polymers

Article
Silane-Treated Basalt Fiber–Reinforced Poly(butylene
succinate) Biocomposites: Interfacial Crystallization
and Tensile Properties
Lin Sang 1 , Mingyuan Zhao 1 , Qiushi Liang 1 and Zhiyong Wei 2, * ID

1 School of Automotive Engineering, State Key Laboratory of Structural Analysis for Industrial Equipment,
Dalian University of Technology, Dalian 116024, China; sanglin@dlut.edu.cn (L.S.);
zhaomingyuan_1111@163.com (M.Z.); liangqiushi@mail.dlut.edu.cn (Q.L.)
2 Department of Polymer Science and Materials, School of Chemical Engineering,
Dalian University of Technology, Dalian 116024, China
* Correspondence: zywei@dlut.edu.cn; Tel.: +86-411-8498-6463

Received: 12 July 2017; Accepted: 7 August 2017; Published: 9 August 2017

Abstract: In this work, an economical modifier silane agent—KH550—was used for surface treatment
of basalt fiber. Then, a biodegradable poly(butylene succinate) (PBS)/modified basalt fiber (MBF)
biocomposite was successfully developed. The effects of silane treatment and fiber mass content on
crystalline structure, isothermal crystallization process and mechanical performance of composites
were evaluated. The interfacial crystallization of PBS on the surface of MBF was investigated by
using a polarized optical microscope (POM). The transcrystalline (TC) structure could be clearly
observed and it grew perpendicular to the surface of MBF, which boosted the nucleation ability on
PBS crystallization and the strong interfacial interaction between PBS and silane-treated basalt fiber.
Under isothermal crystallization kinetics, the incorporation of basalt fiber enhanced the crystallization
rate and reduced the crystallization half-time values of composites compared with that of neat PBS
due to a heterogeneous nucleation effect. Furthermore, tensile results confirmed that the presence
of MBF could greatly improve the tensile strength and modulus. The predicted interfacial shear
strength (IFSS) suggested that an enhancement of interfacial bonding could be realized via interfacial
crystallization, which was also verified by SEM images. The PBS/MBF biocomposites can be applied
in many fields as a low-cost, lightweight, and biodegradable composite material.

Keywords: composites; crystal structure; mechanical properties; structure-property relations

1. Introduction
In recent decades, considering environmental issues and the energy crisis, green biodegradable
polymeric materials and composites have received more and more attention. Basalt fiber–reinforced
plastics (BFRPs) are newly emerging composite materials due to their being recyclable, cost effective,
and lightweight [1–4]. Basalt fiber (BF), produced by abundant natural basalt rocks, is a promising fiber
reinforcement, which endows basalt fiber with excellent chemical, weather, and heat resistance [5,6].
Although it possesses similar compositions to glass fiber (GF), basalt fiber exhibits better strength and
higher elastic modulus characteristics. Among basalt fiber–reinforced thermoplastics, poly(butylene
succinate) (PBS) is an excellent green plastics polymerized from bio-based renewable resources
monomers butanediol and succinic acid. Moreover, PBS possesses a variety of desirable properties
including biodegradability, renewability, and chemical resistance [7–9]. However, few investigations
have been performed on the compatibility between PBS matrix and bare BF, which limits the practical
application of basalt fiber reinforced PBS composites [10].

Polymers 2017, 9, 351; doi:10.3390/polym9080351 www.mdpi.com/journal/polymers

Polymers 2017, 9, 351 2 of 14

Various efforts have been made to improve the fiber/matrix interfacial interaction,
including functionalization of matrix, adding compatibilizer, and surface modification of the
fibers [11–13]. These methods could improve interfacial adhesion, contributing to a certain extent to
an efficient stress transferring from the matrix to fibers. Compared with the functionalization of the
matrix or using a compatibilizer [11], surface modification of fibers is the most common and simplest
method to obtain interfacial interaction. Silane treatment [12,13] is an effective, commercially available,
and low cost method for surface modification of fibers without destroy the structure of the fibers
themselves or weaken fiber strength.
In fiber-reinforced crystalline or semi-crystalline polymer composites, crystallization behavior
has been considerably researched, as it affects both the crystalline structure and crystallization
behavior and also influences the mechanical performance of composites. Specially, the development of
interfacial crystallization occurring in the interface between fiber and matrix would enhance interfacial
adhesion [14–20]. It is generally accepted that the interfacial crystallization would substantially
influence mechanical behavior [21–24]. Some authors have reported that transcrystalline of matrix
polymer (i.e., poly(lactic acid) (PLA) [21], isotatic polypropylene (iPP) [22], or PBS [23]) exhibited
a positive effect on the interfacial and mechanical properties. Wang et al. [25] studied transcrystalline
effects on sisal fiber-reinforced PLA composites. Zhou et al. [9] directly introduced dopamine as
a coupling agent to treat ramie fiber and investigated the interfacial crystallization of PBS. In this
literature, interfacial crystallization with different microstructures and morphologies were extensively
investigated, and interfacial shear stress (IFSS) was discussed from the point of a single fiber. However,
few studies have focused on investigating the effect of interfacial crystallization on mechanical
properties in short fiber–reinforced composites at a certain ratio.
In the present paper, we first treated basalt fibers using the economical silane agent KH550 as
a modifier and then fabricated PBS/untreated fiber and PBS/modified basalt fiber biocomposites with
varying ratios by internal mixer and the injection molding method. The growth of a transcrystalline
structure on the surface of silane-treated basalt fiber was observed by polarized optical microscopy
(POM), and the isothermal crystallization kinetics of PBS and its composites were analyzed by
differential scanning calorimetry (DSC). The effect of silane treatment and fiber loading on the tensile
properties of PBS/MBF biocomposites were compared, and tensile fractured topography was observed
by scanning electron microscope (SEM). Moreover, a mathematical model was adopted to predict the
interfacial shear strength (IFSS), which would provide useful information on the relationship between
interfacial strength and mechanical performance.

