Article

Cite This: Macromolecules XXXX, XXX, XXX−XXX

Toughening of Cocontinuous Polylactide/Polyethylene Blends via an

Interfacially Percolated Intermediate Phase
Ali M. Zolali and Basil D. Favis*
CREPEC, Department of Chemical Engineering, École Polytechnique de Montréal, Montréal, QC, Canada H3C 3A7
*
S Supporting Information

ABSTRACT: It will be shown that an interfacially percolated

rubbery phase in a cocontinuous polylactide (PLA)/linear low-
density polyethylene (LLDPE) blend results in a significant
increase in the impact strength. All blends possess a
tricontinuous phase morphology in which poly(ε-caprolac-
tone) (PCL), poly(ethylene−methyl acrylate) (EMA), and
ethylene−methyl acrylate−glycidyl methacrylate (EMA-GMA)
percolate at the interface of PLA/LLDPE but offer different
toughening and compatibilization effects. Among these
components, the addition of EMA-GMA to the binary PLA/
LLDPE blend reduces the cocontinuous PLA/LLDPE phase
thickness from about 25 to 5 μm and yields a very tough material with an impact strength of about 515 J/m, which is
approximately 13 times greater than the original cocontinuous PLA/LLDPE blend and more than 32 times that of PLA. The
ternary blends show significant improvements in the impact strength within the tricontinuous region; however, the principal
differences in the toughening effects are attributed to interfacial interactions between the phases. The interconnected network of
the rubbery phase is expected to percolate the stress field throughout the tricontinuous system and reduce the detrimental
dilatational stress in the bulk blend.

1. INTRODUCTION
In recent years, the blending of polylactide (PLA), a biobased
and biodegradable polyester which possesses high mechanical
strength and processability, with other bioplastics and
petroleum-based plastics has attracted much attention in both
industry and academia.1,2 These studies mainly report on the
toughening of PLA as its broader application is limited due to
its inherent brittleness. Polyethylene (PE) is one of the most
important commodity polymers that is produced both from oil
and renewable resources and is used in toughening of PLA.3−5
These polymers are thermodynamically immiscible and require
compatibilizers to achieve stable morphologies and superior
mechanical properties.6,7 Polylactide−polyethylene block co-
polymers have been used to compatibilize PLA/PE blends and
were found to be effective in toughening by enhancing the
interfacial adhesion.3,8 Reactive compatibilizers such as
copolymers of ethylene−glycidyl methacrylate (E-GMA) and
ethylene−methyl acrylate−glycidyl methacrylate (EMA-GMA)
have also been employed in the compatibilization of
polylactide/polyolefin blends.4,9 The results show that PLA
end groups react with the epoxide groups of the compatibilizers
and form graft copolymers, which reinforce the interface and
improve mechanical properties. Typically, in those studies the
toughening of PLA was increased by a factor of 2−5.
The majority of toughening studies of polymeric systems
concentrate on the dispersed/matrix morphology. Ternary,
quaternary, and even quinary blending is an emerging field in
polymer blending which is growing and evolving at appreciable
rates. Such polymer blends form discrete phases in which the
control of complex morphologies and multiple interfacial
properties are the keys in obtaining materials with superior
functional properties. In a recent work, we reported on the
ultratoughening of PLA in a multiphase polymer material
composed of percolated poly(ether-b-amide) (PEBA) at the
cocontinuous interface of PLA/PA11.10 It was shown that a
marked improvement in the toughening is only achieved when
a tricontinuous morphology develops. Beyond this composi-
tional region no considerable toughening is observed. Although
the tricontinuous morphology was found to be essential in the
toughening, ultratough behavior was only achieved when
interfacial interactions were promoted by increasing PLA
chain mobility at the interface through plasticization.11
Hashima et al.12 reported toughening of PLA by blending
with hydrogenated styrene−butadiene−styrene block copoly-
mer (SEBS) with the aid of E-GMA as a reactive compatibilizer.
Further incorporation of polycarbonate (PC) to the ternary
blend resulted in a material with ultrahigh toughness and
thermal resistance aging properties. The results were attributed
to the strong interfacial adhesion and negative pressure effect of
SEBS at the interfaces which facilitate the plastic deformation of
the PLA and PC matrices. In another work, Liu et al.13,14
systematically studied the relationship between phase morphol-
Received: March 3, 2018
Revised: April 24, 2018

© XXXX American Chemical Society A DOI: 10.1021/acs.macromol.8b00464

Macromolecules XXXX, XXX, XXX−XXX
Macromolecules Article

ogy and interfacial adhesion with the impact behavior in PLA- speed set to 180/190/180 °C from hopper to nozzle and 100 rpm,
based ternary polymer blends. They found that high impact respectively.
toughening can be achieved through an optimum phase 2.2. Rheological Properties. Rheological measurements were
morphology in conjunction with suitable interfacial adhesion. performed using a controlled-stress rheometer Physica MCR 501 from
Anton Paar equipped with a 25 mm parallel plate disk geometry.
Similar results have been reported in the literature on the effect Samples were first compression molded into disks of 25 mm diameter
of morphology and interfacial adhesion on the toughening of and 1.2 mm thickness and then conditioned at 50 °C in a vacuum
multicomponent polymer blends.15−18 oven before testing. A time sweep test was performed to determine the
The study of the mechanical properties of multiphase temperature stability of samples at 180 °C in which all samples showed
polymer blends with cocontinuous and tricontinuous phase acceptable thermal stability (less than 10% viscosity reduction) over
morphology is rare despite their potential for multifunctional more than 40 min. The frequency sweep tests were performed at 180
applications. Although considerable studies exist on multiphase °C and a strain of 1%, and the complex viscosity of the neat polymers
blends with matrix/dispersed phase structures and the is presented in Figure 1.
relationship between their morphology and interfacial adhesion
with the mechanical properties, it is still largely unknown how
the interfacial interactions can influence the mechanical
properties of systems with tricontinuous morphologies. This
work aims to gain an understanding of the morphology and
interfacial properties in PLA/PE based ternary blends with
cocontinuous and tricontinuous phase structures with a view to
develop high performance biobased materials. The morphology
development of PLA, PE, and three different components, i.e.,
poly(ε-caprolactone) (PCL), poly(ethylene−methyl acrylate)
(EMA), and EMA-GMA, will be investigated. The effects of
morphology and interfacial adhesion on the mechanical
properties will be thoroughly examined.

