materials

Article
Effect of Different Compatibilizers on the Properties
of Poly (Lactic Acid)/Poly (Butylene Adipate-Co-
Terephthalate) Blends Prepared under Intense Shear
Flow Field
Hezhi He 1,2, *, Guozhen Wang 1,2 , Ming Chen 1,2 , Chengtian Xiong 1,2 , Yi Li 3 and Yi Tong 3, *
1 National Engineering Research Center of Novel Equipment for Polymer Processing, Guangdong Provincial
Key Laboratory of Technique and Equipment for Macromolecular Advanced Manufacturing, South China
University of Technology, Guangzhou 510640, China; [email protected] (G.W.);
[email protected] (M.C.); [email protected] (C.X.)
2 Key Laboratory of Polymer Processing Engineering, Ministry of Education, South China University of
Technology, Guangzhou 510640, China
3 COFCO(jilin) Bio-Chemical Technology Co., Ltd., Changchun 130033, China; [email protected]
* Correspondence: [email protected] (H.H.); [email protected] (Y.T.);
Tel.: +86-133-0230-5696 (H.H.)




Received: 13 December 2019; Accepted: 24 April 2020; Published: 1 May 2020


Abstract: In this report, poly(lactic acid) (PLA) and Poly(butylene adipate-co-terephthalate) (PBAT)
with three kinds of compatibilizers were melt blended under intensive shear flow. A self-made
parallel three-screw extruder was developed to generate such flow during the process. Mechanical
properties, chemical reactions among PLA, PBAT and compatibilizers, rheological behavior and
morphology were investigated. The mechanical tests showed that the notched impact strength of
super-tough composite with 10 wt% EGMA is about 20 times than that of pure PLA. The Fourier
transform infrared spectroscopy (FT-IR) results showed that the epoxy functional groups or maleic
anhydride functional groups of KT-20, KT-915 and EGMA reacted with the hydroxyl groups of PLA or
PBAT macromolecules, resulting in a bridge of PLA and PBAT. About rheological properties, the tan
δ—angular frequency curves and the η”- η’ curves confirmed the chemical reactions mentioned above
and indicated better compatibility of η”- η’ between PLA and PBAT, respectively. Meanwhile, the loss
modulus and storage modulus—angular frequency curves demonstrated the discrepancy of different
compatibilizer components. In particular, from scanning electron microscopy (SEM) images, it can be
seen that the phase size and dispersion uniformity of PBAT adjusted by compatibilizer, corresponding
to better compatibility that is described in the η”- η’ curves. The approach for producing super-tough
PLA/PBAT/compatibilizer by intensive shear flow provides a viable direction for further improving
PLA performance.

Keywords: toughening; poly(lactic acid); poly(butylene adipate-co-terephthalate); extrusion;

compatibilization; intensive shear flow

1. Introduction
Poly(lactic acid) (PLA), a green polymer material, can be synthesized via polymerization of
lactic acid which is fermented by glucose [1]. Renewable agricultural resources such as corn
can provide inexhaustible resources for the synthesis of PLA [2], and its products are recyclable
and compostable [3]. Moreover, PLA products, with excellent mechanical strength, have good
bioabsorbability and biocompatibility with the human body [4], which enables more potential

