polymers

Article
PLA/PA Bio-Blends: Induced Morphology
by Extrusion
Violeta García-Masabet 1 , Orlando Santana Pérez 1, * , Jonathan Cailloux 1 , Tobias Abt 1 ,
Miguel Sánchez-Soto 1 , Félix Carrasco 2 and María Lluïsa Maspoch 1
1 Centre Català del Plàstic (CCP)-Universitat Politécnica de Catalunya Barcelona Tech (UPC-EEBE),
C/Colom 114, 08222 Terrassa, Spain; violeta.garcia.masabet@upc.edu (V.G.-M.);
jonathan.cailloux@upc.edu (J.C.); ccp.tobias.abt@gmail.com (T.A.); m.sanchez-soto@upc.edu (M.S.-S.);
maria.lluisa.maspoch@upc.edu (M.L.M.)
2 Department of Chemical Engineering, Universitat de Girona (UdG), Campus Montilivi s/n, 17071 Girona,
Spain; felix.carrasco@udg.edu
* Correspondence: orlando.santana@upc.edu




Received: 28 November 2019; Accepted: 14 December 2019; Published: 19 December 2019


Abstract: The effect of processing conditions on the final morphology of Poly(Lactic Acid) (PLA)
with bio-based Polyamide 10.10 (PA) 70/30 blends is analyzed in this paper. Two types of PLA
were used: Commercial (neat PLA) and a rheologically modified PLA (PLAREx ), with higher melt
elasticity produced by reactive extrusion. To evaluate the ability of in situ micro-fibrillation (µf) of PA
phase during blend compounding by twin-screw extrusion, two processing parameters were varied:
(i) Screw speed rotation (rpm); and (ii) take-up velocity, to induce a hot stretching with different Draw
Ratios (DR). The potential ability of PA-µf in both bio-blends was evaluated by the viscosity (p) and
elasticity (k’) ratios determined from the rheological tests of pristine polymers. When PLAREx was
used, the requirements for PA-µf was fulfilled in the shear rate range observed at the extrusion die.
Scanning electron microscopy (SEM) observations revealed that, unlike neat PLA, PLAREx promoted
PA-µf without hot stretching and the aspect ratio increased as DR increased. For neat PLA-based
blends, PA-µf was promoted during the hot stretching stage. DMTA analysis revealed that the use of
PLAREx PLAREx resulted in a better mechanical performance in the rubbery region (T > Tg PLA-phase )
due to the PA-µf morphology obtained.

Keywords: PLA; BioPA10.10; PLA/PA Bio-blends; in situ MFCs

1. Introduction
The generation of polymers derived from renewable sources, also called bio-based polymers,
has been an important field of research due to the role that these ecofriendly polymers play in the
reduction of plastic residues as a source of pollution, as well as the reduction of carbon dioxide
production, which leads to a decrease in the carbon footprint of its lifecycle [1,2]. Over the past
decade, bio-based polymers, such as Poly (Lactic Acid) (PLA), have gained interest as a substitute
for conventional fossil-based polymers in biomedical and commodity applications. Its main features
are its biodegradable nature, the decrease in the CO2 footprint associated with the product, and the
non-toxic residues released during processing [3–6].
Despite its great potential, PLA still has limitations, such as brittleness, slow crystallization
kinetics, reduced service temperature range, high instability during processing where good melt
strength is required, among others. There is a large amount of research dedicated solving these
drawbacks in order to expand the application window and become a commodity or even engineering
thermoplastic [7–11].

Polymers 2020, 12, 10; doi:10.3390/polym12010010 www.mdpi.com/journal/polymers

Polymers 2020, 12, 10 2 of 22

Among the strategies considered, melt blending of PLA with other polymers has been a practical
and economic way for improving the properties of PLA [6,8,10,12,13]. Recently, blends with bio-sourced
polyamides (PAs) have gained interest, regardless of their limited miscibility [14–18]. The control of
the resulting morphology of these blends has proven to tailor their properties, such as mechanical,
crystallization kinetics, and processability.
It has been demonstrated that, for immiscible blends, a fibril morphology of the dispersed phase,
suitably compatible and oriented during processing, could generate a reinforcing effect. This type of
induced morphology is referred to as in situ microfibrillated composites (MFCs). Some successful
examples of these systems are blends using polyethylene terephthalate (PET) acting as the dispersed
phase in fibrillar form [19–21], and recently PLA/PA blends [14,16,22]. In all of these cases, an increase in
properties, such as fracture toughness, particularly during crack propagation, melt strength, and even
enhancing the crystallization of the matrix has been reported [20,21,23,24].
A common technique to produce these MFCs is based on preparing a polymer blend of the
matrix A and the dispersed phase B. Then, the blend is drawn, either in melted state (hot drawing) or
already solidified (cold drawing), which transforms the spherical domains of B into highly oriented
micro-fibrils with an increased slenderness. The blend can be used in pellet form and produce isotropic
parts, fulfilling the following thermal processing condition: Tm (A) < Tproc < Tm (B).
At this stage, the matrix melts while the microfibrillar dispersed phase maintains its shape.
Subsequently, these pellets are used in the final forming process (part production), thereby obtaining
a product with enhanced mechanical performance. The success of this process is governed by the
composition, rheological behavior and compatibility of the used polymers [20,21,25,26].
Until now, few studies have been developed from a rheological point of view. Some of the
works worth mentioning are Ding et al. [27] with PLA/PCL blends and Yousfi et al. [16] with PLA/PAs
blends. Both studies confirm that through the appropriate choice of blend components in terms
of viscosity and elasticity ratio, flow conditions, and interfacial tensions, the production of in situ
fibrillation morphology allows an improvement in the thermomechanical performance at a reasonable
cost without sacrificing weight and ability to be recycled. Thus, a rheological analysis of parameters,
such as viscosity ratio (p) and elasticity ratio (k’) could be a way to estimate a morphology based on
the behavior of the pristine polymers, even to try to control the final behavior obtained to produce a
desired morphology like MFC’s [16,28].
Fused Deposition Modeling (FDM) can take advantage of the MFC technique. The produced parts
suffer from low mechanical properties and low surface quality, compared to injection molded parts.
The mechanical properties and the surface roughness of parts manufactured by FDM are controlled
by the adhesion quality of filaments and the global porosity of the piece obtained. They both mainly
stem from the flowability and surface tension of the polymer. A controlled generation of a fibrillar
morphology based on knowledge of the rheological behavior of the materials involved in the blend
at the processing conditions used can contribute to a substantial improvement of the piece as far as
mechanical behavior is concerned [22,29].
To comprehend the parameters affecting the morphology generated in blends requires a deep
understanding of the physical process during the mixing condition by which the melted blend is
exposed. So, it is useful to use the microrheology as a guide. Many authors have studied the fluid
mechanics of the mixing process of two immiscible fluids, evaluating the effect of the different types of
uniform flow fields applied (shear or elongational) in the matrix and the dispersed phase in form of
droplets [28,30]. During the flow of the system, the change in geometry of the dispersed phase will
depend on the ratio between the hydrodynamic forces dictated by the viscosity of the phase, which
acts as matrix and the interfacial tension forces between phases, which tend to restore the droplet to a
spherical shape. The aforementioned ratio is called the capillary number (Ca) that in a shear flow field
take the following expression (Equation (1)) [31],
.
ηm γR
Ca = (1)
Γd,m
Polymers 2020, 12, 10 3 of 22