2. EXPERIMENTAL METHOD
2.1. Materials and Sample Preparation. Commercially available
polymers of PLA and LLDPE were used as the main components. In
order to modify the mechanical properties, poly(ε-caprolactone)
(PCL), random poly(ethylene−methyl acrylate) (EMA) copolymer
with 24 wt % methyl acrylate content, and a random terpolymer of Figure 1. Complex viscosity of the neat polymers vs angular frequency
ethylene−methyl acrylate−glycidyl methacrylate (EMA-GMA) with at 180 °C.
24 wt % of methyl acrylate and 8 wt % of glycidyl methacrylate content
were employed as the third component.19 The information on
suppliers and grades of all material used in this study is summarized in 2.3. Scanning Electron Microscopy (SEM). A cryo-microtome
Table 1. PLA and PCL were dried at 50 °C under vacuum overnight machine (Leica RM 2065 equipped with a cryo-chamber LN21) was
before being used in the experiments. employed to prepare samples for SEM observation. The Izod impact
fractured samples were used as is without further modification or were
Table 1. Main Characteristics of Materials Used in the cryo-fractured in a liquid nitrogen batch. PCL was extracted from the
Research microtomed samples using acetic acid, and samples containing EMA or
EMA-GMA were conditioned using cyclohexane to remove EMA or
Mwa density at 25 °C EMA-GMA and create a contrast between phases. The specimens were
material supplier grade (kg/mol) (g/cm3) dried at 50 °C under vacuum in an oven and then coated with gold/
PLA NatureWorks 3001D 152 b
1.24 palladium by plasma deposition. The surfaces were then observed
LLDPE ExxonMobil LL3402 0.94 using a field emission SEM unit (JSM 7600TFE, JEOL) operated at a
PCL Perstorp Capa 6800 80c 1.14
voltage of 2 keV.
2.4. Interfacial Tension Measurement. The interfacial tension
EMA DuPont Elvaloy AC 0.94
12024s between components was measured according to the breaking thread
EMA- Arkema Lotader 45d 0.94
method. The method is based on the distortion and breakup of a
GMA AX8900 molten cylindrical thread of a polymer in the matrix of the other
a polymer. In order to achieve this, threads (40−70 μm in diameter)
Mw: weight-average molecular weight. bObtained from ref 20. were spun out of the melt and then annealed at 40 °C for 24 h under
c
Obtained from ref 21. dMn was obtained from ref 9. vacuum to remove the residual stress. A thread of the polymer with the
higher melting temperature between two films of the other polymer
was placed in a Mettler FP-82HT hot stage operating at 180 °C, and
Ternary blends of PLA/x/LLDPE, where x represents PCL, EMA, the sinusoidal distortions of the thread over time were then recorded
or EMA-GMA, with mass compositions of 50/x/50 were prepared using an optical microscope from Nikon (Optiphot-2) equipped with
through a melt blending process. All sample preparations were carried Streampix v.III recording software. The results of at least 5−10
out on a corotating twin-screw extruder (TSE), Leistritz ZSE 18HP measurements were analyzed using SigmaScan v.5, and the results are
with an L/D ratio of 40, at a screw speed of 100 rpm with a reported in Table 2. Further details of the technique can be found
temperature profile of 160/170/170/180/180/180/180 °C from elsewhere.20
hopper to die. The extrudates were quenched in a cold−water bath 2.5. Phase Morphology Characterization. SEM micrographs
and pelletized and dried prior to injection molding. Dog-bone were used to analyze and quantify the morphology. A digitizing table
specimens of type I (ASTM D638) and impact test bars (dimensions from Wacom and SigmaScan V.5 software was employed to calculate
12.7 × 63.5 × 3.2 mm) were injection molded using a Sumimoto the cocontinuous domain size and the thickness of the middle phase.
SE50S injection molding machine at a temperature profile and screw The measurements were done with the assumption that the

B DOI: 10.1021/acs.macromol.8b00464
Macromolecules XXXX, XXX, XXX−XXX
Macromolecules Article

Table 2. Interfacial Tension Values and Spreading Coefficients at 180 °C

spreading coefficient
system interfacial tension (mN/m) (mN/m) predicted morphology

PLA/PCL/LLDPE γPLA/PE = 6.4 ± 0.2 λPLA/PCL/PE = 1.1 > 0 complete wetting: PCL completely spreads at the interface of PLA and
γPLA/PCL = 2.0 ± 0.7 λPCL/PLA/PE = −5.1 < 0 LLDPE
γPE/PCL = 3.3 ± 0.5 λPCL/PE/PLA = −7.7 < 0

PLA/EMA/LLDPE γPLA/PE = 6.4 ± 0.2 λPLA/EMA/PE = 1.7 > 0 complete wetting: EMA completely spreads at the interface of PLA and
γPLA/EMA = 2.1 ± 1.2a λEMA/PLA/PE = −5.9 < 0 LLDPE
γPE/EMA = 2.6 ± 0.8 λEMA/PE/PLA = −6.9 < 0

PLA/EMA-GMA/LLDPE γPLA/PE = 6.4 ± 0.2 λPLA/EMAGMA/PE = 2.1 > 0 complete wetting: EMA-GMA completely spreads at the interface of
γPLA/EMAGMA = 1.5 ± 0.9a λEMAGMA/PLA/PE = −5.1 < 0 PLA and LLDPE
γPE/EMAGMA = 2.8 ± 0.8 λEMAGMA/PE/PLA = −7.7 < 0
a
Obtained from ref 30.

continuous domains in the PLA/LLDPE cocontinuous network are
successions of cylinders with a diameter D. The interfacial perimeter P
of the PLA/PA interface was measured and used to calculate the
specific PLA/LLDPE interfacial area S using eq 121
P coefficient model, which employs the interfacial tensions
S=
A (1)
where A is the area of the analyzed micrograph. The average pore size
was then determined with eq 222
4ϕp
D=
S (2)
where D represents the average pore diameter and ϕp is the volume
fraction of the extracted phase.
2.6. Solvent Extraction and Gravimetry. The continuity of PLA
and the middle phase component, i.e., PCL, EMA, or EMA-GMA, was
measured using a gravimetric solvent extraction technique. The phase
mass before and after extraction is measured by weighing samples and
then using the following equation
⎛m
− mfinal ⎞
%continuity = ⎜⎜ initial ⎟⎟ × 100
⎝ mx ,initial ⎠ (3)
in which minitial and mfinal are the mass of sample before and after
extraction, respectively, and mx,initial, the mass of component x before
extraction, was used to calculate the continuity of component x.
Chloroform was used to extract the PLA phase, acetic acid to extract
PCL, and cyclohexane to extract EMA and EMA-GMA for 2 weeks
under agitation. The results are the average of four separate
measurements.
2.7. Differential Scanning Calorimetry (DSC). Thermal analysis
was performed using a DSC Q2000 (TA Instruments) in two different
modes. First, the glass transition temperature (Tg) of the components
was determined using a DSC instrument operated at modulated mode
at a heating rate of 2 °C/min with an oscillation amplitude and period
of ±1.27 °C and 60 s, respectively, over the temperature range of −80
to 100 °C. Second, the conventional DSC mode was used to measure
the other thermal transitions. Heating and cooling runs were
performed at a heating/cooling rate of 10 °C/min from 25 to 200
°C. The calculation of the crystallinity of the components was based
on the specific enthalpy of fusion of the perfect crystal, ΔHf = 93.7 J/g
for PLA23 and 293 J/g for LLDPE.24
2.8. Mechanical Tests. A universal tensile testing machine
(Instron 4400R) was used to perform tensile tests as per the ASTM
D638 standard at a crosshead speed of 50 mm/min. An impact tester
unit (CS-137C-176 CSI Custom Scientific Instrument) was employed
to measure impact strength according to the ASTM D256 standard.
All samples were conditioned at room temperature and 50% relative
humidity for at least 40 h prior to testing. An average value of five
replicates was reported for each formulation.
C DOI: 10.1021/acs.macromol.8b00464
3. RESULTS AND DISCUSSION
3.1. Interfacial Tensions and Spreading Coefficients. A
widely used thermodynamic model of predicting the phase
morphology of immiscible ternary blends is the spreading
between components to assess the final thermodynamically
favorable morphology.25,26 This model defines the thermody-
namic tendency of one component to engulf a second
component in the matrix of a third component using eq 425,27
λijk = γik − γij − γjk
(4)
in which λijk are the spreading coefficients and γij are the
interfacial tensions between components. The interfacial
tensions between components used in this study were
measured through the breaking thread method and are listed
along with the associated spreading coefficients for three
different ternary systems in Table 2. As predicted by the
spreading theory, one positive and two negative spreading
coefficients describe the tendency of one phase to segregate the
two other phases from each other which is the case in all three
systems. The positive λPLA/x/PE values presented in Table 2
predict a complete wetting morphology where the x phase, i.e.,
PCL, EMA, or EMA-GMA, completely separates PLA and
LLDPE and forms a complete layer at the PLA/LLDPE
interface. It is worth mentioning that three negative spreading
coefficients predict a partial wetting morphology in which none
of the phases engulf other phases rather all phases meet each
other at a three-phase line of contact.
3.2. Morphology. Figure 2 shows the phase morphology of
the PLA/LLDPE (50/50) blend and those containing 10% of a
third component. The binary PLA/LLDPE 50/50 blend has a
cocontinuous phase morphology where each phase is labeled in
Figure 2a. The LLDPE phase is distinguishable from the PLA
phase from its high roughness due to its higher crystallinity.
The results of gravimetry listed in Table 3 also confirm that the
binary PLA/LLDPE 50/50 blend possesses a high level of
cocontinuity with the PLA phase showing about 88% continuity
and the remaining LLDPE being self-supporting (see Figure
S1). The PLA/LLDPE matrix remains cocontinuous in the
ternary blends for all the formulations with equal PLA and
LLDPE concentrations, and every third component used in the
study is localized as a layer at the interface of PLA/LLDPE.
Figure 2b shows the tricontinuous structure of the PLA/PCL/
LLDPE 45/10/45 ternary blend after extraction of the PCL
phase where voids are clearly detectable at the interface of
Macromolecules XXXX, XXX, XXX−XXX
Macromolecules Article