Materials 2020, 13, 2094; doi:10.3390/ma13092094 www.mdpi.com/journal/materials

Materials 2020, 13, 2094 2 of 16
Materials 2020, 13, x FOR PEER REVIEW 2 of 15

biocompatibility
applications. with thethe
However, human
broad body [4], whichprospect
application enables more
of PLApotential
has beenapplications.
limited However,
due to itsthe poor
broad application
toughness, especiallyprospect of PLA has
its low notched impactbeenstrength.
limited due to its poor toughness, especially its low
notched impact strength.
Poly(butylene adipate-co-terephthalate) (PBAT), a copolymer derived from 1,4-butanediol, adipic
Poly(butylene
acid and terephthalic acid adipate-co-terephthalate)
possesses a tunable balance (PBAT),between
a copolymer derived from
biodegradation 1,4-butanediol,
and desirable physical
adipic acidTherefore,
properties. and terephthalic
PBAT has acidmany
possesses a tunable
excellent balancesuch
properties between biodegradation
as outstanding and desirable
ductility, high heat
physical and
resistance properties.
prominent Therefore,
impactPBAT has many
resistance excellent properties
[5]. PLA/PBAT blends havesuchreceived
as outstanding
extensive ductility,
attention
high heat resistance and prominent impact resistance [5]. PLA/PBAT blends have received extensive
from researchers all around the world [6–10] due to the complementary properties of PLA and PBAT.
attention from researchers all around the world [6–10] due to the complementary properties of PLA
However, S.W.Ko et al. confirmed that PLA and PBAT are immiscible through scanning electron
and PBAT. However, S.W.Ko et al. confirmed that PLA and PBAT are immiscible through scanning
microscopy (SEM) images [11]. Long Jiang et al. also studied the immiscibility of the blends through
electron microscopy (SEM) images [11]. Long Jiang et al. also studied the immiscibility of the blends
DMA and DSC testing [12].
through DMA and DSC testing [12].
Copolymerization, plasticization and blending are three methods commonly industrially used to
Copolymerization, plasticization and blending are three methods commonly industrially used
modify PLA, and can effectively
to modify PLA, and can effectively improve
improvethe themechanical
mechanical properties
properties ofofcomposites
composites[13–16], [13–16], such
such as as
toughness and degradability. Among all the processing methods, blending
toughness and degradability. Among all the processing methods, blending is the most economical is the most economical
andandsimple
simpleapproach
approach by byadding
addingcompatibilizer
compatibilizer for better
for better miscibility.
miscibility. Xue BinXue [17,18]Binprepared
[17,18] prepared
super-
super-tough
tough PLA/PBS/EGMA composites and found that EGMA, which contains epoxy functional functional
PLA/PBS/EGMA composites and found that EGMA, which contains epoxy groups,
groups,
mostlymostly distributed
distributed in theinphasethe phase interface
interface of twoof two incompatible
incompatible systems,
systems, improving
improving thethe interfacial
interfacial
bonding
bondingbetween
betweenthe thetwo twophases.
phases. Teamsinsungvon
Teamsinsungvon [19] [19]prepared
preparedPLA/PBAT
PLA/PBATblends blends using
using maleic
maleic
anhydride
anhydride grafted
graftedPLA PLA (PLA-g-MA)
(PLA-g-MA) by melt processing
by melt and found
processing that tensile
and found that properties of PLA/PBAT
tensile properties of
PLA/PBAT
blend blend were
were enhanced, enhanced,
because because the
the interfacial interfacial
adhesion adhesion
between PLAbetween
and PBAT PLA inand PBAT in the
the compatibilized
compatibilized
blend was improved blendand was evenimproved and even
the thermal the thermal
stability stability
of the blends wasofalso
the blends
improved waswithalso the
improved
presence
with the presence of PLA-g-MA as the compatibilizer. Generally,
of PLA-g-MA as the compatibilizer. Generally, compatibilizers containing maleic anhydride andcompatibilizers containing maleic
anhydride
epoxy and epoxy
functional groupsfunctional groups
are effective are effective
in improving theinmicrostructure
improving thebetween
microstructure
PLA and between PLA
incompatible
and incompatible toughening agents, obtaining
toughening agents, obtaining composites with excellent properties. composites with excellent properties.
The The shearflow
shear flowcompletes
completesthe the blending
blending of of different
differentmaterials,
materials,and
andthetheeffective
effective utilization
utilization of of
thethe
shear flow during the blending process generally results in excellent performance
shear flow during the blending process generally results in excellent performance [20,21]. Sheng-Yang [20,21]. Sheng-
Yang Zhou [21] introduced strong shear flow into the processing of PLA/PBAT blends. It constructed
Zhou [21] introduced strong shear flow into the processing of PLA/PBAT blends. It constructed a
a coexisting structure of tightly arranged shish-kebabs and PBAT fibers at the interface by strong
coexisting structure of tightly arranged shish-kebabs and PBAT fibers at the interface by strong shear
shear flow, which improved the comprehensive mechanics of the material. However, these
flow, which improved the comprehensive mechanics of the material. However, these mentioned
mentioned equipment with strong shear flow only have a small yield, while the self-made parallel
equipment with strong shear flow only have a small yield, while the self-made parallel three-screw
three-screw extruder (L/D = 40, D = 24.5 mm and resident time = 150–180 s at screw speeds of 180
extruder
rpm) shown = 40,
(L/D in D =124.5
Figure mm andstrong
can produce residentsheartime
flow= and
150–180
has aslarge
at screw
yield.speeds
Although of 180
the rpm)
size ofshown
the
in equipment
Figure 1 can produce strong shear flow and has a large yield. Although
may be a small part of the reason that affects the performance of the blend, type the size of the equipment
and
may be a small of
arrangement part
theofscrew
the reason
elementsthatinaffects the performance
the extruder used in thisofwork
the blend,
and the type and arrangement
process conditions of of
thethe
screw elements in the extruder used in this work and the process
equipment operation are the key factors that affect the performance of the blend. Based conditions of the equipment
on this
operation are the key factors that affect the performance of the blend. Based
equipment with fixed type and arrangement of the screw elements as well as fixed process conditions, on this equipment with
fixed
the type
effectand
of arrangement
three different of compatibilizers
the screw elements for as well as fixed
PLA/PBAT wasprocess conditions,
investigated the effect
to achieve of three
excellent
different compatibilizers
mechanical properties. for PLA/PBAT was investigated to achieve excellent mechanical properties.

Figure1.1.Screw
Figure Screwassembly
assembly and
and arrangement
arrangement of
ofthe
theself-made
self-madeparallel
parallelthree-screw extruder.
three-screw extruder.

2. Materials and Methods

2.1. Materials
All information and chemical structures of materials used in this work are display in Table 1 and
Figure 2, respectively.
 PLA (semi-
crystalline material SC M310– COFCO Biomaterial
1.24 6 g/10 min
containing 2% D- A2-HP Co., Ltd. Jilin China
lactide units)
Kingfa SCI. & TECH.
PBAT
Materials 2020, 13, 2094 PBAT 1.20 43 g/10 min Co., Ltd. Guangzhou, 3 of 16
China
Arkema Investment
Compatibilizer1:
EGMA TableAX1. 8900 0.95
Raw material information 6.0 g/10
and basic min
properties. Co., Ltd. (Shanghai,
China)
Material Trademark Density(g/cm−3 ) MFI(190 ◦ C, 2.16 kg) Factory
Shenyang Ketong
Compatibilizer2:
PLA (semi-crystalline KT-20 0.94 1.3 g/10 min Plastic Co., Ltd.
KT-20
material containing 2% SC M310–A2-HP 1.24 6 g/10 min COFCO Biomaterial Co., Ltd. Jilin China
D-lactide units) Shenyang, China
PBAT PBAT 1.20 43 g/10 min Shenyang
Kingfa SCI. & TECH. Ketong China
Co., Ltd. Guangzhou,
Compatibilizer3:
Compatibilizer1: EGMA AX 8900 0.95 6.0 g/10 min Arkema Investment Co., Ltd. (Shanghai, China)
Compatibilizer2: KT-20 KT-20
KT-915 0.94
0.851.3 g/10 min
0.87 g/10 min Plastic Co., Ltd.
Shenyang Ketong Plastic Co., Ltd. Shenyang, China
KT-915
Compatibilizer3: KT-915 KT-915 0.85 0.87 g/10 min Shenyang,
Shenyang Ketong Plastic Co., Ltd. China
Shenyang, China
(Note:
(Note: MnMn of poly(lactic
of poly(lactic acid)acid)
(PLA), (PLA), poly(butylene
poly(butylene adipate-co-terephthalate)
adipate-co-terephthalate) (PBAT),(PBAT), KT-915,
KT-915, KT-20 and KT-20
EGMA
were provided by factories as follows: 2.50 ∗ 10 5 g/mol, 2.12 ∗ 105 g/mol, 1.08 ∗ 10 4 g/mol, 5.42 ∗ 10 4 g/mol4 and 3.25 ∗
and EGMA were provided by factories as follows: 2.50 105 g/mol, 2.12 10 5 g/mol, 1.08 10 g/mol,
104 g/mol.). 4
5.42 10 g/mol and 3.25 10 g/mol.).
4

Figure 2. Chemical structure of PLA, PBAT and three compatibilizers.