.
where (ηm ) is
Polymers
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2020, 12, 10
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Polymers 2020, 12, 12,
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Based
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12, 10Taylor’s for Newtonian
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Polymers2020,
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3 3
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Break-up Break-up
mechanisms Mechanism
inshear
shearflow
flowrelated
related viscosity
to viscosity ratio(p) Description
(p)after
after theCa
Ca
Table 1.1.Break-up
Table
Viscosity
Ratio
Table 1.
(p)
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mechanisms
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reached.
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Description
Ratio (p)
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occurs at the tip of the
Break-up
Description Mechanism
Viscosity
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Much Ratio
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Description
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Description Mechanism
Ratio (p) Break-up
Description Mechanism
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Ratio
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(p)
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Mechanism
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produces
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Interfacialoccurs
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occurs in
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the
the two
ends.
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droplets
produce
dumbbell shape,
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1<1˂ p< ˂ 3.8
p 3.8 Rayleigh
Rayleigh break-up
break-up Interfacial
disturbances
disturbances formed
that
formed that at will
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up the
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1 ˂ p ˂ 3.8 Rayleigh
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break-up Interfacial
disturbances
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Interfacial instabilities
that will
intoinstabilities
a line of breakproduce
droplets. up
produce the
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1 ˂ pp ˂ 3.8 No break-up disturbances
fibril into athat
line will break
of droplets. up the
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break-up
The break-up
disturbances
Interfacial
The break-up
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the
that droplet
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instabilities
of the
will under
break
droplet
break shear
up
produce
under
up theis
the
p ˃ 3.8 No break-up fibril
fibril into
not a
intoaisthat line
possible.
aofline of
of droplets.
droplets.
1 ˂ p ˂ 3.8 Thefibril
break-up
disturbances shear
into linethe
not droplet
breakunder
possible.
will
of droplets. up the
p ˃ 3.8 No
No break-up
break-up The break-up of the droplet under
p ˃ 3.8 No break-up The fibrilshear
break-upinto is anot
of line
the possible.
of droplets.
droplet under
The break-up of the droplet under
p p˃˃3.8
3.8
No break-up shear is
shearisareisnotnot
not possible.
possible.
However, it should be considered that blends of immiscible The polymers
shear
break-up of more
possible.
the complex
droplet fluids
under
However,
p ˃ 3.8 it should be considered that blends of immiscible polymers are more complex fluids
due However, it should be
to their viscoelastic considered
nature. that blends
Therefore, of immiscible
the elastic component, polymers
responsible are
shear is not more
for complex
the
possible. tendency fluids of
due to their viscoelastic
However, it
nature.
should be
Therefore,
considered that
the elastic
blends of
component,
immiscible
responsible
polymers are
for
more
the tendency
complex fluids
of
due to their
deformation
However, viscoelastic
recovery,
it should nature.
must
be be Therefore,
taken
considered intothat the
account elastic
blendssince
of component,
it will
immiscible affect responsible
the
polymers overallare for
morphology
more the tendency
complex obtained
fluids of
However,
deformation recovery, it should
must be
be considered
taken into that blends
account sinceofitimmiscible
will affect thepolymersoverallare more complex
morphology fluidsin
obtained
due
in
duethe to
deformation their
blend
totheir viscoelastic
recovery,
[32,33]. Thus,
theirviscoelastic
viscoelastic nature.
must be Therefore,
taken
depending
nature. intoof
Therefore, the
account
the elastic
since
type
theelastic
elasticanditcomponent,
will
theaffect
component, intensity responsible
the overall
of themorphology
responsible for
stress
forthe the
theflowtendency
obtained
field the
tendency of
due to
However, it should benature. Therefore,
considered that the
blends of component,
immiscible responsible
polymers are for
more tendency
complex ofof
fluids
deformation
in the blend would
morphology
deformation recovery,
recovery, must
[32,33].depend
Thus,
mustbe be
as taken
depending
well
betaken
taken into
oninto
the account
ofaccount
the type
elasticitysince
and
ratio
since it will
(k’)
itwill
will affect
theofaffect
intensity the
the polymeric overall
of theblend
theoverall
overall morphology
stresscomponents,
morphology flow fieldobtained
obtained the
i.e.,
deformation
due tothetheir recovery,
viscoelastic must
nature. into account
Therefore, the since
elastic itcomponent,
affect the responsible morphology
forcomponents,
the obtained
tendency of
in
morphology blend [32,33].
would Thus,
depend asdepending
well on the of the type
elasticity and
ratio the
(k’) of intensity
the polymeric of the stress
blend flow field the
i.e.,
ininthe
theblend
blend[32,33].
[32,33].Thus,
Thus,depending
dependingofofthe thetype
typeand andthe theintensity
intensityofofthe thestress stressflow flowfieldfieldthe the
deformation
morphology
morphology recovery,
would must beas
depend
woulddepend
depend taken
well into
on theaccount since
elasticity it will
ratio (k’) affect
(k’)ofof the the overallblend
polymeric morphology
components, obtainedi.e.,
morphology would asaswell
wellononthethe elasticity
elasticity ratio
ratio (k’) of thepolymeric
the polymeric blend
blend components,
components, i.e.,
i.e.,
in the blend [32,33]. Thus, depending of the type and the intensity of the stress flow field the
morphology would depend as well on the elasticity ratio (k’) of the polymeric blend components, i.e.,
Polymers 2020, 12, 10 4 of 22

the blend [32,33]. Thus, depending of the type and the intensity of the stress flow field the morphology
would depend as well on the elasticity ratio (k’) of the polymeric blend components, i.e., the one acting
as matrix (m) and the one acting as dispersed phase (d). This ratio can be evaluated based on the
.
Weissenberg number at a given shear rate (γ) of the phases involved as follows (see Equation (3)):

Wid (ω)
k0 = (3)
Wim (ω)

Yousfi et al. [16], worked on PLA/PA11 and PLA/PA6 blends, estimated k’ from the shear oscillator
rheometry measurements. Assuming that both fluids behave like Maxwell fluids and applying the
Cox-Merz rule, k’ can be determined from to the storage (G’) and the loss (G”) modulus of each
blend component as a function of the angular frequency (ω) according to the following expression
(Equation (4)):
G0 d ( ω )
G00 d (ω)
k0 = . (4)
G0 m ( ω )
G00 m (ω)

According to Van Oene [28], in order to promote the droplet/fibre transition, this ratio should be
<<1, and, at same time, the viscosity ratio (k) should be <4.
However, the flow field is complex in the usual processes of blend compounding such as extrusion.
A set of processing conditions (temperature profile, screw rotation speed, and take-up conditions)
result in the type and magnitude of the flow and, p and k’ can vary point-to-point, i.e., from the screw
metering zone to the exit of the die. So they can induce a number of changes in multi-phase systems,
which will affect either, the drops or the whole system. The dispersed or minoritary phase can:

(i) undergo deformation from a spherical shape to ellipsoids or fibrils,

(ii) break-up into smaller ones, or
(iii) coalesce when they collide, depending on how well the morphology has been stabilized
(compatibilized).

The die region is extremely important. A representation of the possible morphology changes
based on the flow fields applied is shown in Figure 2. The convergent flow into the die produces strong
elongational forces that, on one hand, elongate the dispersed drops into fibres, which may disintegrate
into fine droplets downstream from the die (die-land region). On the other hand, the convergence
induces coalescence. The net effect of these two competing influences depends on the nature of the
blend and how well its morphology has been stabilized. In the die-land region, the flow is mainly
shear, but the mechanisms present in this zone can vary depending on the position between the walls.
A droplet-to-fibril deformation mechanism is favoured near the wall where the shear field is higher.
However, a coalescence mechanism is favoured at the centre [34].
Finally, depending on the take-up velocity, the extrudate is exposed to a hot stretching process
that can considerably modify the previous morphology obtained in the die, producing a fibrillation of
the dispersed phase. Li et al., working with HDPE/PET, found that the morphological characteristics
of the dispersed PET phase in the blend at a fixed weight composition (15% w/w of PET), an extrusion
temperature profile and screw rotation speed were dependent on the hot stretching ratio. As the hot
stretching ratio was increased, the PET particles changed from spheres (HS = 1, no stretching) to
ellipsoids, to rodlike particles (HS = 11), and finally to microfibrils (HS = 47) [35].
The aim of the present study was to explore the ability to control the morphology obtained in
PLA/PA bio-blends, considering the rheological criteria related to shear viscosity and elasticity of the
phases, and the way they can be regulated by extrusion variables, such as the screw rotation speed and
take-up velocity of the extrudate. The resulting thermo-mechanical behaviour of the blends are related
to the resultant morphology obtained.
Polymers 2020,12,
Polymers2020, 12,1010 5 5ofof2223

Die
Region Take-Up
Convergence Die-land
Shear +
Type of Flow Mainly Shear Mainly Elongational
Elongational

Morphology Coalescence Deformation, Break-up Fibrillation, Break-up

Evolution and Coalescence and Coalescence

Figure
Figure2.2.2.
Figure Relation
Relation between
Relationbetween
between type
type ofofof
type flow
flowflowand
and induced
induced
and morphology
morphology
induced in
morphology different
in different zones
zones
in different extrusion
of anof
zones extrusion die.
die.
an extrusion
die.
2. Materials and Methods

