Materials: Interface Bond Improvement of Sisal Fibre Reinforced Polylactide Composites With Added Epoxy Oligomer

materials
Article
Interface Bond Improvement of Sisal Fibre
Reinforced Polylactide Composites with Added
Epoxy Oligomer
Mingyang Hao 1,2 , Hongwu Wu 1,2, * ID
, Feng Qiu 1,2 and Xiwen Wang 1
1 The Key Laboratory of Polymer Processing Engineering of Ministry of Education,
South China University of Technology, Guangzhou 510640, China; hmyang1992@163.com (M.H.);
qiufeng868@gmail.com (F.Q.); wangxwen0623@163.com (X.W.)
2 National Engineering Research Center of Novel Equipment for Polymer Processing,
South China University of Technology, Guangzhou 510640, China
* Correspondence: mmhwwu@scut.edu.cn
Received: 31 January 2018; Accepted: 2 March 2018; Published: 7 March 2018
Abstract: To improve the interfacial bonding of sisal fiber-reinforced polylactide biocomposites,

polylactide (PLA) and sisal fibers (SF) were melt-blended to fabricate bio-based composites via in
situ reactive interfacial compatibilization with addition of a commercial grade epoxy-functionalized
oligomer Joncryl ADR@ -4368 (ADR). The FTIR (Fourier Transform infrared spectroscopy) analysis
and SEM (scanning electron microscope) characterization demonstrated that the PLA molecular
chain was bonded to the fiber surface and the epoxy-functionalized oligomer played a hinge-like
role between the sisal fibers and the PLA matrix, which resulted in improved interfacial adhesion
between the fibers and the PLA matrix. The interfacial reaction and microstructures of composites
were further investigated by thermal and rheological analyses, which indicated that the mobility
of the PLA molecular chain in composites was restricted because of the introduction of the ADR
oligomer, which in turn reflected the improved interfacial interaction between SF and the PLA matrix.
These results were further justified with the calculation of activation energies of glass transition
relaxation (∆Ea ) by dynamic mechanical analysis. The mechanical properties of PLA/SF composites
were simultaneously reinforced and toughened with the addition of ADR oligomer. The interfacial
interaction and structure–properties relationship of the composites are the key points of this study.
Keywords: polymer-matrix composites; natural fiber reinforcement; interface/interphase; microstructural

analysis; crystallization behavior; rheological behavior
1. Introduction
Due to increasing concerns about environment and sustainability issues, natural fibers have
attracted extensive attention for their renewable and sustainable nature. The development of natural
fiber-reinforced polymer composites has attracted wide attention both in academia and industry, due to
their low cost, light weight, ability to be recycled, good structural properties, and so on [1–4].
The mechanical properties of fiber-reinforced polymer composites are influenced not only by
the intrinsic properties of fibers and polymer matrix, but also by the interfacial properties of the
composites [5]. The stress is transferred from the polymer matrix to the fibers via the interface of the
composite under load-bearing. Therefore, a fundamental study of the fiber–matrix interface is critical to
the development of fiber-reinforced polymer composites. Numerous studies have proved that a good
interfacial adhesion is of great importance for obtaining good mechanical properties of composites
materials [6]. Good interfacial compatibility between the fibers and the polymer matrix will result in
efficient stress transferring from matrix to the fiber, and thus improve the mechanical performance of
Materials 2018, 11, 398; doi:10.3390/ma11030398 www.mdpi.com/journal/materials

Materials 2018, 11, 398 2 of 22
composites. For natural fiber-reinforced polymer composites, the interfacial compatibility between
natural fibers and matrix is generally poor due to the hydrophilic nature of natural fiber and the
hydrophobic nature of polymer matrix. In natural fiber-reinforced polymer composites, the two phases
are mechanical and/or chemically combined, and the fiber–matrix interface can be considered as a
diffusion or reaction zone. Poor chemical and physical interfacial interaction between natural fiber
and polymer matrix are regarded as the most important mechanisms of bond failure.
To improve the interfacial interaction of natural fiber-reinforced polymer composites, many
surface modification methods were applied to natural fibers to improve the compatibility between
fibers and matrix [7]. It had been proved that chemical treatments of natural fiber surface were
an effective way to improve the interfacial compatibility and adhesion of natural fiber-reinforced
polymer composites [8]. Several types of chemical treatment methods were developed for surface
modification of natural fiber, including silane treatment [9,10], acetylation treatment [11], benzoylation
treatment [12], acrylation and acrylonitrile grafting [13,14], dopamine treatment [15], N-methylol
acrylamide grafting [4], and so on. Alkali treatment with sodium hydroxide is one of the most widely
used chemical treatment methods for natural fibers [16,17]. It can remove the lignin, natural fats,
waxes, and impurities from natural fiber surfaces. Therefore, the surface roughness of natural fibers is
improved and more reactive functional groups and other reactive functional groups are revealed on
the fiber surface. Alkali treatment with sodium hydroxide has been widely used before other chemical
treatment is performed in natural fibers surface modification to promote the interfacial interaction [18].
These chemical treatment methods could improve the interfacial adhesion of natural fibers and
polymer matrices, but sometimes weaken the fiber strength itself at the same time. Furthermore, these
methods generally require a long time for soaking the natural fibers in the corresponding solution.
They are inefficient. Meanwhile, the organic solvents used in these methods are usually not friendly
to the environment. Reaction processing can improve the interfacial compatibility of composites via
in-situ reaction during melt-blending processing, thus it is a promising method for preparing natural
fiber-reinforced polymer composites without the disadvantages of chemical treatment methods.
Joncryl ADR® -4368 is a kind of commercial grade multi-epoxy-functionalized styrene-acrylic
oligomer (ADR) [19–21]. We consider that ADR has the potential to be an efficient reactive
compatibilizer in natural fiber reinforced polymer composites. In this study, polylactide and sisal
fibers were used to fabricate bio-based natural fiber reinforced polymer composites. To improve the
interfacial adhesion of PLA/sisal fibers composites, polylactide resin and sisal fibers were melt-blended
via in situ reactive interfacial compatibilization with the addition of ADR oligomer. The in-situ reaction
processing method has the possibility of bonding PLA molecule chains onto the fiber surface via
interfacial reaction of the functional groups on the natural fibers’ surface and the end group of PLA.
The phase morphology, thermal behaviors, rheological behaviors, dynamic mechanical analysis, and
tensile properties of PLA/sisal fiber composites were investigated. The interfacial interaction and
structure–properties relationship of composites are key points of this study.
2. Experimental Section
2.1. Materials
The PLA (trade name 4032D), a semi-crystalline extrusion grade with 1.2–1.6% D-isomer lactide
and density of 1.25 g/cm3 , from Nature Works LLC (Minnetonka, MN, USA) was used. It was dried
in an air-dry oven at 80 ◦ C for 8 h before use. The chopped sisal fibers (6 mm) were purchased from
Dongfang Sisal Co. (Guangdong, China) and the properties of the fiber provided by the supplier
are shown in Table 1. Joncryl ADR® -4368 was provided by Shanghai Kingpont Chemical Company,
China P. R.
Materials 2018, 11, 398 3 of 22
Table 1. Properties of sisal fibers.
Fiber Diameter Fiber Density Cellulose Content Hemicellulose Content Lignin Content
(µm) (g/cm3 ) (%) (%) (%)
25–200 1.45 67–78 10–14 8–11
2.2. Preparation of the Composites

Sisal fibers were soaked in sodium hydroxide solution (5 wt %) for 1 h to remove lignin, pectin,
and waxy substances on sisal fibers surface, then were vacuum dried at 80 ◦ C for 8 h. Melt blending of
PLA, sisal fibers (SF), and ADR was performed using an internal mixer (RTOI-55, Potop, Guangzhou,
China) at 200 ◦ C for 5 min with a roller speed of 80 rpm. A series of PLA/SF and PLA/SF/ADR
composites with different ADR addition and different SF content were prepared. Then, the obtained
mixtures were compression-molded at 200 ◦ C for 3 min under 10 MPa into standard specimens for
rheological dynamic frequency sweep tests and mechanical tests. At the same time, to characterize
the internal reaction of the composites melt, rheological dynamic time sweep tests were performed.
The PLA/SF/ADR composites samples were prepared using an internal-mixer at a relatively low
temperature (180 ◦ C) for 2 min without any further melt processing. The dynamic time sweep tests
were executed at a melt mixing temperature of 200 ◦ C.
2.3. Measurements of Mechanical Properties

Notched Izod impact tests were performed following the ISO 180, using a 5.5 J pendulum at
room temperature. The tensile tests were carried out on a universal tensile testing machine (Instron
5566, Norwood, MA, USA) according to ISO 527-2 with a crosshead speed of 2 mm/min. At least five
specimens for each composite were tested. The average values were calculated and the standard errors
were obtained as well.
2.4. Morphological Characterization

The specimens after the tensile tests and Izod impact tests were used for morphological
characterization. The tensile and impact fracture surfaces morphology of the composites were recorded
by scanning electron microscopy (SEM, FEI Quatan 250, Thermo Fisher Scientific, Hillsboro, OR, USA).
Fracture surfaces were sputtered with gold before SEM observation to provide enhanced conductivity.
2.5. FTIR Measurement

In order to estimate the interfacial bonding between PLA and sisal fibers via reaction with ADR
oligomer during the melt-blending processing, the sisal fibers were obtained from composites by
Soxhlet extraction using dichloromethane as solvent and dried at 80 ◦ C for 8 h in a vacuum oven,
and then ground into powder for FTIR analysis. The FTIR spectroscope (Nexus 670, Thermo Nicolet
Co. Ltd., Waltham, MA, USA, KBr powder) was used to characterize the extracted fibers over a range
of 4000–400 cm−1 . For comparison, FTIR characterization of PLA resin was also carried out.
2.6. Thermal Analysis

