Composites Part B 218 (2021) 108930

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Composites Part B
journal homepage: www.elsevier.com/locate/compositesb

Interfacial localization of organoclay enhances the peelability of

polyethylene/polybutene-1/organoclay nanocomposite films
Raziyeh S. Mohammadi a, Ali M. Zolali b, 1, Seyed H. Tabatabaei c, Abdellah Ajji a, *
a
3SPack NSERC-Industry Chair, CREPEC, Department of Chemical Engineering, Polytechnique Montreal, C.P. 6079, Succ. Centre-ville, Montreal, QC, H3C 3A7,
Canada
b
Microcellular Plastics Manufacturing Laboratory, Department of Mechanical and Industrial Engineering, University of Toronto, Toronto, Ontario, M5S 3G8, Canada
c
ProAmpac, 12025 Tricon Road, Cincinnati, OH, 45209, USA

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

Keywords: Premature failure in polymer blends originates mainly at interfaces between immiscible polymers which is
Polymer nanocomposite deemed detrimental to mechanical properties in many applications. Here we exploit this phenomenon in
Peel fracture developing a peelable film with a very wide peelable seal-temperature window (ΔTp) of over 90 ◦ C. A melt-cast
Polybutene-1
films of low-density polyethylene (PE) containing both 5 wt% isotactic polybutene-1 (PB-1) and 1 phr organoclay
Organoclay
Polymorphism
shows peel strength well within the peelable region (150–650 N/m), whereas the PE/5 wt% PB-1 blend, and PE/
1 phr organoclay nanocomposite films are lock sealed similar to the neat PE film after the sealing process.
Furthermore, the characteristic aging of the PE/PB-1 blends is eliminated by the addition of organoclay to the
system. The results indicate a synergistic interaction between organoclay and PB-1 that plays a key role in the
formation and consistent propagation of cracks throughout the system. The localization of organoclay at the
interface of the PE/PB-1 blend significantly reduces the thickness of the fibrillar PB-1 phase more than three
times to 60 nm. This suggests an increase in the interfacial area that can facilitate interfacial cracking and failure
at the interface. The nanoconfinement induced by the PE matrix and organoclay at the interface also enhance the
formation of the thermodynamically stable form I and form III PB-1 crystals rendering a consistent peel
performance.

1. Introduction shown to be effective in toughening PP/CaCO3 nanocomposite up to 4

Most polymers are thermodynamically incompatible and phase
separate when they are melt blended to generate materials with com­
plementary mechanical or thermal properties [1]. The interfaces of
immiscible polymers in polymer blends and composites are regarded as
the weak mechanical points where premature failure is originated [2–4].
The compatibilization of polymer blends and nanocomposites to rein­
force the polymer interfaces through different approaches such using
copolymers or nanomaterials has drawn tremendous attention over the
past decades [5–7]. These studies focus on improving the interfacial
adhesion between components to enhance the mechanical performance,
particularly, the impact strength [7,8]. In contrast, a few studies have
reported exploiting the interfacial incompatibility in polymer blends or
composites in favor of practical applications. The interfacial debonding
at the interface of polypropylene (PP) and CaCO3 nanoparticles has
times more than the impact strength of the neat PP [9]. Lightweight
microcellular polylactide (PLA)/polyolefin blends with significantly
improved mechanical properties, i.e. high strength, high modulus, and
increased impact resistance as compared with the neat PLA, were re­
ported through taking advantage of the poor interfacial compatibility
between PLA and polyolefins [10]. The materials were cold drawn over a
range of uniaxial strains (10–90%) at room temperature which resulted
in the formation of microvoids at the interface of PLA/polyolefin and a
weight reduction of up to 34%.
The interfacial incompatibility along with a unique elongated phase
morphology of a dispersed phase in polyolefin-based binary blend films
are being exploited in the packaging industry for producing cohesive
easy-to-open packings, i.e. peelable seals. The peelable seals are
increasingly employed in a vast variety of packages for merchandise,
electrical, food and medical packaging applications [11,12]. In contrast

* Corresponding author.
E-mail address: abdellah.ajji@polymtl.ca (A. Ajji).
1
Present address: Performance Materials Research, BASF Corporation, 1609 Biddle Ave., Wyandotte, MI 48192, United States.