The aim of the present study was to explore the ability to control the morphology obtained in
2.1. Materials
PLA/PA bio-blends, considering the rheological criteria related to shear viscosity and elasticity of the
Bio-blends were prepared using as matrix two forms of PLA. One of the PLA form is a commercial
phases, and the way they can be regulated by extrusion variables, such as the screw rotation speed
Poly(lactid acid) grade (Ingeo 4032D® ) from NatureWorks (Arendonk, Belgium), with a D-lactide
and take-up velocity of the extrudate. The resulting thermo-mechanical behaviour of the blends are
molar content of 2%, a Mn of 90,000 g/mol and Mw of 181,000 g/mol, and a melting temperature (Tm ) of
related to the resultant morphology obtained.
167 ◦ C.
The second
2. Materials andtype of matrix was a rheologically modified form of the previous PLA, referred
Methods
to later on as PLAREx. This modification was obtained by a reactive extrusion (REx) process
following the same procedure and conditions previously reported in [36], using as reagent a
2.1. Materials
styrene-acrylic multifunctional-epoxide oligomeric agent (Joncryl-ADR-4400® , kindly supplied by
Bio-blends were prepared using as matrix two forms of PLA. One of the PLA form is a
BASF, Ludwigshafen, Germany), with an epoxy equivalent weight of 485 g/mol and a functionality
commercial Poly(lactid acid) grade (Ingeo 4032D® ) from NatureWorks (Arendonk, Belgium), with a
of 14. Under these processing conditions, chain extension and sparsely three-arm star branching are
D-lactide molar content of 2%, a Mn of 90,000 g/mol and Mw of 181,000 g/mol, and a melting
promoted in PLA which results in a content of approximately 24% w/w of modified chains, causing an
temperature (Tm) of 167 °C.
increase in its melt elasticity [18,37].
The second type of matrix was a rheologically modified form of the previous PLA, referred to
As dispersed phase, a bio-based PA10.10 (Zytel RS LC1000 BK385) was used, manufactured by
later on as PLAREx. This modification was obtained by a reactive extrusion (REx) process following
DuPont (Wilmington, DE, USA), with a melting temperature (Tm ) of 200 ◦ C, a Mn of 11,000 g/mol, and
the same procedure and conditions previously reported in [36], using as reagent a styrene-acrylic
Mw of 33,000 g/mol.
multifunctional-epoxide oligomeric agent (Joncryl-ADR-4400® , kindly supplied by BASF,
The blend compositions and codes used along this work are summarized in Table 2.
Ludwigshafen, Germany), with an epoxy equivalent weight of 485 g/mol and a functionality of 14.
Under these processing conditions,
Table 2. Composition and chain extension
nomenclature usedand
in thesparsely three-arm
investigated star branching are
bio-blends.
promoted in PLA which results in a content of approximately 24% w/w of modified chains, causing
an increase in its meltSample
elasticity [18,37]. % w/w of Pristine Polymers
Nomenclature
As dispersed phase, a bio-based PA10.10 (Zytel PLA RS LC1000
PLARExBK385) was used, manufactured by
PA10.10
DuPont (Wilmington, DE, USA), PLA/PAwith a melting temperature
70 (T
- m) of 200 °C,
30 a Mn of 11,000 g/mol, and
Mw of 33,000 g/mol. PLAREx /PA - 70 30
The blend compositions and codes used along this work are summarized in Table 2.
2.2. Bio-blends Preparation
Table 2. Composition and nomenclature used in the investigated bio-blends.
Bio-blends were prepared by melt mixing in an intermeshing co-rotating twin-screw extruder,
featuring three kneading blocks, each 100 mm in length% w/w of pristine
equally polymers
distributed along the screws length
Sample Nomenclature
(Kneter 25X24D, COLLIN Lab and Pilot Solutions PLA PLAREx
GmbH, Maintenbeth, Germany),
PA10.10 using a circular
cross section die with a nominal diameter of 3 mm70
PLA/PA and a temperature
- extrusion
30 profile of 145, 160,
180, 190, 200, 205, and 215 ◦PLA
C from/PA
the feeding zone -to die, respectively
70 (See Figure 3). The distance
30
REx
between the die-exit and the first contact of the extrudate with the cooling bath (at 20 ◦ C) remained
fixed at 100 mm.
morphology was evaluated by applying three take-up velocities (regulated by rpm of the take-up
rolls located after the cooling bath) such that nominal draw ratios (DR) of 0 (no stretch), 1, and 3 were
obtained. The nominal DRs were estimated according to the following expression (Equation (5)):
𝐶𝑟𝑜𝑠𝑠 𝑠𝑒𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝑡ℎ𝑒 𝑑𝑖𝑒 𝑒𝑥𝑖𝑡
Polymers 2020, 12, 10 𝑑𝑟𝑎𝑤 𝑟𝑎𝑡𝑖𝑜 = (5)22
6 of
𝐶𝑟𝑜𝑠𝑠 𝑠𝑒𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝑠𝑡𝑟𝑒𝑡𝑐ℎ𝑒𝑑 𝑒𝑥𝑡𝑟𝑢𝑑𝑎𝑡𝑒

PLA 4032D [NatureWorks] or PLAREx

PA10.10 [DuPont]
Drying: 80ºC for 4h
(dew point: -40ºC)

N2 Blanket Vacuum
Kneading Blocks

Water Bath
(20 C)
145 C 160 C 180 C 190 C 200 C 205 C 215 C
Twin Screw Extruder (D=25mm, L/D=36) Take-Up
Screw Speed: 35 rpm and 100 rpm Draw Ratio: 1 and 3

Figure 3. Scheme
Figure
Figure 3. Scheme
3. Schemeof of
the
of processing
the
the processingmethod
processing methodemployed
method for bio-blend
employed for
employed Bioblendspreparation
bio-blend preparation
preparation through
through
through twin-screw
twin-screw
twin-screw
extrusion indicating
extrusion
extrusion the
indicating
indicating processing
the
the processingconditions
processing used.
conditionsused.
conditions
.
In
A order to evaluate
preliminary studythe effect of
showed the under
that, shear rate (γ) onprocessing
the used the morphology, two different
conditions, screwfilaments
all extruded rotation
speeds
showedwere selected: 30 and
no crystallinity 100
of the rpm.
PLA The effect
phase, of theto
according hotthe
stretching process
differential on thecalorimetry
scanning morphology was
(DSC)
evaluated by applying
results obtained from thethree take-up
first heatingvelocities (regulated
cycle (10–230 °C) atby10°C·
rpmminof the
–1. take-up rolls located after the

cooling bath)
Prior to such that
all the nominal compounding,
extrusion draw ratios (DR) ofmaterials
the 0 (no stretch),
were1,always
and 3 were obtained.
dried at 80 °CThe
for nominal
4 h in a
DRs were
Piovan estimated according
hopper-dryer (dew pointto the following
= −40 °C) andexpression
processed(Equation
with a N2(5)):blanket in the feeding zone to
prevent a possible degradation. Vacuum was applied in the metering zone to remove volatiles created
during the reactive stage. draw ratio = Cross section o f the die exit
(5)
Cross section o f stretched extrudate
2.3. Rheological Characterisation
A preliminary study showed that, under the used processing conditions, all extruded filaments
showedThenorheological
crystallinitycharacterization
of the PLA phase,of according
the pristine polymers
to the andscanning
differential preparedcalorimetry
bio-blends(DSC)
was
performed
results usingfrom
obtained a Small-Amplitude
the first heating Oscillatory
cycle (10–230 ◦ C) at
Shear 10 ◦ C·min−1(SAOS).
Methodology . An AR-G2 rheometer
(TA Prior
Instruments,
to all theNew Castle,
extrusion DE, USA) was
compounding, theused underwere
materials dryalways
N2 atmosphere in◦ C
dried at 80 parallel
for 4 hplate
in a
configuration
Piovan with a constant
hopper-dryer (dew pointgap=of−40 ◦
1 mm. Priorprocessed
C) and to testing,with
pellets
a Nwere vacuum-dried
2 blanket overnight
in the feeding zone toat
55 °C over
prevent silica gel.
a possible Measurements
degradation. werewas
Vacuum performed
applied inin the
the linear viscoelastic
metering region under
zone to remove controlled
volatiles created
deformation
during conditions
the reactive stage.at 2%, the dynamic frequency sweeps at 215 °C (i.e., the blend processing
temperature) were in the frequency (ω) range 0.0628 < ω < 628 rad/s.
2.3. Rheological Characterisation
The rheological characterization of the pristine polymers and prepared bio-blends was performed
using a Small-Amplitude Oscillatory Shear Methodology (SAOS). An AR-G2 rheometer (TA Instruments,
New Castle, DE, USA) was used under dry N2 atmosphere in parallel plate configuration with a
constant gap of 1 mm. Prior to testing, pellets were vacuum-dried overnight at 55 ◦ C over silica
gel. Measurements were performed in the linear viscoelastic region under controlled deformation
conditions at 2%, the dynamic frequency sweeps at 215 ◦ C (i.e., the blend processing temperature)
were in the frequency (ω) range 0.0628 < ω < 628 rad/s.

2.4. Morphological Characterization

Bio-blend morphologies were assessed at different directions of observation, as proposed in
Figure 4, using a scanning electron microscope (JSM-7001F, JEOL Ltd., Tokyo, Japan); the accelerating
voltage used was 2 kV. The samples were broken under cryogenic conditions and a selective etching
was performed to improve the morphology analysis. The samples were immersed in a dissolution
of sodium hydroxide at 0.025 mol/L in water with methanol, at a volumetric concentration of 1:2,
respectively, for 96 h at 23 ◦ C. All the samples were coated with platinum-palladium 80–20 wt % prior
to the observation.
 Bio-blend morphologies were assessed at different directions of observation, as proposed in
Figure 4, using a scanning electron microscope (JSM-7001F, JEOL Ltd., Tokyo, Japan); the accelerating
voltage used was 2 kV. The samples were broken under cryogenic conditions and a selective etching
was performed to improve the morphology analysis. The samples were immersed in a dissolution of
sodium hydroxide at 0.025 mol/L in water with methanol, at a volumetric concentration of 1:2,
Polymers 2020, 12, 10 7 of 22
respectively, for 96 h at 23 °C. All the samples were coated with platinum-palladium 80–20 wt % prior
to the observation.
Direction of Direction of
Observation Observation
MD TD

(a) (b)
1 Figure4.4. Scheme
Figure Scheme of
ofthe
theobservation
observationdirections
directionsfor
forthe
themorphology
morphologyanalysis:
analysis: (a)
(a) melt
meltflow
flowdirection
direction
Figure 4. Scheme of the observation directions for the morphology analysis: (a) melt flow direction (MD);
(MD);
(MD); (b)
(b) transversal
transversal to
to melt
melt flow
flow direction
direction
(b) transversal to melt flow direction (TD). (TD).
(TD).