The thermal behavior of the composites was studied using a differential scanning calorimeter
(DSC-204C, NETZCH, Selb, Germany). For isothermal melt crystallization, the samples were heated
from 30 ◦ C to 190 ◦ C and held for 5 min at 190 ◦ C to eliminate the thermal history, and then cooled
down to 110 ◦ C at a rate of 50 ◦ C/min and held for a period of time until the isothermal crystallization
was complete. The isothermal crystallization behaviors at different crystallization temperature were
also performed. For non-isothermal melt crystallization, the samples were first heated from room
temperature to 190 ◦ C and held for 5 min to eliminate the thermal history, and then cooled back to
30 ◦ C at a rate of 10 ◦ C/min. After 2 min in 30 ◦ C, the second heating scan from 30 ◦ C to 190 ◦ C at
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22
°C/min was performed. The cooling-crystallization of PLA/SF/ADR composites at 5 °C/min was also
10 ◦ C/min
carried out.was performed.
In the The cooling-crystallization
whole process, all samples were keptofunder
PLA/SF/ADR composites
nitrogen flow at 5 ◦ C/min was
of 25 mL/min.
also carried out. In the whole process, all samples were kept under nitrogen flow of 25 mL/min.
2.7. Rheological Characterization
2.7. Rheological Characterization
Viscoelastic behavior of composites was measured by a dynamic oscillatory rheometer (Anton
Viscoelastic behavior of composites was measured by a dynamic oscillatory rheometer (Anton
paar, MCR 302, Graz, Austria), equipped with a plate diameter of 25 mm and a gap of 1 mm parallel
paar, MCR 302, Graz, Austria), equipped with a plate diameter of 25 mm and a gap of 1 mm parallel
plate geometry. The following tests were performed: (a) dynamic small amplitude oscillatory
plate geometry. The following tests were performed: (a) dynamic small amplitude oscillatory frequency
frequency sweep tests from 0.0628 rad/s to 628 rad/s at 180 °C with a strain amplitude of 1%; and (b)
sweep tests from 0.0628 rad/s to 628 rad/s at 180 ◦ C with a strain amplitude of 1%; and (b) dynamic
dynamic time sweep test using 1% strain amplitude and an angular frequency of 10 rad/s at 200 °C.
time sweep test using 1% strain amplitude and an angular frequency of 10 rad/s at 200 ◦ C.
2.8.
2.8. Dynamic
DynamicMechanical
Mechanical Analysis
Analysis (DMA)
(DMA) Testing
Testing
The
The DMA
DMA measurements
measurements (DMA-242
(DMA-242E, E,NETZSCH,
NETZSCH,Selb,Selb,Germany)
Germany)werewerecarried
carriedout
outat
at0.1,
0.1,0.5,
0.5,
1.0, 5, and 10 HZ, respectively, under a heating rate of 2 °C/min,
◦ using three point bending
1.0, 5, and 10 HZ, respectively, under a heating rate of 2 C/min, using three point bending 40 mm 40 mm
measurement
measurement method.
method. The
The temperature
temperature range
range was
was from
from 30
30 °C
◦ C to
to 110
110 °C.
◦ C.
3.
3. Results
Resultsand
andDiscussion
Discussion
3.1.
3.1. Morphology
Morphology Analysis
Analysis
The
The impact
impactfracture
fracturesurfaces
surfacesof ofPLA/SF
PLA/SFand andPLA/SF/ADR
composites with constant
with constant 20 wt
20 %wtSF %
content
SF contentandand different
differentADR ADR addition
addition areare
shown
shown in in
Figure
Figure 1. 1.
It Itcan
canbebeseen
seenfromfromFigure
Figure1a, 1a,that
that for
for
PLA/SF
PLA/SFcomposites
compositesmany manyfibers
fiberswereweredirectly
directlypulled
pulledout outfrom
from PLA PLA matrix,
matrix, andand many
many holes holes were
were
formed
formedin inthe
thefracture
fracturesurfaces,
surfaces, reflecting
reflecting poorpoorinterfacial
interfacialadhesion
adhesion between the PLA
between matrix
the PLA and sisal
matrix and
fibers. However,
sisal fibers. However, the addition
the addition of ADRof ADR intointocomposites
compositesduring duringmelt-blending
melt-blendingprocessing
processing could could
effectively
effectively counteract
counteract this this phenomenon,
phenomenon,as as shown
shown in in Figure
Figure 1b–f
1b–f for for which
which thethe ADR
ADR content
content varied
varied
from
from0.20.2wt
wt%%toto 1.01.0
wtwt%.%. ForFor
PLA/SF/ADR
PLA/SF/ADR composites, the fibers
composites, were tightly
the fibers connected
were tightly with matrix
connected with
and it was
matrix andobserved that more
it was observed fibers
that more were broken
fibers wereup or torn
broken upoff or in composites
torn with ADRwith
off in composites addition
ADR
compared with that of
addition compared withPLA/SF
that ofcomposites. These phenomena
PLA/SF composites. demonstrated
These phenomena the improved
demonstrated theinterfacial
improved
adhesion
interfacialofadhesion
PLA/SF/ADR composites via
of PLA/SF/ADR additionvia
composites of ADR compared
addition of ADRwith that of PLA/SF
compared with thatcomposites.
of PLA/SF
In order to In
composites. further
order confirm
to furtherthis result,
confirm this the impact
result, fracturefracture
the impact surfaces of PLA/SF
surfaces composites
of PLA/SF and
composites
PLA/SF/ADR composites with different SF content are presented
and PLA/SF/ADR composites with different SF content are presented in Figure 2. For PLA/SF in Figure 2. For PLA/SF composites,
similar phenomena
composites, were observed.
similar phenomena were Many fibersMany
observed. were directly
fibers were pulled out from
directly pulled PLAoutmatrix
from PLA and matrix
many
holes wereholes
and many formed werein formed
the fracture
in thesurfaces,
fracture reflecting poor interfacial
surfaces, reflecting adhesionadhesion
poor interfacial (Figure 2a–d).
(FigureIt2a–d).
was
also observed
It was that thethat
also observed more theSFmore
was SF added,
was theadded,more fracture
the defects occurred.
more fracture The presence
defects occurred. of ADR
The presence
improved the interfacial
of ADR improved adhesion adhesion
the interfacial between SF and PLA
between SFmatrix
and PLA (Figure
matrix 2e–h). Furthermore,
(Figure the tensile
2e–h). Furthermore,
fracture surfaces
the tensile fracture of surfaces
PLA/SF of composites and PLA/SF/ADR
PLA/SF composites composites with
and PLA/SF/ADR different
composites withSF different
content are SF
shown
contentinareFigure
shown 3. in
It can
Figurebe seen from
3. It can beFigure
seen from 3a–dFigure
that the3a–dsisal
that fibers werefibers
the sisal directly
werepulled
directly outpulled
from
the
outPLA
frommatrix
the PLA in PLA/SF
matrix in composites, which impairs
PLA/SF composites, the reinforcing
which impairs theeffect of SF during
reinforcing effect of tensile tests.
SF during
However, forHowever,
tensile tests. PLA/SF/ADR composites, the
for PLA/SF/ADR improvedthe
composites, interfacial
improved adhesion between
interfacial adhesionthe SF and PLA
between the
matrix
SF and caused
PLA matrixmanycausedfibers many
to be broken
fibers toup beor torn off
broken upinorthe
torntensile
off in fracture surface,
the tensile fracturewhich indicated
surface, which
that the fibers
indicated that bore the load
the fibers boreinthe
theload
tensile tests.
in the tensile tests.
Figure 1. Cont.
Materials 2018, 11, 398 5 of 22
Materials 2018, 11, x FOR PEER REVIEW 5 of 22
Figure 1. The impact fracture surfaces of polylactide (PLA)/sisal fibers (SF) (80/20) (a1,a2) and
Figure 1.
Figure The impact
1. The impact fracture
fracture surfaces
surfaces ofof polylactide
polylactide (PLA)/sisal fibers (SF)
(PLA)/sisal fibers (SF) (80/20) (a1,a2) and
(80/20) (a1,a2) and
PLA/SF/ADR composites with different ADR content: (80/20/0.2) (b1,b2); (80/20/0.4) (c1,c2);
PLA/SF/ADRcomposites
PLA/SF/ADR composites with
with different
different ADR
ADR content:
content: (80/20/0.2) (b1,b2);
(80/20/0.2) (b1,b2); (80/20/0.4) (c1,c2);
(80/20/0.4) (c1,c2);
(80/20/0.6) (d1,d2); (80/20/0.8) (e1,e2); (80/20/1.0) (f1,f2).
(80/20/0.6)(d1,d2);
(80/20/0.6) (d1,d2);(80/20/0.8)
(80/20/0.8) (e1,e2);
(e1,e2); (80/20/1.0)
(80/20/1.0) (f1,f2).
(f1,f2).
Figure 2. Cont.
Materials 2018, 11, 398 6 of 22
Figure 2. The impact fracture surfaces of PLA/SF composites (90/10) (a1,a2); (80/20) (b1,b2); (70/30)
Figure 2. The impact fracture surfaces of PLA/SF composites (90/10) (a1,a2); (80/20) (b1,b2);
Figure
(c1,c2); 2. The(d1,d2)
(60/40) impact and
fracture surfaces ofcomposites
PLA/SF/ADR PLA/SF composites (90/10)
(90/10/0.6) (a1,a2);
(e1,e2); (80/20)(f1,f2);
(80/20/0.6) (b1,b2);(70/30/0.6)
(70/30)
(70/30) (c1,c2);
(c1,c2); (60/40)
(60/40)
(d1,d2)
(d1,d2)
and
and PLA/SF/ADR
PLA/SF/ADR
composites
composites (90/10/0.6)
(90/10/0.6)
(e1,e2);
(e1,e2);(f1,f2);
(80/20/0.6)
(80/20/0.6) (f1,f2);
(70/30/0.6)
(g1,g2); (60/40/0.6) (h1,h2) with different SF content.
(70/30/0.6) (g1,g2); (60/40/0.6) (h1,h2) with different
(g1,g2); (60/40/0.6) (h1,h2) with different SF content. SF content.
Figure 3. The tensile fracture surfaces of PLA/SF composites (90/10) (a); (80/20) (b); (70/30) (c); (60/40)
Figure 3.
Figure Thetensile
3.The tensilefracture
fracture surfaces
surfaces of of PLA/SF
PLA/SF composites
composites (90/10)
(90/10) (a); (80/20)
(a); (80/20) (b); (70/30)
(b); (70/30) (c);
(c); (60/40)
(d) and PLA/SF/ADR composites (90/10/0.6) (e); (80/20/0.6) (f); (70/30/0.6) (g); (60/40/0.6) (h) with
(60/40)
(d) (d) and PLA/SF/ADR
and PLA/SF/ADR composites(e);
composites (90/10/0.6) (90/10/0.6)
(80/20/0.6) (e); (80/20/0.6)
(f); (70/30/0.6) (g);(f); (70/30/0.6)
(60/40/0.6) (g);
(h) with
different SF content.
(60/40/0.6)
different (h) with different SF content.
SF content.
Materials 2018, 11, 398 7 of 22
Manymodification
Many modificationmethods
methodsofof PLAPLA resin
resin areare based
based on the
on the reaction
reaction ability
ability ofend
of the the group
end group
of PLAof
PLA molecule
molecule chain,
chain, that are that are hydroxyl
hydroxyl and by
and carboxyl, carboxyl,
which the bytypical
whichworks
the typical workstoughening
are reaction are reactionof
toughening
PLA [22–26].of PLA
The [22–26].
presence ofThe presence
hydroxyl of hydroxyl
groups groupsfiber
on the natural on the natural
surface fiberthe
enables surface
bondingenables the
of PLA
bonding
by of PLA
functional groupby functional
reaction, group
therefore reaction,the
improving therefore improving
interfacial the interfacial
compatibility compatibility
between fibers and PLA
between
matrix. Infibers and PLA
this study, PLA matrix.
and sisalInfibers
this study, PLA and sisal
were melt-blended to fibers were
fabricate melt-blended
bio-based to fabricate
composites via in
bio-based
situ reactivecomposites via in situ reactive
interfacial compatibilization interfacial
with additioncompatibilization with addition
of an epoxy-functionalized of anFigure
oligomer. epoxy- 4
functionalized
presents oligomer.
the illustration of Figure 4 presents
interfacial the illustration
compatibilization of interfacial
between PLA and SF compatibilization
via in situ reactionbetween
with
PLA
the andoligomer
ADR SF via in during
situ reaction with the ADR
the melt-blending oligomer during
processing. ADR is the melt-blending
a kind processing. ADR is
of multi-epoxy-functionalized
a kind of [19–21],
oligomer multi-epoxy-functionalized
which can react with oligomer [19–21],
end group which
of PLA andcanhydroxyl
react with end group
groups of PLAfiber
on natural and
hydroxylItgroups
surfaces. on natural
might bond fiber surfaces.
PLA molecules onto It
themight
fiber bond
surfacePLA
andmolecules onto therole
play a hinge-like fiber surfacesisal
between and
play aand
fibers hinge-like
the PLArole between
matrix. sisal fibers
Therefore, and the
the addition ofPLA
ADRmatrix. Therefore,
can improve the addition
the interfacial of ADR can
compatibility of
improve the
composites. Theinterfacial
improved compatibility of composites.
interfacial adhesion of PLA/SF/ADR The improved
compositesinterfacial adhesion
can be observed of