2. Materials and Methods

2.1. Materials
Poly(butylene succinate) (PBS, Anqing Hexing Chemical, Ltd., Anqing, China) is a thermoplastic
polymer with a melting flow index (MFI) of 15–25 g·10 min−1 (150 ◦ C, 2.16 kg) and a density of
1.26 g·cm−3 . Its melting point is 113 ◦ C, and its number-average molecular weight is 1.7 × 105 g·mol−1 ,
as reported by the manufacture. The continuous basalt fibers (GBF 9-800, Shanxi Basalt Fiber
Technology Co., Ltd., Taiyuan, China) possess the following characteristics: their density is 2.8 g·cm−3 ,
and their tensile strength and tensile modulus is 3.0 and 90–110 GPa, respectively. The silane coupling
agent KH550 (NH2 CH2 CH2 CH2 Si(OC2 H5 )3 ), acetone, ethanol (95% purity), and other chemicals used
in this study were purchased from Kelong Chemical reagent Ltd., Chengdu, China.

2.2. The Silane Treatment of Bbasalt Fiber (BF)

The surface treatment of BF was performed according to previous work [26]. Basalt fibers were
first cleaned with acetone/ethanol for 2 h to remove the organic residues from the fiber surfaces.
The fibers were repeatedly washed with deionized water to neutrality. After that, BF was immersed
Polymers 2017, 9, 351 3 of 14

in the silane coupling agent (KH550, 0.75 wt %) in water/ethanol for 30 min. Finally, the fibers were
reacted and dried in a vacuum oven at 120 ◦ C for 2 h. The silane-treated fibers were marked as MBF.

2.3. Preparation of PBS/MBF Biocomposites

The continuous untreated and silane-treated basalt fibers were cut into a settled length of 10 mm.
Basalt fibers and PBS granules were dried in a vacuum oven at 80 ◦ C for 12 h to before blending.
PBS and silane-treated basalt fibers were compounded via a two-roll mill method. The blending was
conducted via the following procedure: First, about half of the PBS was placed inside the mixing
chamber at 130 ◦ C for about 1 min at 30 rpm. Then, varying BF (or MBF) content was added over
a period of 3 min. Then, the rest of PBS resin was introduced into the mixing chamber. The mixing
speed was increased to 60 rpm, and mixing continued for another 8 min. The melting composites were
cooled and subsequently chopped to granules.
The resulted granules were dried at 85 ◦ C overnight and then molded using an injection molding
machine (XTK 1200, Xiatian General Machinery, Ningbo, China). The temperatures at the three
injection regions were 140 ◦ C, 155 ◦ C and 155 ◦ C, respectively, and the nozzle temperature was 145 ◦ C.
The fiber contents were set at 2, 5, 10, and 15 wt %, respectively. According to the different loadings of
basalt fiber, the injection-molded specimens reinforced with untreated and silane-treated basalt fibers
were marked as PBS/MBF (98/2), PBS/BF (95/5), PBS/MBF (95/5), PBS/MBF (90/10), and PBS/MBF
(85/15), respectively. PBS/BF (95/5) were prepared and set as control sample.

2.4. Characterization

2.4.1. Scanning Electron Microscope (SEM)

The surface morphology of basalt fiber and tensile fractured surface of composites were examined
using a field emission scanning electron microscope (S-4800N-FESEM, Zeiss, Oberkochen, Germany).
The specimens were pre-coated with a thin gold layer before observation.

2.4.2. X-ray Photoelectron Spectrometer (XPS)

The possible interaction between the fiber and silane agent was examined using an X-ray
photoelectron spectrometer (XPS, ESCALABTM 250Xi, Thermo Fisher Scientific, Waltham, MA, USA)
focused monochromatized Al Kα radiation (15 kV). The survey spectra were collected over a wide
binding energy range from 0 to 1350 eV at a take-off angle of 45◦ . High resolution spectra of C1s peak
were specially recorded.

2.4.3. Polarized Optical Microscope (POM)

The dynamic process of interfacial crystallization morphology during isothermal crystallization
on the surface of MBF were in situ observed by a polarized optical microscope (POM, Leica DM4500P,
Heidelberg, Germany), which was equipped with a (Linkam THMS600, Linkam Scientific instruments,
Tadworth, UK) hot-stage and a digital camera (Leica CCD, Heidelberg, Germany). Composites with
varying BF loading were made into sandwiches between two cover slips. Then, they were heated to
130 ◦ C, kept at this temperature for 5 min to allow complete melting, and quickly quenched to 89 ◦ C
for isothermal crystallization.