Figure 2. Chemical structure of PLA, PBAT and three compatibilizers.

2.2.2.2. Sample
Sample Preparation
Preparation
TheThe PLA
PLA waswas dried
dried in in a blast
a blast oven
oven atat
8585
◦ C°C for1010h.h.PBAT
for PBATandandthree
threecompatibilizers
compatibilizerswere
were dried
dried at
80 atC80
◦ °C10
for forh.10Each
h. Each group
group of aoffinal
a final blend
blend is ismixed
mixeduniformly
uniformly according
according to
tothe
theratio
ratioininTable
Table2 and
2 and
then added to the extruder. The temperature forming the feed section to the die of the self-made
then added to the extruder. The temperature forming the feed section to the die of the self-made triple triple
screw extruder was set as 100—125—150—175—190—190—190—190—180 ◦ C. The rotation speed
was 120 rpm/min, and the blends were pelletized after extrusion. The pelletized material was pressed
into a sheet 1 mm thick at 190 ◦ C and 15 MPa after dried completely, and then cut into wafers with a
diameter of 25 mm for rheological testing. Standard samples were obtained for mechanical testing and
SEM by applying an injection molding machine (105GE Welltec Machinery Ltd., shanghai, China),
wherein the temperature from the feed section to the nozzle was 190—190—190—200 ◦ C.

2.3. Scanning Electron Microscopy (SEM)

After the sample was immersed in liquid nitrogen for 30 min, brittle fracture was performed,
and then the obtained surface was coated with gold for scanning electron microscopy (S-3700N, Hitachi,
Tokyo, Japan) observation at an applied voltage of 5 kV.

2.4. Fourier Transform Infrared (FT-IR) Spectroscopy

FT-IR spectroscopy (Bruker vector 3, Bruker Optics, Karlsruhe City, Germany) was used to study
the molecular group reactions between PLA and PBAT with presence of compatibilizers. Each sample
was scanned by FT-IR spectroscopy with a frequency of 64 scans in a range of 400 to 4000 cm−1 after
Materials 2020, 13, 2094 4 of 16

getting a small amount of PLA, PBAT, PLA/PBAT Blend, 10 wt% EGMA/Blend, 10 wt% KT-915/Blend,
10 wt% KT-20/Blend and three compatibilizers samples, and pressing the samples into films with a
hot stamper.

Table 2. Component mass ratio.

Abbreviation Various Matrix Weight

Blank group (Blend) PLA/PBAT (75 wt%/25 wt%)
2.5 wt% EGMA/Blend PLA/PBAT/EGMA (75 wt%/25 wt%/2.5 wt%)
5 wt% EGMA/Blend PLA/PBAT/EGMA (75 wt%/25 wt%/5 wt%)
7.5 wt% EGMA/Blend PLA/PBAT/EGMA (75 wt%/25 wt%/7.5 wt%)
10 wt% EGMA/Blend PLA/PBAT/EGMA (75 wt%/25 wt%/10 wt%)
2.5 wt% KT-915/Blend PLA/PBAT/KT-915 (75 wt%/25 wt%/2.5 wt%)
5 wt% KT-915/Blend PLA/PBAT/KT-915 (75 wt%/25 wt%/5 wt%)
7.5 wt% KT-915/Blend PLA/PBAT/KT-915 (75 wt%/25 wt%/7.5 wt%)
10 wt% KT-915/Blend PLA/PBAT/KT-915 (75 wt%/25 wt%/10 wt%)
2.5 wt% KT-20/Blend PLA/PBAT/KT-20 (75 wt%/25 wt%/2.5 wt%)
5 wt% KT-20/Blend PLA/PBAT/KT-20 (75 wt%/25 wt%/5 wt%)
7.5 wt% KT-20/Blend PLA/PBAT/KT-20 (75 wt%/25 wt%/7.5 wt%)
10 wt% KT-20/Blend PLA/PBAT/KT-20 (75 wt%/25 wt%/10 wt%)

2.5. Rheological Characterization Measurements

The rheological behavior of the PLA/PBAT blend and the PLA/PBAT/compatibilizer blends were
investigated by using a rotational rheometer (MCR 302, Anton Paar Gmbh, Graz, Austria). All tests
were implemented at a temperature of 190 ◦ C with a scanning frequency ranging from 0.0628 to
628 rad/s, and the strain amplitude was kept at 1%.

2.6. Mechanical Testing

Referring to GB/T 1843-2008, the Izod Impact Tester (Zwick5117, Zwick GmbH, Ulmer, Germany)
was used to test the impact strength.