to over 95% for EMA and EMA-GMA. The continuity of the

PLA phase is also found to be at 88−99% which, considering
the remaining self-supporting porous LLDPE, suggests a
tricontinuous morphology for the all ternary blends with the
PLA/x/LLDPE 45/10/45 concentration. However, the third
components used in these blends result in different
compatibilization effects. The PLA (DPLA) and LLDPE (DPE)
phase sizes of the blends are summarized in Table 3. The binary
PLA/LLDPE 50/50 blend shows a phase size in the range of
22−26 μm, which remains at the same size scale with the
addition of 10% PCL to the PLA/LLDPE (1:1) system. In
contrast, the addition of EMA and EMA-GMA significantly
reduces the PLA/LLDPE phase to about 5 μm, which is almost
5 times smaller than the original binary blend. The marked
decrease in the phase size of the cocontinuous PLA/LLDPE is
important since it shows that an interfacially percolated phase
can act as a compatibilizer at the interface and reduce the phase
size of a cocontinuous system.
Figure 3 displays a schematic of phase ordering and possible
interfacial interactions in these systems. In the PLA/LLDPE

Figure 2. SEM micrographs of (a) 50PLA/50LLDPE, (b) 45PLA/

10PCL/45LLDPE, (c, c′) 45PLA/10EMA/45LLDPE, and (d, d′)
45PLA/10EMA-GMA/45LLDPE. Note that acetic acid is used to
extract PCL and cyclohexane is employed to extract EMA and EMA-
GMA.

PLA/LLDPE. Also, some very tiny voids of about 300 nm,

extracted from the PLA phase, are identified as PCL dispersed
particles trapped within the PLA phase due to the high viscosity
of polymeric systems. EMA forms a completely wet layer at the
interface of PLA/LLDPE with a thickness of 0.6 μm which is
significantly lower than the 1.9 μm thickness of the system with
10% (see Figure 2c). It will be shown that this can be attributed
to the greater interfacial interactions of EMA with both the
PLA and LLDPE phases compared with PCL, which only
interacts with PLA as reported in the literature.28 Similar to Figure 3. Schematic illustrating the interfacial interactions in the PLA/
EMA, EMA-GMA also develop into a 0.5 μm completely wet x/LLDPE systems.
layer at the PLA/LLDPE interface (see Figure 2d). These are
typical phase morphologies observed in a ternary blend with
complete wetting behavior.26,29 50/50 blend, no interfacial interaction is envisaged and the
The results of morphology quantification and continuity cocontinuous phase size is the largest. Although the PCL phase
measurements for the blends are presented in Table 3. As the thermodynamically favors to the formation of a completely wet
SEM images indicate, the gravimetry analysis also proves the layer at the interface of the PLA and LLDPE phases, no
existence of a tricontinuous phase morphology in all ternary appreciable reduction in the phase size is observed. This can be
blends with equal PLA and LLDPE concentrations. The attributed to the very limited interfacial interaction of PCL with
continuity of the middle phase is in the range of 82% for PCL PLA and no interaction with LLDPE. However, EMA and

Table 3. Morphological Characteristics of the Blends

layer thickness PLA phase (LDPE + x) phase middle phase
sample (μm) DPLA (μm) DPE (μm) continuitya (%) continuitya (%) continuitya (%)
PLA/LLDPE 50/50 22.6 ± 8.2 26.6 ± 7.3 88 ± 11
PLA/PCL/LLDPE 45/10/45 1.9 ± 0.7 23.6 ± 8.7 22.1 ± 8.7 90 ± 9 82 ± 5
PLA/PCL/LLDPE 60/10/30 39 ± 5
PLA/EMA/LLDPE 45/10/45 0.6 ± 0.2 5.8 ± 2.5 8.5 ± 5 98 ± 6 97 ± 6
PLA/EMA/LLDPE 60/10/30 43 ± 6
PLA/EMA-GMA/LLDPE 45/10/45 0.5 ± 0.2 4.6 ± 1.6 5.3 ± 3.1 99 ± 5 95 ± 6
PLA/EMA-GMA/LLDPE 60/10/30 41 ± 5

a
Obtained from the gravimetry analysis.