2.4.4. Differential Scanning Calorimetry (DSC)

Isothermal crystallization behavior of PBS, PBS/BF and PBS/MBF composites were performed
in a nitrogen atmosphere on a differential scanning calorimeter (DSC1, Mettler-Toledo, Zurich,
Switzerland). The samples with 6–8 mg were melted at 130 ◦ C for 5 min to eliminate the previous
thermal history and then quick-cooled at a rate of 60 ◦ C·min−1 to a series of isothermal crystallization
temperatures (Tc ). The Tc was held for a period of time to ensure the completion of crystallization.
The heat flows during the crystallization process were recorded for data analysis.
Polymers 2017, 9, 351 4 of 14
Polymers 2017, 9, 351 4 of 14

2.4.5. Tensile Properties

Properties
properties were
Tensile properties were measured
measured according
according toto GB/T1040-92
GB/T1040-92 standard
standard using a universal tester
UTM5105X,Shenzhen,
(Sans UTM5105X, Shenzhen,China).
China).The
Thetensile
tensile specimens
specimens werewere carried
carried out out at room
at room temperature
temperature (RT)
and about 50% relative humidity with a 10 kN load cell and a cross-head speed of 5 mm·min−−11..
(RT) and about 50% relative humidity with a 10 kN load cell and a cross-head speed of 5 mm·min
The average values of tensile parameters of PBS and its composites were calculated from five
successful samples.

3. Results

3.1. Modification of
3.1. Modification of Basalt
Basalt Fiber
Fiber
The modification process
The modification process is isphotographically
photographically shownshown in Figure in Figure
1a. KH550 1a.
KH550 (NH CH
(NH2CH2CH22CH22Si(OC CH CH Si(OC H ) ),
2 2H25)3), an2 economical
5 3 an economical organo-silane, was adopted
organo-silane, was adopted in this study. Silanein this study.
Silane treatment has proved to be a
treatment has proved to be a low-cost and efficient low-cost and efficient
method methodthe
to endow tofiber-matrix
endow the an fiber-matrix
improved
an
interfacial bonding [26–28]. It is clearly visible that raw basalt fibers were brownish in color,brownish
improved interfacial bonding [26–28]. It is clearly visible that raw basalt fibers were whereas
in
thecolor, whereas
modified basaltthe modified
fiber basalt fibera (MBF)
(MBF) displayed displayed
light brownish a light
color. brownish
During silane color. During
treatment, the silane
silane
treatment, the silane agent first hydrolyzed, formed reactive silanol, and then
agent first hydrolyzed, formed reactive silanol, and then adsorbed and condensed on the fiber adsorbed and condensed
on the fiber
surface. surface. Furthermore,
Furthermore, the functional the–NH
functional –NH2 groups
2 groups could
could bewith
be connected connected
the –COOHwith theend–COOH
groups
end groups of PBS by covalent bonds. Thus, after silane treatment,
of PBS by covalent bonds. Thus, after silane treatment, efficient interfacial bonding betweenefficient interfacial bondingthe
between the reinforcing element (BF) and the polymeric matrix (PBS) was
reinforcing element (BF) and the polymeric matrix (PBS) was expected to have been established. To expected to have been
established. To confirm the
confirm the modification of modification
the basalt fibers,of the SEM basalt
wasfibers, SEM on
conducted was conducted
the pristine and on the pristine
modified and
basalt
modified
fibers. Asbasalt
shownfibers. As shown
in Figure 1b,c, ainrough
Figuresurface
1b,c, awith
rough surface
small with small
residues residues
was found on was foundsurface,
the MBF on the
MBF surface, whereas a clean and smooth surface was observed on pristine
whereas a clean and smooth surface was observed on pristine basalt fiber. This indicated that thebasalt fiber. This indicated
that the
silane silane
agent agentsuccessfully
KH550 KH550 successfully
interacted interacted on the
on the fiber fiber surfaces.
surfaces.

Figure 1. (a) The modification process of BF; (b,c) SEM micrograph of BF and MBF.
Figure 1. (a) The modification process of BF; (b,c) SEM micrograph of BF and MBF.