https://doi.org/10.1016/j.compositesb.2021.108930
Received 20 August 2020; Received in revised form 8 April 2021; Accepted 18 April 2021
Available online 22 April 2021
1359-8368/© 2021 Elsevier Ltd. All rights reserved.
R.S. Mohammadi et al.
to adhesive peels that possess a relatively high risk of leakage and are
more sensitive to seal parameters, i.e. pressure and temperature [13],
cohesive peels are welded to a substrate and minimize the chances of
leakage [14]. Blending of polyolefins such as polyethylene (PE) and
ethylene-vinyl acetate copolymer (EVA) with polybutene-1 (PB-1) is a
promising approach to produce cohesive peelable seals [15]. PB-1 has
attracted much attention due to its superior impact properties, tough­
ness, elastic recovery and creep resistance [16,17]. PB-1 is immiscible
with PE and its counterpart polyolefins and possesses decent tensile and
yield strengths required for seal applications. It has been shown that at
least 10 wt% of PB-1 is required to achieve peelable seal with reasonable
heat seal temperature window (ΔTp) [18]. ΔTp is a temperature window
in which a cohesive peelable seal is obtained and typically is very nar­
row for most of conventional peel formulations. By increasing the heat
seal temperature, the peel performance may convert to lock seal due to
intense polymer chain inter-diffusion, disintegration of the fibrillar
morphology, or increase in crystalline anchors at the weld zone [19,20].
Depending on crystallization conditions, PB-1 exhibit different
crystalline structures including twined hexagonal form I with 3/1 helix
[21], untwined hexagonal form Iʹ with 3/1 helix [22], twinned tetrag­
onal form II with 11/3 helix [23] and orthorhombic form III with 4/1
helix conformation [24]. Crystals form Iʹ and III are usually obtained
from solution and can be converted to crystal form II when dried and
heated up to 90 ◦ C [24]. When cooled from melt to ambient tempera­
ture, PB-1 forms more kinetically favored crystalline form II. Then, the
metastable crystal form II spontaneously converts to crystalline form I,
which is thermodynamically stable [22,25]. Because of the significantly
different melting temperatures and densities of the crystal forms II and I,
the transition of crystalline form II to form I results in profound thermal
and mechanical changes [26,27]. So far, extensive efforts have been
made to accelerate form II to form I crystal transition through various
methods such as pressure [28], orientation and drawing [29–33],
incorporation of additives [34] and copolymerization [35,36]. Some
studies have reported direct formation of form I or form Iʹ under peculiar
conditions such as from ultrathin films [37], through self seeding [38],
stereodefects [39] and manipulating the melt temperature [40,41].
Nevertheless, complicated polymorphism and inconsistent thermal,
physical and mechanical properties of PB-1 after melt processing re­
mains a challenging issue that restricts its commercial development.
It has been shown that small amounts of nanoparticles can effectively
change the morphology, thermal, and mechanical properties of immis­
cible blends [42]. Nanoclay is one of widely used nanoparticles in
polymer-based composites. Due to its unique two-dimensional structure,
it significantly affects the phase morphology by refining and coarsening
dispersed domains, inducing/broadening cocontinuity, and compatibi­
lizing phases. Generally, thermodynamics governs the morphology
development in polymer blends and nanocomposites, however, kinetic
effects can also play a major role in the localization of nanoparticles due
to high viscosity of polymer components. The addition of nanoclay to
immiscible poly(vinylidene fluoride) (PVDF)/polyamide-6 (PA6) blends
has reduced the dispersed PVDF phase size [43]. The dispersion and
localization of the nanoclay were identified to control the degree of
compatibilization induced by the nanoclay. The compatibilization is
achieved by suppressing coalescence or/and reduction in the interfacial
tension when the nanoclay is placed at the interface [42]. A significant
reduction in the polystyrene (PS) phase size was reported in PP/PS
blends when organically modified nanoclay was resided in the PP phase
and at the interface of PP/PS. The addition of organoclay improved the
tensile strength and modulus while a decrease was noted for elongation
at break and impact strength of the nanocomposite blends at low PS
contents [44]. A micromechanical deformation analysis of PLA/natural
rubber (NR)/organoclay nanocomposite blends has showed that orga­
noclays act as preferential sites for the craze formation at the PLA/NR
interface [45]. It appears that at an optimum 1 wt% of organoclay
content, organoclays both generate multiple crazes and preclude craze
development and transformation into cracks during uniaxial stretching.
2
Composites Part B 218 (2021) 108930
Organoclays are effective in inducing peelability in the PE nano­
composites films through initiating cracks within the electrostatically
bonded clay stacks/layers when they are well dispersed and distributed
throughout the system [46]. The localization of organoclay at the