Image
Imageanalysis
analysiswas
wasmade to representative
made zoneszones
to representative of theofSEMtheimages with an open-source
SEM images software
with an open-source
(ImageJ version 1.51p, NIH, Bethesda, MD, USA). A discrete distribution of
software (ImageJ version 1.51p, NIH, Bethesda, MD, USA). A discrete distribution of sizes was sizes was determined
by histograms
determined bythat were adjusted
histograms to aadjusted
that were lognormal to afunction.
lognormal Thefunction.
number-average dn was
particle size particle
The number-average
̅
determined based on the adjust for several regions in the bio-blends, according
size 𝑑𝑛 was determined based on the adjust for several regions in the bio-blends, according to Equation (6), where
to
nEquation
i is the number of dispersed
(6), where domainsofand
ni is the number di its size.
dispersed Meanwhile,
domains and di the dispersion
its size. was measured
Meanwhile, with
the dispersion
the
wasfull width half
measured maximum
with of thehalf
the full width distribution:
maximum of the distribution:
P∑
𝑑 ̅𝑛 = n d𝑛𝑖 𝑑𝑖
dn = P i∑ 𝑛i 𝑖. . (6)
(6)
ni

2.5.
2.5. Thermo-Mechanical
Thermo-Mechanical Characterisation
Characterisation
A
Adynamic
dynamicthermo-mechanical
thermo-mechanical analyzer
analyzer(DMA
(DMA Q800, TATA
Q800, Instruments, NewNew
Instruments, Castle, DE, USA)
Castle, was
DE, USA)
used to obtain the thermo-mechanical properties spectrum: Storage Modulus (E’), Loss
was used to obtain the thermo-mechanical properties spectrum: Storage Modulus (E’), Loss Modulus Modulus (E”),
and
(E”),the specific
and the specific lossδ).(tan
loss (tan Theδ).filaments were tested
The filaments using ausing
were tested tensile mode at
a tensile 1 Hzatand
mode 0.02%
1 Hz and strain
0.02%
with a temperature range from 30 to 106 ◦ C at 2 ◦ C/min. A static force of 0.01 N and a force track of
strain with a temperature range from 30 to 106 °C at 2 °C/min. A static force of 0.01 N and a force
125%
track were used.
of 125% were used.

3.
3. Results
Results and
and Discussions
Discussions
The
Theresults
resultsand
anddiscussions
discussionsareare
presented in two
presented in sections: First, aFirst,
two sections: rheological study ofstudy
a rheological the pristine
of the
polymers and bio-blends to evaluate the potential to produce a fibrillated morphology, and;
pristine polymers and bio-blends to evaluate the potential to produce a fibrillated morphology, and;a second
part basedpart
a second on the analysis
based on theofanalysis
the relationship between the
of the relationship morphology
between obtained, obtained,
the morphology using different
using
extrusion parameters, and the thermo-mechanical properties of the bio-blends.
different extrusion parameters, and the thermo-mechanical properties of the bio-blends.
3.1. Microfibrillation Potential Using a Rheological Analysis
3.1. Microfibrillation Potential Using a Rheological Analysis
Applying Cox-Merz rule as a valid approximation for the pristine polymers, the steady-shear
Applying Cox-Merz rule as a valid approximation for the pristine polymers, the steady-shear
viscosity can be applied to correlate with complex viscosity. In this study, the maximum shear rate
viscosity can be applied to correlate with complex viscosity. In this study, the maximum shear rate
could be found in the die and can be calculated using Equation (7), where rdie is the radius of the die
could be found in the die and can be calculated using Equation (7), where rdie is the radius of the die
and Qv the volumetric flow that will depend on the extrusion parameters and the pristine polymer
and Qv the volumetric flow that will depend on the extrusion parameters and the pristine polymer
used [38]. This preliminary study was based in the shear rates obtained during the preparation of the
used [38]. This preliminary study was based in the shear rates obtained during the preparation of the
bio-blends; the values of shear rate found were around 161 to 332 s−1−1, which is equivalent to the same
bio-blends; the values of shear rate found were around 161 to 332 s , which is equivalent to the same
range in angular frequency:
range in angular frequency: . 4Qv
γdie = 4𝑄 3
. (7)
𝛾̇ 𝑑𝑖𝑒 π
=(rdie )𝑣 3 . (7)
𝜋(𝑟 )
𝑑𝑖𝑒
The analysis of the rheological behavior of the pristine polymers is presented in Figure 5. As shown
in Figure 5a, the neat PLA presented a Newtonian behavior in frequencies lower than ten (10) rad/s.
In contrast, the PLAREx showed a shear-thinning region with a significant increase in viscosity compared
to the neat PLA and did not reach the Newtonian region. In the area of interest for the extrusion process,
the viscosity increase was over a magnitude scale of difference. These results were expected due to
the structural modification by the chain extension and the branching of the reactive extrusion, which
increase the number of interactions and entanglements per chain, altering the molecular mobility [39,40].
 The analysis of the rheological behavior of the pristine polymers is presented in Figure 5. As
shown in Figure 5a, the neat PLA presented a Newtonian behavior in frequencies lower than ten (10)
rad/s. In contrast, the PLAREx showed a shear-thinning region with a significant increase in viscosity
compared to the neat PLA and did not reach the Newtonian region. In the area of interest for the
extrusion
Polymers 2020,process,
12, 10 the viscosity increase was over a magnitude scale of difference. These results8 wereof 22
expected due to the structural modification by the chain extension and the branching of the reactive
extrusion, which increase the number of interactions and entanglements per chain, altering the
Moreover,
molecularthe PA had[39,40].
mobility a similar behaviorthe
Moreover, to the
PAPLA
hadREx with a behavior
a similar complete to
clear
theshear
PLARExthinning
with a region in
complete
the range tested and higher strain rate sensitivity with the shear rate. Also, PA was presented
clear shear thinning region in the range tested and higher strain rate sensitivity with the shear rate.upward
inAlso,
the trace,
PA was which can be associated
presented upward inwith a post-condensation
the trace, process in low
which can be associated withfrequencies, and has
a post-condensation
been found in studies of PA11 and PA6 [16,41,42].
process in low frequencies, and has been found in studies of PA11 and PA6 [16,41,42].

PLA
Complex Viscosity, * (Pa.s)
4 PLAREx
10 PA10.10

103

102
10-1 100 101 102 103
Angular frequency,  (rad/s)
(a)

PLA
105 PLAREx
Storage Modulus, G' (Pa)

PA10.10

104

103

102

101

100
10-1 100 101 102 103
Angular frequency,  (rad/s)
(b)
1 ◦ C. (a) Complex Viscosity (η*) versus
Figure
Figure 5.Rheological
Figure5.5. Rheological behavior
Rheological behavior ininthe
behaviorin the pristine
theraw polymers
materials
pristine atat
at 215°
polymers C.215
(a) Complex
215 ViscosityViscosity
°C. (a) Complex (η*) versus angular
(η*) versus
frequency
angular (ω),
angularfrequency (b)
frequency(ω),Storage
(ω),(b) Modulus
(b)Storage (G’)
StorageModulus versus
Modulus(G’) angular
(G’)versus frequency
versusangular (ω). The(ω).
angularfrequency
frequency shadowed
(ω).The region inregion
Theshadowed
shadowed gray
region
represents
iningrey the equivalent angular frequencies (ω) used in the extrusion process to prepare the bioblends.
greyrepresents
represents the
the equivalent angular frequencies
equivalent angular frequencies(ω) (ω)used
usedininthe theextrusion
extrusion process
process to to prepare
prepare the
the bio-blends.
bio-blends.

In relation to the storage modulus (G’) presented in Figure 5b, the PLA had the lowest values and
reached the terminal region. This represented a lower elastic component that could produce a less
effective transmission of stress in the secondary phase during mixing. In the case of the PLAREx , the G’
increased considerably and did not reach the terminal region. This can be explained by the possible
increase of entanglements and change in the mobility of the chains [39].
 Polymers 2020, 12, 10 9 of 23

In relation to the storage modulus (G’) presented in Figure 5b, the PLA had the lowest values
and reached the terminal region. This represented a lower elastic component that could produce a
Polymers 2020, 12, transmission
less effective 10 of stress in the secondary phase during mixing. In the case of the PLA9 of REx
22 ,

the G’ increased considerably and did not reach the terminal region. This can be explained by the
possible increase of entanglements and change in the mobility of the chains [39].
The viscosity ratio (p) between the two phases evidenced a tendency to decrease due to the
The viscosity ratio (p) between the two phases evidenced a tendency to decrease due to the
difference in strain rate sensitivities of each material (See Figure 6). When using PLA as matrix,
difference in strain rate sensitivities of each material (See Figure 6). When using PLA as matrix, the
the change in the p was more pronounced due to the significant difference between the viscosities,
change in the p was more pronounced due to the significant difference between the viscosities, the
the PA with a shear-thinning behavior over the whole angular frequency range, and the PLA with
PA with a shear-thinning behavior over the whole angular frequency range, and the PLA with a
a Newtonian behavior. On the other hand, using PLAREx as matrix, the p in the complete range of
Newtonian behavior. On the other hand, using PLAREx as matrix, the p in the complete range of
extrusion is near the unit due to the similarities in the PA and the PLAREx . The viscosity ratios, in both
extrusion is near the unit due to the similarities in the PA and the PLAREx. The viscosity ratios, in both
kinds of materials for the extrusion shear rate, could produce a behavior that promotes a break-up in
kinds of materials for the extrusion shear rate, could produce a behavior that promotes a break-up in
the secondary phase when the ratio falls below 4, as proposed in Table 1 [16,28].
the secondary phase when the ratio falls below 4, as proposed in Table 1 [16,28].