Prior to compounding, XPS was used to detect the elements and interactions after silane
treatment to
Prior of compounding, XPSAs
the basalt fibers. was used to
shown in detect
Figurethe2a,elements
the XPSandwideinteractions afterrevealed
scan spectra silane treatment
that the
of the basalt fibers. As shown in Figure 2a, the XPS wide scan spectra revealed
presence of carbon and oxygen, and a slight amount of nitrogen could be detected on the that thesurface
presenceof
of
BFcarbon
and MBF.andForoxygen, and a slight
MBF samples, the amount
relative of nitrogen
amount could beoxygen
of detected detectedwasonincreased,
the surface of BFmost
which and
MBF. For MBF
probably samples,
originated fromthethe
relative amount
chemical of detected
composition ofoxygen was increased,
silane agent. Moreover,which
the most
recordedprobably
high
originated from theofchemical
resolution spectra the carboncomposition of silane
element were agent. and
evaluated Moreover, the recorded
curve-fitted. high resolution
The detailed chemical
spectra
analysisofofthe
C1scarbon
high element
resolutionwere evaluated
scan spectra ofandBFcurve-fitted.
and MBF are The detailed chemical
illustrated in Figureanalysis
2b,c. Theof C1s
C1s
high resolution scan spectra of BF and MBF are illustrated in Figure 2b,c. The C1s spectra
spectra of the MBF can be curve-fitted with three peaks. Beside the aliphatic C–C/C–H peak at 284.8 of the MBF
eV (taken also for charge shift referencing) [29], one is at binding energy (BE) of 286.3 eV for –C–O
species and the other is at BE of 288.8 eV for the –C=O species. These rational-derived peaks of C1s
Polymers 2017, 9, 351 5 of 14

can be curve-fitted with three peaks. Beside the aliphatic C–C/C–H peak at 284.8 eV (taken also for
charge shift2017,
Polymers referencing)
9, 351 [29], one is at binding energy (BE) of 286.3 eV for –C–O species and the 5other
of 14
is at BE of 288.8 eV for the –C=O species. These rational-derived peaks of C1s attributed to different
attributedenvironment
chemical to different imply
chemical
that environment imply on
the silane treatment thatBFthe silanewas
surface treatment on BF surface was
successfully.
successfully.
(a) BF (b) BF (c) MBF
C1s
MBF
O1s C1s
C1s
-CH2-

Counts / s
Intensity (a.u.)

Counts / s
N1s

C-O

-C=O

700 600 500 400 300 200 100 0 290 288 286 284 282 280 290 288 286 284 282 280
Binding Energy (eV) Binding Energy (eV) Binding Energy (eV)

Figure 2.2. (a)

(a)X-ray
X-ray photoelectron
photoelectron spectrometer
spectrometer (XPS)
(XPS) widewide scan spectra
scan spectra offiber
of basalt basalt
(BF)fiber
and (BF) and
modified
basalt fiberbasalt
modified (MBF) with
fiber labeled
(MBF) photoelectron
with (C1s, O1s, and
labeled photoelectron N1s),
(C1s, O1s,and
andXPS high
N1s), and resolutions, C1s spectra
XPS high resolutions,
of
C1s(b) BF andof(c)
spectra (b)MBF.
BF and (c) MBF.