interface of PE/ethylene-methyl acrylate copolymer (EMA) blends has
recently presented a promising strategy to generate systems with com­
patibilized but weak interfaces suitable for peel applications [47]. Here,
we report a high performance peelable PE/PB-1/organoclay nano­
composite film with exceptional ΔTp and consistent peel strength. Only
1 wt% organoclay localized at the PE/PB-1 interface was enough to
markedly tune the fibrillar structure of the 5 wt% dispersed PB-1 phase.
By studying the morphology development and thermal properties of the
systems, we reveal the role of confinement imposed upon the PB-1 phase
on the polymorphism of PB-1 and mechanical properties of the nano­
composite films. We also show that the typical aging problem of films
containing PB-1 can be successfully eliminated while retaining a
consistent peel strength within the limits of easy-to-open packaging.
2. Experimental
2.1. . Materials
Low density polyethylene (PE) with the trade name of Novapol LF-
0219-A was obtained from Nova chemicals. Polybutene-1 (PB-1),
PB0300 M, with a density of 0.915 g cm− 1, melt flow index of 4 g/10 min
(190 ◦ C/2.16 kg) and molecular weight of 374 kg/mol was kindly pro­
vided by Lyondellbasell. Organomodified montmorillonite clay nano­
particles with the trade name of Cloisite 15 was obtained from Byk
Company. The organoclay was modified with dimethyl dehydrogenated
tallow with approximately 65% C18, 30% C16, 5% C14 with cation
exchange capacity (CEC) of 125.
2.2. Sample preparation
PE/PB-1 blends containing 5 (B5), 10 (B10) and 20 (B20) wt% of PB-
1 were prepared using a Leistritz ZSE 18HP twin screw extruder (TSE)
with an L/D ratio of 40. A masterbatch of PB-1 containing 20 wt%
Cloisite 15 was prepared using the same TSE equipped with a separate
nanoclay feeder. The master-batch was then diluted with PE to prepare
PE/PB-1/organoclay nanocomposites containing 5 (NB5), 10 (NB10)
and 20 (NB20) wt % PB-1 and 1 phr Cloisite 15. PE containing 1 phr
Cloisite 15 (PE/C1) was also prepared as a reference. The screw speed of
100 rpm and a temperature profile of 150/160/170/180/180/190/190/
190, from hopper to die, were used for all compoundings. The blends
and nanocomposites were prepared in a separate melt casting process
into thin films using the same TSE equipped with a slit die with a die
opening of 500 μm. The extruded films were passed through an air knife
and drawn with calendar rolls chilled with cold water (see Fig. 1a). The
collection speed and draw ratio were manipulated to achieve films of 70
μm in thickness.
To examine the peeling performance of the nanocomposite films,
they were first welded through a sealing process. The sealing process
was performed using a hot tack/seal tester from LakoTool &
Manufacturing Inc, USA. Two strips of the films with 2.54 cm in width
were cut to be welded on themselves. The films were sandwiched be­
tween two acetate films in order to prevent sticking of the films to the
hot seal bars. A sealing pressure of 0.5 N/mm2, a dwell time of 1 s and an
identical sealing temperature for upper and lower seal bars were set as
the seal parameters (see Fig. 1b). Samples were sealed at temperatures
ranging from 110 to 200 ◦ C with intervals of 5 ◦ C.
T-peel tests were carried out using a tensile testing machine (Instron
E3000) per ASTM F88 to evaluate the peel performance of the sealed
films. The samples were peeled at room temperature with a peeling rate
of 200 mm/min (see Fig. 1c). The plateau of the force-displacement
curves was reported as the peel force for each sample. To ensure
reproducibility of the data, the average peel force of at least 5 specimens
R.S. Mohammadi et al.
Fig. 1. Film preparation process and T-peel test: (a) schematic of the melt casting process of plastic films. The calendaring parameters are controlled to obtain films
with an average thickness of 70 μm; (b) the sealing process at a constant temperature and pressure; (c) T-peel testing of sealed films.
of each sample was reported as the final peel force.
2.3. Characterizations
Wide angle X-ray diffraction (WAXD) analysis was performed using a
Phillips X’pert apparatus. The anode was copper (Cu) with a K<α
wavelength of 1.54 Å and the generator voltage and tube current were
set at 50 kV and 40 mA, respectively, at room temperature. The scans
were run over a 2θ range of 2–30◦ with a scan rate of 0.02◦ /s and a 20 cm
distance between the sample and detector. In order to maximize the
diffraction intensity, several layers of each sample were stacked to make
samples with an approximately 2 mm in thickness. The d-spacing of the
clay layers was calculated using Bragg’s equation: λ = 2d<sinθ in which
λ is the wavelength of the X-ray radiation, <d is the distance between the
clay layers and θ is the diffraction peak angle. A transmission electron
microscopy (TEM) from JEOL JEM-2100F, Japan, operating at 200 kV
was used to examine the localization of organoclay in the nano­
composite blends. For sample preparation, an ultra-cryomicrotome,
Leica Microsystem EM-UC7/FC7, operating at − 120 ◦ C and equipped
with a diamond knife was employed to cut thin 100 nm slices of nano­