24
PA/PLA
PA/PLA
20 REx
Viscosity ratio, p

16

12

0
10-1 100 101 102 103
Angular frequency,  (rad/s)
(a)

14 k'PA/k'PLA

12 k'PA/k'PLA REx
Elasticity ratio, k'

10
8
6
4
2
0

10-1 100 101 102 103

Angular frequency,  (rad/s)
(b)
1
Figure 6. Relative Rheological Parameters between the pristine polymers versus the angular
6. Relative Rheological Parameters betweenthethe raw
pristine polymersversus
versus the
the angular frequency
Figure 6. Figure
Relative Rheological Parameters between materials angular frequency (ω) at
frequency ◦
(ω)Viscosity (ω)
at 215 C: (a) at 215 °C:
Viscosity (a) Viscosity Ratio (p); (b) elasticity ratio (k’). The shadowed region in gray
215°C: (a) Ratio (p); Ratio (p); (b) elasticity
(b) Elasticity ratio ratio
(k’).(k’).
The Theshadowed
shadowed region
region in gray represents
in gray represents the
represents
equivalenttheangular
equivalentthe equivalent angular
angular frequencies
frequencies frequencies
(ω) used(ω)in used (ω) used
in the extrusion
the extrusion in the extrusion
process
process process
to prepare
to prepare the to
the prepare the
bio-blends.The
bioblends. bio-horizontal
The
horizontal
lines marked linegraph
in the markedrepresents
in the graph the
represents
limit the limit values
values of viscosity
of viscosity ratio(a)
ratio (a) and
and elasticity
elasticityratio
ratio (b) to
(b) to produce a fibrillated
produce a fibrillated morphology. morphology.
Polymers 2020, 12, 10 10 of 23

blends. The horizontal line marked in the graph represents the limit values of viscosity ratio (a) and
Polymers 2020, 12,
elasticity 10 (b) to produce a fibrillated morphology.
ratio 10 of 22

Furthermore, the elasticity ratio (k’) between the pristine polymers of the bio-blends obtained
Furthermore, the elasticity ratio (k’) between the pristine polymers of the bio-blends obtained had
had a different behavior, depending on the kind of PLA used. For the PLA matrix, an extensive scope
a different behavior, depending on the kind of PLA used. For the PLA matrix, an extensive scope of k’
of k’ in the extrusion range was found, which produced values higher than 2 when the range to
in the extrusion range was found, which produced values higher than 2 when the range to produce the
produce the maximum elongational deformation of the droplets had estimated values around 1. This
maximum elongational deformation of the droplets had estimated values around 1. This matrix failed
matrix failed the theoretical elasticity ratio requirements. However, the PLAREx with the similarity in
the theoretical elasticity ratio requirements. However, the PLA with the similarity in the rheological
the rheological behavior of the pristine polymers produced REx a k’ near 1, which could lead to the
behavior of the pristine polymers produced a k’ near 1, which could lead to the formation of a fibrillated
formation of a fibrillated morphology in the second phase, as predicted by Mighri et al. and used by
morphology in the second phase, as predicted by Mighri et al. and used by Yousfi et al. [16,28,43,44].
Yousfi et al. [16,28,43,44].
A SAOS study was performed in order to study and elucidate any change in the rheological
A SAOS study was performed in order to study and elucidate any change in the rheological
behavior in the bio-blends prepared and to get more insight. Although, the values of viscosity increased
behavior in the bio-blends prepared and to get more insight. Although, the values of viscosity
as compared to the viscosity of neat PLA, as shown in Figure 7, the PLA bio-blend had a shear-thinning
increased as compared to the viscosity of neat PLA, as shown in Figure 7, the PLA bio-blend had a
behavior in almost all the frequency range studied. It did not completely follow an additive rule
shear-thinning behavior in almost all the frequency range studied. It did not completely follow an
of mixture (ARM) behavior between pristine polymers, showing a positive deviation in frequencies
additive rule of mixture (ARM) behavior between pristine polymers, showing a positive deviation in
higher than 1 rad/s [40,45].
frequencies higher than 1 rad/s [40,45].

Additive Rule prediction PLAREx/PA PLA/PA

Complex Viscosity, * (Pa.s)

PLAREx/PA
104 PLA
PLAREx
PA

103
Additive Rule prediction PLA/PA

102
10-1 100 101 102 103
Angular frequency,  (rad/s)
Figure 7. Complex viscosity (η*) vs. angular frequency (ω) at 215 ◦ C of pristine polymers (hole scatter
Figure 7. Complex viscosity (η*) vs. angular frequency (ω) at 215 °C of pristine polymers (hole scatter
points) and prepared bio-blends (filled scatter points). Dashed lines represent the prediction of the
points) and prepared bio-blends (filled scatter points). Dashed lines represent the prediction of the
additive rule.
additive rule.
The PLAREx bio-blend showed a lower viscosity in all ω compared to the pristine polymers.
The PLAREx bio-blend showed a lower viscosity in all ω compared to the pristine polymers. The
The behavior obtained had a negative deviation compared to the additive rule prediction. This anomaly
behavior obtained had a negative deviation compared to the additive rule prediction. This anomaly
behavior has been associated with an interfacial slip between the phases in the interface. The interface
behavior has been associated with an interfacial slip between the phases in the interface. The interface
between the phases during imposed stress can produce drainage due to a decrease in the viscosity
between the phases during imposed stress can produce drainage due to a decrease in the viscosity of
of the zone between two PA domains. This phenomenon can occur when the entanglements of the
the zone between two PA domains. This phenomenon can occur when the entanglements of the
dispersed phase in the interfacial zone are lower than the bulk material [26,45–47].
dispersed phase in the interfacial zone are lower than the bulk material [26,45–47].
G’ of the bio-blends are shown in Figure 8. The PLAREx bio-blends presented a higher elastic
G’ of the bio-blends are shown in Figure 8. The PLAREx bio-blends presented a higher elastic
behavior as compared to the PLA bio-blends. This can be related to the higher elastic behavior of
behavior as compared to the PLA bio-blends. This can be related to the higher elastic behavior of
PLAREx as compared to PLA. It is worth noting that PLA bio-blends showed a shoulder around 4 rad/s
PLAREx as compared to PLA. It is worth noting that PLA bio-blends showed a shoulder around 4 rad/s
in G’. This could reveal the existence of two well defined phases, one of them dispersed with different
in G’. This could reveal the existence of two well defined phases, one of them dispersed with different
elasticity in the system due to a biphasic nature produced by the changes in the relaxation times [48].
elasticity in the system due to a biphasic nature produced by the changes in the relaxation times [48].
Furthermore, the PLAREx bio-blends had a smooth shoulder for lower frequencies. According to
Furthermore, the PLAREx bio-blends had a smooth shoulder for lower frequencies. According to
Palierne, this could be attributed to a decrease in the sizes of the second phase, or the diminishing of
Palierne, this could be attributed to a decrease in the sizes of the second phase, or the diminishing of
the interfacial tension between the phases [25,31].
the interfacial tension between the phases [25,31].
 Polymers 2020,
Polymers 12, 10
2020, 12, 10 11 of
11 of 23
22
Polymers 2020, 12, 10 11 of 23

5
PLA/PA
PLA/PA
10
105 PLAREx/PA

(Pa)
PLAREx/PA

Modulus,G'G'(Pa)
PLA
PLA
PLAREx
4 PLAREx
10
104
PA10.10
PA10.10
StorageModulus,
3
10
103
2
10
Storage

102
1
10
101

-1 0 1 2 3
10
10-1 10
100 10
101 10
102 10
103
Angular frequency,  (rad/s)
Angular frequency, (rad/s)
11 Figure 8. Storage modulus
8. Storage modulus (G’)
(G’) versus
versus angular
angular frequency
frequency (ω)
(ω) at
at 215 ◦ C of pristine polymers (hole
215 °C
Figure of pristine polymers (hole
Figure 8. Storage modulus (G’) versus angular frequency
Figure
scatter
scatter 8. Storage
points)
points) modulus
and prepared
and prepared (G’) versus
bio-blends
bio-blends angular
(filled scatter
(filled scatter frequency (ω)°Catof215°
(ω)
points).
points).
at 215 pristine polymers (hole
C of raw materials
Figure
scatter 8.
points)Storage
and modulus
prepared (G’)
bio-blendsversus
(filled angular
scatter frequency
points). (ω) at 215°C of raw materials
(hole scatter points) and prepared bioblends (filled scatter points).
(hole scatter points) and prepared bioblends (filled scatter points).
The weighted relaxation spectrum was calculated using the commercial Rheology Trios software
The weighted relaxation spectrum was calculated using the commercial Rheology Trios software
The weightedNew
(TA Instruments, relaxation
Castle,spectrum was As
DE, USA). calculated
observed using the commercial
in the spectrums in Rheology
Figure 9, Trios
the software
PLA
(TA Instruments, New Castle, DE, USA). As observed in the spectrums in Figure 9, the PLARExREx
(TA Instruments,
produced a wideningNew
andCastle, DE, USA).
an increase As observed
in the maximum in the time
relaxation spectrums
from 10in Figure
−3 to 10 −2 s9,asthe PLAREx
compared
produced a widening and an increase in the maximum relaxation time from 10 −3to 10 −2s as compared
−3 −2
produced
to a widening
neat PLA. andbeanattributed
This could increase in
tothe maximum
a change relaxation
in the molecular time from 10
weight dueto to10
the sramifications
as compared
to neat PLA. This could be attributed to a change in the molecular weight due to the ramifications
to neat PLA.
generated by This could be of
the addition attributed
the chaintoextender
a changewhich
in the produces
molecularaweight
systemdue
withtoathe
moreramifications
restricted
generated by the addition of the chain extender which produces a system with a more restricted
mobility [39]. The PA presented a unimodal distribution with a wide amplitude centered atrestricted
generated by the addition of the chain extender which produces a system with a more 4s.
mobility [39]. The PA presented a unimodal distribution with a wide amplitude centered at 4s.
mobility [39]. The PA presented a unimodal distribution with a wide amplitude centered at 4s.
(Pa.s)
()(Pa.s)

