patterns of EP(D)M samples stretched at
deformations close to the break, the maximum increment of crystallinity
achieved upon stretching Δxcs may be extracted by comparing the radial
WAXS profiles of the highly stretched samples Ps (e.g. Fig. 5B’,E′ , H′ and
K′ ) with the corresponding radial WAXS profiles of the unstretched
samples Pu (e.g. Fig. 5A’,D′ , G′ and J’), as shown in Fig. S4. In practice,
after subtraction for the background contribution, the values of Δxcs are
calculated as Δxcs = 100 (APs–APu) A−Ps1, where APs and APu are the areas
subtending the radial WAXS profiles of the stretched and unstretched
9
Polymer 227 (2021) 123848
samples, respectively (Fig. S4).
As mentioned above, upon releasing the tension the high degree of
orientation achieved by stretching is only partially lost (Fig. 5C, F, I and
L). Moreover, the patterns of Fig. 5C, F, I and L seem to indicate that
partial melting of the new oriented crystals formed by stretching also
occurs after releasing the tension [16]. The residual incremental degrees
of crystallinity after releasing the tension, with respect to the unde­
formed samples, have been also calculated as Δxcr = 100(APr–APu)A−Pr1,
where APr is the area subtending the radial WAXS profile of the relaxed
samples Pr. The so calculated values are reported in Table 3 and in Fig. 6
as a function of the ethylene content and the mole fraction of ethylene
sequences of length 7 (p(E ≥ 7)) relative to the ethylene sequences of all
lengths. The values of total crystallinity index, achieved by stretching at
high deformation and after releasing the tension, are also reported. This
parameter is calculated as the product xc(WAXS) (1+ Δxcs/100) and
xc(WAXS) (1+ Δxcr/100) for the stretched and relaxed samples,
respectively.
It is apparent that the increment of crystallinity achieved by the EP
(D)M samples upon stretching increases with increasing the ethylene
content and the p(E ≥ 7) fraction up to reach a maximum around 80 mol%
and 0.20, respectively, then decreases for the sample EPM-83 with 83.5
mol% ethylene content (Fig. 6A and B). Upon release of the tension, the
samples show a residual incremental crystallinity, which is lower than
that achieved upon stretching. Furthermore, whereas the residual in­
cremental crystallinity of EPDM samples increases with the increase of
the ethylene content and the p(E ≥ 7) fraction, it is constant for the EPM
samples. In particular the EPM copolymers show a residual incremental
crystallinity higher than that of EPDM samples (Fig. 6A and B). This is in
agreement with the smaller values of elastic recovery shown by the EPM
samples compared with those of the EPDM samples (Fig. 4F and F’).
It is worth recalling that from a thermodynamical standpoint, the
decrease of conformational entropy of the amorphous chains induced by
F. Auriemma et al.
Fig. 6. Increment of crystallinity (A and B) and crystallinity index (C and D) obtained by stretching the EP(D)M samples at deformation close to breaking (Δxcs, full
symbols) and after the release of the tension (Δxcr, open symbols) as a function of ethylene content (A and C) and of the mole fraction of the ethylene sequences of
length 7 (p(E ≥ 7)) relative to the ethylene sequences of all lengths (B and D).
stretching induces, in turn, a decrease of the values of the melting en­
tropy ΔSm. As a consequence, since the crystallization takes place at
temperatures T for which TΔSm is lower than the melting enthalpy ΔHm,
the strain induced crystallization occurs at higher temperatures than in
the unstretched state [52]. However, the so formed crystals are stable at
room temperature only as long as the samples are kept in tension. By
releasing the tension, the high degree of orientation of the amorphous
chains is lost, inducing a neat increase of the ΔSm value, and a conse­
quent melting of the newly formed crystals.
On the other hand, the fact that the loss of crystallinity that occurs by
releasing the tension is only partial suggests that the new crystals that
form by stretching at room temperature are characterized by different
degrees of stability. It may be inferred that a portion of the crystals that
survive even in absence of the tension are those affected by a major
degree of perfection. The crystallization of these crystals does not occur
spontaneously for kinetic reasons, but it is accelerated by a decrease of
kinetic energy barriers caused by the application of the tensile stress
field. A portion of the surviving crystals may consist also of crystals that
remain entrapped in the entangled elastomeric network, even if they are
affected by only a minor stabilty. The portion of crystals that melt in
absence of the tension are instead those which are less stable, being
characterized by a small size and/or a high degree of structural disorder.