composites suitable for TEM imaging.
Differential scanning calorimetry (DSC) was performed using a DSC
instrument Q2000 from TA Instruments. About 10 mg of each sample
was placed in an aluminum pan and then heated from 25 to 150 ◦ C to
remove thermal history. Then, it was cooled to 0 ◦ C and finally heated
again to 150 ◦ C. All experiments were performed under nitrogen at­
mosphere with a scan rate of 10 ◦ C/min. The heat of fusion (ΔHm) of the
samples was measured using TA Universal Analysis software to calculate
the degree of crystallinity according to equation (1) in which Xc is de­
gree of crystallinity, x is the weight fraction of PE and ΔHm,100 is the
enthalpy of 100% crystal of low density PE, which is reported to be 298
J/g [48].
/ at the PE/PB-1 interface (see Supporting Information). However, to
Xc = ΔHm xΔHm,100 (1)
Scanning electron microscopy (SEM) was conducted using a Field
Emission SEM machine (JSM 7600TFE, JEOL) operated at a voltage of 2
kV. Films were embedded in an epoxy mold in machine and transvers
directions (MD and TD) and then cryo-microtomed using a glass knife at
− 150 ◦ C. The cryo-microtomed samples were then treated using cyclo­
hexane at 50 ◦ C to extract the dispersed PB-1 phase and create contrast
between phases for SEM imaging. The cryo-microtomed samples were
gold/palladium coated under plasma vacuum deposition before SEM
performed in MD direction.
3. Results and discussion
Films preparation and heat sealing process. The blends and
nanocomposite blends were all prepared through a melt-mixing process
using a twin-screw extruder as illustrated in Fig. 1a. Twin-screw ex­
truders (TSEs) are considered ideal mixing equipment for melt-blending
3
Composites Part B 218 (2021) 108930
of polymers and solid inclusions as they provide high levels of dispersion
and distribution of components by vigorous shear and extensional
mixing. The flat cast die attached to the TSE in our work shapes the
polymer melt into a thin film with a controlled thickness. The thickness
is further adjusted using a calendar by fine tuning the drums’ speed and
cooling rate. The phase morphology of the blends and nanocomposite
blends were examined through SEM analysis. Fig. 2 and Fig. S1 show the
morphology of the blends and nanocomposites, respectively. A fibrillar
phase morphology is identified in both blends and nanocomposites. The
cross-section of the PB-1 fibers can be seen in the micrographs taken in
the machine direction (MD) which are used to calculate the fiber size
and interparticle distance between the fibers. The elongated features
observed in the transverse direction (TD) micrographs prove that the
holes detected in the MD are fibers extended along the films. Due to high
extensional deformation exerted on the systems inside the flat die, the
dispersed PB-1 phase, which was dispersed and distributed into spher­
ical domains during the mixing process in the TSE, extends into thin
elongated PB-1 fibrils. This basically creates thin films with the PB-1
fibrillar domains elongated along the films. Table 1 summarizes the
main morphological characteristics of the blends and nanocomposite
blends. The thickness of the PB-1 nanofibers increases from 100 nm to
200 nm by the PB-1 content from 5 to 20 wt%.
The morphology analysis results show that the addition of organo­
clay affect the phase morphology of PB-1. Although a similar trend to the
blends is observed in the nanocomposite blends, a significant reduction
in the PB-1 thickness to 60 nm can be seen for the nanocomposite
containing 5 wt% PB-1 (see Table 1). The dispersion and distribution of
organoclay as well as its localization can significantly influence the PB-1
phase morphology [49]. A thermodynamic model based on the inter­
facial energies of constituent components is widely used for predicting
the localization of solid inclusions in polymer nanocomposite blends.
The thermodynamic analysis shows that the organoclay would localize
assess the predictions, TEM imagings were performed to provide a
qualitative understanding of the distribution and localization of the
organoclay. Fig. 3 shows the TEM micrographs of the
PE/PB-1/organoclay nanocomposite films containing different PB-1
contents in the machine direction. The darker domains marked by ar­
rows are organoclay stacks which are distinct from the gray PB-1 do­
mains dispersed within the PE matrix. These results suggest that
organoclay layers/stacks are mainly located at the interface of the PE
and PB-1 phases. This is in line with the thermodynamic predictions and
confirms that the organoclay thermodynamically tends to migrate to the
PE/PB-1 interface despite being first incorporated into the PB-1 phase.
Almost no organoclay layers/stacks can be detected in the PE matrix
whereas some are observed inside the PB-1 domains. This can be related
to the mixing sequence as the organoclay was first melt-blended with
PB-1 and then the masterbatch was diluted by PE. The kinetic barrier
due to the high viscosity of the PB-1 phase can prevent the full segre­
gation of the organoclay at the interface, and thus some may be stuck
R.S. Mohammadi et al. Composites Part B 218 (2021) 108930