in the
above-mentioned SEM images.can be observed in the above-mentioned SEM images.
Figure4.4. Illustration
Figure Illustration of
of interfacial
interfacial compatibilization
compatibilization between
between PLA
PLA and
and SF
SF via
via in
in situ
situ reaction
reaction with
with
ADRoligomer
ADR oligomerduring
duringthe
themelt-blending
melt-blendingprocessing.
processing.
3.2. FTIR
3.2. FTIR Characterization
Characterization
To demonstrate
To demonstrate the thereaction
reactionofofthethe
ADR oligomer
ADR withwith
oligomer PLA and
PLASF, and theSF,
FTIRthespectra
FTIR of alkaline-
spectra of
treated SF and extracted SF from corresponding composites are shown in Figure
alkaline-treated SF and extracted SF from corresponding composites are shown in Figure 5. The peak 5. The peak at 1735
cm1735
at cm−1 represents
−1 represents the stretching vibrationvibration
the stretching peak of carbonyl (C=O) groups.
peak of carbonyl (C=O)The absence
groups. Theof this 1735
absence of cm
this−1
peakcm
1735 −
in alkaline-treated
1 SF showedSF
peak in alkaline-treated theshowed
alkalinethe
treatment
alkalineremoved
treatmentthe lignin, impurities,
removed pectin, and
the lignin, impurities,
pectin, and waxy substances of sisal fibers [16,17]. It was also observed that no obvious 1735 cm−1
waxy substances of sisal fibers [16,17]. It was also observed that no obvious 1735 cm −1 peak occurred
in theoccurred
peak SF extracted
in the from PLA/SFfrom
SF extracted composites,
PLA/SFreflecting
composites,thereflecting
poor interfacial
the poorinteraction
interfacial between
interactionSF
and PLASF
between matrix
and in PLA/SF
PLA matrix composites.
in PLA/SF However, it wasHowever,
composites. found thatitthewas1735 cm−1that
found peakthewas cm−1
enhanced
1735
with was
peak the addition
enhancedofwith ADR theinto PLA/SF
addition ofcomposites,
ADR into PLA/SFespecially for PLA/SF/ADR
composites, especially composites with 0.4,
for PLA/SF/ADR
0.6, and 0.8with
composites wt %0.4,
ADR0.6,addition.
and 0.8 wtThis phenomenon
% ADR addition.indicated the reaction
This phenomenon of the ADR
indicated oligomerofwith
the reaction the
PLA and SF during the melt-blending processing, which resulted in the bonding
ADR oligomer with PLA and SF during the melt-blending processing, which resulted in the bonding of PLA molecular
chains
of PLA to sisal fibers.
molecular chains to sisal fibers.
Materials 2018, 11, 398 8 of 22
Figure 5.
Figure 5. The
The FTIR spectra of
FTIR spectra of alkaline-treated
alkaline-treated SF,
SF, extracted
extracted SF
SF from
from the
the composites,
composites,and
andPLA
PLAresin.
resin.
3.3. DSC
3.3. DSC Thermal
Thermal Behaviors
Behaviors
Figure 6a
Figure 6a shows
showsthe theDSC
DSCthermograms
thermogramsofofPLA/SF PLA/SFcomposites
compositesand andPLA/SF/ADR
composites
withconstant
with constant2020wtwt % % SF
SF and
and different
differentADR ADRaddition,
addition,from from0.20.2wtwt% %to to 1.0
1.0 wt
wt %,
%, at
at the
the second
second heating
heating
scan. A cold crystallization peak and melting peak occurred in Figure 6a.
scan. A cold crystallization peak and melting peak occurred in Figure 6a. At the second heating At the second heating scan,
as theastemperature
scan, the temperature elevated, the frozen
elevated, PLAPLA
the frozen chain segments
chain segmentsregain movement
regain movement ability, resulting
ability, resultingin
the presence of cold crystallization. It can be seen from Figure 6a that
in the presence of cold crystallization. It can be seen from Figure 6a that the cold crystallization the cold crystallization
temperature (T
temperature (Tcc)) of
of PLA/SF/ADR
compositesshiftsshiftsto to aa higher
higher temperature
temperature region compared with
region compared with
cc
PLA/SF composites.
PLA/SF composites. The cold crystallization
The cold crystallization temperatures
temperatures (T(Tcc)) for forPLA/SF
PLA/SFand andPLA/SF/ADR
PLA/SF/ADR
cc
composites with different ADR additions are listed in Table 2. The T cc was improved with the addition
composites with different ADR additions are listed in Table 2. The Tcc was improved with the addition
of ADR
of ADR oligomer,
oligomer,whichwhichmeant
meantthat thatPLA/SF/ADR
composites need higher temperature
need higher temperature to to regain
regain
chain segments
chain segments movement
movement ability
ability in in comparison
comparison with withthat thatofofPLA/SF
PLA/SF composites.
composites. Therefore,
Therefore, this
this
phenomenon demonstrated the restricted chain movement ability of
phenomenon demonstrated the restricted chain movement ability of PLA/SF/ADR composites [27]. PLA/SF/ADR composites [27].
This result
This resultcan
canbebeascribed
ascribedtotothe
theimproved
improvedinterfacial
interfacial interaction
interaction between
between PLAPLA andand
SF SF
viavia addition
addition of
of ADR. However, the Tcc of PLA/SF/ADR (80/20/1.0) composites was 114.1 ◦°C, which was reduced
ADR. However, the Tcc of PLA/SF/ADR (80/20/1.0) composites was 114.1 C, which was reduced
comparedwith
compared withthat
thatofofPLA/SF/ADR
PLA/SF/ADR (80/20/0.8)
(80/20/0.8) composites
composites(115.5(115.5 °C),
◦ C), which
which implied
implied that excessive
that excessive
addition of
addition of ADR
ADR might
might bebe detrimental
detrimental to to the
the connecting
connectingeffecteffectofofADR
ADRbetween
betweenSF SFand
andPLA
PLAmatrix.
matrix.
Table2.2.The
Table Thecold
coldcrystallization
crystallizationtemperatures
temperatures(T(T)cc)for
forPLA/SF
PLA/SFand
andPLA/SF/ADR
composites with
with
cc
different ADR additions.
different ADR additions.
PLA/SF/ PLA/SF/ PLA/SF/ PLA/SF/ PLA/SF/
PLA/SF PLA/SF/ PLA/SF/ PLA/SF/ PLA/SF/ PLA/SF/
CompositesPLA/SF ADR ADR ADR ADR ADR
Composites 80/20 ADR
80/20/0.2 ADR
80/20/0.4 ADR 80/20/0.8
80/20/0.6 ADR 80/20/1.0ADR
Tcc (°C) 80/20
107.7 80/20/0.2
110.8 80/20/0.4
112.1 80/20/0.6
115.7 80/20/0.8 114.1
115.5 80/20/1.0
Tcc (◦ C) 107.7 110.8 112.1 115.7 115.5 114.1
Materials 2018,
Materials 11,11,
2018, 398x FOR PEER REVIEW 9 of9 22
of 22
(a) (b)
Figure 6. Differential scanning calorimetry (DSC) thermograms of PLA/SF composites and
Figure 6. Differential scanning calorimetry (DSC) thermograms of PLA/SF composites and
PLA/SF/ADR composites with different ADR addition (a) and different SF content (b) at the second
PLA/SF/ADR composites with different ADR addition (a) and different SF content (b) at the second
heating scan with a rate of 10 °C/min.
heating scan with a rate of 10 ◦ C/min.
At the same time, it was also found that with the addition of ADR oligomer, an obvious shoulder
At appeared
peak the same in time,
the it was
left alsomelting
of the found endothermal
that with thepeak addition of ADR
(Tm 169.5 oligomer,
°C) for PLA/SF/ADRan obvious shoulder
composites,
peak appeared in the ◦
which indicated theleft of the melting
formation of poor endothermal
crystalline regionspeak within
(Tm 169.5
PLAC) for PLA/SF/ADR
[28,29], correspondingcomposites,
to lower
which indicated
melting the formation
temperature. of poor interfacial
The improved crystallineinteraction
regions within PLA [28,29],composites
of PLA/SF/ADR corresponding to lower
resulted in
melting temperature.
restricted molecular Thechainimproved
movement interfacial
of PLA and interaction
then more ofpoor
crystalline regions formed resulted
in the in
crystal growth
restricted stage,
molecular therefore
chain a shoulder
movement peakand
of PLA corresponding
then moreto lower
poor melting temperature
crystalline regions formed occurred
in the
for PLA/SF/ADR
crystal growth stage, composites.
therefore aThe presence
shoulder of a corresponding
peak peak shoulder might alsomelting
to lower be ascribed to the formation
temperature occurred
forofPLA/SF/ADR
different crystalline structures
composites. Thewithin
presencePLA,of areferred to as transcrystallinity
peak shoulder [15].
might also be ascribed to the formation
of different crystalline structures within PLA, referred to as transcrystallinity of
To further confirm these results, Figure 6b presents the DSC thermograms PLA/SF composites
[15].
andTo PLA/SF/ADR
further confirm composites withFigure
these results, different SF content
6b presents at the
the DSC second heating
thermograms scan. The
of PLA/SF cold
composites
crystallization temperatures are presented in Table 3. For PLA/SF/ADR
and PLA/SF/ADR composites with different SF content at the second heating scan. The cold composites, the T cc increased
considerably in comparison with PLA/SF composites, and an obvious shoulder peak arose in the left
crystallization temperatures are presented in Table 3. For PLA/SF/ADR composites, the Tcc increased
of the melting endothermal peak. These results were consistent with Figure 6a. At the same time, it
considerably in comparison with PLA/SF composites, and an obvious shoulder peak arose in the left
was found that the change of SF content had little effect on Tcc of PLA/SF composites. However, the
of the melting endothermal peak. These results were consistent with Figure 6a. At the same time,
Tcc of PLA/SF/ADR composites improved with increasing SF content. For PLA/SF composites, poor
it was found that the change of SF content had little effect on Tcc of PLA/SF composites. However,
interfacial interaction between SF and PLA matrix revealed that excessive addition of SF has little
the Tcc of PLA/SF/ADR composites improved with increasing SF content. For PLA/SF composites,
effect on the movement of PLA chain segments. By contrast, for PLA/SF/ADR composites, the more
poor
SF interfacial
was added, interaction
the morebetween
the sisalSFfibers
and PLA matrix revealed
participated that excessive
in the interfacial addition
reaction. As aofresult,
SF hasthe little
effect on the movement of PLA chain segments. By contrast, for PLA/SF/ADR
improved interfacial interaction between SF and the PLA matrix caused more severe restriction of composites, the more
SF PLA
was added, the more
chain segment the sisal fibers
movement and theparticipated in the interfacial
Tcc of PLA/SF/ADR reaction.
composites As a result, the improved
increased.
interfacial interaction between SF and the PLA matrix caused more severe restriction of PLA chain
segment movement
Table 3. The cold the Tcc of PLA/SF/ADR
andcrystallization temperatures (Tcomposites
cc) for PLA/SF increased.
and PLA/SF/ADR composites with
Table 3. The cold crystallization temperatures (Tcc ) for PLA/SF and PLA/SF/ADR composites with
Composites Tcc (°C) Composites Tcc (°C)
PLA/SF 90/10 wt % 107.1 PLA/SF/ADR 90/10/0.6 wt % 115.4
PLA/SF 80/20 wt %
Composites T107.5
◦ PLA/SF/ADR 80/20/0.6 wt % T115.7◦
cc ( C) Composites cc ( C)
PLA/SF
PLA/SF 60/40
80/20 wtwt
% % 107.4
107.5 PLA/SF/ADR
PLA/SF/ADR 60/40/0.6 wt%%
80/20/0.6 wt 117.8
115.7
The DSC thermograms of PLA/SF composites and PLA/SF/ADR composites117.8
PLA/SF 60/40 wt % 107.4 PLA/SF/ADR 60/40/0.6 wt % with different ADR
addition and different SF content at a cooling rate of 5 °C/min are shown in Figure 7. It was found
that
ThetheDSC
cooling crystallization
thermograms exothermal
of PLA/SF peak declined
composites with the addition
and PLA/SF/ADR of ADR with
composites oligomer (Figure
different ADR
7a). In terms of previous analyses, the incorporation
◦ of ADR oligomer into PLA/SF composites
addition and different SF content at a cooling rate of 5 C/min are shown in Figure 7. It was found that
theimproved the interfacialexothermal
cooling crystallization interaction peak
between SF and
declined PLA
with the matrix,
additionthus the movement
of ADR of PLA7a).
oligomer (Figure
In terms of previous analyses, the incorporation of ADR oligomer into PLA/SF composites improved
Materials 2018, 11, 398 10 of 22