3.2. MBF-Induced Transcrystallization (TC) of

Transcrystallization (TC) of PBS
PBS
ordertotoinvestigate
In order investigate thethe effect
effect of fiber
of fiber treatment
treatment on PBS on crystalline
PBS crystalline morphology,
morphology, polarizedpolarized
optical
optical microscope (POM) images of crystalline structure at the interface
microscope (POM) images of crystalline structure at the interface between PBS and MBF are presented between PBS and MBF are
presented
in Figure 3. in The
Figure 3. The isothermal
isothermal crystallization
crystallization temperaturetemperature
was set was ◦
at 89setCatfor 89 °C
35 for
min. 35 For
min.neat
For PBS,
neat
PBS, several
several well-developed
well-developed spherulites
spherulites with diameters
with diameters in a range in aofrange
70–100ofµm 70–100
were μm clearlywere clearly
observed.
observed.
Figure 3b–fFigure
depicted 3b–fthe depicted the PBS of
PBS spherulites spherulites
composites of in
composites
the presence in the presenceand
of untreated of untreated
silane-treatedand
silane-treated
basalt fiber. Forbasalt
the same fiber. For the same
crystallization crystallization
time, more crystals time,
weremore observedcrystals
in thewere observedthan
composites in the
composites than the neat PBS, which indicated that the presence of basalt
neat PBS, which indicated that the presence of basalt fiber played an accelerating role in the nucleation fiber played an accelerating
role
of in the
PBS. Fornucleation
compositesofreinforced
PBS. For with composites
pristinereinforced with pristine
BF, no crystallization of BF,
PBSno oncrystallization
the untreated BF of surface
PBS on
the untreated
was observedBF surface
(Figure 3c).wasOnobserved
the other(Figurehand, 3c). On the other
for PBS/MBF hand, afor
system, PBS/MBF
special system, a special
transcrsytalline (TC)
transcrsytalline (TC) structure was successfully induced on the surface
structure was successfully induced on the surface of silane-treated fibers (as shown in Figure 3b). Also, of silane-treated fibers (as
shown
the in Figure
formation of 3b). Also, the was
TC structure formation
prior to of regular
TC structure was prior tosince
PBS spherulites, regular
some PBS spherulites,
regular since
spherulites
some regular spherulites were extremely small. In contrast, the crystallized
were extremely small. In contrast, the crystallized size of spherulites in PBS/BF (95/5) composites size of spherulites in
PBS/BF (95/5) composites was relatively uniform. This phenomenon indicated
was relatively uniform. This phenomenon indicated that the surface of the silane-treated basalt fibers that the surface of the
silane-treated
showed basaltheterogeneous
improved fibers showednucleationimprovedability
heterogeneous
for PBS, which nucleation ability the
can induce for molecular
PBS, which can
chain
induce the molecular chain to crystallize into orderly structure. However,
to crystallize into orderly structure. However, at a fixed crystallization temperature, a higher density at a fixed crystallization
temperature,
of TC structure a higher density ofatTC
was obtained structure
lower was obtained
BF loading (i.e., 2 at wtlower
% and BF 5loading
wt %),(i.e., while2 wta% and 5 wt
mixture of
%), while a and
spherulites mixture of spherulites
TC structure was foundand TC in structure
higher BFwas found
loading (10inwt higher
% and BF15loading
wt %). (10 With wtincreasing
% and 15
wt %). With
amounts increasing amounts
of silane-treated fibers, the of heterogeneous
silane-treated fibers,
nucleationthe heterogeneous
effect was expected nucleation
to be effect
enhanced,was
expected
which to be enhanced,
accelerated the formationwhich of accelerated
spherulites. theOn formation
the otherofhand, spherulites.
the numberOn the of other hand,sites
nucleation the
number of nucleation sites was also increased, which induced an interfacial
was also increased, which induced an interfacial crystallization structure. Therefore, one may obtain crystallization structure.
Therefore,crystalline
different one may structures
obtain different crystallinefiber
in silane-treated structures
reinforced in silane-treated
PBS composites fiber
by reinforced
controllingPBS the
composites
modified by loading.
fiber controlling the modified fiber loading.
Figure 44 showed
Figure showed the the nucleation
nucleation and and growth
growth of of the
the transcrystalline
transcrystalline structure
structure of of the
thePBS/MBF
PBS/MBF
(98/2) composite
(98/2) compositeas as aa representative
representative sample. sample. As As shown
shown in in Figure
Figure 4a, bright interfacial
4a, bright interfacial TC TC structure
structure
was gradually
was gradually formed
formed as as the
thecrystallization
crystallizationtime timeincreased
increased(10 (10minmin→→ 4545min).
min). After nucleation
After nucleation on
the surface for 10 min, interfacial crystallization morphology was
on the surface for 10 min, interfacial crystallization morphology was observed and identified. observed and identified. However,
almost noalmost
However, PBS spherulites
no PBS spheruliteswere observed
were observedfar awayfar away fromfrom the thesilane-treated
silane-treatedfiber. fiber.When
When the the
crystallization time increased to 15 min, the transcrystalline (lamellae)
crystallization time increased to 15 min, the transcrystalline (lamellae) structure began to grow structure began to grow
perpendiculartotothethe
perpendicular silane-treated
silane-treated fiber fiber
surface,surface,
and theand the TC was
TC structure structure
formed.was formed.
As the As the
crystallization
crystallization
time prolonged,time the prolonged,
growth of lamella the growth of lamellaalong
was restricted was restricted
the long axis along the long
of fiber, and axis
the TCof fiber, and
thickness
the TC thickness was further increased. By plotting crystallization time and crystalline size, almost a
linear relationship can be observed, as shown in Figure 4b. The TC layer on the silane-treated basalt
fiber grew to about 8 μm after 10 min and gradually expanded into 87 μm after 45 min. Additionally,
the crystalline structure of PBS in the presence of BF is recorded in Supporting Information (Figure S1)
during the crystallization process. Comparing the formation processes of crystalline structures, it is
Polymers 2017, 9, 351 6 of 14

was further increased. By plotting crystallization time and crystalline size, almost a linear relationship
can be observed, as shown in Figure 4b. The TC layer on the silane-treated basalt fiber grew to about
8 µm after 10 min and gradually expanded into 87 µm after 45 min. Additionally, the crystalline
structure of PBS in the presence of BF is recorded in Supporting Information (Figure S1) during the
Polymers 2017, 9, 351 6 of 14
crystallization process.
Polymers 2017, 9, 351 Comparing the formation processes of crystalline structures, it is predictable
6 of 14
that the presence
predictable that oftheMBF should be
presence of favorable in heterogeneous
MBF should nucleation
be favorable and transcrystalline
in heterogeneous nucleationgrowthand
predictable
compared with that
that the
of presence of MBF should be favorable in heterogeneous nucleation and
BF.
transcrystalline growth compared with that of BF.
transcrystalline growth compared with that of BF.

Figure
Figure 3. 3.Polarized
Polarizedoptical
optical microscope
microscope(POM)
(POM) images
imagesof (a)
of PBS, (b) PBS/MBF
(a) PBS, (98/2),(98/2),
(b) PBS/MBF (c) PBS/BF
(c) (95/5),
PBS/BF
Figure 3. Polarized optical microscope (POM) images of (a) PBS, (b) PBS/MBF (98/2),◦ (c) PBS/BF (95/5),
(d) PBS/MBF
(95/5), (95/5), (95/5),
(d) PBS/MBF (e) PBS/MBF (90/10), and
(e) PBS/MBF (f) PBS/MBF
(90/10), and (f) (85/15)
PBS/MBFat 89(85/15)
°C for 35
at min.
89 C for 35 min.
(d) PBS/MBF (95/5), (e) PBS/MBF (90/10), and (f) PBS/MBF (85/15) at 89 °C for 35 min.