Fig. 2. SEM images of (a, a’) B5, (b, b’) B10 and (c, c’) B20 in the machine and transverse directions, respectively (The white bars denote 1 μm).

nanocomposite blends with 10 and 20 wt% PB-1, minor phase size re­
Table 1
ductions are obtained which are within the margin of the errors (see
The morphological and thermal characteristics of the blends and nanocomposite
Table 1). By increasing the PB-1 content, the interfacial area increases
blends.
and consequently more organoclay is needed to completely cover and
Sample Fiber Aspect ratio Interfibrillar Ti ΔTp
saturate the interface. However, a constant amount of organoclay (1
thickness (L/D) distance (nm) (◦ C) (◦ C)
(nm) phr) is used in all the systems which seems not enough to cover the
interfacial area in the two systems with 10 and 20 wt% of PB-1. This
PE 110 5
explains why only a slight decrease in the PB-1 phase size is achieved at
– – –
PE/C1 – – – 110 5
B5 100 ± 20 ~40 365 ± 25 110 10 higher PB-1 contents. The TEM results support these morphological
B10 190 ± 35 >50 300 ± 17 115 20 observations. More organoclay stacks/layers are located at the interface
B20 200 ± 50 >50 290 ± 15 120 70 of PE/PB-1 in the nanocomposite blend containing 5 wt% PB-1 (see
NB5 60 ± 8 ~30 165 ±7 110 90 <
Fig. 3a). Much less organoclay stacks/layers can be seen at the interface
NB10 170 ± 15 >50 260 ± 11 115 45
NB20 190 ± 20 >50 270 ± 18 120 65–70 when the PB-1 content is increased to 10 and 20 wt% as shown in Fig. 3b
and c. Thus, much less compatibilization effect is observed in these
systems.
inside the PB-1 phase. The peel performances of the PE/PB-1 blends and PE/PB-1/clay
The morphologies observed in the nanocomposite blends are directly nanocomposites are demonstrated in Fig. 4. The nanocomposite films
affected by the localization of organoclay at the interface. The organo­ with a peel force value within the easy-to-open window (150–650 N/m)
clay layers at the interface prevent the coalescence of the PB-1 domains are considered as peelable films [51]. The seal initiation temperature
by both compatibilizing the interface and creating a physical barrier at (Ti), a minimum temperature at which two films are welded, and ΔTp are
the interface. This leads to a marked reduction in the phase size of the listed in Table 1. Ti of the neat PE film is around 110 ◦ C, very close to its
dispersed PB-1 phase in the NB5 nanocomposite blend containing 5 wt% melting temperature. By increasing the seal temperature to 115 ◦ C, the
PB-1. This is another indication that the organoclay is localized at the peel force of the PE significantly increases beyond 650 N/m showing a
interface and act as a compatibilizer to reduce the dispersed PB-1 phase lock seal behavior. Blending PE with 5 wt% of PB-1 slightly enhances its
size as reported elsewhere [43]. Whereas, the localization of organoclay peelability window ΔTp from 5 to 10 ◦ C. ΔTp is further increased to
within the dispersed phase generally increases the viscosity of the 20 ◦ C for B10 and to 70 ◦ C for B20. In addition, Ti of B10 and B20 in­
dispersed phase and results in coarsening its morphology [50]. In the crease to 115 and 120 ◦ C, respectively. The widening of Ti by increasing