the interfacial interaction between SF and PLA matrix, thus the movement of PLA segments were
segments
restricted, were restricted,
especially especially
in the PLA matrix in the to
close PLA
the matrix close
interface. In to
thethe interface.
crystal growthIn stage
the crystal
duringgrowth
cooling,
stage during cooling, the mobility of polymer segments is significant for crystallization. It can be
the mobility of polymer segments is significant for crystallization. It can be deduced that during
deduced that during the cooling process, no more PLA chain segments participated in cooling
the cooling process, no more PLA chain segments participated in cooling crystallization with the
crystallization with the further addition of oligomer ADR due to restricted movement of the PLA
further addition of oligomer ADR due to restricted movement of the PLA chain segments, therefore the
chain segments, therefore the crystallization of PLA/SF/ADR composites declined. Similar
crystallization of PLA/SF/ADR composites declined. Similar crystallization behaviors were found in
crystallization behaviors were found in PLA/SF composites and PLA/SF/ADR composites with
PLA/SF composites and PLA/SF/ADR composites with different SF content (Figure 7b,c). The cooling
different SF content (Figure 7b,c). The cooling crystallization exothermal peaks of PLA/SF/ADR
crystallization exothermal
composites were peaksdecreased
significantly of PLA/SF/ADR
comparedcomposites
with that of were
PLA/SF significantly
composites.decreased compared
At the same time,
with that of PLA/SF composites. At the same time, it was found that the crystallization
it was found that the crystallization temperature improved as SF content increased, corresponding to temperature
improved as SF content
an enhanced increased, corresponding
crystal nucleation to an addition
ability with greater enhancedofcrystal nucleation
SF. This ability withtogreater
can be attributed the
addition of SF. This
heterogeneous can be attributed
nucleation to the heterogeneous nucleation effect of SF.
effect of SF.
Figure
Figure 7. 7.
DSCDSC thermogramsofofPLA/SF
thermograms PLA/SFcomposites
composites andand PLA/SF/ADR
PLA/SF/ADRcomposites with
composites different
with ADR
different ADR
addition (a) and different SF content (b,c) at a cooling rate of 5 °C/min.
◦
addition (a) and different SF content (b,c) at a cooling rate of 5 C/min.
The isothermal crystallization behavior of PLA/SF composites and PLA/SF/ADR composites was
The isothermal
investigated at 110crystallization
°C. Figure 8a,bbehavior
illustrate of
thePLA/SF
isothermalcomposites and PLA/SF/ADR
crystallization thermograms ofcomposites
PLA/SF
was investigated at 110 ◦ C. Figure 8a,b illustrate the isothermal crystallization thermograms of PLA/SF
composites and PLA/SF/ADR composites with different ADR addition and different SF content at
composites
110 °C. Theandthermograms
recorded with(dH/dt)
heat flow different
as aADR addition
function and From
of time. different
the SF content at
isothermal
◦ C. The thermograms recorded heat flow (dH/dt) as a function of time. From the isothermal
110crystallization thermograms, the relative crystallinity as a function of crystallization time can be
crystallization
calculated by thermograms, the relative crystallinity as a function of crystallization time can be
the following equation:
calculated by the following equation:
⁄
(1)
⁄ )dt
Rt
Qt 0 (dH/dt
Xt = = R∞ (1)
where X(t) is the relative crystallinity, andQQ ∞ ∞ and0 Q(tdH/dt
are the)dt
heat generated at infinite time and at
time t. Figure 8c,d presents the change in relative crystallinity as a function of crystallization time. To
where X(t)
further is the relative
analyze crystallinity,
the crystallization andof
kinetics Qcomposites,
∞ and Qt are the heat
a classic generated
Avrami at infinite
equation was usedtime and at
[30,31].
time t. Figure 8c,d presents the change in relative crystallinity as a function of crystallization time.
1
To further analyze the crystallization kinetics of composites, (2)
a classic Avrami equation was used [30,31].
Materials 2018, 11, 398 11 of 22
Materials 2018, 11, x FOR PEER REVIEW X (t) = 1 − exp(−ktn ) 11 of 22(2)
where
whereX(t)X(t)
is the
is relative crystallinity,
the relative k is the
crystallinity, k iscrystallization rate constant,
the crystallization and n and
rate constant, is thenAvrami exponent
is the Avrami
reflecting the mechanisms of crystal nucleation and growth, and the following equation
exponent reflecting the mechanisms of crystal nucleation and growth, and the following equation can be deduced
can
from Equationfrom
be deduced (2) Equation (2)
ln{− ln[1 − X (t)]} = ln k + n ln t (3)
ln ln 1 ln ln (3)
ByBy
plotting ln [−
plotting lnln(1 − X(t))]
[−ln(1 versus
− X(t))] ln(t),ln(t),
versus the Avrami exponent,
the Avrami n, andn,crystallization
exponent, rate constant,
and crystallization rate
k, were determined.
constant, k, were Meanwhile,
determined.theMeanwhile,
crystallization the half-time t1/2 , reflecting
crystallization half-timethet1/2crystallization rate,
, reflecting the
cancrystallization
be calculatedrate,
withcan
thebebelow equation:
calculated with the below equation:
⁄
ln 2 1/n
ln 2 (4)
t1/2⁄= (4)
k
The obtained Avrami parameters of n and k, and calculated t1/2 are summarized in Tables 4 and
5. The obtained Avrami parameters of n and k, and calculated t1/2 are summarized in Tables 4 and 5.
Figure 8. Isothermal crystallization of PLA/SF and PLA/SF/ADR composites: DSC thermograms (a,b);
Figure 8. Isothermal crystallization of PLA/SF and PLA/SF/ADR composites: DSC thermograms
relative crystallinity (c,d) and Avrami plots (e,f).
(a,b); relative crystallinity (c,d) and Avrami plots (e,f).
Table 4. Isothermal crystallization half time and kinetic parameters of PLA/SF/ADR composites with
different ADR addition.
Materials 2018, 11, 398 12 of 22
Table 4. Isothermal crystallization half time and kinetic parameters of PLA/SF/ADR composites with
different ADR addition.
Samples n k (min−n ) t1/2 (min)