Figure 4. (a) The growth of transcrystallization (TC) on MBF of PBS/MBF (98/2) composites crystallized
at 89 °C with different time; (b) thickness of TC layer; (c) schematic illustration of TC structure.
Figure 4. (a) The growth
growth ofoftranscrystallization
transcrystallization(TC)
(TC)on
onMBFMBFofofPBS/MBF
PBS/MBF(98/2)
(98/2) composites crystallized
at 89 ◦
°C
Figure with different time; (b) thickness
C 4c illustrates the evolution ofofTC of TC layer;
TCstructure(c) schematic illustration
at the interface
layer; (c) schematic of TC
between
illustration of TCthe
structure.
fiber and PBS
structure.
matrix. The nuclei sites on the surfaces of silane-treated basalt fiber were sufficiently high and
Figure 4crandomly,
distributed illustrates thus
the evolution of TC
the initiated structure at from
crystallization the interface
the nuclei between
and the thedevelopment
fiber and PBS
matrix. The nuclei
perpendicular sites
to the ondirection
fibre the surfaces of silane-treated
occurred simultaneously.basalt
Whenfiber were sufficiently
the crystallized high and
time increased,
distributed randomly,
the spherulites impinged thuseachtheother
initiated crystallization
and grew only in onefrom the nuclei
direction due spaceandconfinement
the development
and
finally developed
perpendicular to theinto
fibrea direction
transcrystalline region.
occurred The formation
simultaneously. of TC
When thestructure has proven
crystallized to be
time increased,
thebeneficial to enhance
spherulites impinged the interfacial
each otherinteraction
and grewbyonlycontributing to effective
in one direction due stress transforming
space confinement from
and
the matrix to the fiber inside [9,22]. In addition, it has been reported that a rough
finally developed into a transcrystalline region. The formation of TC structure has proven to be fiber surface with
Polymers 2017, 9, 351 7 of 14

Figure 4c illustrates the evolution of TC structure at the interface between the fiber and PBS matrix.
The nuclei sites on the surfaces of silane-treated basalt fiber were sufficiently high and distributed
randomly, thus the initiated crystallization from the nuclei and the development perpendicular to
the fibre direction occurred simultaneously. When the crystallized time increased, the spherulites
impinged each other and grew only in one direction due space confinement and finally developed
into a transcrystalline region. The formation of TC structure has proven to be beneficial to enhance
the interfacial interaction by contributing to effective stress transforming from the matrix to the
fiber inside [9,22]. In addition, it has been reported that a rough fiber surface with low surface
energy provides abundant
Polymers 2017, 9, 351 heterogeneous nucleation sites to induce transcrystallinity in 7crystalline
of 14
polymers [30,31].
low surface energy provides abundant heterogeneous nucleation sites to induce transcrystallinity in
3.3. Isothermal Crystallization
crystalline Behaviors
polymers [30,31].

Differential
3.3. Isothermalscanning calorimetry
Crystallization Behaviors (DSC) was further used to monitor the overall isothermal
crystallization process of PBS and its composites at varying crystallization temperatures. By adopting
Differential scanning calorimetry (DSC) was further used to monitor the overall isothermal
approximate crystallization time, the Tc intervalatof
crystallization process of PBS and its composites
PBS and its composites was 72–78 ◦ C. To erase
varying crystallization temperatures. By adopting
previous thermal history,
approximate all composites
crystallization time, the Twere quick-cooled to the targeted crystallization temperature
c interval of PBS and its composites was 72–78 °C. To erase

(Tc ). The DSC crystallization

previous thermal history,exotherms of neatwere
all composites PBS,quick-cooled
PBS/BF, andtoPBS/MBF
the targetedcomposites are shown
crystallization
temperature
in Figure (Tc). TheitDSC
5. As expected, crystallization
is observed as Tc increased,
that exotherms of neat PBS, PBS/BF, and PBS/MBF
the exothermal composites
peak became broader for
all the are shown suggesting
samples, in Figure 5. As expected, it crystallization
a decreased is observed that as Tc increased,
rate the exothermal
and an increased peakcrystallization
time for became
completion. On the other hand, the crystallization rate of PBS was obviously enhanced for
broader for all the samples, suggesting a decreased crystallization rate and an increased time with the
crystallization completion. On the other hand, the crystallization rate of PBS was obviously enhanced
increased amount of reinforced fiber.
with the increased amount of reinforced fiber.
(a) (b) (c)
Heat flow (mW) Endo up

Heat flow (mW) Endo up

Heat flow (mW) Endo up

d d d
c c c o
o a) 72 C
a) 72 C
o
b a) 72 C
b b)
o
74 C b)
o
74 C b b)
o
74 C
o
o c) 76 C
a c)
o
76 C a c) 76 C
o
d)
o
78 C
a d)
o
78 C
d) 78 C
0 3 6 9 12 15 18 0 3 6 9 12 15 18 0 3 6 9 12 15 18
Time(min) Time(min) Time(min)
(d) (e) (f)
Heat flow (mW) Endo up
Heat flow (mW) Endo up
Heat flow (mW) Endo up

d
d d c
c c o o
a) 72 C
o a) 72 C b a) 72 C
b o b b)
o
74 C b)
o
74 C
b) 74 C
o
o c) 76 C a c)
o
76 C
c) 76 C
a d)
o
78 C a d)
o
78 C d)
o
78 C