Fig. 3. TEM images of (a) NB5, (b) NB10 and (c) NB20 nanocomposite films. The arrows indicate clay particles at the PE/PB-1 interface.

4
R.S. Mohammadi et al. Composites Part B 218 (2021) 108930

Fig. 4. Peel force versus seal temperature of (a) the blends and (b) the nanocomposites.

Fig. 5. Force-displacement curves of (a) B5, (b) NB5, (c) B10, (d) NB10, (e) B20 and (f) NB20 at different sealing temperatures.

5
R.S. Mohammadi et al.
the PB-1 content is attributed to the higher melting point of PB-1 crystals
compared to that of PE as Ti depends directly on the crystallinity of
components [19,20]. Fig. 4b shows that the peelability of the blend
systems was significantly improved upon the incorporation of 1 phr
organoclay to the blends. ΔTp is markedly broadened for NB5 when it is
compared to that of NB10. Also, despite the NB5 and NB10 nano­
composite blends that demonstrate a significant improvement, the peel
force of the NB20 nanocomposite blend slightly increases while showing
a ΔTp similar to the neat B20 blend.
To better understand these results, the force-displacement curves of
the blend films were examined against the nanocomposite films during
the peeling experiments and the results are presented in Fig. 5. It should
be noted that the curves with a wide plateau represent a cohesive peel
behavior. Films with a partially cohesive peel behavior show a small
plateau and then an increase in the force due to elongation upon further
peeling. The curves without plateau are similar to stress-strain curves
and represent the lock seal behavior as lock seals usually yield and
deform until rupture. Fig. 5a indicates that the B5 blend displays a lock
seal performance at seal temperatures beyond 120 ◦ C while the NB5
nanocomposite is cohesively peeled over all the tested temperatures
from 120 to 200 ◦ C (Fig. 5a’). The B10 blend demonstrates a cohesive
peel performance when sealed under 130 ◦ C whereas increasing the seal
temperature to 135 ◦ C results in partial peeling followed by elongation
of the films (Fig. 5b). At seal temperatures above 140 ◦ C, the B10 blend
yields and becomes elongated before being peeled. In contrast, the NB10
nanocomposite film shows a plateau force-displacement curves up to the
seal temperature of about 160 ◦ C and just yields beyond that seal tem­
perature (Fig. 5b’). The peel performance of the B20 blend and NB20
nanocomposite are very similar as displayed in Fig. 5c and c’ showing
that the organoclay has almost no effect on the peeling of the system.
These results can be explained through understanding the mechan­
ical properties and microstructure of the films. The peeling of two
welded films will occur when the yield strength of the film is greater
than the adhesion strength of the interface inside the welded area.
However, if the yield strength of the film is smaller than the interfacial
adhesion, the film will yield and become elongated prior to being peeled
at the interface. The force-displacement curves of the B10 films in
Fig. 5b at 135 and 145 ◦ C are good examples of the elongation of the
films before the peeling of the system. The effect of the yield strength of
the blend and nanocomposite films on the peeling performance is further
discussed in the Supporting Information. In cohesive peel fracture,
cracks are initiated at the interface and then propagate to the nearest
domain to form a consistent fracture throughout the blend. Thus, the
morphology of the dispersed phase and particularly the distance be­
tween neighboring domains plays an important role on the peel per­
formance of the sealed blend films. The SEM micrographs of the blend
and nanocomposite films in Fig. 2 and Figure S1 are quantified and the
results are presented in Table 1. The results indicate that the fibrillar PB-
1 domains in the B5 and B10 blend films are dispersed with an average
interparticle distance of 364 and 302 nm, respectively. The morphology
of the B20 blend is more sheet like rather than fibril like with an average
interparticle distance of 287 nm. The peel force seems to have a direct
relationship with the interparticle distance in the blend films. By
decreasing the interparticle distance the peel force reduces over a rela­
tively wide ΔTp of 70 ◦ C for the B20 blend when compared to the B5 and
B10 blends with a narrower ΔTp of 10 and 20 ◦ C, respectively. The
interparticle distance of the dispersed PB-1 phases in the nanocomposite
films decrease to 160, 260 and 170 nm for NB5, NB10 and NB20,
respectively. The results suggest that the change in the peel behavior of
the systems containing 5 wt% PB-1 from lock seal to peelable by the
incorporation of 1 phr organoclay can be partly attributed to the
reduction in the interparticle distance. The crack propagation is facili­
tated when the interparticle distance reduces. The nanocomposite films