3000
3000 PLA/PA
PLA/PA
PLAREx/PA
2500 PLAREx/PA
Spectrum,()

2500 PLA
PLA
PLAREx
2000 PLAREx
2000 PA10.10
PA10.10
RelaxationSpectrum,

200
200
WeightedRelaxation

100
100

0
0
Weighted

10-4-4 10-3-3 10-2-2 10-1-1 1000 1011 1022

10 10 10 10 10 10 10
Relaxation time,  (s)
Relaxation time, (s)
1
1 Figure 9. The weighted relaxation spectrum at °C
215° C pristine
of raw materials (hole scatter points)
Figure 9. The
The weighted
weighted relaxation
relaxation spectrum
spectrum at
at 215 ◦ C of polymers (hole scatter points) and
Figure
Figure 9.
Figure
9.
and The 9. The weighted
weighted
prepared
relaxation
relaxation
bioblends (filledspectrum at 215
spectrum 215
scatter points).
at °C of
ofCpristine
215° pristine polymers
of raw materials
polymers (hole
(hole
(hole scatter
scatter points)
points) and
points)
scatter and
prepared
preparedandbio-blends
prepared (filled scatter
bioblends points).
(filled scatter points).
prepared bio-blends
bio-blends (filled
(filledscatter
scatterpoints).
points).

Furthermore,
Furthermore, the PLAPLA bio-blends
bio-blends had
had aa bimodal
bimodal distribution
distribution with
with aa maximum
maximum time time ofofrelaxation
relaxation
Furthermore, −2
the PLA bio-blends had a bimodal distribution with a maximum time of relaxation
centered
centered at 1 ××10
10 s swhich
−2 whichcorresponds
correspondstotothe
thePLA
PLAphase.
phase.This
Thisevidences
evidencesan anincrease
increasefrom
fromthe
thepristine
pristine
centered at 1 × 10−2 s which corresponds to the PLA phase. This evidences an increase from the pristine
polymer
polymer value of 10−3
of 22×× 10 −3 s. Also, the peak
peak for
for the
the PA
PA phase
phase appeared
appeared to to maintain
maintain a a
timetime similar
similar to
to the
polymer value of 2 × 10−3 s. Also, the peak for the PA phase appeared to maintain a time similar to
the pristine polymer, near 3 s [25]. Both relaxation times could be related to the presence of two
pristine polymer, near 3 s [25]. Both relaxation times could be related to the presence of two defined
the pristine polymer, near 3 s [25]. Both relaxation times could be related to the presence of two
defined phases without
phases without interaction
interaction in the molecular
in the molecular mobilitymobility
betweenbetween
them. them.
defined phases without interaction in the molecular mobility between them.
 Polymers 2020, 12, 10 12 of 22

Polymers 2020, 12, 10 12 of 23

On other hand, the PLAREx bio-blends appeared to have an overlapped bimodal distribution
withOn otherin
a shift hand,
the the PLAREx bio-blends
maximum appeared to
times of relaxation as have an overlapped
compared to thosebimodal distribution
of the pristine with
polymers.
aThe
shift
maximum time related with the PLAREx phase increased to 3 × 10 s and the one related toThe
in the maximum times of relaxation as compared to those of
−2 the pristine polymers. the
maximum time related
PA phase decreased to 1with the PLA
s. These REx phase
results indicate increased
that thereto was
3 × 10 −2 s and the one related to the PA
more interaction between the phases
phase
due todecreased
the use ofto 1 s.
the These
chain results that
extender indicate
could that there was
decrease more interaction
the interface tension, between
as proventhe byphases
Yousfi due
et al.
to the use of the
in blends of PA11. chain extender that could decrease the interface tension, as proven by Yousfi et al. in
blendsFigure
of PA11.10 shows the SEM micrographs in the TD (Transverse to flow direction) and MD (Parallel to
flow direction)shows
Figure 10 the SEM
observation micrographs
planes in the TD
for unstretched (Transverse
extruded blendstoatflow direction)
a screw and
rotation MDof
speed (Parallel
35 rpm.
to flow direction) observation planes for unstretched extruded blends at a
Analyzing the TD direction, a sea-island structure was found for both bio-blends and it can be clearlyscrew rotation speed of 35
rpm.
seen Analyzing
that the use the
ofTDPLAdirection, a sea-island structure was found for both bio-blends and it can be
REx as matrix of the blend (Figure 10c) favoured a better dispersion of the
clearly seen that the use of
secondary (minority) phase, showing PLA REx as matrix of the
a decrease inblend (Figure
particle size as10c)
wellfavoured a better
as a narrower dispersion
size distribution.of
the secondary (minority) phase, showing a decrease in particle size
The observation was corroborated with the quantitative analysis performed (Table 3). This situationas well as a narrower size
distribution.
would be expectedThe observation
as p is lowerwasthancorroborated
1 for these with the quantitative
blends, which would analysis
promote performed (Table 3).
the mechanisms of
This situation would be expected as p is lower than 1 for these blends,
“End Pinching” and “Necking break-up” referenced in Table 1. On the other hand, it would lead to a which would promote the
mechanisms
lower probabilityof “End Pinching” and
of coalescence that“Necking
could occur break-up” referenced
in the convergent in Table
flow zone in1.the
Onhead
the other hand, it
(see Figure 2),
would lead to a lower probability of coalescence that could occur in the convergent
as a consequence of the increase in “surface energy” that the reactive modification causes in the PLAREx flow zone in the
head (see Figure
and that has been 2),reported
as a consequence
by Cailloux of the
et increase in “surface to
al. [18]. According energy” that the reactive
these authors, modification
the surface energy of
causes
PLA isin themJ/m
46.4 PLAREx
2 vs.and
51.5that
mJ/mhas for
2 beenPLAreported
REx . by Cailloux et al. [18]. According to these authors,
the surface energy of PLA is 46.4 mJ/m2 vs. 51.5 mJ/m2 for PLAREx.
DR=0
MD TD
PLA/PA

35 rpm

(a) (b)
PLAREx/PA

(c) (d)
1
Figure
Figure10.
Figure 10.SEM
10. SEM
SEM Micrographs
Micrographs
Micrographsofofbio-blends
bio-blends
of atataaat
bioblends screw
screw speed
a screwspeed rotation
rotation
speed ofof35
rotation 35rpm.
35(a)
rpm.
of (a)and
rpm.and (b)
(b)
(a) PLA/PA
andPLA/PA
(b)
bio-blend
PLA/PA TD
bio-blend TD and
and MD
bioblend TDobservation,
MD observation, respectively;
respectively;
and MD observation, (c)
(c) and
and (d)
respectively;(d) PLA
PLA
(c) and
REx
REx /PA
/PA
(d)bio-blend
bio-blend
PLA REx
TD,
/PATD, and
and
bioblendMD
MD
observation,
TD and MD
observation, respectively.
observation respectively.
respectively.
Polymers 2020, 12, 10 13 of 22

Table 3. Average size and size distribution obtained from the quantitative analysis of SEM observations
in TD for bio-blends processed at a screw rotation speed of 35 rpm.

PLA/PA PLAREx /PA

Mean Size (µm) 1.26 0.94
Full Width at Half Maximum (µm) 1.29 0.90

However, when analyzing the MD views, as shown in Figure 10b,d, it can be seen that the PLAREx
bio-blends actually presented a fibrillar morphology in the extrusion conditions used. This was
expected considering the relationship of elasticity between the phases that occurs in this case (next to
1). This aspect shows that the elasticity of the PLAREx phase was great enough to transmit the stresses
generated during the flow (combination of shear and elongation in the die-land) and deformed the
drop of PA to generate the elongated morphology, in apparent contradiction with the shear viscosity
ratio (p) criteria (See Table 1). In the case of PLA bio-blends, the lower elasticity of the matrix is thought
to make the transmission of stress between phases less effective. Even considering the greater elasticity
of PA, the chances of reaching the conditions for the phenomenon of Rayleigh instability as a precursor
to the elongated gout rupture are greater. Evidence of this process can be seen in several regions of
Figure 10b. To this aspect, it should be added that the probabilities of dispersed phase coalescence
are slightly higher in this system, considering the lower surface energy that PLA presents in this
temperature range [28,32].
Similar trends have been observed for the bio-blends processed with a screw rotation speed of
100 rpm.