PLA/SF 80/20 wt % 1.954 0.172 2.04
PLA/SF/ADR 80/20/0.2 wt % 2.030 0.139 2.21
PLA/SF/ADR 80/20/0.4 wt % 2.159 0.0965 2.49
PLA/SF/ADR 80/20/0.6 wt % 2.341 0.0272 3.99
PLA/SF/ADR 80/20/0.8 wt % 2.159 0.0604 3.09
PLA/SF/ADR 80/20/1.0 wt % 2.094 0.0879 2.68
Table 5. Isothermal crystallization half time and kinetic parameters of PLA/SF and PLA/SF/ADR
composites with different SF content.
Samples n k (min−n ) t1/2 (min)

PLA/SF 90/10 wt % 2.218 0.464 1.20
PLA/SF 80/20 wt % 1.954 0.172 2.04
PLA/SF 70/30 wt % 1.933 0.373 1.38
PLA/SF 60/40 wt % 2.041 0.506 1.17
PLA/SF/ADR 90/10/0.6 wt % 1.921 0.0678 3.35
PLA/SF/ADR 80/20/0.6 wt % 2.341 0.0272 3.99
PLA/SF/ADR 70/30/0.6 wt % 2.245 0.0491 3.25
PLA/SF/ADR 60/40/0.6 wt % 2.141 0.105 2.41
For PLA/SF and PLA/SF/ADR composites with different ADR addition (Figure 8a), the isothermal
crystallization rate decreased with the addition of ADR oligomer. As can be seen from Table 4,
the crystallization half-time is 2.04 min for PLA/SF composites, and t1/2 increased with addition of
ADR. The crystallization half-time increased to 3.99 min for composites with 0.6 wt % ADR. However,
t1/2 tended to decrease for composites with 0.8 wt % and 1.0 wt % ADR, for which the t1/2 values were
3.09 min and 2.68 min, respectively. The calculated crystallization half-time was consistent with the
crystallization thermograms. In terms of the analyses mentioned above, the incorporation of ADR into
PLA/SF composites improved the interfacial interaction between SF and PLA, but it also restricted the
movement of the PLA chain segments. The decline in the crystallization rate of the composites with
addition of ADR can be credited to the restricted movement of the PLA chain segments. The ADR
oligomer connected PLA to the fiber surface via in situ reaction. However, it was found that excessive
addition of ADR was detrimental to the bonding effect of ADR between SF and the PLA matrix.
The increased crystallization rate of composites with 0.8 and 1.0 wt % ADR addition can be ascribed to
the decline of the bonding effect of the ADR oligomer. In addition, ADR is a kind of oligomer with low
molecular weight, and it might plasticize the PLA matrix in excessive quantities, thus facilitating chain
segment movement and improving the crystallization rate. It was found that for PLA/SF composites
and PLA/SF/ADR composites with different ADR addition, the n value varied from 1.954 to 2.341,
reflecting that the crystals tended to grow in two dimensions.
For PLA/SF composites and PLA/SF/ADR composites with different SF content (Figure 8b),
a similar crystallization behavior occurred. The addition of 0.6 wt % ADR decreased the crystallization
rate for each SF content, from 10 wt % to 40 wt %. It was also found that as the SF content increased,
the crystallization half-time improved, then decreased significantly (see Table 5). This phenomenon
occurred in both PLA/SF composites and PLA/SF/ADR composites with different SF content.
These results are related to the heterogeneous nucleation effect of SF. Excessive addition of SF restricted
the movement of PLA chain segments; meanwhile, it provided more heterogeneous nucleation points.
The enhanced heterogeneous nucleation resulted in increase in the crystallization rate of composites
with high SF content (30 wt % and 40 wt %).
Materials 2018, 11, 398 13 of 22
3.4. Dynamic Rheological Behaviors

The2018,
Materials viscoelastic response
11, x FOR PEER REVIEW of polymers and polymer composites are very sensitive to changes 13 of of
22
microstructure, including chain structure and phase morphology, which has attracted fundamental
interest
interest in this study.
study. Dynamic
Dynamic small amplitude
amplitude oscillatory
oscillatory shear (SAOS) was performed to probe the
effect
effect of melting reactive
reactive processing
processing withwith ADR
ADR oligomer
oligomer on the microstructure
microstructure of of PLA/SF composites.
PLA/SF composites.
To
To detect the in situ reaction of composite melts, dynamic time sweep
situ reaction of composite melts, dynamic time sweep tests were performedtests were performed in
in
thisthis study.The
study. Therelative
relativecomplex
complexviscosity
viscosity(η*(t)/η*(0))
(η*(t)/η*(0))versus
versus time
time of PLA/SF composites and
PLA/SF composites
PLA/SF/ADR
PLA/SF/ADR compositescompositeswith with different
different ADRADR addition
addition areare shown
shown in in Figure
Figure 9a.9a. It was
It was foundfound
thatthat
the
the complex viscosity of PLA/SF (80/20 wt %) composites decreased dramatically
complex viscosity of PLA/SF (80/20 wt %) composites decreased dramatically within the time sweep within the time
sweep
becausebecause of thermal
of thermal degradation.
degradation. However,
However, the the presence
presence of ofADR
ADRoligomers
oligomers counteracted
counteracted the
degradation of the composite melts. The relative complex viscosity
degradation of the composite melts. The relative complex viscosity even increased at even increased at thethe
early stage
early stageof
the time
of the sweep.
time sweep. This
Thisphenomenon
phenomenoncan canbebeascribed
ascribedtotothetheimproved
improvedinterfacial
interfacialinteraction
interaction between
between
SF and the the PLA
PLAmatrix
matrixvia viaininsitu
situreaction
reactionofofADR ADR oligomers
oligomers with
with SF SF
andand PLA,
PLA, andand meanwhile,
meanwhile, the
the chain extension effect of ADR on PLA also contributed to the improvement
chain extension effect of ADR on PLA also contributed to the improvement of complex viscosity. of complex viscosity.
Furthermore,
Furthermore, ititwas wasfound
foundthatthatthe η*(t)/η*(0)value
theη*(t)/η*(0) valueofofPLA/ADR/ADR
PLA/ADR/ADR(80/20/0.6 (80/20/0.6 wtwt %)
%) composites
possess the most significant
significant improvement in the early stage of the time
early stage of the time sweep.sweep. These results were
consistent
consistent with the analyses mentioned above. Excessive addition of ADR oligomer, more 0.6
with the analyses mentioned above. Excessive addition of ADR oligomer, more than thanwt0.6%
content, did not
wt % content, didimprove the interfacial
not improve interaction
the interfacial of the of
interaction composites.
the composites.
Figure 9.
Figure 9. Relative
Relative complex
complexviscosity
viscosity(η*(t)/η*(0))
(η*(t)/η*(0))versus
versustime
timeofofPLA/SF
PLA/SFand
andPLA/SF/ADR
composites
with different ADR addition (a) and different SF content (b).
with different ADR addition (a) and different SF content (b).
Figure 9b shows the relative complex viscosity (η*(t)/η*(0)) versus time of PLA/SF composites
Figure 9b shows the relative complex viscosity (η*(t)/η*(0)) versus time of PLA/SF composites
and PLA/SF/ADR composites with different SF content. For PLA/SF composites with different SF
and PLA/SF/ADR composites with different SF content. For PLA/SF composites with different SF
content, the complex viscosity declined severely within the time sweep. The addition of 0.6 wt %
content, the complex viscosity declined severely within the time sweep. The addition of 0.6 wt %
ADR oligomer effectively inhibited the reduction of the complex viscosity of the composites. As can
ADR oligomer effectively inhibited the reduction of the complex viscosity of the composites. As can
be seen from Figure 10b, the η*(t)/η*(0) value of PLA/SF/ADR composites tended to be enhanced
be seen from Figure 10b, the η*(t)/η*(0) value of PLA/SF/ADR composites tended to be enhanced
within the time sweep. Furthermore, it was found that for PLA/SF composites, the more SF was
within the time sweep. Furthermore, it was found that for PLA/SF composites, the more SF was
added, the more the η*(t)/η*(0) value would decrease. That is because the presence of SF aggravated
added, the more the η*(t)/η*(0) value would decrease. That is because the presence of SF aggravated
the thermal degradation of composites. However, for PLA/SF/ADR composites with 0.6 wt % ADR
the thermal degradation of composites. However, for PLA/SF/ADR composites with 0.6 wt % ADR
oligomer, the η*(t)/η*(0) value of composites increased with increasing SF content because more SF
oligomer, the η*(t)/η*(0) value of composites increased with increasing SF content because more SF
addition could improve the interfacial interaction between SF and the PLA matrix. The PLA/SF/ADR
addition could improve the interfacial interaction between SF and the PLA matrix. The PLA/SF/ADR
(60/40/0.6 wt %) composites exhibited the greatest improvement in the η*(t)/η*(0) value.
(60/40/0.6 wt %) composites exhibited the greatest improvement in the η*(t)/η*(0) value.
Materials 2018, 11, 398 14 of 22
Figure 10. Changes in storage modulus (a); loss modulus (b); complex viscosity |η*| (c), and tan δ (d) as
Figure 10. Changes in storage modulus (a); loss modulus (b); complex viscosity |η*| (c), and tan δ (d)
functions of angular frequency for PLA/SF and PLA/SF/ADR composites with different ADR addition.
as functions of angular frequency for PLA/SF and PLA/SF/ADR composites with different ADR
addition. 0
The changes of storage modulus (G ), loss modulus (G”), complex viscosity |η*| and loss tangent
as functions
The changesof angular
of storagefrequency
modulus for(G′),
PLA/SF and PLA/SF/ADR
loss modulus (G″), complex composites withand
viscosity |η*| different ADR
loss tangent
addition are shown in Figure 10. It can be seen from Figure 10a,b
as functions of angular frequency for PLA/SF and PLA/SF/ADR composites with different ADR that the addition of ADR oligomer
improved
addition are theshown
storage in modulus
Figure 10.and It canloss
bemodulus
seen fromofFigure
PLA/SF 10a,bcomposites. It reflects
that the addition of ADRthe enhanced
oligomer
viscoelastic response of PLA/SF/ADR composites compared
improved the storage modulus and loss modulus of PLA/SF composites. It reflects the with that of PLA/SF composites.
enhanced
Figure 10c presents
viscoelastic responsethe changes of complex
of PLA/SF/ADR composites viscosity
comparedas a with
function
that of angular composites.
of PLA/SF frequency. Figure It can
be
10c presents the changes of complex viscosity as a function of angular frequency. It can be seen low
seen that the complex viscosity improved with addition of ADR oligomer, especially in the that
angular frequency
the complex region.
viscosity In addition,
improved withthe patternof
addition of ADR
dependence
oligomer,of complex
especially viscosity
in the on lowfrequency
angular
(the changeregion.
frequency tendency In of complexthe
addition, viscosity
patternwith frequency) varied
of dependence to some
of complex extent due
viscosity on to the addition
frequency (the
of ADR. For PLA/SF composites and PLA/SF/ADR composites with
change tendency of complex viscosity with frequency) varied to some extent due to the addition low ADR content (0.2 wt % and of
0.4
ADR.wt %)
Forthe complex
PLA/SF viscosity and
composites remained nearly constant
PLA/SF/ADR in thewith
composites low low
angular
ADRfrequency
content (0.2 region,
wt %and andthen
0.4
decreased as angular
wt %) the complex frequency
viscosity increased.
remained nearly This transition
constant from
in the lowthe Newtonian
angular plateau
frequency to the
region, andpower
then
law regime at the inflection point is a typical phenomenon of polymer materials.
decreased as angular frequency increased. This transition from the Newtonian plateau to the power However, it was found
that
law the Newtonian
regime plateau region
at the inflection pointdecreased
is a typical with the additionofofpolymer
phenomenon ADR oligomer. For However,
materials. compositesitwith was
high ADR content (0.6 wt %, 0.8 wt %, and 1.0 wt %), the shear-thinning
found that the Newtonian plateau region decreased with the addition of ADR oligomer. For behavior occurred in the whole
angular
compositesfrequency
with highregion,ADR which more(0.6
content obviously
wt %, 0.8 exhibited the power
wt %, and 1.0 wtlaw%),regime [32,33]. The enhanced
the shear-thinning behavior
shear-thinning behavior of PLA/SF/ADR composites can be ascribed
occurred in the whole angular frequency region, which more obviously exhibited the power law to the improved interfacial
interaction of composites.
regime [32,33]. The enhanced For PLA/SF/ADR
shear-thinningcomposites,
behavior of for which the interfacial
PLA/SF/ADR composites interaction
can be ascribedbetween to
SF and PLA matrix were enhanced, the sisal fibers can act as physical
the improved interfacial interaction of composites. For PLA/SF/ADR composites, for which crossing points in composite melts.
the
Therefore, it can be deduced
interfacial interaction betweenthat morePLA
SF and significant disentanglement
matrix were enhanced, theofsisal the polymer
fibers canchain act asoccurred
physical
as
crossing points in composite melts. Therefore, it can be deduced that more than
the angular frequency increased, resulting in more obvious shear-thinning behavior that of
significant
PLA/SF composites. Figure 10d chain
presents the changes 0
disentanglement of the polymer occurred as the of loss tangent
angular frequency(tanincreased,
δ = G”/G resulting
) as a function
in moreof
angular frequency. It can be seen that the tan δ of PLA/SF/ADR composites
obvious shear-thinning behavior than that of PLA/SF composites. Figure 10d presents the changes of decreased in comparison
with that of PLA/SF
loss tangent (tan δ =composites.
G″/G′) as aThe PLA/SF/ADR
function of angularcomposites
frequency. possess
It cana bemore dramatically
seen that the tan elastic
δ of
PLA/SF/ADR composites decreased in comparison with that of PLA/SF composites. The
PLA/SF/ADR composites possess a more dramatically elastic response. The frequency dependence
Materials 2018, 11, 398 15 of 22
of the lossThe
response. tangent can bedependence
frequency used to characterize the
of the loss gel point
tangent canofbethe
usedcross-linking
to characterizesystem
the[34,35].
gel pointThis
of
method
the can be adopted
cross-linking systemfor polymer
[34,35]. Thiscomposites
method can to be
evaluate
adopted thefor
percolation thresholds of
polymer composites tothe fillers
evaluate
[36,37].
the The tanthresholds
percolation δ of PLA/SF/ADR composites
of the fillers [36,37]. displayed
The tan δ ofless dependence on
PLA/SF/ADR the angular
composites frequency,
displayed less
which exhibited
dependence a gel-like
on the angularbehavior.
frequency,In terms
whichof the analyses
exhibited mentioned
a gel-like above,
behavior. the presence
In terms of ADR
of the analyses
improved the
mentioned interfacial
above, interaction
the presence of composites,
of ADR improved the andinterfacial
the physical crossing of
interaction points of sisal fibers
composites, and thein
composite
physical melts. points
crossing Therefore, the fibers
of sisal stressin
relaxation
composite ofmelts.
the PLA molecular
Therefore, thechain
stressbecame more
relaxation difficult
of the PLA
in the meltchain
molecular state; became
the elastic response
more of the
difficult PLA/SF/ADR
in the melt state; composite
the elastic melt was enhanced
response and tended
of the PLA/SF/ADR
to exhibit amelt
composite gel-like
wasbehavior.
enhanced and tended to exhibit a gel-like behavior.
3.5. DMA Characterization