3. Results and Discussion

3.1. Morphological Analysis

The microstructures of the PLA/PBAT/compatibilizer blends observed by SEM are shown in
Figure 3. In Figure 3a, the pure PLA section is very smooth and level, while the PLA/PBAT control
group in Figure 3b presents island structures which consist of PBAT in a dispersed phase with a circular
cross section and the PLA in a continuous phase. In order to make a subtle discussion, four identifiers
are used as follows: yellow circles are used to show significant phase gaps with the PLA matrix and
approximate circular PBAT dispersed phase morphology; red circles indicate a morphology of tight
interfacial bonding between PBAT and PLA; yellow squares represent an irregularly shaped PBAT
dispersed phase morphology; and red squares are assumed to have a very small PBAT dispersed
phase morphology in this paper. For details, first, it can be observed from the yellow circles in
Figure 3b that PBAT dispersed phases are elliptical-like shaped with not only obvious gaps between
PBAT and PLA but also significant holes formed by the debond of PBAT. After using the 2.5 wt%
dosage of any one of those three compatibilizers, as Figure 3c–e show, the size of PBAT dispersed
phases got smaller and phase gaps became less and narrower. When the dosage of compatibilizer
is 10 wt%, as shown in Figure 3d’, the holes decrease conspicuously, and the shape of the dispersed
phase even gets into a shape that we cannot define. Secondly, from red circles in Figure 3, it is easy
to find the perfectly indistinct gaps as the dosage of compatibilizer is just 2.5 wt%. Furthermore,
the area of fairly tight interfacial bonding between PBAT and PLA as described above spread more
when the usage of compatibilizer was up to 10 wt%; typically we can see the most area like that in
using the 2.5wt% dosage of any one of those three compatibilizers, as Figure 3c–e show, the size of
PBAT dispersed phases got smaller and phase gaps became less and narrower. When the dosage of
compatibilizer is 10wt%, as shown in Figure 3d’, the holes decrease conspicuously, and the shape of the
dispersed phase even gets into a shape that we cannot define. Secondly, from red circles in Figure 3, it is
easy to 2020,
Materials find 13,
the2094
perfectly indistinct gaps as the dosage of compatibilizer is just 2.5wt%. Furthermore, 5 of 16
the area of fairly tight interfacial bonding between PBAT and PLA as described above spread more
when the usage of compatibilizer was up to 10wt%; typically we can see the most area like that in
Figure
Figure 3e’. Thirdly, the
3e’. Thirdly, the yellow
yellow squares
squares show
show thethe irregular
irregular shapes
shapes ofof PBAT
PBAT dispersed
dispersed phases
phases which
which
transformed
transformed from the elliptical-like shapes into some irregular shapes as shown in Figure 33 by
from the elliptical-like shapes into some irregular shapes as shown in Figure by using
using
compatibilizer. At the same time, it is worthy to note that the area of irregular PBAT
compatibilizer. At the same time, it is worthy to note that the area of irregular PBAT dispersed phases dispersed phases
became
became bigger and more
bigger and more collective when the
collective when the usage
usage of of the
the compatibilizer KT-915 was
compatibilizer KT-915 was added
added up up toto
10 wt%, which is not reasonable because the changes can be seen, from
10wt%, which is not reasonable because the changes can be seen, from Figure 3d to Figure 3d’ and Figure 3d to Figure 3d’ and
from Figure 3e
from Figure 3e to
to Figure
Figure3e’,3e’,that
thatirregular
irregularpartspartsgot
gotless
lessand
andgotgot more
more dispersive
dispersive with
with thethe increase
increase of
of compatibilizer. In addition, there are some very tiny PBAT dispersed
compatibilizer. In addition, there are some very tiny PBAT dispersed phases that turned up phases that turned up after
after
introducing compatibilizers as
introducing compatibilizers as the
the red
red squares
squares show,
show, andand itit is
is interesting
interesting that
that the
the size
size of
of tiny
tiny PBAT
PBAT
dispersed
dispersed phases in KT-915 components is smaller than those in KT-20 and EGMA components. the
phases in KT-915 components is smaller than those in KT-20 and EGMA components. On On
other hand,
the other it seems
hand, to be
it seems toabe
contradiction
a contradiction thatthat
the the
KT-915 component
KT-915 component with 10 wt%
with 10wt% compatibilizer
compatibilizer in
Figure
in Figure 3c 3c
shows
shows some
some PBAT
PBAT dispersed
dispersedphases
phasesobservably
observablybiggerbiggerthan
thanthetheKT-915
KT-915 component
component with with
2.5 wt% compatibilizer in Figure 3c’, while KT-20 components
2.5wt% compatibilizer in Figure 3c’, while KT-20 components and EGMA components and EGMA components display display
smaller
PBAT
smaller dispersed phases. phases.
PBAT dispersed

Figure 3.
Figure 3. Scanning
Scanning electron
electron microscopy
microscopy (SEM)
(SEM) micrographs
micrographs ofof cross-sections
cross-sections (a)
(a) neat
neat PLA,
PLA, (b)
(b) Blend,
Blend,
(c) 2.5
(c) 2.5wt%
wt% KT-915/Blend, (c’) 10wt%
KT-915/Blend, (c’) 10 wt%KT-915/Blend,
KT-915/Blend, (d)
(d) 2.5wt%
2.5 wt%KT-20/Blend,
KT-20/Blend, (d‘)
(d‘) 10wt%
10 wt%KT-20/Blend,
KT-20/Blend,
(e) 2.5
(e) 2.5wt%
wt% EGMA/Blend
EGMA/Blend and and (e’)
(e’) 10wt%
10 wt%EGMA/Blend.
EGMA/Blend.

The statistics, calculated using the software called “Image Pro”, of the particle size and dispersion
of the blends are shown in Figure 4; they are based on 5 SEM micrographs with 150–250 counts and use
a nonparametric regression method to fit the distribution curve. It can be seen that when compatibilizer
was added up to 10 wt%, the peaks of size distribution curves moved to the left compared with 2.5 wt%
compatibilizer components’ peaks respectively, and the size of distribution curves of the dispersed
phases of PBAT were concentrated in lower size values and narrower range. The reason is that the
compatibility between two phases was enhanced by the compatibilizer, which drives PBAT from
agglomeration into dispersion.
Materials 2020, 13, 2094 6 of 16
Materials 2020, 13, x FOR PEER REVIEW 7 of 15

Figure4.4.The
Figure Thestatistical
statisticalanalyses
analyseswith
withrespect
respectto
tothe
thedistribution
distributionof
ofthe
thediameters
diametersofofPBAT
PBATdispersed
dispersed
phases: (a)
phases: (a) Blend,
Blend, (b)
(b) 2.5
2.5wt%
wt%KT-915/Blend,
KT-915/Blend,(c)(c)10wt%
10 wt%KT-915/Blend,
KT-915/Blend,(d)(d)
2.5wt% KT-20/Blend,
2.5 wt% (e)
KT-20/Blend,
10wt% KT-20/Blend, (f) 2.5wt% EGMA/Blend and (g) 10wt% EGMA/Blend.
(e) 10 wt% KT-20/Blend, (f) 2.5 wt% EGMA/Blend and (g) 10 wt% EGMA/Blend.