The values of total crystallinities of EPM and EPDM samples achieved
upon stretching and successive release of the tension increase according
to a single trend with increasing ethylene content (Fig. 6C) and
10
Polymer 227 (2021) 123848
according to two separate trends with increasing the fraction p(E ≥ 7)
(Fig. 6D). In particular, the total crystallinities achieved by the EPM
samples are higher than those achieved by the EPDM samples with
identical p(E ≥ 7) values (Fig. 6D), in agreement with the higher values of
the corresponding initial crystallinity xc(WAXS) (Fig. 2).
The tendency of EP(D)M samples with ethylene contents larger than
70 mol% to undergo incremental crystallization upon stretching is evi­
denced also by the increase of the fractional contribution to the total
equatorial intensities of the (110)o/(100)h reflection of the
orthorhombic/pseudo-hexagonal forms of PE (equatorial crystallinity
index) [16]. However, the values of the equatorial crystallinity indices,
as evaluated in literature [16], represent an upper limit, as they over­
estimate by a factor of 2–3 the effective values of Δxcs shown in Fig. 6.
Effect of the incremental crystallinity on the strain hardening
behavior of EP(D)M. A longstanding, controversial question in the
realm of polymer physics and rubber elasticity in particular, is the role of
SIC on the strain hardening behavior of amorphous entangled networks.
The strain induced formation of new chain-extended crystallites, well
oriented along the stretching direction at high deformations, is triggered
by the chain extension of the network strands, as a result of application
of uniaxial forces. On the one hand, according to the theory of rubber
elasticity, the formation of the new oriented crystals should necessarily
induce a relaxation of the connected amorphous segments, resulting, as
a consequence, in a decrease of the stress [52,71]. On the other hand, the
newly formed crystals should also produce an increase of the cross-link
F. Auriemma et al.
density and a consequent reinforcement effect especially at high defor­
mation, i.e. strain hardening [51,72–74]. Even though strain hardening
may be well-explained just on the basis of the limited extensibility of the
entangled polymer network without the occurrence of SIC [75,76], a
role of the crystals should not be discarded a priori.
The EP(D)M samples of our study, that undergo incremental crys­
tallinity by stretching, are not chemically crosslinked and are not
amorphous. They show small but significant levels of crystallinity
already in the unstretched states and tendency to increment the crys­
tallinity level upon stretching (Figs. 1 and 6 and Tables 1 and 3). In
general, strain hardening may be considered as the result of the
concomitant reinforcement due to the high level of orientation achieved
by crystal fragments derived from pristine crystals in the unstrained
sample, the high orientation attained by the amorphous chain segments
and the consequent formation of new and well-oriented crystals.
Accordingly, three different types of mechanical behavior at high de­
formations may be distinguished in EP(D)M samples depending on the
ethylene content.
This is illustrated in Fig. 7, where the stress-strain curves of samples
showing different crystallinity in the undeformed state and different
increment of crystallinity upon stretching are compared. As an example,
the stress-strain curve of the most crystalline EPM-V83 sample, with
xc(WAXS) = 16%, which experiences a medium increment of crystal­
linity upon stretching, viz. Δxcs = 13%, is compared in Fig. 7A with the
stress-strain curve of the EPDM-V80-N1.2 sample, showing a smaller
degree of crystallinity in the undeformed state, xc(WAXS) = 10%, but
the highest incremental crystallinity value Δxcs = 17%, and in Fig. 7B
with the stress-strain curve of the sample EPDM-V73-D0.3, showing the
smallest initial crystallinity degree xc(WAXS) = 3%, and an incremental
crystallinity value Δxcs of 10%.
The samples EPM-V83 and EPDM-V80-N1.2 show values of initial
crystallinity xc(WAXS) of 16% and 10%, respectively and similar values
of stress at yield (1.8 vs. 1.1 MPa, Table S2) and deformation at break
(≈1600 vs. 1400%, Table S2). Moreover, the two samples show large
differences in modulus and stress at break. In particular, the Young
modulus of the sample EPM-V83 (11 MPa, Table S2) is larger than that
of the sample EPDM-V80-N1.2 (3.3 MPa, Table S2), whereas the value of
stress at break of the sample EPM-V83 (≈7 MPa, Table S2) is lower than
that of the sample EPDM-V80-N1.2 (12 MPa, Table S2).
The differences in Young moduli of these two samples are due to the
presence, in the undeformed state, of stable and well-ordered crystals in
the sample EPM-V83 and small, weak and highly disordered crystals in
the sample EPDM-V80-N1.2. The reversed difference in the values of
stress at break, instead, is essentially due to the higher strain hardening
experienced by the sample EPDM-V80-N1.2 compared with the sample
EPM-V83. Interestingly, also the value of incremental crystallinity
experienced by the sample EPDM-V80-N1.2 (Δxcs = 17%) is larger than
that of the sample EPM-V83 (Δxcs = 13%).