In order to evaluate the dynamic mechanical properties and investigate the effect of ADR on the
glass transition
transition of
of composites,
composites, the theDMA
DMAmeasurements
measurementsofofPLA/SFPLA/SFcomposites
compositesand andPLA/SF/ADR
PLA/SF/ADR
composites with different SF content were carried out at different frequencies. The effect of different
frequencies on thethe loss
loss tangent
tangent(tan(tanδ)δ)ofofPLA/SF
PLA/SFand andPLA/SF/ADR composites with
PLA/SF/ADR composites with different SF
content with a heating ◦
heating rate
rate of
of 22 °C/min
C/min is is shown
shown in Figure 11. It It was observed that in the whole
temperature range,
range, the
the ααrelaxation
relaxationforforPLA/SF
PLA/SF and PLA/SF/ADR composites ◦C
and PLA/SF/ADR composites waswas between
between 60and
60 °C
and ◦ C which corresponds to the glass transition temperature (T ) of the composites. The glass
70 which
70 °C corresponds to the glass transition temperature (Tg)g of the composites. The
transition
transition temperature
temperature of of the
the composites
composites is is summarized
summarizedin in Table
Table6. The TTgg of the
6. The the composites
composites increased
as the frequencies elevated. It was found that the T
the frequencies elevated. was found that the Tg g of PLA/SF/ADR of PLA/SF/ADR composites was improved
compared
compared withwith that
that of PLA/SF composites at
PLA/SF composites at the
the same
same test
testfrequencies,
frequencies, which
which demonstrated
demonstrated that PLA
chain segment mobility was restrained.
restrained. This result confirmed the enhanced enhanced interfacial
interfacial interaction
interaction
between SF and the PLA matrix via in situ interfacial reaction.
interfacial reaction.
Figure 11. Cont.

Materials 2018, 11, 398 16 of 22
Figure 11.
Figure 11. Effect
Effect of
of different
different frequencies
frequencies onontan
tanδ δofofPLA/SF
PLA/SFand
andPLA/SF/ADR
composites with
with
different SF content at a heating rate of 2 °C/min.
◦
different SF content at a heating rate of 2 C/min.
Table 6.
Table 6. The
The glass
glasstransition
transitiontemperature
temperatureofofPLA/SF
PLA/SFcomposites
compositesand
andPLA/SF/TGIC
PLA/SF/TGIC composites with
composites with
different ADR addition at different frequencies of tan
different ADR addition at different frequencies of tan δ.δ.
Temperature Tg ◦(°C)
Samples Temperature Tg ( C)
Samples 0.1 (HZ) 0.5 0.5(HZ)
(HZ) 11(HZ)(HZ) 55(HZ) 2020
(HZ)
0.1 (HZ) (HZ) (HZ)
PLA/SF 90/10
PLA/SF 90/10 wt %
wt % 58.6
58.6
62.0
62.0
62.9
62.9
64.9
64.9
67.9
67.9
PLA/SF/ADR 90/10/0.6
PLA/SF/ADR 90/10/0.6 wt wt
% % 61.8
61.8 63.2
63.2 64.6
64.6 67.9
67.9 69.9
69.9
PLA/SF
PLA/SF80/20 wtwt
80/20 % % 61.1
61.1 62.9
62.9 63.4
63.4 67.0
67.0 69.4
69.4
PLA/SF/ADR 80/20/0.6 wt % 61.3 62.9 64.6 67.5 68.95
PLA/SF/ADR
PLA/SF 70/3080/20/0.6
wt % wt % 61.3
61.2 62.9
63.0 64.6
63.1 67.5
66.4 68.95
68.9
PLA/SF70/30/0.6
PLA/SF/ADR 70/30 wtwt%% 61.2
60.7 63.0
63.1 63.1
63.6 66.4
66.5 68.9
68.4
PLA/SF 60/40 wt %
PLA/SF/ADR 70/30/0.6 wt % 60.2
60.7 61.9
63.1 62.5
63.6 65.9
66.5 67.5
68.4
PLA/SF/ADR
PLA/SF60/40/0.6
60/40 wtwt%% 61.0
60.2 62.7
61.9 63.2
62.5 66.1
65.9 67.8
67.5
PLA/SF/ADR 60/40/0.6 wt % 61.0 62.7 63.2 66.1 67.8
To further analyze the glass transition of the composites, the activation energies of glass transition
relaxation (∆Ea ) analyze
To further were calculated
the glassbased on the of
transition dependence of Tg on
the composites, frequency.
the activationThe ∆Ea represents
energies of glass
the energyrelaxation
transition barrier of (∆E
glass transition
a) were relaxation.
calculated basedItoncanthebedependence
adopted to characterize the relationship
of Tg on frequency. The ∆Ea
represents
between the energy
polymer chain barrier
segmentofmobility
glass transition relaxation.
and the time It can
scale. Five be adopted
different to characterize
test frequencies the
were used
relationship
in between
this study (0.1, 0.5, 1,polymer
5, and 20chain segment
HZ). The changesmobility
of glassand the time
transition scale. Five
temperature were different test
interrelated
frequencies
with were used
test frequencies in the
using thisArrhenius
study (0.1, 0.5, 1, [38,39].
equation 5, and On 20 HZ). Theofchanges
the basis of glass transition
classic Arrhenius equation,
temperature
the molecularwere interrelated
relaxation time canwith test frequencies
be expressed as: using the Arrhenius equation [38,39]. On the
basis of classic Arrhenius equation, the molecular relaxation time can be expressed as:
∆E−γσ
τ = τ0 e ∆ RT (5)
(5)
where ∆E and σ are the activation energy of relaxation and the stress, respectively, τ 0 is the hypothetical
where ∆E and σ are the activation energy of relaxation and the stress, respectively, τ0 is the
relaxation time at an infinite temperature, T is the absolute temperature, γ is the variable and R is the
hypothetical relaxation time at an infinite temperature, T is the absolute temperature, γ is the variable
gas constant.
and R is the gas constant.
Here, the stress (σ) is small, thus Equation (5) can be simplified as:
Materials 2018, 11, 398 17 of 22
Here, the stress (σ) is small, thus Equation (5) can be simplified as:
Materials 2018, 11, x FOR PEER REVIEW ∆E 17 of 22