D DOI: 10.1021/acs.macromol.8b00464
Macromolecules XXXX, XXX, XXX−XXX
Macromolecules Article

particularly EMA-GMA are copolymers of ethylene and methyl strength significantly increases to about 360 J/m and the
acrylate and are expected to interact with both the PLA and elongation at break to about 40%. A substantial enhancement in
LLDPE phases (c, d). It is worth mentioning that a commonly the impact strength and elongation at break at 515 J/m and
employed method to compatibilize cocontinuous blends is to 70%, respectively, is achieved by the addition of 10% EMA-
add premade block copolymers or to use in situ generation of GMA to the cocontinuous PLA/LLDPE 50/50. Although the
graft block copolymers through a reactive process at inter- impact strength and elongation at break improve through the
face.30−32 Block copolymers with suitable design of chemistry, addition of the third component to the cocontinuous PLA/
molecular weight, and chain structure can localize at the LLDPE system, only modest improvements in the elastic
interface and stabilize the morphology; however, micelle modulus and tensile strength are observed which are typically
formation often occurs and can reduce the effectiveness of observed in the toughening of glassy polymer using rubbery
additives by lowering the interfacial concentration of block components.33 Figure 4 shows the photographs of impact
copolymer. In contrast to block copolymers, no such a problem
as micellation occurs in tricontinuous immiscible blends since
the morphology of phase-separated multicomponent polymer
blends is thermodynamically driven and is related to the
interfacial energy between components. 25,27 Thus, the
compatibilization effect observed here can be attributed to
the thermodynamically favored phase morphology and
interfacial interactions at the interfaces. These interfacial
interactions are evaluated in section 3.4.
3.3. Mechanical Properties. Table 4 compares the impact
strength, elastic modulus, tensile yield strength, and elongation

Table 4. Mechanical Properties of the Pure Components and Figure 4. Photographs of impact fracture testing bar of (a) PLA/PCL/
Various Melt Blended Systems LLDPE 45/10/45, (b) PLA/EMA/LLDPE 45/10/45, and (c) PLA/
EMA-GMA/LLDPE 45/10/45.
Young’s tensile
Izod impact modulus strength elongation at
sample strength (J/m) (GPa) (MPa) break (%) fracture testing bars of the three different ternary blends. A
PLA 15.9 ± 0.7 4.3 ± 0.3 65.6 ± 1.2 3.6 partial break is observed in these samples in which the sample
LLDPE 470 ± 22 0.7 ± 0.2 18.2 ± 2 >500 containing EMA-GMA shows the toughest fracture behavior
PLA/LLDPE 39.5 ± 2.3 1.5 ± 0.2 21.3 ± 0.4 20 ± 2 with a clear whitening at the fracture area.
50/50
As discussed in the Morphology section, the ternary blends
PLA/LLDPE 29.6 ± 1.2 2.2 ± 0.1 34.3 ± 0.2 15 ± 4
70/30 with the PLA/LLDPE ratio maintained at 1 possess a
PLA/PCL/LLDPE 51.4 ± 6.5 2.1 ± 0.1 26.7 ± 0.6 22 ± 5 tricontinuous morphology. Increasing the concentration of
60/10/30 PLA in the samples containing a fixed 10% of middle
PLA/PCL/LLDPE 100.0 ± 6.8 1.7 ± 0.2 22.8 ± 0.5 35 ± 5 component, i.e., changing the composition ratio of PLA/
45/10/45
LLDPE, converts the tricontinuous morphology to a matrix/
PLA/EMA/ 89.8 ± 8.5 1.9 ± 0.1 29.2 ± 0.1 25 ± 6
LLDPE
dispersed where a core−shell morphology possibly forms, in
60/10/30 which LLDPE is the core phase and the middle component is
PLA/EMA/ 358.8 ± 30.7 1.6 ± 0.1 22.2 ± 1.2 39 ± 5 the shell phase. The mechanical properties listed in Table 4
LLDPE indicate that the impact strength of the ternary blends
45/10/45
PLA/EMA-GMA/ 138.1 ± 18.4 1.8 ± 0.1 28.1 ± 0.9 36 ± 4
deteriorates upon the change in the PLA/x/LLDPE composi-
LLDPE tion from 45/10/45 to 60/10/30. The gravimetry analysis
60/10/30 results also show that the continuity of the LLDPE phase is
PLA/EMA-GMA/ 514.6 ± 18.4 1.6 ± 0.1 24.4 ± 0.9 70 ± 12 around 40%, implying low continuity, i.e., approaching a
LLDPE
45/10/45 dispersed phase morphology. These results suggest that the
cocontinuous morphology plays a critical role in the toughening
of the PLA/x/LLDPE systems. Figure 5 compares the notched
at break of the neat polymers and blends. PLA is a glassy Izod impact strength of the ternary PLA/x/LLDPE blends as a
semicrystalline polymer demonstrating high modulus and function of PLA content. The PLA content is given as a
tensile strength but poor elongation at break and notched function of PLA in (PLA plus LLDPE), which is equal to 90%
Izod impact strength. Although it has been reported that the in the ternary systems containing a fixed third component at
addition of linear low-density polyethylene to PLA can result in 10%. Thus, 50% PLA in Figure 5 refers to 45% PLA/10% x/
a significant improvement over the impact toughness of PLA,3 45% LLDPE blend. Figure 5 shows that an important increase
the binary blend of PLA/LLDPE 50/50 and 70/30 only show a in impact strength is obtained at 50% PLA with an impact
slightly improved impact and tensile toughness of 39.5 and 29.6 strength up to 515 J/m for the PLA/EMA-GMA/LLDPE blend
J/m, respectively (see Table 4). This suggests that interfacial while limited improvements are achieved above 60% PLA.
modification is necessary for obtaining enhanced mechanical Similar results have been reported for the ternary PLA/
properties as reported in the literature.5,8,19 The addition of polyether-b-amide/polyamide-11 blends in the literature in
10% PCL to the binary PLA/LLDPE 50/50 increases the which the highest toughness has been achieved when all phases
notched Izod impact strength to 100 J/m with a limited are fully continuous constructing a tricontinuous morphology.10
improvement in the elongation at break up to 35%. When 10% It should be noted that the tricontinuous region is estimated
EMA is added to the binary PLA/LLDPE 50/50, the impact from the gravimetry and morphological analyses results.
E DOI: 10.1021/acs.macromol.8b00464
Macromolecules XXXX, XXX, XXX−XXX
Macromolecules
Figure 5. Impact strength and phase continuity of ternary blend
formulations. The weight fraction of PLA is based on (PLA +
LLDPE). The third, intermediate phase is held at 10% of the total
weight. Hence, the compositions follow PLA/10/LLDPE where PLA
+ LLDPE = 90. Note that 0% and 100% represent pure LLDPE and
PLA, respectively. The dashed lines are a guide to the eye.
To evaluate the influence of the middle phase content on
impact strength, the concentration of this phase was varied
from 0 to 15% in the ternary PLA/x/LLDPE blends, and the
results are presented in Figure 6. For all three different middle
Figure 6. Impact strength as a function of the middle phase content in
PLA/x/LLDPE where the PLA:LLDPE ratio is maintained at 1:1.
phase components, the impact strength increases with middle
phase content and levels off at 10% at values of about 100, 370,
and 530 J/m for PCL, EMA, and EMA-GMA, respectively.
These results can be attributed to the interfacial coverage of the
middle phase at the PLA/LLDPE interface which has been
shown to correlate with impact strength of ternary systems with
interfacially percolated rubbery phase.10
3.4. Interfacial Interactions. A range of interfacial
interactions are possible between the components in the
ternary PLA/x/LLDPE blends studied here. PLA and LLDPE
are thermodynamically immiscible as is reflected in the high
interfacial tension of PLA/LLDPE at 6.4 mN/m, which is
presented in Table 2. The thermal properties of the binary
PLA/LLDPE 50/50 blend also confirm that there are no
F DOI: 10.1021/acs.macromol.8b00464
Article
specific interactions between PLA and LLDPE as no change in
the glass transition temperature (Tg) and melting temperature
(Tm) of the components is observed. The crystallinity of PLA,
though, is increased from 2 to about 17%, which can be
attributed to the enhanced nucleation of PLA by the molten
LLDPE at the interface between the two phases.34
It has been reported that compatibilization with a suitable
block copolymer is necessary to obtain a high performance
PLA/LLDPE blend.3,6 The addition of PCL replaces the PLA/
LLDPE interface with the two new interfaces of PLA/PCL and
LLDPE/PCL that possess significantly lower interfacial
tensions than that of PLA/LLDPE at 6.4 mN/m (see Table
2). PLA and PCL have some interfacial interactions28 resulting
in partial miscibility which is reflected in their low interfacial
tension at 2.0 mN/m. LLDPE/PCL also shows a low interfacial
tension at 3.3 mN/m. Although the addition of PCL is
expected to improve the interfacial adhesion between the
components, almost no change in the size of the phase
morphology of the PLA/PCL/LLDPE system is observed when
it is compared to that of the binary PLA/LLDPE 50/50 blend
(see Figure 2b and Table 3). This suggests limited interfacial
interactions exist between phases during morphology develop-
ment, in particular between PCL and LLDPE. EMA, which is a
copolymer of ethylene and methyl acrylate, however, has
interactions with both the PLA and LLDPE phases. It has been
shown that EMA is partially miscible with PLA due to the
interactions between the methyl acrylate segments of EMA and
PLA.35 Additionally, there is a natural affinity between the
ethylene blocks of EMA and LLDPE which promotes the
interfacial adhesion between the LLDPE and EMA phases.
Accordingly, the significant reduction observed in the size of
the cocontinuous PLA/LLDPE phase morphology can be
attributed to the improved interfacial interaction of EMA with
both PLA and LLDPE phases (see Figure 2c and Table 3). The
thermal properties of the binary PLA/EMA and LLDPE/EMA
blends are listed in Table 5 to further examine the possible
interfacial interactions between components (see Figure S2).
The Tg of EMA is increased from −48 to −30 °C in the blend
of PLA/EMA 80/20. The other second-order transitions of
LLDPE/EMA are difficult to characterize through DSC analysis
due to segmental similarity between the ethylene blocks of
EMA and LLDPE; however, the natural affinity between
ethylene segments can potentially enhance the interfacial
interactions.
The interfacial interactions between EMA-GMA and PLA/
LLDPE are supposed to be further enhanced due to the
presence of the reactive epoxide groups (glycidyl group) of
GMA segments. In addition to the interactions of methyl
acrylate groups of EMA-GMA with PLA chains,35,36 it has been
shown that the reactive groups can react with the terminal
groups of PLA (hydroxyl and carboxyl groups)12,37 and form
graft copolymers at interface.13,14,38 The reduced interfacial
tension of PLA/EMA-GMA at 1.5 mN/m suggests a much
more compatible interface compared to the PLA/EMA
interface due to the interfacial interactions and reactions at
the interface. The LLDPE/EMA-GMA interface also possesses
a reduced interfacial tension at 2.8 mN/m in comparison to
that of the PLA/LLDPE interface at 6.4 mN/m
The thermal properties of the PLA/EMA-GMA/LLDPE
system also indicate good interactions between EMA-GMA and
PLA/LLDPE. The Tg of EMA-GMA increases from −35 to
−30 °C, and the Tg of PLA shows a 2 °C reduction in the
Macromolecules XXXX, XXX, XXX−XXX
Macromolecules Article