Additionally, it can be seen that when the dosage of compatibilizer is 2.5 wt%, the small dispersed
phases, especially the very tiny PBAT dispersed phases described by red circles in Figure 3 and red
arrows in Figure 4b of PBAT in the KT-915 component were remarkably more than the KT-20 and
EGMA components and the control group, according to the distribution curves from Figure 4a,d,f.
Materials 2020, 13, 2094 7 of 16

Due to the dispersion trait of PBAT in the KT-915 component, the component might have a better
mechanical property. When the dosage of compatibilizer is 10 wt%, even though there were a number
of very tiny PBAT dispersed phases as depicted by the left arrow in Figure 4c, dramatically bigger
PBAT dispersed phases as depicted by the right arrows in Figure 4d could impair its mechanical
property. In stark contrast, despite no tiny small PBAT dispersed phases, small PBAT dispersed phases
distribute more widespreadly and uniformly. This dispersion trait of PBAT in the EGMA component
tends to facilitate the mechanical property of the blend.
It can be seen from Figure 5 that the characteristic absorption peak of maleic anhydride in the
KT-915 curve appeared at 1712 cm−1 and 1780 cm−1 [22–24], indicating that its chemical structure is
roughly as shown in the Figure 2. Characteristic absorption peaks of the epoxy group in the EGMA
curve and the KT-20 curve can be seen at 910 cm−1 [25], indicating that the two compatibilizers contain
a large number of epoxy groups and the structures of EGMA and KT-20 according to what is shown in
Figure 2. The reaction of the reactive functional group with the hydroxyl group necessarily drives the
amount of the reactive functional groups to be less, meaning the characteristic absorption peak curves
rise. However, there are a large number of C = O groups corresponding to the characteristic peak at
1750 cm−1 which shields the characteristic peaks at 1712 cm−1 and 1780 cm−1 of maleic anhydride.
Materials 2020, 13, x FOR PEER REVIEW 8 of 15

Figure 5. Infrared
Figure 5. Infrared characteristic
characteristic peak
peak of
of each
each component.
component.

The Blend component has the lowest peak (blending vibration peak) height at 1407 cm−1 [26],
which indicates that its hydroxyl group content is the most, and the same characteristic peak of the
KT-915 component is significantly higher than that of the Blend component in Figure 6, demonstrating
that the reaction between maleic anhydride and the hydroxyl group [27,28] caused a decline of the
hydroxyl group content. Similarly, the introduction of the other two compatibilizers also consumes the
hydroxyl group so that the peaks at 1407 cm−1 are higher than the peak of the Blend component. It is
worth noting that the peak at 1407 cm−1 of the KT-20 component is the highest, as shown in Figure 6,
but in Figure 7, the KT-20 curve is just slightly lower than the EGMA curve at the characteristic peak
(910 cm−1 ) of the epoxy group. It means that the content of KT-20 epoxy groups is relatively small.
However, the highest characteristic absorption peak of the KT-20 component in Figure 6 means that
most of the hydroxyl groups were consumed. Therefore, this contradiction confirmed the presence of
maleic anhydride in KT-20, although the characteristic peak of maleic anhydride is shielded by the
peak of C = O at 1750 cm−1 . In summary, the structure of the three compatibilizers can be proved
to correspond to the structure shown in Figure 2 and “bridge macromolecules” are exhibited in red

Figure 6. Characteristic absorption peak at 1407 cm−1.

Materials 2020, 13, 2094 8 of 16

Figure 5. Infrared characteristic peak of each component.

dotted boxes formed by Figure 5. Infrared
chemical reactionscharacteristic peak of each component.
among each compatibilizer and PLA or PBAT, as illustrated
in Figure 8 in the melting process, as discussed above.

Figure 6. Characteristic absorption peak at 1407 cm−1.

Figure 6. Characteristic
Figure 6. Characteristicabsorption
absorption peak
peak at 1407
at 1407 cm−1cm
. .
−1

Figure
Figure7.7.Characteristic
Characteristic absorption peakatat
absorption peak 910
910 cmcm
−1 .−1.

Figure 7. Characteristic absorption peak at 910 cm−1.

3.2. Dynamic Rheology Properties Analysis
In this study, the rheological behavior of the PLA/PBAT/Compatibilizer blends in response to
shear frequency via the dynamic rheological technique illustrates the compatibility [29–31] between
PLA and PBAT. A number of literature articles indicated that the Cole–Cole diagram can judge the
compatibility of a blend [32–35]: If the curve contains one and only one smooth semi-circular arc,
the compatibility of the blend is good; if the curve contains two semicircles or only one semicircle
with the right end upturned, it indicates poor compatibility. In Figure 9d, the curve of the PLA/PBAT
control group typically has two semicircles, indicating that the compatibility of the two phases is
very poor, which is also reflected in the significant phase gap in the SEM image shown in Figure 3b.
The Cole–Cole curve of the system is no longer a distinct semi-circular shape when the EGMA dosage
is 2.5 wt%; just half of the right semicircle exists and the curvature of the arc is larger than that of
the blank group. As the amount of compatibilizer increases, the left semicircle becomes more and
more flat and the right semicircle no longer shows a downward bending tendency, but a significant
upturn, and the slope of the upturn gets larger, which is equivalent to greater dynamic viscosity and
Materials 2020, 13, 2094 9 of 16

loss viscosity. The shape changes of the curves indicate that the chemical reaction between EGMA
and PLA or PBAT leads to “bridge macromolecules” as the tight interfacial bonding between PBAT
and PLA shown by Figure 3, which significantly improves the compatibility between PLA and PBAT.
In Figure 9e, the curves of KT-20 components with the same compatibilizer content gradient in the
Cole–Cole diagram present little changes in dynamic viscosity compared with the curves of EGMA
components. It shows a remarkable decline of loss viscosity (η”(EGMA/Blend)> η” (KT-20/Blend)),
but the compatibility of the PLA and PBAT is also significantly improved due to the very similar
changing trend of KT-20 components curves with EGMA components curves. However, in Figure 9f the
shape of curves for KT-915 components does not show the same change pattern as that of the KT-20 and
EGMA components. The four curves of the KT-915 components with the same compatibilizer content
gradient are significantly different: the 2.5 wt% KT-915/Blend curve position is the highest, while the
KT-20 and EGMA components with dosage of 2.5 wt% have the lowest curve position. With the
increase of KT-915 dosage, the dynamic viscosity and loss viscosity tend to be getting smaller, which is
different from the phenomenon that the dynamic viscosity and loss viscosity of the components using
EGMA and KT-20 are getting larger. As shown in the average diameters distribution curve of the
PBAT dispersed phase in Figure 4b,c and the yellow squares in Figure 3c’, with the increase of the
compatibilizer KT915, the subjects of more large-sized dispersions of the PBAT dispersed phases
might have negative effects on the ability for deformation of “bridge macromolecules “ and the ability
for force transmission of “bridge macromolecules”, since the “bridge macromolecules” are situated
between PLA and PBAT. Therefore, the decrease of dynamic viscosity and loss viscosity may be caused
by the increase of PBAT dispersed phase size.
Materials 2020, 13, x FOR PEER REVIEW 9 of 15