τ = τ0 e RT (6)
∆E ∆
ln τ = ln τ0 + (6)
(7)
RT
The relaxation times were calculated from ∆
ln the
ln relationship: (7)
1
The relaxation times were calculated from τthe
= relationship: (8)
f
1
A combination of Equations (7) and (8) leads to: (8)
A combination of Equations (7) and (8) leads to: ∆E

ln f = − ln τ0 − (9)
∆
RT
ln ln (9)
According to Equation (9), a plot of lnf versus 1/T should give a straight line with a slope that
According to Equation
is proportional activation(9), a plotassociated
energy of lnf versusto 1/T
the should give a straight
glass transition line with
relaxation. a slope
Figure that is
12 shows
proportional
the Arrheniustoplots
activation energytimes
of relaxation associated
versusto1/T,
the glass transitionlinear
the respective relaxation.
fits of Figure
PLA/SF 12composites
shows the
Arrhenius plots of relaxation
and PLA/SF/ADR compositestimes
withversus 1/T, the
different respective
SF content, andlinear
the fits of PLA/SF
calculated composites
activation and
energies
of glass transition with As
relaxation. different
can beSF content,
seen from andTablethe calculated
7 and Figureactivation energies of∆E
12c, the calculated glass
a of
transition
compositesrelaxation.
increased As can
with thebeaddition
seen from Tableoligomer
of ADR 7 and Figure 12c,SFthe
at equal calculated
content, which∆Eimplied
a of composites
that the
increased
improved with the addition
interfacial adhesionof of
ADR oligomerincreased
composites at equal SF thecontent, which implied
energy barrier that theof
of the mobility improved
the PLA
interfacial adhesion
chain segments. of composites
In addition, for bothincreased
PLA/SFthe energy barrier
composites of the mobility
and PLA/SF/ADR of the PLA
composites, ∆Ea
thechain
segments.
value In addition,
increased for both SF
with increasing PLA/SF
content.composites
Furthermore,and PLA/SF/ADR
the improvement composites, the ∆E
in activation a value
energy of
increased
PLA/SF/ADR withcomposites
increasingcompared
SF content.withFurthermore,
that of PLA/SF thecomposites
improvement at thein activation
identical energywas
SF content of
PLA/SF/ADR
elevated with composites
increased SF compared withFigure
content (see that of12c).
PLA/SF Thecomposites
greater theataddition
the identical
of SF,SF thecontent was
more sisal
elevated with increased
fibers participated SF content
in interfacial (see Figure
reaction, 12c).inThe
resulting greaterrestriction
increased the addition of SF,chain
of PLA the more sisal
segments.
fibers results
These participated
are in in interfacialwith
accordance reaction, resulting
the thermal andinrheological
increased analyses
restriction of PLA chain
mentioned above. segments.
These results are in accordance with the thermal and rheological analyses mentioned above.
Table 7. The calculated activation energies of glass transition relaxation for PLA/SF composites and
PLA/SF/ADR
Table composites
7. The calculated with different
activation SFof
energies content.
glass transition relaxation for PLA/SF composites and
PLA/SF/ADR composites with different SF content.
PLA/SF PLA/SF PLA/SF PLA/SF PLA/SF/ PLA/SF/ PLA/SF/ PLA/SF/
PLA/SF PLA/SF PLA/SF PLA/SF PLA/SF/ PLA/SF/ PLA/SF/ PLA/SF/
Samples ADR ADR ADR ADR
Samples 90/10 80/20 70/30 60/40 ADR ADR ADR ADR
90/10 80/20 70/30 60/40 90/10/0.6 80/20/0.6 70/30/0.6 60/40/0.6
90/10/0.6 80/20/0.6 70/30/0.6 60/40/0.6
∆E
∆Eaa (KJ/mol)
(KJ/mol) 557.21
557.21 578.37
578.37 597.82
597.82 621.40 581.02
621.40 581.02 611.28
611.28 655.52
655.52 716.76
716.76
Figure 12. Cont.