The stretching of the most crystalline samples EPM-V83 and EPDM-
V80-N1.2 produces, in the initial stages, lamellar breaking coupled with
mechanical melting/recrystallization phenomena and orientation of the
amorphous phase [16]. As already discussed above, the increment of
crystallinity in these samples starts already occurring at deformations
close to the yield point and, after a steep increase up to a deformation of
100%, gradually approaches a quasi-plateau value at deformations
higher than 100–200%. The increase of crystallinity at low deformations
stems from the high degree of orientation attained by the amorphous
chains and the presence of crystal fragments, which not only act as
physical links of the entangled network, but also as nuclei triggering
further crystallization [16].
Therefore, the data of Fig. 7A suggest that a first type of strain
hardening behavior may be envisaged in EP(D)M copolymers with
ethylene contents larger than 80 mol%, for which the presence of stable
and ordered crystals in the undeformed state is the hallmark that the
majority of regular ethylene sequences have already crystallized, so that,
the fraction of crystallizable sequences available for further
11
Polymer 227 (2021) 123848
Fig. 7. Comparison of the stress-strain curves of the samples EPM-V83 and
EPDM-V80-N1.2 (A), and EPM-V83 and EPDM-V73-D0.3 (B).
crystallization by stretching is expected to be modest. As a consequence,
also the increment of crystallinity induced by strain is expected to be not
too high. Indeed, for EP(D)M samples with ethylene contents larger than
80 mol%, which are initially characterized by the presence of large and
well-ordered crystals, such as the sample EPM-V83, the reinforcement
effects occurring at high deformations (strain hardening) is essentially
due to the high orientations attained by the amorphous chain segments
and is augmented by the high orientations achieved by the fragments
derived from the pristine crystals in the undeformed state rather than by
the newly formed oriented crystals. The crystal fragments originating
from the initial crystals, indeed, produce a high increment of the cross-
link density of the elastomeric network at high deformations.
A second type of strain hardening behavior can be identified for the
EP(D)M samples with ethylene contents around 80 mol%, such as the
sample EPDM-V80-N1.2 (Fig. 7A). These samples are characterized by
unstable and highly disordered crystals in the undeformed state and
experience a high level of incremental crystallinity upon stretching.
Strain hardening, in these samples, is enhanced by the high orientation
achieved by the amorphous chain segments and the consequent forma­
tion of new, highly oriented crystals. The contribution from the well
oriented fragment derived from the pristine crystals is less important.
The formation of new and well oriented crystals by effect of stretching
results in a remarkable increase of the cross-link density of the elasto­
meric network at high deformations and, hence, in values of stress at
break higher than those of samples with higher ethylene content
(Fig. 7A).
The third type of behavior arises for the low crystalline EPDM sam­
ples with ethylene content lower than 73 mol% and can be identified by
comparing the stress-strain curves of the sample EPM-V83 and the
sample EPDM-V73-D0.3 in Fig. 7B, as an example. The initial degree of
crystallinity of the sample EPDM-V73-D0.3 is only 3%. The increment of
crystallinity as a result of stretching for EP(D)M samples with ethylene
contents smaller than 73 mol% starts only at deformations higher than a
threshold, after the attainment of a high degree of orientation of the
amorphous chains, and is similar to SIC occurring in non-crosslinked
natural rubber [16,46,67–70]. The EPDM-V73-D0.3 sample, in partic­
ular, shows a low Young modulus (1.1 MPa, Table S2), a high ductility
(deformation at break equal to 3800%, Table S2) and no remarkable
F. Auriemma et al.
strain hardening. Furthermore, the incremental crystallinity induced by
stretching is smaller (10%) than that achieved by the sample EPM-V83
(13%). This is due to the intrinsic features of the chain microstructure,
as the p(E ≥ 7) value for the EPM-V73-D0.3 sample of ≈0.09, is close to
the threshold limit necessary for the occurrence of a significant crys­
tallinity increment induced by strain. Therefore, the third type of me­
chanical behavior at high deformation may be identified for the low
crystalline EP(D)M samples with ethylene contents around 73 mol%,
such as the sample EPM-V73-D0.3. For these samples, the small degrees
of crystallinity coupled with the moderate tendencies towards devel­
opment of incremental crystallinity by stretching, induce only a small or
negligible increase of the cross-link density of the elastomeric network
at high deformations, and hence only very little or no strain hardening at
high deformations, even though the amorphous chains achieve a high
degree of orientation with the chain axes parallel to the stretching di­
rections [16].