Table 5. Thermal Properties of the Pure Polymers and Blendsa

samples Tg (°C) Tm,PLA (°C) Tm,LLDPE (°C) Xc,PLA (%) Xc,LLDPE (%)
PLAb 61 170 2
LLDPEc 125.1 19.7
PCLd −50 56
EMAe −48, −10 61e
EMA-GMAf −35 50f
PLA/PCL 80/20 168.6 15
LLDPE/PCL 80/20 124.5 17.2
PLA/EMA 80/20 59b/−30e 166 4
LLDPE/EMA 80/20 −46e 124.3 17.5
PLA/EMA-GMA 80/20 59b/−30f, −8f 167 7
LLDPE/EMA-GMA 80/20 −35f 124.6 12.5
PLA/LLDPE 50/50 61b 169.3 124.9 17.3 14.5
PLA/PCL/LLDPE 45/10/45 167.9 124.2 13 12.5
PLA/EMA/LLDPE 45/10/45 168.4 124.1 18.7 15.6
PLA/EMA-GMA/LLDPE 45/10/45 168.5 124.2 24.5 17.6
a
Tg: glass transition temperature; Tcc: cold crystallization temperature; Tm: melting temperature; Xc: crystallinity (%). bPLA. cLLDPE. dPCL. eEMA.
f
EMA-GMA.

Figure 7. SEM micrographs of the impact fracture surface at the notch root of (a, a′) PLA/LLDPE 50/50, (b, b′) PLA/PCL/LLDPE 45/10/45, (c,
c′) PLA/EMA/LLDPE 45/10/45, and (d, d′) PLA/EMA-GMA/LLDPE 45/10/45. The white bars denote 10 μm.