Materials 2018, 11, 398 18 of 22
Figure 12. Arrhenius plots of relaxation times versus 1/T and the respective linear fits of PLA/SF
Figure 12. Arrhenius plots of relaxation times versus 1/T and the respective linear fits of PLA/SF
composites (a) and PLA/SF/ADR composites (b) with different SF content and the calculated
composites (a) and PLA/SF/ADR composites (b) with different SF content and the calculated activation
activation energies (∆Ea) of glass transition relaxation (c).
energies (∆Ea ) of glass transition relaxation (c).
3.6. Mechanical Properties
3.6. Mechanical Properties
Figure13
Figure 12. shows
Arrhenius theplots of relaxation
tensile times and
properties versusimpact
1/T and strength
the respective linear fits composites
of PLA/SF of PLA/SF and
Figure composites
PLA/SF/ADR13 shows (a)
composites and PLA/SF/ADR
the tensile composites
properties
with different ADRand (b) with
impact
addition. different
It was SF
strength content
found of and
thatPLA/SF the calculated
the addition composites
of ADR and
activation energies (∆Ea) of glass transition relaxation (c).
oligomer
PLA/SF/ADR improved
composites the tensile
withstrength
different of the
ADR composites
addition. (Figure
It was 13a).found
Moreover, that as thetheaddition
ADR content of ADR
increased,
oligomer improvedthe tensile strength of PLA/SF/ADR composites increased at first and then decreased. The
3.6. Mechanicalthe tensile strength of the composites (Figure 13a). Moreover, as the ADR content
Properties
PLA/SF/ADR
increased, the tensile(80/20/0.6 wt %)ofcomposites
strength PLA/SF/ADR possessed the highestincreased
composites tensile strength.
at firstA and similarthenvariation
decreased.
tendency Figure 13 shows
occurred for thethe tensile
tensile properties
modulus of theand impact strength
composites, of PLA/SF
which reflected compositesstiffness
the enhanced and
The PLA/SF/ADR (80/20/0.6
PLA/SF/ADR composites wt %) composites possessed the highest tensile strength. A similar
of PLA/ADR/SF compositeswith different
compared withADRthataddition.
of PLA/SF It was found that
composites. the addition
Furthermore, of ADR
it was found
variation tendency
oligomer occurred
improved for the tensileof modulus of the composites, whichasreflected the enhanced
that the elongation atthe tensile
break andstrength
the impact thestrength
composites of (Figure
PLA/SF/ADR 13a). Moreover,
composite the
were ADR content
improved in
stiffness of PLA/ADR/SF
increased, composites
the tensile strength compared
of PLA/SF/ADR with that
composites of PLA/SF
increased
comparison with that of PLA/SF composites (Figure 13b), which indicated an enhanced toughness composites.
at first Furthermore,
and then decreased. The it was
of
PLA/SF/ADR
foundcomposites
that the elongation(80/20/0.6 wt %) and
at break composites possessed
the impact the highest
strength tensile strength.
ofdemonstrated
PLA/SF/ADR A similar variation
composite were improved
with addition of ADR oligomer. These results that the incorporation of
tendency occurred for the tensile modulus of the composites, which reflected the enhanced stiffness
in comparison
ADR oligomers with simultaneously
that of PLA/SFreinforce composites (Figure the
and toughen 13b), whichcomposites.
PLA/SF indicated an enhanced
Figure 14 shows toughness
the
of PLA/ADR/SF composites compared with that of PLA/SF composites. Furthermore, it was found
of composites with addition
tensile properties and impact of ADR oligomer.
strength of PLA/SFThesecomposites
results demonstrated
and PLA/SF/ADR that the incorporation
composites with of
that the elongation at break and the impact strength of PLA/SF/ADR composite were improved in
different
ADR oligomers SF
comparison
content.
simultaneously For PLA/SF
with that of PLA/SF
composites,
reinforce the
and(Figure
composites
tensile
toughen 13b),
strength
the PLA/SF
which
decreased
indicated
as
composites. SF
an enhanced
content
Figure increased.
toughness 14 shows
of the
However,
tensile properties
composites for PLA/SF/ADR
and addition
with impact of composites
strength ofwith
PLA/SF
ADR oligomer. 0.6 wtcomposites
These % ADRdemonstrated
results oligomer, thethat
and PLA/SF/ADRtensile
the strength improved
composites
incorporation of with
with
differentADR
SFthecontent.
increase For
oligomers of SFPLA/SF
content, composites,
simultaneously exhibiting thatthe
reinforce and thetensile
toughengreater the addition
thestrength
PLA/SF of SF, Figure
composites.
decreased the
as greater
SF14 the tensile
shows
content the
increased.
strength
tensile compared
properties with
and that
impact of PLA/SF
strength of composites
PLA/SF at
composites the identical
and SF
PLA/SF/ADR content (Figure
composites 14a).
with In
However, for PLA/SF/ADR composites with 0.6 wt % ADR oligomer, the tensile strength improved
addition, the tensile modulus of PLA/SF and PLA/SF/ADR composites
different SF content. For PLA/SF composites, the tensile strength decreased as SF content increased. were enhanced with high SF
with the increase of SF content, exhibiting that the greater the addition of SF, the greater the tensile
content,
However,and for
the PLA/SF/ADR
elevation of tensile modulus
composites withbecame
0.6 wt %greater at higher the
ADR oligomer, SF content. Figure 14b
tensile strength presents
improved
strength
thatcompared
the with
elongation that
at of
break PLA/SF
of the composites
composites at the
decreases identical
with SF content
increasing
with the increase of SF content, exhibiting that the greater the addition of SF, the greater the tensile SF (Figure
content, 14a).
and In
ataddition,
the
the tensile modulus
identical
strength SFcompared
content of PLA/SF
thewith and
elongation
that of PLA/SF/ADR
at breakcomposites
PLA/SF composites
is improved at via
the additionwereof
identical enhanced
SF ADR
content with high
oligomer.
(Figure The
14a). SFIncontent,
impact
and the elevation
addition,
strength theof
of PLA/SF/ADR tensile
tensile modulus
modulus became
of PLA/SF
composites with and greater
PLA/SF/ADR
different at higher
SF content wasSF
composites content.
also were Figure
enhanced
improved 14bhigh
with
in comparison presents
with that
SF
content,
the elongation
that of PLA/SFand the
at break elevation of tensile
of the composites
composites modulus became greater at higher SF content. Figure
decreases with increasing SF content, and at the identical SF
(see Figure 14c). 14b presents
contentthat
the the elongationatatbreak
elongation breakisofimproved
the composites decreases of
via addition with increasing
ADR SF content,
oligomer. and atstrength
The impact the of
identical SF content the elongation at break is improved via addition of ADR oligomer. The impact
PLA/SF/ADR composites with different SF content was also improved in comparison with that of
strength of PLA/SF/ADR composites with different SF content was also improved in comparison with
PLA/SFthat
composites
of PLA/SF (see Figure(see
composites 14c).
Figure 14c).
Figure 13. Tensile strength and tensile modulus (a), elongation at break and impact strength (b) of
PLA/SF/ADR composites with different ADR addition and constant 20 wt % SF content.
Materials 2018, 11, 398 19 of 22
Figure 14. Tensile strength and tensile modulus (a); elongation at break (b), and impact strength (c)
Figure 14. Tensile strength and tensile modulus (a); elongation at break (b), and impact strength (c) of
of PLA/SF and PLA/SF/ADR composites with different SF content and constant 0.6 wt % ADR
PLA/SF and PLA/SF/ADR composites with different SF content and constant 0.6 wt % ADR addition.
addition.
In
In brief,
brief, when
when thethe fiber-reinforced
fiber-reinforced plastic
plastic is
is bearing
bearing force,
force, the
the role
role ofof the
the interface
interface is is to
to transmit
transmit
stress from the polymer matrix to the fibers; therefore, the mechanical
stress from the polymer matrix to the fibers; therefore, the mechanical properties of PLA/SF properties of PLA/SF
composites
composites in in this
this study
study were
were significantly
significantly influenced
influenced by by fiber–matrix
fiber–matrix interaction
interaction [40].
[40]. According
According to to
the
the microstructure characterization and analyses mentioned above, the addition of ADR oligomer
microstructure characterization and analyses mentioned above, the addition of ADR oligomer
improved
improved the the interfacial
interfacialadhesion
adhesionofofPLA/SF
PLA/SF composites
composites via via in situ
in situ interfacial
interfacial reactionreaction
during during
melt-
melt-blending and processing. The improved interfacial interaction of
blending and processing. The improved interfacial interaction of PLA/SF composites enhanced thePLA/SF composites enhanced
the efficiency
efficiency of transmitting
of transmitting stress
stress from
from the
the PLAmatrix
PLA matrixtotosisal
sisalfibers,
fibers,thus
thus improving
improving the the mechanical
mechanical
properties.
properties. However, excessive addition of ADR was detrimental to the connecting effect of
However, excessive addition of ADR was detrimental to the connecting effect of ADR
ADR
between SF and the PLA matrix, which did not facilitate the enhancement
between SF and the PLA matrix, which did not facilitate the enhancement of interfacial adhesion. of interfacial adhesion.
Therefore,
Therefore, thethe interfacial
interfacial adhesion
adhesion of of PLA/SF/ADR
composites with
with high
high ADR ADR addition
addition (0.8(0.8
wtwt% or%
or 1.0 wt %) slightly decreased as compared with composites with
1.0 wt %) slightly decreased as compared with composites with 0.6 wt % ADR. ADR is a kind of 0.6 wt % ADR. ADR is a kind
of oligomer
oligomer with
with lower
lower molecularweight
molecular weightand anda amore
moreflexible
flexiblechain
chaincompared
compared with with PLA.
PLA. It It had
had aa
plasticizing
plasticizing effect
effect on
on aa PLA
PLAmatrix,
matrix,which
whichalso
alsocontributed
contributedto tothe
thetoughening
tougheningof ofcomposites.
composites.
At
At the same time, poorer interfacial adhesion resulted in more microstructural defects
the same time, poorer interfacial adhesion resulted in more microstructural defects of of the
the
composites (Figures 1–3). The microstructure defects would cause
composites (Figures 1–3). The microstructure defects would cause stress concentration points when stress concentration points
when the composites
the composites bearing bearing
force,force,
whichwhich
werewerebad bad for the
for the mechanical
mechanical properties
properties of composites.
of composites. In
In addition, the low interfacial bonding of PLA/SF composites
addition, the low interfacial bonding of PLA/SF composites permitted composites to debond permitted composites to debond
facilely.
facilely. These factors
These factors resulted resulted in forward
in forward breakage
breakage of PLA/SF
of PLA/SF composite
composite samplessamples compared
compared with withthatthat
of
of PLA/SF/ADR composites in tensile tests. The elongation at break
PLA/SF/ADR composites in tensile tests. The elongation at break of PLA/SF/ADR composites were of PLA/SF/ADR composites
were improved
improved compared
compared with with
that ofthat of PLA/SF
PLA/SF composites.
composites.
Improving
Improvingthe theinterfacial
interfacialinteraction between
interaction betweenSF andSFtheand PLA thematrix
PLA contributed to the formation
matrix contributed to the
of a moderate interface in the composites. A moderate interface can
formation of a moderate interface in the composites. A moderate interface can effectively relieve effectively relieve the stressthe
concentration underunder
stress concentration loading conditions,
loading and and
conditions, transmit
transmitstress uniformly
stress uniformly from
fromthe thematrix
matrixto to the
the
fibers [41,42]. For PLA/SF composites with different SF content, the greater
fibers [41,42]. For PLA/SF composites with different SF content, the greater the addition of sisal fibers, the addition of sisal
fibers,
the more the more microstructural
microstructural defects
defects werewere present
present in the
in the composites.
composites. This
This resultedininaadecline
resulted decline in in the
the
mechanical properties of PLA/SF composites with increased SF content. By contrast, the mechanical
Materials 2018, 11, 398 20 of 22
mechanical properties of PLA/SF composites with increased SF content. By contrast, the mechanical
properties of PLA/SF/ADR composites were improved because of enhanced interfacial adhesion of
the composites via in situ reactive interfacial compatibilization by the addition of ADR oligomers.
4. Conclusions
In this study, polylactide/sisal fibers biocomposites were fabricated using a simple in situ
reactive melt-blending method with the addition of an epoxy-functionalized oligomer. ADR oligomer
played a hinge-like role between sisal fibers and PLA matrix during melt blending and processing,
resulting in improved interfacial interaction between SF and the PLA matrix. SEM morphology
characterization confirmed the improved interfacial adhesion of PLA/SF/ADR composites, and FTIR
analysis demonstrated the bonding of the PLA molecular chain with SF. The effects of in-situ reaction
with ADR oligomer on the thermal and rheological properties of PLA/SF composites were investigated.
The results indicated that the crystallization ability of composites declined and the viscoelastic response
was enhanced with the addition of ADR. In turn, these results further reflected the restricted mobility
of the PLA molecular chains because of the enhanced interfacial interaction with SF. The activation
energies of glass transition relaxation (∆Ea ) of the composites calculated by dynamic mechanical
analysis justified the results as well. The tensile properties and impact strength of composites were
improved because of the improved interfacial compatibility, which demonstrated that the incorporation
of ADR oligomers could simultaneously reinforce and toughen the PLA/SF composites.
Acknowledgments: This work was financial supported by the National Key Research and Development Program
of China (Grant No. 2016YFB0302302 and Grant No. 2016YFB0302301) and Key Program of National Natural
Science Foundation of China (Grant No. 51435005).
Author Contributions: Hongwu Wu and Mingyang Hao conceived the idea of this study, designed the
experiments and analyzed the results; Mingyang Hao, Feng Qiu, and Xiwen Wang performed the experiments,
analyzed the data and discussed the experimental results; Mingyang Hao and Hongwu Wu wrote the paper.
All authors of the article provided substantive comments.
Conflicts of Interest: The authors declare no conflict of interest.
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Materials: Interface Bond Improvement of Sisal Fibre Reinforced Polylactide Composites With Added Epoxy Oligomer

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Received: 31 January 2018; Accepted: 2 March 2018; Published: 7 March 2018

Abstract: To improve the interfacial bonding of sisal fiber-reinforced polylactide biocomposites,

Keywords: polymer-matrix composites; natural fiber reinforcement; interface/interphase; microstructural

Materials 2018, 11, 398; doi:10.3390/ma11030398 www.mdpi.com/journal/materials

Table 1. Properties of sisal fibers.

2.2. Preparation of the Composites

2.3. Measurements of Mechanical Properties

2.4. Morphological Characterization

2.5. FTIR Measurement

2.6. Thermal Analysis

Materials 2018, 11, x FOR PEER REVIEW 6 of 22

Materials 2018, 11, x FOR PEER REVIEW 10 of 22

Materials 2018, 11, x FOR PEER REVIEW X (t) = 1 − exp(−ktn ) 11 of 22(2)

Samples n k (min−n ) t1/2 (min)

Samples n k (min−n ) t1/2 (min)

3.4. Dynamic Rheological Behaviors

3.5. DMA Characterization

Figure 11. Cont.

Materials 2018, 11, x FOR PEER REVIEW ∆E 17 of 22

A combination of Equations (7) and (8) leads to: ∆E

Figure 12. Cont.

Materials 2018, 11, x FOR PEER REVIEW 18 of 22

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