Figure 8. Chemical reaction in blend preparation process (taking the compatibilizer KT-20 as an
Figure 8. Chemical reaction in blend preparation process (taking the compatibilizer KT-20 as
example).
an example).

3.2. Dynamic Rheology

Moreover, Properties
it can be Analysis
seen from Figure 9a–c, that in the low frequency region the tanδ (value of
the loss factor)
In this decreases
study, as the amount
the rheological of compatibilizer
behavior increases, continuously.
of the PLA/PBAT/Compatibilizer The decrease
blends in the
in response to
tan δ value of the composite indicates that the elastic response of the composite
shear frequency via the dynamic rheological technique illustrates the compatibility [29–31] betweenbecomes stronger
and
PLAtheandviscoelastic response
PBAT. A number of of the composite
literature articlesmelt changes
indicated thatfrom liquid-likediagram
the Cole–Cole behaviorcanto solid-like
judge the
behavior [36,37].
compatibility of aThe low
blend tan δ value
[32–35]: revealscontains
If the curve less energy lossonly
one and and one
better interface
smooth strength [38–40],
semi-circular arc, the
which
compatibility of the blend is good; if the curve contains two semicircles or only one semicirclecircles
can be verified by the morphology of tight interfacial bonding that is indicated by the red with
in
theFigure
right 3.end
Obviously,
upturned,theitloss factor-angular
indicates frequency curve
poor compatibility. of the KT-915
In Figure 9d, thecomponent is significantly
curve of the PLA/PBAT
control group typically has two semicircles, indicating that the compatibility of the two phases is very
poor, which is also reflected in the significant phase gap in the SEM image shown in Figure 3b. The
Cole–Cole curve of the system is no longer a distinct semi-circular shape when the EGMA dosage is
2.5wt%; just half of the right semicircle exists and the curvature of the arc is larger than that of the
blank group. As the amount of compatibilizer increases, the left semicircle becomes more and more
Materials 2020, 13, 2094 10 of 16

different from the curves of KT-20 and EGMA components. The KT-20 and EGMA components have
lower curves than the Blend component over the entire shear frequency range. But the curves of the
2.5 wt% KT-915/Blend component and the 10 wt% KT-915/Blend component are higher than the curve
of the Blend component around the peak of tan δ value; additionally, the 10 wt% KT-915/Blend curve is
also higher than the Blend curve in the high frequency region. This indicates that simply increasing the
‘bridge macromolecules’ by using more KT-915 compatibilizer may not further improve compatibility
and dynamic rheology properties.
Materials 2020, 13, x FOR PEER REVIEW 11 of 15

Figure 9. The loss

Figure loss factor-angular
factor-angular frequency curves (left column) and dynamic viscosity—loss viscosity
curves (right
curves (right column).
column).

Dynamic
From therheology
complexproperties could confirm
viscosity-angular chemical
frequency curvereactions among
in Figure 10d,compatibilizers, PLA and
as the shear frequency
PBAT molecules
increases, corresponding
the complex viscositywith the FT-IR
decreases, analysis.
showing For the EGMA
a significant shearcomponent, the loss modulus
thinning phenomenon of the
curve
powerand
lawthe storage
fluids. Themodulus
behaviorcurve of each
of power lawcomponent
fluids [41] increase
is more with the increase
pronounced withof
thetheincrease
scanning
of
EGMA dosage according to the increasing of complex viscosity with increased EGMA dosage. It
contributes to the result mentioned above that larger molecular chains formed by reactions between
the epoxy functional group and PLA or PBAT, following the increased chain entanglement of the
molecular chains of the system. The complex viscosity curves of the compatibilizer KT-20 component
also show the same trend. It can be seen that the complex viscosity curves of 5wt% KT-20/Blend and
Materials 2020, 13, 2094 11 of 16