3.2. Morphological Analysis of the Hot Stretched Bio-blends

Figures 11 and 12 show the SEM micrographs in the TD and MD observation planes for the
different processing conditions, with stretching applied at the die exit of the blends, based on PLA
(PLA/PA), and PLAREx (PLAREx /PA), respectively. Figure 13 shows the distribution of sizes obtained in
these, after the quantitative analysis performed.
Generally, the combined view of both observation planes shows the generation of a fibrillar
morphology with different degrees of slenderness (aspect ratio and localized coalescence, depending
on the matrix and levels of stretching applied). Focusing on the PLA/PA bio-blends, the aspect ratio
of the fibrils that are generated at low DR (DR=1) decreased with increasing screw rotation speed
(see micrographs a,b,e, and f in Figure 11). Possibly, for this extrusion condition, the probability of
coalescence of the PA phase within the converging region of the die increased, generating “precursor”
droplets of greater diameter. In this case the fibrils will have a larger diameter for the same magnitude
of extensional stresses generated in the die exit by the take-up speed applied. Under these conditions
it appeared that the chances of reaching Rayleigh instability were higher, given the high amount
of oblong structures that appear in the MD observations. A similar but less obvious trend is seen
for PLAREx -based bio-blends coupled with some coalescence of fibrils for a screw rotation speed of
100 rpm (see Figure 12d).
Increasing the DR to 3 resulted in a general increase for all blends in the aspect ratio of the fibrils
generated, along with the narrowing in the distribution of their diameters (see Figure 13) which is a
much more marked effect for PLAREx -based bio-blends. It is noteworthy that in this case (DR = 3),
regardless of the screw rotation speed used, a certain degree of interconnection between fibrils can be
seen (see encircled regions in Figures 11 and 12). This interconnection can be a consequence of the
squeezing effect between two adjacent PA filaments on the PLA or PLAREx phase, which promotes
drainage and subsequent local coalescence between filaments and which is favored when low interfacial
tension between phases is observed [49].
 Polymers 2020, 12, 10
Polymers 2020, 12, 10 14 of 22
figure. Arrows represent the melt flow direction.
Figure 11. SEM micrographs of hot stretched PLA/PA bio-blends at the conditions referenced in the

PLA/PA bioblends
DR=1 DR=3
TD MD TD MD
35 rpm

(a) (b) (c) (d)

100 rpm

(e) (f) (g) (h)

1
Figure 11. SEM micrographs of hot stretched PLA/PA bio-blends at the conditions referenced in the figure. Arrows represent the melt flow direction.
Figure 11. SEM micrographs of hot stretched PLA/PA bioblends at the conditions

14 of 23
referenced in the figure. Arrows represent the melt flow direction.
 Polymers 2020, 12, 10
Polymers 2020, 12, 10 15 of 22
the figure. Arrows represent the melt flow direction.
Figure 12. SEM micrographs of hot stretched PLAREx/PA bio-blends at the conditions referenced in

PLAREx/PA bioblends
DR=1 DR=3
TD MD TD MD
35 rpm

(a) (b) (c) (d)

100 rpm

(e) (f) (g) (h)

1 Figure 12. SEM micrographs of hot stretched PLA /PA bioblends at the conditions referenced in
Figure 12. SEM micrographs of hot stretched PLAREx /PA bio-blends at the conditions
REx referenced in the figure. Arrows represent the melt flow direction.

16 of 23
the figure. Arrows represent the melt flow direction.
Polymers 2020, 12, 10 16 of 22
Polymers 2020, 12, 10 17 of 23

PLA/PA PLAREx/PA

0.3 0.3
PLA/PA 35rpm DR0 PLARExPA 35rpm DR0
PLA/PA 35rpm DR1 PLARExPA 35rpm DR1
PLA/PA 35rpm DR3 d=0.35m PLARExPA 35rpm DR3
Relative Frequency

Relative Frequency
d=0.38m FWHM=0.21m
FWHM=0.24m
0.2 0.2
d=0.94m
FWHM=0.9m
d=0.48m
35rpm

FWHM=0.35m d=1.26m
FWHM=1.29m d=0.43m
FWHM=
0.1 0.1 0.32m

0.0 0.0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 0.0 0.5 1.0 1.5 2.0 2.5 3.0
Particle Diameter (m) Particle Diameter (m)
(a) (b)

0.3 0.3
d=0.22m
PLA/PA 100rpm DR0 PLARExPA 100rpm DR0
FWHM=0.16m
PLA/PA 100rpm DR1 PLARExPA 100rpm DR1
PLA/PA 100rpm DR3 PLARExPA 100rpm DR3
Relative Frequency

Relative Frequency d=0.76m

FWHM=0.82m
0.2 d=0.77m 0.2
FWHM=0.82m
100rpm

d=0.36m d=0.54m
FWHM= FWHM=
0.26m 0.36m

d=0.59m
0.1 FWHM= 0.1
0.61m

0.0 0.0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 0.0 0.5 1.0 1.5 2.0 2.5 3.0
Particle Diameter (m) Particle Diameter (m)
(c) (d)
1 Figure 13.
Figure Size
Size distribution
distribution of the
theofPA
thedomains
PA domains
determineddetermined
imageby
by image imagefrom
analysis analysis from SEM
SEM micrographs
micrographs
Figure 13.
13. Size distribution of PA domains determined by analysis from SEM
micrographs
in in TD observation as function of the extrusion screw rotation speed (rpm) inand
in TD observation as
TD observation as function
function of the extrusion
of the extrusion screw
screw rotation
rotation speed
speed (rpm)
(rpm) and
and draw
draw ratios
ratios (DR)
(DR) in the
the
draw
hot
ratios
stretching
(DR)
stage.
in
(a)
the
and
hot
(b)
stretching
PLA/PA
stage.
and PLA
(a) and
/PA
(b)
at
PLA/PA
35rpm,
and PLA
respectively; REx
(c)
/PA
and
at
(d)
35rpm,
PLA/PA
hot stretching stage.
respectively; (c) and(a)(d)
andPLA/PA
(b) PLA/PAand and
PLAPLA REx/PA at 35rpm, respectively; (c) and (d) PLA/PA
REx
REx/PA at 100 rpm, respectively.
and
and PLA
PLAREx /PA at 100 rpm, respectively.
REx/PA at 100 rpm, respectively.

3.3. Dynamic Mechanical-Thermal Analysis

3.3. Dynamic Mechanical-Thermal Analysis
Figure 14 shows the storage modulus (E’) spectra obtained for the studied materials. As can be
seen,Figure 14 shows
the most the storage
appreciable modulus
differences (E’) spectra
occurred in theobtained
rubbery for the studied
region. materials.
The simple As can
addition be
of PA
seen, the most appreciable differences occurred in the rubbery region. The simple addition
promoted a decrease of around 10 ◦ C, whereas the effect related to cold crystallization of the system is of PA
promoted awhich
presented, decrease of case
in the around
of PLA10 °C, whereasatthe
is located 98 ◦effect
C andrelated
for PLAto cold crystallization
◦ of the system
REx at 95 C. The greatest decrease
is presented, which in the case of PLA is located at 98 °C and for PLA REx at 95 °C. The greatest decrease
occurred in those systems where the aspect ratio (slenderness) of the PA fibril was high (mixtures with
occurred
higher DRinapplied).
those systems
A similarwhere
trendthehasaspect ratio (slenderness)
been observed by Park etofal.the
[14]PA fibril wasmixtures,
in PLA/PA6 high (mixtures
which
with higher DR applied). A similar trend has been observed by Park et al. [14]
they attributed to a nucleating effect of the PA phase. This becomes more pronounced by promotingin PLA/PA6 mixtures,
which they attributed
microfibrillation due totothea nucleating
increase ineffect of the surface
the specific PA phase.areaThis becomes more
by providing morepronounced
heterogeneousby
promoting sites
nucleation microfibrillation
to the crystals.due to the increase in the specific surface area by providing more
heterogeneous nucleation
Another interesting detailsites is
to that
the crystals.
the addition of PA in the form of microfibrils caused a notable
increase in E’ throughout this region, between 500% and 1300% with respect to the PLA in the PLA/PA
bio-blends, and between 1300% and 1600% for the PLAREx /PA bio-blends.
Both observations are especially relevant where the target of the mixtures under study is
considered: FDM processing, especially at the deposition stage. This improvement provides greater
mechanical stability of the filament deposited in the substrate, which would gain accuracy in the
process. Additionally, the maximum service temperature range of the finished product could increase,
given cold crystallization at lower temperatures may generate an increase in the crystallinity of the
Polymers 2020, 12, 10 17 of 22

previously deposited layers. This is due to an annealing effect that can be generated when the second
layer is2020,
Polymers deposited.
12, 10 18 of 23

Tg-PLA=71ºC
1000

Storage Modulus (MPa) (a)

86ºC
100

PLA/PA 35rpm DR1

PLA/PA 35rpm DR3 83ºC
PLA/PA 100rpm DR1 98ºC
PLA/PA 100rpm DR3
10
PLA
PA

30 40 50 60 70 80 90 100
Temperature (°C)

Tg-PLA =71ºC
REx

1000
Storage Modulus (MPa)

(b) 86ºC

100

PLAREx/PA 35rpm DR1

PLAREx/PA 35rpm DR3 95ºC
PLAREx/PA 100rpm DR1
10 PLAREx/PA 100rpm DR3
PLAREx
PA

30 40 50 60 70 80 90 100
Temperature (°C)