with higher PB-1 contents show similar peel force with wider peelable
window when are compared with the blend films.
In order to better understand the peeling mechanism in the PE/PB-1
6
Composites Part B 218 (2021) 108930
blends and nanocomposites, the fracture surface of the sealed films after
peeling is investigated by SEM and the results are shown in Fig. 6. A
rough and highly fibrillated peeled fracture surface indicates a high peel
strength and resistance upon peeling. In contrast, a smooth and less
rough peeled surface with less plastic deformations suggests lower
resistance to peeling. Fig. 6a and b shows the peeled fracture surface of
the B5 and NB5 films sealed at 130 and 200 ◦ C, respectively. The B5 film
is not peelable at 130 ◦ C while the NB5 nanocomposite film is cohesively
peeled even when sealed at 200 ◦ C. These fracture results are in line with
the morphological observations and T-peel test results. The peeled sur­
face of the easily peelable NB5 nanocomposite blend is uniformly frac­
tured with less fibrillations whereas the B5 blend film is fractured with
significant amount plastic deformations. It should be noted that the NB5
nanocomposite film shows similar peeled fracture surface to the one
sealed at 200 ◦ C over its entire peelable region. The NB10 nano­
composite film is peelable up to the seal temperature of 160 ◦ C (Fig. 6c)
and at a seal temperature beyond 160 ◦ C it is not easily peelable
(Fig. 6d). These results also agree with the peel force experiments where
the NB10 nanocomposite film revealed a lock seal behavior at the seal
temperature of 160 ◦ C. The NB20 nanocomposite film demonstrates the
easy-to-open peelable character even when is sealed at 190 ◦ C (Fig. 6e).
A slightly higher seal temperature at 195 ◦ C changes the peeling per­
formance to a lock-seal behavior with high plastic deformation at the
peeled surface (Fig. 6f).
The NB5 nanocomposite film containing only 5 wt% of PB-1 and 1
phr of organoclay shows markedly improved peel performance
compared to the other blend and nanocomposite films. The mechanical
and microstructure analyses suggest that there is a synergistic effect
between organoclay and PB-1. The addition of organoclay enhances the
yield strength of the NB5 film to a value that surpasses the interfacial
adhesion of the welded area. On the other hand, the reduction of the PB-
1 nanofibril size significantly increases the interfacial area and conse­
quently promotes crack bridging during peeling fracture. Also, the
WAXD results show that organoclay forms intercalated/partially exfo­
liated stacks during the melt mixing process (see Supporting Informa­
tion). It has been shown that dispersion and distribution of partially
exfoliated organoclay stacks in the PE matrix induces peelability in PE
films [46]. A moderate peelability performance has also been reported
for polyolefin based nanocomposite blends through the localization of
the organoclay at the interface [47]. The organoclay stacks can be
delaminated at the interface and create multiple crazes which promote
the cohesive peeling of the system. By increasing the PB-1 content, the
thickness of the PB-1 fibrils grows while the interparticle distance re­
duces (Table 1). Although the addition of 1 phr organoclay slightly re­
duces the interparticle distance and thickness of the PB-1 nanofibrils in
the nanocomposite blends with 10 and 20 wt% PB-1, the reduction is
much significant in the system with 5 wt% PB-1. This can be attributed
to the higher interfacial coverage of organoclay particles at the interface
in the latter system.
One major drawback of PB-1 and its blends is their aging due to PB-
1’s polymorphism which changes the physical and mechanical proper­
ties [52,53]. It has been reported that upon aging of PB-1 at room
temperature the peel strength of its polyolefin blends reduces by aging
time [54,55]. Fig. 7 shows the peel force of the PE/PB-1 blends and
nanocomposite films with the aging time after the sealing process. The
peel force of the B5 blend sealed at 130 ◦ C slightly decreases from 1010
to 936 N/m after 24 h and remains constant afterwards. The B10 blend
shows a peel force of 645 N/m when sealed at 135 ◦ C while its peel force
decreases to 490 N/m after 72 h and then remains unchanged. The peel
force of the B20 film sealed at 150 ◦ C decreases from 310 to 195 N/m
after 7 days and then levels off. In general, the peel force decreases by
time indicating an aging effect in all the PE/PB-1 blend films. The DSC
thermal results in Figure S3 confirm that the metastable form II crystal of
PB-1 forms after the sealing process. The endotherm peaks at 115 ◦ C
correspond to the melting peak of crystal form II in these systems.
Although the melting peak of PE is at 110 ◦ C, which is very close to the
R.S. Mohammadi et al. Composites Part B 218 (2021) 108930