frequency, and the complex modulus value and the loss modulus value of the Blend component are
smallest in the low frequency region, but the corresponding values of the Blend component in the high
frequency region are the largest. The loss modulus is significantly larger than the storage modulus
in the high scanning frequency range from the low scanning frequency, and the storage modulus
curves and the loss modulus curves are higher with more use of EGMA. The loss modulus value in
the high frequency region is smaller than the storage modulus value, and the loss modulus curve
and the storage modulus curve are lower as the EGMA dosage increases. It demonstrates that the
viscosity response is dominant and the response gets stronger with increasing amounts of EGMA,
while the elastic response is dominant in the high frequency region and the elastic response is weaker
with increasing EGMA usage. As analyzed by infrared characterization, the reactive functional groups
of the compatibilizer chemically bond with the PLA molecular chain and the PBAT molecular chain
to form a macromolecule with a longer molecular chain, such a longer molecular chain having a
longer segment. The kinematics of the kinematic unit are weaker, so that the material exhibits a more
pronounced viscous response in the low frequency region and a more pronounced elastic response
in the high frequency region. The storage modulus and loss modulus of the KT-20 component also
have similar features. Different from the features of the above two compatibilizer components, KT-915
components cause similar viscoelastic response as caused by the other two compatibilizers only when
the dosage is 2.5 wt%. After the dosage of KT915 was added, both storage moduli–the angular
frequency curve of the 10 wt% KT-915 component and the loss modulus–are lower than the curves of
the Blend component in Figure 10. At the same time, the viscous response is dominant over the entire
scanning frequency range. The improvement of storage modulus and loss modulus of the 2.5 wt%
KT-915/Blend component and the consumption of hydroxyl groups in the infrared spectrum indicate
that maleic anhydride has reacted with both PLA and PBAT macromolecules to form a similar structure
(”bridge macromolecules”) with longer molecules and the branched chain shown in Figure 2. However,
the storage modulus and loss modulus decreased when the introduction of KT-915 compatibilizer was
more than 2.5 wt%, since the maleic anhydride reaction was incomplete, making the ethylene soft
segment of KT-915 molecular chain impair the storage modulus and loss modulus.
From the complex viscosity-angular frequency curve in Figure 10d, as the shear frequency
increases, the complex viscosity decreases, showing a significant shear thinning phenomenon of the
power law fluids. The behavior of power law fluids [41] is more pronounced with the increase of EGMA
dosage according to the increasing of complex viscosity with increased EGMA dosage. It contributes
to the result mentioned above that larger molecular chains formed by reactions between the epoxy
functional group and PLA or PBAT, following the increased chain entanglement of the molecular
chains of the system. The complex viscosity curves of the compatibilizer KT-20 component also show
the same trend. It can be seen that the complex viscosity curves of 5 wt% KT-20/Blend and 7.5 wt%
KT-20/Blend are higher than the Blend curve in the high frequency region, and different from the
curves of the EGMA component, which are lower than the Blend curve in the high frequency region.
It is likely that the discrepancy in flexibility between the two compatibilizer molecules of EGMA
and KT-20 occurred after uniform dispersion by an intense shear field. As shown in Figure 10f, the
complex viscosity curve of the KT-915 component at the dose of 2.5 wt% is higher than the Blend
component in the low frequency region. Compared with the 2.5 wt% EGMA/Blend curve and the
2.5 wt% KT-20/Blend curve in Figure 10d,e respectively, the 2.5 wt% KT-915/Blend curve is higher
than the Blend curve in a larger shear frequency range. However, using more KT-915 led to the result
that KT-915 component complex viscosity curves are below the complex viscosity curve of the Blend
component over the entire shear frequency range and the complex viscosity of the composite decreases
as the KT-915 content increases. The reason for this phenomenon could also be the poor dispersion
and distribution of PBAT dispersion phases mentioned above.
2.5wt% KT-20/Blend curve in Figure 10d,e respectively, the 2.5wt% KT-915/Blend curve is higher than
the Blend curve in a larger shear frequency range. However, using more KT-915 led to the result that
KT-915 component complex viscosity curves are below the complex viscosity curve of the Blend
component over the entire shear frequency range and the complex viscosity of the composite
decreases as 13,
Materials 2020, the2094
KT-915 content increases. The reason for this phenomenon could also12be the poor
of 16

dispersion and distribution of PBAT dispersion phases mentioned above.

Figure
Figure10.
10.Loss
Loss modulus andstorage
modulus and storage modulus-angular
modulus-angular frequency
frequency curvecurve (left column),
(left column), and complex
and complex
viscosity-angular frequencycurve
viscosity-angular frequency curve(right
(right column).
column).

3.3. Mechanical Properties Analysis

3.4. Mechanical Properties Analysis
In this section, as seen in Figure 11, The toughness of the PLA/PBAT blend has been significantly
In this section, as seen in Figure 11, The toughness of the PLA/PBAT blend has been significantly
improved after the introduction of compatibilizer. The pure PLA notched impact strength was only
improved after
2.0 ±0.1 kJ/m the introduction
2 through of compatibilizer.
the same processing. When theThe pure
25 wt% PLAwas
PBAT notched
added,impact strength
the notched impactwas only
2.0strength
±0.1 kJ/m 2 through
of the the same system
two-component processing. When
was just 3.2 the 25wt%
± 0.5 kJ/m2PBAT was added,
. Furthermore, theminimum
at the notched impact
strength of the two-component system was just 3.2 ± 0.5 kJ/m 2. Furthermore, at the minimum
compatibilizer amount (2.5 wt%) the components with compatibilizers EGMA, KT-20 and KT-915
compatibilizer
were comparedamountwith pure(2.5wt%) the components
PLA. In these withimpact
cases, the notched compatibilizers
strength wasEGMA,
up to 5.7KT-20 and KT-915
± 1.1 kJ/m2,
2
were
(2.9 compared
times), 10.5 with
± 1.6 pure
kJ/m2PLA. In these
(5.2 times) andcases,
14.6 ±the
2.5 notched
kJ/m (7.3impact
times), strength wasThe
respectively. up remarkable
to 5.7 ± 1.1 kJ/m2,
enhancement of toughness is mainly because of the enhanced interfacial
(2.9 times), 10.5 ± 1.6 kJ/m2 (5.2 times) and 14.6 ± 2.5 kJ/m (7.3 times), respectively. The
2 bond since the “bridge
remarkable
enhancement of toughness is mainly because of the enhanced interfacial bond sincephases.
macromolecules” formed by the chemical reaction promoting the compatibility of the two the “bridge
As the red square formed
macromolecules” in Figureby3cthe
andchemical
the distribution
reactioncurve of the diameters
promoting of PBAT dispersed
the compatibility of the twophases
phases. As
in Figure 4b show, the very small-sized PBAT dispersed phases in 2.5 wt% KT-915/Blend were more
the red square in Figure 3c and the distribution curve of the diameters of PBAT dispersed phases in
than those in 2.5 wt% KT-20/Blend and 2.5 wt% EGMA/Blend. The feature of PBAT dispersed phases
Figure 4b show, the very small-sized PBAT dispersed phases in 2.5wt% KT-915/Blend were more
in 2.5 wt% KT-915/Blend contributes to the best impact strength among the blends with 2.5 wt%
Materials 2020, 13, x FOR PEER REVIEW 13 of 15