Figure 14. Storage Modulus (E’) variation with temperature for the different processing conditions
Figure 14. Storage Modulus (E’) variation with temperature for the different processing conditions
(extrusion screw rotation speed, rpm, and draw ratios, DR): (a) PLA/PA and (b) PLAREx /PA bio-blends
(extrusion screw rotation speed, rpm, and draw ratios, DR): (a) PLA/PA and (b) PLAREx/PA bio-blends
and their respective pristine polymers.
and their respective pristine polymers.
A detailed analysis of the obtained parameter values is presented in Figure 15. In this case the E’
Another interesting detail is that the addition of PA in the form of microfibrils caused ◦a notable
has been considered in three characteristic regions of the spectrum: in the glassy region (30 C), at the
increase in E’ throughout this region, between 500% and 1300% with respect to the PLA in the
Tg value of each respective matrix without blending (PLA and PLAREx ) (taken as the temperature
PLA/PA bio-blends, and between 1300% and 1600% for the PLA REx/PA bio-blends.
at the maximum value of specific loss (Tan δ), around 70.6 ◦ C), at 84.5 ◦ C, the mean temperature,
Both observations are especially relevant where the target of the mixtures under study is
where the bio-blends showed the onset of the new increase on E’ in the rubbery region associated
considered: FDM processing, especially at the deposition stage. This improvement provides greater
to the effect of cold crystallization. It should be taken into account that, according to a preliminary
mechanical stability of the filament deposited in the substrate, which would gain accuracy in the
DSC study, the matrix in both groups of blends did not show evidence of crystallinity in any of the
process. Additionally, the maximum service temperature range of the finished product could
processed blends. With respect to the PA phase, the crystallinity ratio did not show any variation with
increase, given cold crystallization at lower temperatures may generate an increase in the crystallinity
the processing conditions.
of the previously deposited layers. This is due to an annealing effect that can be generated when the
In the same figure, predictions made by the additive model for long fibre composites (i.e., with a
second layer is deposited.
fibre length greater than the critical reinforcement length) with good adhesion to the matrix have been
A detailed analysis of the obtained parameter values is presented in Figure 15. In this case the
included. This model considers that the maximum value that the composite can reach (upper limit) is
E’ has been considered in three characteristic regions of the spectrum: in the glassy region (30 °C), at
when both fibril and matrix deform equally during mechanical solicitation (Iso-strain condition), while
the Tg value of each respective matrix without blending (PLA and PLAREx) (taken as the temperature
the lower limit of prediction occurs when both phases bear the same tension; but, as a consequence of
at the maximum value of specific loss (Tan δ), around 70.6 °C), at 84.5 °C, the mean temperature,
a moderate adhesion and/or disposition of the dispersed phase, each one is deformed independently.
where the bio-blends showed the onset of the new increase on E’ in the rubbery region associated to
the effect of cold crystallization. It should be taken into account that, according to a preliminary DSC
study, the matrix in both groups of blends did not show evidence of crystallinity in any of the
processed blends. With respect to the PA phase, the crystallinity ratio did not show any variation
with the processing conditions.
 In the same figure, predictions made by the additive model for long fibre composites (i.e., with
a fibre length greater than the critical reinforcement length) with good adhesion to the matrix have
been included. This model considers that the maximum value that the composite can reach (upper
limit) is when both fibril and matrix deform equally during mechanical solicitation (Iso-strain
condition), while the lower limit of prediction occurs when both phases bear the same tension; but,
Polymers 2020, 12, 10 18 of 22
as a consequence of a moderate adhesion and/or disposition of the dispersed phase, each one is
deformed independently.
30°C
71°C
84°C PLA/PA PLAREx/PA

1 Figure 15. Storage module (E’) determined at: (a), (b) 30 ◦ºC for PLA/PA and PLAREx/PA bioblends,
Figure 15.Storage
Figure15. Storage moduli (E’) determined at: (a),
(a),(b)
(b)3030 C
°Cfor
forPLA/PA
PLA/PAand
andPLA /PA
/PAbio-blends,
respectively; (c), (d) atmoduli
71 °C (E’) determined
for PLA/PA andat:PLA PLAREx
REx bio-blends,
REx/PA bioblends, respectively; (e) and (f) at◦84 °C
respectively; (c), (d) atat7171◦ C for PLA/PA and PLA /PA bio-blends, respectively; (e) and (f)(f)atat8484 C
for PLA/PA and PLAREx/PA bioblends, respectively. Red line represents the upper limit model. °C
respectively; (c), (d) °C for PLA/PA and PLARExREx/PA bio-blends, respectively; (e) and Blue
forrepresents
line PLA/PA, and thePLAlower /PA bio-blends,
RExlimit model. respectively. Red line represents the upper limit model. Blue
line represents the lower limit model.

In the glassy region of the material (30 ◦ C) (Figure 15a,b), both bio-blends, with the exception of
PLA/PA, processed at 35 rpm with a DR = 3 presented values within the prediction window. In this
case it should be recalled that this blend was the one with a relatively high degree of interconnection
Polymers 2020, 12, 10 19 of 22

or coalescence (Figure 11c,d). This causes the specific surface area to decrease, limiting its potential
reinforcement capacity and may not even reach the critical fibre length dimensions to act as an effective
reinforcement. It is important to highlight that in both types of bio-blends, those prepared at 100 rpm
of screw rotation speed and with an applied DR of 3, reach the value predicted by the upper limit of
the long fibre composites model. This indicates that the slenderness reached by the PA fibrils exceeds
the critical length so that they act as long fibre reinforcement.
At the Tg of the respective unmixed matrices, both bio-blends enter into the model prediction
window, being closer to the lower limit in the case of the bio-blend PLA/PA (Figure 15c). It is noteworthy
that E’ increased as the DR increased for this blend, which did not occur for PLAREx based bio-blends
(Figure 15d). However, considering the magnitude of values that were measured (88 to 197 MPa),
any trend must be considered with caution. What is clear is that PLAREx -based blends have higher
values in this temperature range.
At the onset of the cold crystallization process of the blends (around 84–85 ◦ C), the trend is similar
to that observed in the temperature range discussed previously. In this case, for the PLA bio-blends,
an increase in DR promoted an increase in E’ (Figure 15e), coinciding with the generation of highly
microfibrillated morphology presented (Figure 11g,h). On the other hand, the PLAREx bio-blend had
virtually no dependence on the extrusion parameters used, showing in all cases values above those
obtained for the PLA bio-blends.
It is important to note that caution must be taken when trying to correlate the morphology
obtained and evaluated at room temperature (Figures 11 and 12) with the mechanical parameters
evaluated above the Tg of the matrix. As a consequence of the greater molecular mobility at these
temperatures, spinodal decomposition may occur, promoting phase coalescence. This phenomenon
can be much more pronounced in mixtures based on PLA if one considers the lowest interfacial tension
that these mixtures present, especially in those with morphology in which the degree of fibrillation is
not that high (Figure 11a,b,e,f).

4. Conclusions
SEM observations revealed that, unlike neat PLA, PLAREx promoted PA-µf without hot stretching
(DR = 0). This observation agrees with the predicted viscosity (p) and elasticity (k’) predictions at the
temperature and shear rates estimated at the die. For neat PLA based blends PA microfibrillation could
be promoted, thereby inducing a hot stretching stage during the take-up process.
As the DR increased, the general effect for all blends was that the aspect ratio of the fibrils
generated increased along with the narrowing in the distribution of their diameters, being much more
pronounced for PLAREx based bio-blends. However, regardless of the screw rotation speed used,
a certain degree of interconnection between fibrils is observed, generating a stratified-like morphology.
This effect could be attributed to the low interfacial tension between phases, which promotes the PLA
phase drainage due to the squeezing effect exerted by two adjacent PA fibrils.
DMTA analysis showed that at 30 ◦ C the storage modulus (E’) was close to the iso-strain predictions
(upper limit) of the additive model for long fiber composites, indicating that the critical length of the
fibril for effective reinforcement was reached. In the rubbery region of the blends (T > TgPLA-phase ), the
use of PLAREx promoted a better mechanical performance in the rubbery region due to the microfibrillar
morphology obtained.

Author Contributions: The general conceptualization of the work described here was performed by O.S.P., M.S.-S.,
F.C. and M.L.M. All the experiments and their analysis were performed by V.G.-M., J.C. and T.A., under the
supervision of O.S.P., M.S.-S., F.C. and M.L.M.; J.C. and V.G.-M. designed the methodology of etching needed
to visualize the morphology generated. The paper was written by V.G.-M., O.S.P. and M.L.M. The review and
editing was performed by V.G.-M., O.S.P. and T.A. All authors have read and agreed to the published version of
the manuscript.
Funding: This research was funded by the financial support from the Spanish Ministry of Economy and
Competitiveness through the Project MAT2016-80045-R (AEI/FEDER,UE).
Polymers 2020, 12, 10 20 of 22

Acknowledgments: The authors acknowledge DuPont for the supply of the PA10.10, BASF for the supply of
the reagent Joncryl-ADR-4400® , DuPont for the supply of biobased PA10.10 (Zytel RS LC1000 BK385), and the
Spanish Ministry of Economy and Competitiveness for the funding.
Conflicts of Interest: The authors declare no conflict of interest.

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