Fig. 6. SEM micrographs of the peel fractured surface of (a) B5 sealed at 130 ◦ C, (b) NB5 sealed at 200 ◦ C, (c) NB10 sealed at 160 ◦ C, (d) NB10 sealed at 165 ◦ C, (e)
NB20 sealed at 180 ◦ C and NB20 sealed at 195 ◦ C (The white bars denote 20 μm).

Fig. 7. Aging of the peel force of the blend and nanocomposite films after the
sealing process.
melting peak of the form II crystals, the melting peak at 115 ◦ C can be
only assigned to the form II crystal as the melting peak of the form I
crystal appears at 120 ◦ C. These results imply that the metastable form II
converts to the stable and thermodynamically favored form I upon time
aging. As the form I is denser than the form II, the dispersed PB-1
nanofibrils shrink during the form II to form I transition and conse­
quently the peel force diminishes by the aging time until it reaches a
constant value. The aging results reveal that the form II to form I tran­
sition progresses faster in the B5 blend film (24 h) compared to the B10
and B20 blends that require 72 and 168 h to complete the transition,
respectively.
In contrast to the blend films, the peel force of the nanocomposite
blends remains constant after the sealing process with no aging (Fig. 7).
This can be attributed to the absence of the form II crystal in the
nanocomposite films as the aging is a direct consequence of the from II to
form I transition. The WAXD results in Fig. 8 confirm the formation of
form I/I’ in the nanocomposite films immediately after the heat-sealing
process. The reflection at 2θ = 10◦ corresponds to (110) plane of form I
or Iʹ and is only observed in nanofibrillar blends of the PE/PB-1 blends
and nanocomposites [56]. The PE/PB-1 blend films show reflections at
2θ = 11.9, 16.9 and 18.2 corresponding to (200), (220) and (213)/(311)
planes of crystal form II which are absent in the WAXD patterns of the
nanocomposite blends. It has been shown that both the nanofibrillated
morphology of the PB-1 domains and the localization of organoclay at

7
R.S. Mohammadi et al.
Fig. 8. WAXD patterns of the blend and nanocompositefilms of PE/PB-1 con­
taining 5, 10 and 20 wt% of PB-1 immediately after the heat-seal process.
the interface alter the kinetics of the PB-1 crystallization [56].
Furthermore, the PE matrix solidifies before the PB-1 domains after the
heat-sealing process due to its lower crystallization temperature
compared to that of the PB-1 phase, and thus imposes a nanoconfine­
ment restriction on the nanofibrillated PB-1 domains. The nano­
confinement effect in conjunction with the hindrance effect created by
the organoclay layers at the interface limit the movement of the PB-1
chains. This may disrupt the crystallization kinetic of the form II and
supress its formation as the form II crystal is kinetically favored. The
result is the direct formation of form I and form III modification in the
nanocomposite films which are not observed in the blend films under the
similar sealing process.
4. Conclusions
A novel PE/PB-1/organoclay nanocomposite with a broad peelable
seal-temperature range is reported for seal/peel applications. The
incorporation of either 1 phr organoclay or 5 wt% of PB-1 into PE results
in films with a lock-seal performance after the sealing process similar to
that of the neat PE. However, the PE/PB-1/organoclay containing both 1
phr organoclay and 5 wt% of PB-1 renders a peelable film with a very
broad ΔTp of 90 ◦ C. The TEM and thermodynamic analysis confirm that
organoclay is localized at the interface of the PE and nanofibrillar PB-1
phases. The localization of organoclay at the interface compatibilizes the
morphology and reduces the PB-1 nanofibrillar thickness which justifies
the observed versatile peel performance in the nanocomposite blends.
Although organoclay is found very effective in enhancing the peelability
of the PE/PB-1 films, increasing the PB-1 content to 20 wt% negatively
affects the peelability of the nanocomposite blends. This was attributed
to the shortage of organoclay particles to cover the increased interfacial
area in the systems with higher PB-1 contents. Furthermore, it was found
8
Composites Part B 218 (2021) 108930
that the organoclay and nanoconfinement effect induced on the PB-1
phase significantly affect the crystallinity of PB-1 and its aging. The
blend films containing different amount of PB-1 show the aging of the
peel force in which the peel force decreases by time after the sealing
process. The aging effect is significant for the blends with higher PB-1
contents. The reduction of the peel force is attributed to the trans­
formation of form II to form I crystals in the blend films after sealing. It
was shown that the incorporation of organoclay to the blends
completely eliminates the aging in the nanocomposite films. This is
achieved by suppressing the formation of the metastable form II crystals
and promoting the direct formation of thermodynamically stable form I
and III crystals after the sealing process. These results indicate the
importance of both a nanofibrillar morphology and interfacial locali­
zation of organoclay particles in obtaining films with a high peeling
performance.
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.
Acknowledgement
The authors acknowledge the financial support from the Natural
Sciences and Engineering Research Council of Canada (NSERC) and
industrial partner ProAmpac for the 3S Pack NSERC-Industrial research
chair that supported this work.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.compositesb.2021.108930.
Author statement
Raziyeh S. Mohammadi: Conceptualization, Methodology, Inves­
tigation, Validation, Formal analysis, Data curation, Writing-Original
draft, Writing-Review & Editing.
Ali M. Zolali: Conceptualization, Methodology, Validation, Formal
analysis, Writing-Review & Editing.
Seyed H. Tabatabaei: Funding acquisition, Resources.
Abdellah Ajji: Supervision, Funding acquisition, Project adminis­
tration, Writing- Review & Editing.
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