than those in 2.5wt% KT-20/Blend and 2.5wt% EGMA/Blend. The feature of PBAT dispersed phases
in 2.5wt% KT-915/Blend
Materials 2020, 13, 2094 contributes to the best impact strength among the blends 13with of 16 2.5wt%
compatibilizer. With the gradual increase of the amount of the compatibilizer, the impact strength of
each component was With
compatibilizer. obviously improved.
the gradual increase of When the amount
the amount of compatibilizer
of the compatibilizer, the impactis strength
5wt% or of 7.5wt%,
impact strength of the was
each component KT-20 component
obviously improved. is better than
When the the KT-915
amount or the EGMA
of compatibilizer is 5 wt%component,
or 7.5 wt%, which
is probably duestrength
impact to the twoof thekinds
KT-20 of reactionisfunctional
component groups.
better than the KT-915When
or the the
EGMAamount of eachwhich
component, compatibilizer
is
probably due to the two kinds of reaction functional groups. When the amount
(EGMA, KT-20 and KT-915) is the largest (10wt%) respectively, the notched impact strength is increased of each compatibilizer
(EGMA, KT-20 and KT-915) is the largest (10 wt%) respectively, the notched impact strength is increased
to 38.8 ± 1.4 kJ/m2 (up 19.4 2 times), 35.8 ± 2.3 kJ/m2 (up 2 17.9 times) and 29.0 ± 3.6 kJ/m2 (up 14.5 times). As
to 38.8 ± 1.4 kJ/m (up 19.4 times), 35.8 ± 2.3 kJ/m (up 17.9 times) and 29.0 ± 3.6 kJ/m2 (up 14.5 times).
the red square
As the red and circle
square andincircle
Figure 3e’ and
in Figure thethe
3e’ and distribution curveofof
distribution curve thethe diameters
diameters of dispersed
of PBAT PBAT dispersed
phases in Figure
phases 4g show,
in Figure the the
4g show, small-sized
small-sizedPBAT dispersed
PBAT dispersed phases
phases in 10inwt%
10wt% EGMA/Blend
EGMA/Blend are moreare more
than thosethaninthose
10wt% in 10KT-20/Blend
wt% KT-20/Blend andand10wt%
10 wt% KT-915/Blend.
KT-915/Blend. TheThe feature
feature ofdispersed
of PBAT PBAT dispersed
phases in phases
10 wt% EGMA/Blend contributes to the dramatic improvement
in 10wt% EGMA/Blend contributes to the dramatic improvement of impact strength. of impact strength.

Figure 11.11.
Figure Impact
Impactstrength ofallallcomponents.
strength of components.
4. Conclusions
4. Conclusions
In this paper, a series of blends consisting of three different compatibilizers and PLA/PBAT was
In this paper,
prepared by aa self-made
series ofparallel
blendsthree-screw
consisting of three
extruder withdifferent compatibilizers
intense shearing andresistance,
flow. The impact PLA/PBAT was
compatibility and microscopic morphology of different blends
prepared by a self-made parallel three-screw extruder with intense shearing flow. with the same compatibilizer content
The impact
gradient were studied and compared. The results of FT-IR spectroscopy indicated that the epoxy
resistance, compatibility and microscopic morphology of different blends with the same
groups or maleic anhydride groups in the three compatibilizers reacted with the hydroxyl groups
compatibilizer content gradient were studied and compared. The results of FT-IR spectroscopy
of PLA or PBAT, and the changes of storage and loss modulus of dynamic rheology also confirmed
indicatedthethat the epoxy
reaction. groups or
The occurrence of maleic anhydridebond
the micro-interface groups in the three
improvement alsocompatibilizers
reflects the effect ofreacted
the with
the hydroxyl groups
reaction. of PLA
Comparison of theordynamic
PBAT,rheological
and theproperties
changesofofthestorage
different and loss modulus
compatibilizer of dynamic
components
rheologymanifests that the introduction
also confirmed the reaction. of the
Thecompatibilizer
occurrencepromotes the compatibilitybond
of the micro-interface of PLAimprovement
and PBAT, also
moreover, the SEM cross-section also demonstrates the improvement of compatibility.
reflects the effect of the reaction. Comparison of the dynamic rheological properties of the different By analyzing
the SEM cross-section morphology, the interface bonding between the PBAT phase and the PLA
compatibilizer components manifests that the introduction of the compatibilizer promotes the
matrix phase caused by compatibilizer is the main factor for toughness. Furthermore, the size and
compatibility of PLA
size uniformity and
of the PBAT PBAT, moreover,
phase play the effect
a nonnegligible SEMoncross-section also demonstrates
the toughening. Finally, the smaller the
improvement of uniformity
size, better compatibility. of sizeBy analyzing
of PBAT phase and thetighter
SEMinterface
cross-section morphology,
bonding could the interface
have synergistic
bondingeffect on improving
between the PBAT toughness,
phase which
and thematches
PLAthe interesting
matrix phasechange in impact
caused strength of different
by compatibilizer is the main
compatibilizer components shown in Figure 11.
factor for toughness. Furthermore, the size and size uniformity of the PBAT phase play a
nonnegligible effect on theConceptualization,
Author Contributions: toughening. H.H. Finally, the investigation,
and G.W.; smaller size, better
G.W., uniformity
M.C. and of size of PBAT
C.X.; writing—original
draft preparation, G.W.; writing—review and editing, H.H. and Y.T.; project administration, Y.L. and Y.T. All authors
phase and tighter interface bonding could have synergistic effect on improving toughness, which
have read and agree to the published version of the manuscript.
matches the interesting change in impact strength of different compatibilizer components shown in
Figure 11.
Author Contributions: Conceptualization, H.H. and G.W.; investigation, G.W, M.C and C.X.; writing—original
draft preparation, G.W.; writing—review and editing, H.H., Z.Z. Z.H. and Y.T.; project administration, Y.L and
Materials 2020, 13, 2094 14 of 16

Funding: This research was funded by National Natural Science Foundation of China (Grant No. 51435005 and
51873075).
Acknowledgments: We thank laboratory administrator Mengmeng Wang and Guixiang Tang for their
administrative support, and we appreciate Zhiwen Zhu, Zhaoxia Huang and Yi Tong for their help in review
and editing.
Conflicts of Interest: The authors declare that there is no conflict of interest regarding the publication of this paper.

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