binary PLA/EMA-GMA 80/20 blend, implying interfacial
interactions between PLA and EMA-GMA.
Figure 2d′ shows nanometer size fibrils, which bridge the gap
between the PLA and LLDPE phases (the extracted EMA-
GMA phase); however, the gap in Figure 2c′ is completely
extracted (the EMA phase). These fibrils are likely graft
copolymers of PLA and EMA-GMA, PLA-g-(EMA-GMA),
which extend from the PLA phase to the LLDPE phase and are
not affected by cyclohexane due to the insolubility of PLA
segments with the solvent. These are covalently bound to the
PLA chains on the PLA side and physically interact on the
LLDPE side through the ethylene segments of EMA-GMA.39
These interactions can reduce the interfacial energy and alter
the dynamics of interface and the pressure difference across the
interface which can consequently result in the formation of
smaller interconnected domains.40−42
3.5. Toughening Mechanism. The mechanical properties
can be explained based on the interfacial interactions between
components. PLA and LLDPE are immiscible polymers with a
very weak interfacial adhesion.6 This results in a poor stress
transfer at the interface and failure of the blend under
mechanical testing. The poor impact strength of the binary
PLA/LLDPE 50/50 blend at about 39 J/m can be attributed to
the coarse morphology and weak interfacial adhesion of PLA/
G DOI: 10.1021/acs.macromol.8b00464
LLDPE. The addition of 10% PCL to the system replaces the
weak PLA/LLDPE interface with two new interfaces which are
stronger, at least the PLA/PCL interface, than the PLA/LLDPE
interface. The higher interfacial adhesion along with the
interconnected rubbery-like PCL network result in a consid-
erable improvement in the impact strength to 100 J/m. The
addition of 10% EMA as a middle phase to PLA/LLDPE,
however, creates two new highly interactive interfaces which
significantly enhances the mechanical performances. The high
impact strength at about 360 J/m can be directly related to the
higher interfacial adhesion and finer PLA/LLDPE domain size
in the PLA/EMA/LLDPE 45/10/45 system. The highly
reactive EMA-GMA demonstrates significantly more improved
impact strength at about 515 J/m owing to the enhanced
interfacial adhesion along with its very fine phase morphology.
Multiple interfaces in multicomponent blends can affect the
crystallinity of components through mainly nucleation enhance-
ment at the interface.43 The crystallinity of PLA is increased
through melt blending in the binary and ternary blends (see
Table 5). In particular, the very low crystallinity of PLA at 2% is
increased to above 13% (13−24.5%) in the ternary PLA/x/
LLDPE 45/10/45 blends. The nucleation at the rubber/matrix
interface produces crystallographically oriented material at the
interface region.3,44 These oriented layers possess a reduced
Macromolecules XXXX, XXX, XXX−XXX
Macromolecules
Figure 8. SEM micrographs of the cryo-fractured surface of a cross section underneath the Izod impact fracture surface of (a, a′) PLA/LLDPE 50/
50, (b, b′) PLA/PCL/LLDPE 45/10/45, (c, c′) PLA/EMA/LLDPE 45/10/45, and (d, d′) PLA/EMA-GMA/LLDPE 45/10/45. The white bars
denote 10 μm.
resistance to plastic deformation45 which percolates at the
interconnected interface of the cocontinuous phase morphol-
ogy, resulting in tough behavior. Thus, in addition to the effect
of the tricontinuous phase morphology and interfacial adhesion,
the increased toughness in the ternary blends with
tricontinuous phase morphology can also be attributed to the
presence of overlapping crystalline layers at the interface.
SEM micrographs of the impact fracture surface of the binary
and ternary PLA/LLDPE based blends are presented in Figure
7. The binary PLA/LLDPE 50/50 blend shows a very rough
fracture surface but a closer look at the fracture area reveals a
brittle fracture behavior of the PLA domains as marked by
arrows in Figure 7a′. The cryo-fractured surface under the
impact fracture area in Figure 8a,a′ clearly shows interfacial
debonding and crazing at the PLA/LLDPE interface. This
suggests that the low impact strength of this sample at 39 J/m
can be attributed to the brittle fracture of the PLA domains
mainly due to the very poor interfacial adhesion between PLA
and LLDPE at the interface. The ternary PLA/PCL/LLDPE
45/10/45 blend also demonstrates a rough fracture surface, but
with some plastic deformation (Figure 7). Despite the rougher
surface which is manifested in the improved impact strength at
100 J/m, the brittle fracture of the PLA domains as indicated by
arrows in Figure 7b′ still limits the impact toughness of the
system. Although the interfacial adhesion between the PLA and
PCL phases is good, the relatively low impact strength obtained
in this blend is attributed to the brittle fracture of the PLA
domains mainly due to the poor stress transfer and crazing at
the PCL/LLDPE interface with poor interfacial adhesion. The
brittle fracture of the PLA domains and the interfacial
debonding are indicated by arrows in Figures 7b′ and 8b′,
respectively.
Replacing PCL with EMA in the PLA/PCL/LLDPE 45/10/
45 blend results in a much tougher system with a notched
impact strength at about 360 J/m. This is reflected in the
topography of the impact fracture surface in Figure 7c, showing
a uniform rough surface with significant plastic deformation.
Although the roughness of the surface seems to be reduced in
these blends, the fine and uniform roughness implies much
more energy dissipation as compared with the PCL middle
phase blend due to a higher fracture surface formed during the
fracture process. No domains demonstrating brittle fracture
mode is found upon closer observation of the fracture surface
of PLA/EMA/LLDPE 45/10/45, implying effective stress
H DOI: 10.1021/acs.macromol.8b00464
Article
transfer along the PLA/EMA and EMA/LLDPE interfaces
due to good interfacial adhesion (see Figure 7c′). Figure 8c,c′
shows the cryo-fractured surface of the PLA/EMA/LLDPE 45/
10/45 blend in which no debonding is observed, confirming
substantial interfacial adhesion between components.
A similar fracture behavior with much more intense matrix
plastic deformation is observed in the fracture surface of the
PLA/EMA-GMA/LLDPE 45/10/45 blend which is shown in
Figure 7d. Furthermore, the cryo-fractured surface under the
fractured area reveals no interfacial debonding in Figure 8d,d′.
The fracture surface result and high notched Izod impact
strength of 515 J/m obtained from this blend suggest that the
very fine tricontinuous morphology and reinforcement of the
PLA/EMA-GMA interface due to the interfacial interactions are
very effective in the toughening of this ternary polymer blend.
These results suggest a shear yielding mechanism in the
toughening of the PLA/EMA/LLDPE and PLA/EMA-GMA/
LLDPE 45/10/45 blends which are in line with the previous
studies on the toughening of multicomponent polymer
blends.10,46
The results suggest that the interfacial adhesion is the main
controlling factor in the toughening of the PLA/x/LLDPE
systems with tricontinuous morphology. While some improve-
ment in the interfacial adhesion is likely to occur due to
entanglements at the interface,47 a significant enhancement is
expected when specific interactions exist between compo-
nents.48,49 Upon the addition of PCL to the binary 50/50
blend, the weak PLA/LLDPE interface is replaced by the PLA/
PCL and PCL/LLDPE interfaces. The PLA/PCL interface