0 3 6 9 12 15 18 0 3 6 9 12 15 18 0 3 6 9 12 15 18

Time(min) Time(min) Time(min)

Figure 5. Differential scanning calorimetry (DSC) thermograms of (a) PBS, (b) PBS/MBF (98/2), (c)
Figure 5. Differential scanning calorimetry (DSC) thermograms of (a) PBS, (b) PBS/MBF (98/2),
PBS/BF (95/5), (d) PBS/MBF (95/5), (e) PBS/MBF (90/10), and (f) PBS/MBF (85/15) at different
(c) PBS/BF (95/5), (d)
crystallization PBS/MBF (95/5), (e) PBS/MBF (90/10), and (f) PBS/MBF (85/15) at different
temperatures.
crystallization temperatures.
The well-known Avrami equation was used to track the isothermal crystallization kinetics and
PBS and its composites,
The well-known Avramiwhich contribute
equation to antounderstanding
was used of the evolution
track the isothermal of crystallinity.
crystallization kinetics The
and PBS
equation is listed as follows [32,33]:
and its composites, which contribute to an understanding of the evolution of crystallinity. The equation
is listed as follows [32,33]: 1 − = exp − (1)
n
1−
where Xt is the relative crystallinity, t is t = exp(− kt time,
theXcrystallization ) n is the Avrami exponent (which is (1)
dependent on the mechanism of nucleation and growth geometry), and k is the crystallization rate
Xt is theEquation
where constant. relative(1)
crystallinity, t is the crystallization
can also be rewritten time, nform
as a double logarithmic is the
as Avrami
follows: exponent (which is
dependent on the mechanism of nucleation and growth geometry), and k is the crystallization rate
ln −ln 1 − = ln + ln (2)
constant. Equation (1) can also be rewritten as a double logarithmic form as follows:
Figure 6a illustrates the Avrami plots of relative crystallinity (Xt) versus crystallization time (t)
obtained by exotherm data for thelnisothermal
[− ln (1 −crystallization
Xt )] = ln k +at n
various
ln t temperatures (PBS/MBF (95/5) (2)
as representative examples). The curves of PBS/MBF (95/5) composites showed S-shaped, which was
related to nucleation and the growth process. It was also found that the time of isothermal
crystallization completion was strongly dependent on Tc. As illustrated in Figure 6b, a linearity in the
Avrami plots was corresponded to crystallinity in a wide range between 5% and 95%. Similar Avrami
plots of Xt and the corresponded linear plots of PBS/BF (95/5) was obtained and shown in Supporting
Polymers 2017, 9, 351 8 of 14

Figure 6a illustrates the Avrami plots of relative crystallinity (Xt ) versus crystallization time
(t) obtained by exotherm data for the isothermal crystallization at various temperatures (PBS/MBF
(95/5) as representative examples). The curves of PBS/MBF (95/5) composites showed S-shaped,
which was related to nucleation and the growth process. It was also found that the time of isothermal
crystallization completion was strongly dependent on Tc . As illustrated in Figure 6b, a linearity in the
Avrami plots was corresponded to crystallinity in a wide range between 5% and 95%. Similar Avrami
Polymers 2017, 9, 351 8 of 14
plots of Xt and the corresponded linear plots of PBS/BF (95/5) was obtained and shown in Supporting
Information (Figure S2). The Avrami parameters n and k can be obtained from the slope and the
Information (Figure S2). The Avrami parameters n and k can be obtained from the slope and the
intercept of Avrami plots and are summarized in Table 1.
intercept of Avrami plots and are summarized in Table 1.

(a)100 (b) 2
Relative degree crystallinity(%)

ab c d 1 a b c d
80

ln[-ln(1-Xt)]
0
60
o
a) 72 C -1
o
40
b)
o
74 C a) 72 C
o
o b) 74 C
c) 76 C -2 o
20 o c) 76 C
d) 78 C o
d) 78 C
-3
0
0 3 6 9 12 15 18 -1 0 1 2 3
Time(min) lnt

Figure
Figure 6. (a)Relative
6. (a) Relativedegree
degreeofof crystallinity
crystallinity with
with time
time andand
(b) (b)
the the Avrami
Avrami plotsplots of ln[−−ln(1
of ln[−ln(1 Xt)] − Xt )]
versus
versus lnt for isothermal crystallization of PBS/MBF (95/5) at different crystallized
lnt for isothermal crystallization of PBS/MBF (95/5) at different crystallized temperatures.temperatures.