4. Conclusions
The effects of the polymer chain microstructure of EP(D)M samples
in terms of ethylene contents and fractional contents of ethylene se­
quences longer than a threshold value on the deformation behavior and
the crystallization induced by stretching have been investigated,
focusing the analysis on EP(D)M samples polymerized using conven­
tional V-based catalysts and more modern metalorganic catalysts. The
analysis of the chain microstructure reveals that, compared with V-
based counterparts, the adopted (post-)metallocene catalysts show a
lower tendency toward the propagation of hetero-sequences of the co-
monomeric units and the incorporation of regiomistakes (viz. 2,1-pro­
pylene units).
EP(D)M samples with ethylene contents in the range 73–83 mol%
show an initial degree of crystallinity increasing from 3 to 16% with
increasing ethylene content and similar melting temperatures (in the
range 40–44 ◦ C). The samples with ethylene contents smaller than 63
mol% are instead amorphous. The initial crystallinity of EPM co­
polymers is higher than those of EPDM terpolymers with similar frac­
tional contents of ethylene sequences of lengths equal to or longer than 7
ethylene units relative to the ethylene sequences of all lengths p(E ≥ 7).
The small differences in the crystallization properties of samples with
similar ethylene content prepared with the two different catalytic sys­
tems are accounted for the small difference in the chain microstructure.
The analysis of the mechanical properties has shown that the values
of the Young modulus and of the strain at yield are essentially sensitive
to the ethylene content. Other tensile properties, such as the strain and
stress at break, the stress at yield and the recovered strain values, follow
two different trends as a function of p(E ≥ 7) for EPM and EPDM samples.
In particular, for identical values of the fraction p(E ≥ 7), the values of
yield stress of EPM copolymers are larger and the values of stress at
break and elastic recovery are smaller than those of EPDM terpolymers.
This indicates that the presence of about 1 mol% diene co-units in EPDM
copolymers induce a small but significant decrease of the stress at yield
whereas the ultimate tensile strength is larger than that of EPM co­
polymers due to occurrence of strong strain hardening. Strain hard­
ening, in turn, is related to the occurrence of further crystallization upon
stretching, and its extent is dependent on the initial degree of crystal­
linity in the samples.
The EP(D)M samples with ethylene contents larger than 73 mol%
experience small but significant increments of crystallinity by stretch­
ing. The incremental crystallinity has been evaluated for samples
stretched at deformations close to rupture and is around 10% for EP(D)
M samples with ethylene contents of 73 mol%, increases to 15 and 17%
for samples with ethylene contents of 78 and 80 mol% and then drops to
13% for the most crystalline EPM sample with an ethylene content of 83
mol%. The incremental crystallinity induced by stretching influences
the strain hardening behavior. Strain hardening generally originates
from the contributions of at least three factors, i.e. i) the reinforcement
12
Polymer 227 (2021) 123848
due to the high levels of orientation achieved by crystal fragments
derived from pristine crystals initially present in the undeformed sam­
ple, ii) the high orientation attained by the amorphous chains and iii) the
possible consequent formation of new and well-oriented crystals.
Accordingly, three different types of strain hardening behavior are
distinguished, depending on the nature of the governing factors. The
first type of strain hardening behavior is observed for EP(D)M samples
with ethylene content larger than 80 mol%, which form large and well-
ordered crystals in the undeformed state. For these samples, the rein­
forcement effect occurring at high deformations is enhanced by crystal
fragmentation, and the high orientations achieved by these fragments
along the stretching direction, coupled with the high orientations of the
amorphous chains. The second type of strain hardening behavior occurs
in EP(D)M samples with ethylene contents around 80 mol%, which are
characterized by lower crystallinity and less perfect and less stable
crystals in the undeformed state. These samples experience high levels of
incremental crystallinity upon stretching, leading to remarkable strain
hardening. In these samples, strain hardening is determined by the high
orientations achieved by the amorphous chains and the consequent
formation of new highly oriented crystals. Finally, the third type of
strain hardening behavior may be identified for the EP(D)M samples
with ethylene contents around 70 mol%, which are characterized by
small initial degrees of crystallinity. For these samples, the small degrees
of crystallinity combined with moderate tendencies towards the devel­
opment of incremental crystallinity by stretching induce only a small or
negligible increase of the cross-link density of the elastomeric network
at high deformations and, hence, only very little or no strain hardening,
even though the amorphous chains achieve high degrees of orientation
with the chain axes parallel to the stretching directions.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.polymer.2021.123848.
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