possesses a good interfacial adhesion while the PCL/LLDPE
interface is still a weak one (Figure 3b). However, the
interconnected rubbery network of PCL facilitates the process
of stress transfer throughout the system and a marginal
improvement in the impact strength is obtained. In contrast to
PCL, EMA is a rubbery copolymer of ethylene and methyl
acrylate which has good interactions with both the PLA and
LLDPE phases (Figure 3c). It is well-known that rubber
cavitation is the main dilatational deformation process and an
important part of the toughening mechanism in rubber-
toughened polymers.50 The cocontinuous structure of the
PLA/LLDPE matrices provides a continuous interface in which
the interfacially percolated rubbery network can cavitate
throughout the sample. Thus, the percolated EMA at the
PLA/LLDPE interface markedly improves the impact strength
Macromolecules XXXX, XXX, XXX−XXX
Macromolecules
of the system as it significantly lowers the dilatational stress by
percolating stress throughout the system and effectively
transferring stress along the phases. This significantly facilitates
the dilatational deformation of the PLA domains and yielding
process. In contrast to the tricontinuous PLA/EMA/LLDPE
45/10/45 system, the interconnected interfacial area, which
extends over the entire sample, is significantly reduced in the
systems beyond the tricontinuous composition region. This
means that only discrete interfacial areas within the PLA matrix
exist, and the stress fields around rubbery domains cannot
effectively percolate throughout the sample. EMA-GMA is even
more effective than EMA in the toughening of the PLA/
LLDPE blend due to the possibility of enhanced interfacial
reactions, i.e., formation of graft copolymers at the PLA/EMA-
GMA interface13,14,38 and interpenetration of LLDPE segments
of EMA-GMA into the amorphous phase of the LLDPE
phase.39 Knowing that the only difference between the systems
with EMA and EMA-GMA is the possibility of a graft reaction
between the glycidyl groups of EMA-GMA and PLA, it shows
to what extent strong interfacial adhesion can influence the
toughening of a system with a tricontinuous morphology.
4. CONCLUSION
Three different systems based on the cocontinuous PLA/
LLDPE system are shown to form thermodynamically driven
tricontinuous structures in which PCL, EMA, or EMA-GMA is
percolated at the PLA/LLDPE interface as the middle phase.
These components possess different levels of interfacial
interactions with the PLA/LLDPE matrices which influence
the morphology and toughness of the systems. The middle
phase is found to compatibilize the cocontinuous PLA/LLDPE
phase morphology where EMA-GMA results in the highest
compatibilization effect by reducing the domain size from about
25 μm to about 5 μm while only a slight decrease is obtained
with PCL at 22 μm. EMA is also effective in compatibilizing the
morphology by reducing the cocontinuous domain size to
about 7 μm. The toughness of the binary PLA/LLDPE 50/50
blend increases from about 40 to 100 J/m upon addition of
PCL and further increases to about 360 J/m with EMA.
However, an impact strength of about 515 J/m, a 13-fold
improvement over the neat PLA/LLDPE blend and more than
32-fold improvement over the neat PLA, is achieved with EMA-
GMA. The results clearly indicate the importance of both a
tricontinuous morphology and strong interfacial interactions in
obtaining materials of high toughness. Since it is also possible
to obtain polyethylene from renewable sources, these results
provide a route to achieve high performance materials at high
biobased content.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.macro-
mol.8b00464.
Figures S1 and S2 (PDF)
■
AUTHOR INFORMATION
Corresponding Author
*E-mail basil.favis@polymtl.ca; tel +1 514 340-4711 ext 4527;
fax +1 514 340-4159 (B.D.F.).
ORCID
Ali M. Zolali: 0000-0002-8459-068X
I DOI: 10.1021/acs.macromol.8b00464
Article
Basil D. Favis: 0000-0002-7980-3740
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The authors thank the NSERC Network for Innovative Plastic
Materials and Manufacturing Processes (NIPMMP) for
supporting this work.
■
REFERENCES
(1) Anderson, K. S.; Schreck, K. M.; Hillmyer, M. A. Toughening
Polylactide. Polym. Rev. 2008, 48 (1), 85−108.
(2) Liu, H.; Zhang, J. Research Progress in Toughening Modification
of Poly(lactic Acid). J. Polym. Sci., Part B: Polym. Phys. 2011, 49 (15),
1051−1083.
(3) Anderson, K. S.; Lim, S. H.; Hillmyer, M. A. Toughening of
Polylactide by Melt Blending with Linear Low-Density Polyethylene. J.
Appl. Polym. Sci. 2003, 89 (14), 3757−3768.
(4) Brito, G. F.; Agrawal, P.; Araújo, E. M.; Mélo, T. J. A. de
Polylactide/Biopolyethylene Bioblends. Polim.: Cienc. Tecnol. 2012, 22
(5), 427−429.
(5) Thurber, C. M.; Xu, Y.; Myers, J. C.; Lodge, T. P.; Macosko, C.
W. Accelerating Reactive Compatibilization of PE/PLA Blends by an
Interfacially Localized Catalyst. ACS Macro Lett. 2015, 4 (1), 30−33.
(6) Wang, Y. B.; Hillmyer, M. A. Polyethylene-poly(L-Lactide)
Diblock Copolymers: Synthesis and Compatibilization of poly(L-
Lactide)/polyethylene Blends. J. Polym. Sci., Part A: Polym. Chem.
2001, 39 (16), 2755−2766.
(7) Zolali, A. M.; Favis, B. D. Partial and Complete Wetting in
Ultralow Interfacial Tension Multiphase Blends with Polylactide. J.
Phys. Chem. B 2016, 120 (49), 12708−12719.
(8) Anderson, K. S.; Hillmyer, M. A. The Influence of Block
Copolymer Microstructure on the Toughness of Compatibilized
Polylactide/polyethylene Blends. Polymer 2004, 45 (26), 8809−8823.
(9) Xu, Y.; Loi, J.; Delgado, P.; Topolkaraev, V.; McEneany, R. J.;
Macosko, C. W.; Hillmyer, M. A. Reactive Compatibilization of
Polylactide/Polypropylene Blends. Ind. Eng. Chem. Res. 2015, 54 (23),
6108−6114.
(10) Zolali, A. M.; Heshmati, V.; Favis, B. D. Ultratough Co-
Continuous PLA/PA11 by Interfacially Percolated Poly(ether- B
-Amide). Macromolecules 2017, 50 (1), 264−274.
(11) Heshmati, V.; Zolali, A. M.; Favis, B. D. Morphology
Development in Poly (Lactic acid)/polyamide11 Biobased Blends:
Chain Mobility and Interfacial Interactions. Polymer 2017, 120 (3),
197−208.
(12) Hashima, K.; Nishitsuji, S.; Inoue, T. Structure-Properties of
Super-Tough PLA Alloy with Excellent Heat Resistance. Polymer 2010,
51 (17), 3934−3939.
(13) Liu, H.; Chen, F.; Liu, B.; Estep, G.; Zhang, J. Super Toughened
Poly(lactic Acid) Ternary Blends by Simultaneous Dynamic Vulcan-
ization and Interfacial Compatibilization. Macromolecules 2010, 43
(14), 6058−6066.
(14) Liu, H.; Song, W.; Chen, F.; Guo, L.; Zhang, J. Interaction of
Microstructure and Interfacial Adhesion on Impact Performance of
Polylactide (PLA) Ternary Blends. Macromolecules 2011, 44 (6),
1513−1522.
(15) Bai, S. L.; Wang, G. T.; Hiver, J. M.; G’Sell, C. Microstructures
and Mechanical Properties of Polypropylene/polyamide 6/polyethe-
lene-Octene Elastomer Blends. Polymer 2004, 45 (9), 3063−3071.
(16) Zhang, K.; Mohanty, A. K.; Misra, M. Fully Biodegradable and
Biorenewable Ternary Blends from Polylactide, Poly(3-Hydroxybuty-
rate-Co-Hydroxyvalerate) and Poly(butylene Succinate) with Balanced
Properties. ACS Appl. Mater. Interfaces 2012, 4 (6), 3091−3101.
(17) Zhang, K.; Nagarajan, V.; Misra, M.; Mohanty, A. K.
Supertoughened Renewable PLA Reactive Multiphase Blends System:
Phase Morphology and Performance. ACS Appl. Mater. Interfaces 2014,
6 (15), 12436−12448.
Macromolecules XXXX, XXX, XXX−XXX
Macromolecules Article

(18) Dou, R.; Zhou, Y.; Shen, C.; Li, L.; Yin, B.; Yang, M. (38) Dong, W.; Jiang, F.; Zhao, L.; You, J.; Cao, X.; Li, Y. PLLA
Toughening of PA6/EPDM-G-MAH/HDPE Ternary Blends via Microalloys versus PLLA Nanoalloys: Preparation, Morphologies, and
Controlling EPDM-G-MAH Grafting Degree: The Role of Core− Properties. ACS Appl. Mater. Interfaces 2012, 4 (7), 3667−3675.
shell Particle Size and Shell Thickness. Polym. Bull. 2015, 72 (2), 177− (39) Zhao, H.; Lei, Z.; Wang, Z.; Huang, B. Studies on Blends of
193. LLDPE and Ethylene-Methacrylic Acid Random Copolymer. Eur.
(19) Feng, Y.; Zhao, G.; Yin, J.; Jiang, W. Reactive Compatibilization Polym. J. 1999, 35 (2), 355−360.
of High-Impact Poly(lactic Acid)/ethylene Copolymer Blends (40) Yuan, Z.; Favis, B. D. Coarsening of Immiscible Co-Continuous
Catalyzed by N,N-Dimethylstearylamine. Polym. Int. 2014, 63 (7), Blends during Quiescent Annealing. AIChE J. 2005, 51 (1), 271−280.
1263−1269. (41) Saito, H.; Yoshinaga, M.; Mihara, T.; Nishi, T.; Jinnai, H. The
(20) Elemans, P. H. M.; Janssen, J. M. H.; Meijer, H. E. H. The Interface Dynamics of Bicontinuous Phase Separating Structure in a
Measurement of Interfacial Tension in Polymer/polymer Systems: Polymer Blend. J. Phys. Conf. Ser. 2009, 184 (1), 012029.
(42) López-Barrón, C. R.; Macosko, C. W. A New Model for the
The Breaking Thread Method. J. Rheol. 1990, 34 (8), 1311−1325.
Coarsening of Cocontinuous Morphologies. Soft Matter 2010, 6 (12),
(21) Galloway, J. A.; Montminy, M. D.; Macosko, C. W. Image
2637.
Analysis for Interfacial Area and Cocontinuity Detection in Polymer (43) Sakai, F.; Nishikawa, K.; Inoue, Y.; Yazawa, K. Nucleation
Blends. Polymer 2002, 43, 4715−4722. Enhancement Effect in Poly(L-Lactide) (PLLA)/Poly(ϵ-Caprolac-
(22) Li, J.; Favis, B. D. Characterizing Co-Continuous High Density tone) (PCL) Blend Induced by Locally Activated Chain Mobility
Polyethylene/polystyrene Blends. Polymer 2001, 42 (11), 5047−5053. Resulting from Limited Miscibility. Macromolecules 2009, 42 (21),
(23) Garlotta, D. A Literature Review of Poly (Lactic Acid). J. Polym. 8335−8342.
Environ. 2001, 9 (2), 63−84. (44) Muratoglu, O. K.; Argon, A. S.; Cohen, R. E.; Weinberg, M.
(24) Mathot, V. B. F. Temperature Dependence of Some Toughening Mechanism of Rubber-Modified Polyamides. Polymer
Thermodynamic Functions for Amorphous and Semi-Crystalline 1995, 36 (5), 921−930.
Polymers. Polymer 1984, 25, 579−599. (45) Bartczak, Z.; Argon, A. S.; Cohen, R. E.; Weinberg, M.
(25) Hobbs, S. Y.; Dekkers, M. E. J.; Watkins, V. H. Effect of Toughness Mechanism in Semi-Crystalline Polymer Blends: I. High-
Interfacial Forces on Polymer Blend Morphologies. Polymer 1988, 29 Density Polyethylene Toughened with Rubbers. Polymer 1999, 40 (9),
(9), 1598−1602. 2331−2346.
(26) Valera, T. S.; Morita, A. T.; Demarquette, N. R. Study of (46) Ravati, S.; Beaulieu, C.; Zolali, A. M.; Favis, B. D. High
Morphologies of PMMA/PP/PS Ternary Blends. Macromolecules Performance Materials Based on a Self-Assembled Multiple-Percolated
2006, 39 (7), 2663−2675. Ternary Blend. AIChE J. 2014, 60 (8), 3005−3012.
(27) Torza, S.; Mason, S. G. Three-Phase Interactions in Shear and (47) Cole, P. J.; Cook, R. F.; Macosko, C. W. Adhesion between
Electrical Fields. J. Colloid Interface Sci. 1970, 33 (1), 67−83. Immiscible Polymers Correlated with Interfacial Entanglements.
(28) Newman, D.; Laredo, E.; Bello, A.; Grillo, A.; Feijoo, J. L.; Macromolecules 2003, 36 (8), 2808−2815.
Müller, A. J. Molecular Mobilities in Biodegradable Poly(dl-lactide)/ (48) Benkoski, J. J.; Flores, P.; Kramer, E. J. Diblock Copolymer
Poly(ε-Caprolactone) Blends. Macromolecules 2009, 42 (14), 5219− Reinforced Interfaces between Amorphous Polystyrene and Semi-
5225. crystalline Polyethylene. Macromolecules 2003, 36 (9), 3289−3302.
(29) Omonov, T. S.; Harrats, C.; Groeninckx, G. Co-Continuous and (49) Chaffin, K. A.; Knutsen, J. S.; Brant, P.; Bates, F. S. High-
Encapsulated Three Phase Morphologies in Uncompatibilized and Strength Welds in Metallocene Polypropylene/Polyethylene Lami-
Reactively Compatibilized Polyamide 6/polypropylene/polystyrene nates. Science 2000, 288 (5474), 2187−2190.
Ternary Blends Using Two Reactive Precursors. Polymer 2005, 46 (50) Bucknall, C. B.; Paul, D. R. Notched Impact Behavior of
Polymer Blends: Part 1: New Model for Particle Size Dependence.
(26), 12322−12336.
Polymer 2009, 50 (23), 5539−5548.
(30) Bell, J. R.; Chang, K.; Lopez-Barron, C. R.; Macosko, C. W.;
Morse, D. C. Annealing of Cocontinuous Polymer Blends: Effect of
Block Copolymer Molecular Weight and Architecture. Macromolecules
2010, 43 (11), 5024−5032.
(31) Gani, L.; Tence-Girault, S.; Millequant, M.; Bizet, S.; Leibler, L.
Co-Continuous Nanostructured Blend by Reactive Blending: Incor-
poration of High Molecular Weight Polymers. Macromol. Chem. Phys.
2010, 211 (7), 736−743.
(32) Pu, G.; Luo, Y.; Wang, A.; Li, B. Tuning Polymer Blends to
Cocontinuous Morphology by Asymmetric Diblock Copolymers as
the Surfactants. Macromolecules 2011, 44 (8), 2934−2943.
(33) Bartczak, Z.; Galeski, A. Mechanical Properties of Polymer
Blends. In Polymer Blends Handbook; Springer Netherlands:
Dordrecht, 2014; pp 1203−1297.
(34) Ojijo, V.; Sinha Ray, S.; Sadiku, R. Role of Specific Interfacial
Area in Controlling Properties of Immiscible Blends of Biodegradable
Polylactide and Poly[(butylene Succinate)-Co-Adipate]. ACS Appl.
Mater. Interfaces 2012, 4 (12), 6690−6701.
(35) Zolali, A. M.; Favis, B. D. Compatibilization and Toughening of
Co-Continuous Ternary Blends via Partially Wet Droplets at the
Interface. Polymer 2017, 114, 277−288.
(36) Eguiburu, J. L.; Iruin, J. J.; Fernandez-Berridi, M. J.; San Román,
J. Blends of Amorphous and Crystalline Polylactides with Poly(methyl
Methacrylate) and Poly(methyl Acrylate): A Miscibility Study. Polymer
1998, 39 (26), 6891−6897.
(37) Oyama, H. T. Super-Tough Poly(lactic Acid) Materials:
Reactive Blending with Ethylene Copolymer. Polymer 2009, 50 (3),
747−751.

J DOI: 10.1021/acs.macromol.8b00464
Macromolecules XXXX, XXX, XXX−XXX