As shown in Table 1, the average n values of PBS and its composites ranged ranged from
from 2.162.16 to
to 2.59.
2.59.
For pure PBS with high crystallizability,
crystallizability, the the nn values
values were
were from
from 2.402.40 to 2.58. These values were mainly
attributed to a self-nucleation and the homogeneous nucleation mechanisms of PBS. After blending
reinforced fibers,
with reinforced fibers, heterogeneous
heterogeneous nucleation
nucleation tooktook place
place in in aa predominant
predominant way way forforPBS/MBF
PBS/MBF
composites. For For untreated
untreated and and silane-treated
silane-treated fiber-reinforced
fiber-reinforced composites,
composites, the average n values of
PBS/BF (95/5)
PBS/BF (95/5)andandPBS/MBF
PBS/MBF(95/5) (95/5)composites
compositeswere were2.26
2.26and
and2.30,2.30,respectively.
respectively. As As shown
shown in POM
images (Figure
images (Figure3),3), there
there werewere two different
two different crystalline
crystalline structures structures
observed observed in thecomposites,
in the PBS/MBF PBS/MBF
composites,
including includingand
spherulites spherulites and transcrystalline
transcrystalline layers. Although layers. Although
TC structure wasTCobserved
structure in was observed
the PBS/MBF
in the PBS/MBF
composites, composites, transcrystallization
transcrystallization was essentially
was essentially identical identical with
with spherulites sincespherulites
these two since these
crystalline
two crystalline
structures consiststructures
of the same consist of theand
lamellae samethelamellae andgrowth
same linear the same ratelinear growth
[25,34,35]. rate
The [25,34,35].
visual The
difference
visual difference between them is that the spherulites began to grow radially
between them is that the spherulites began to grow radially from the nuclei, while the transcrystallines from the nuclei, while
the transcrystallines
grew perpendicular togrew perpendicular
the surface to the surface
of silane-treated fibers. of
Thus,silane-treated fibers. Thus,
the slight variation of thethe slight
n values
variation of
indicated thethe
that n values indicated
incorporation that the incorporation
of untreated of untreated
or silane-treated fibers into orPBS
silane-treated
bulk did not fibers intoalter
greatly PBS
bulk did not greatly alter the growth dimensionality during the isothermal
the growth dimensionality during the isothermal crystallization process. This might also explain the crystallization process.
This might also
phenomenon thatexplain the phenomenon
spherulitic and TC structure that co-existed
spheruliticinand TC structure
higher MBF loading co-existed in higher
composites MBF
(observed
loading
in Figurecomposites
3). At a given(observed in Figuretemperature,
crystallization 3). At a given crystallization
the temperature,
k values of composites werethehigher
k values of
than
composites
that of purewere
PBS, higher
which thanimpliesthatthat
of pure PBS, which implies
the heterogeneous that the
nucleation washeterogeneous
accelerated by nucleation
the addition was
accelerated
of fibers. Asbythetheamount
addition ofof fibers.
basalt As the
fiber amount
loading of basalt
increases, fiber
it is alsoloading
found increases,
that the k itvalues
is alsofurther
found
that the kwhich
increase, valueswould
further increase,the
accelerate which would of
completion accelerate the completion
crystallization. As a result,of in
crystallization.
combination with As a
result,images,
POM in combination
it can be with POM images,
concluded that the it can be concluded
incorporation of basaltthatfibers
the incorporation
contributed toofan basalt fibers
improved
contributed to nucleation
heterogeneous an improved heterogeneous
ability, nucleation basalt
and the silane-treated ability,fibers
and provided
the silane-treated
abundantbasalt fibers
nucleation
sites to induce transcrystallinity in PBS. However, it is expected that the formation of spherulitesthat
provided abundant nucleation sites to induce transcrystallinity in PBS. However, it is expected or
the formation of spherulites
transcrystallinity or transcrystallinity
may not influence the growth rate may ofnot
PBSinfluence
crystals. the growth rate of PBS crystals.
The half time of crystallization t1/2, usually defined as the time required to achieve 50% of the
final crystallization kinetics, was introduced to evaluate the crystallization rate of crystalline or semi-
crystalline polymers. The t1/2 values can be obtained as the following equation:
ln2 /
/ = (3)
where n and k can be achieved according to Equation (3).
Polymers 2017, 9, 351 9 of 14

The half time of crystallization t1/2 , usually defined as the time required to achieve 50% of
the final crystallization kinetics, was introduced to evaluate the crystallization rate of crystalline or
semi-crystalline polymers. The t1/2 values can be obtained as the following equation:
 1/n
ln 2
t1/2 = (3)
k

where n and k can be achieved according to Equation (3).

Table 1. Avrami parameters of isothermal crystallization kinetics of PBS, PBS/BF, and PBS/MBF.

Sample T c (◦ C) t1/2 (min) 1/t1/2 (min−1 ) k·(min−n ) n Average (n)

72 2.68 0.373 0.054 2.58
74 4.50 0.222 0.017 2.47
PBS 2.47
76 7.30 0.137 0.006 2.43
78 11.4 0.088 0.002 2.40
72 2.28 0.439 0.080 2.67
74 3.42 0.292 0.031 2.55
PBS/MBF (98/2) 2.59
76 4.88 0.205 0.013 2.55
78 7.53 0.133 0.004 2.58
72 1.63 0.613 0.232 2.34
74 2.32 0.413 0.102 2.33
PBS/BF (95/5) 2.26
76 3.47 0.288 0.046 2.20
78 5.33 0.188 0.020 2.17
72 1.58 0.633 0.245 2.36
74 2.22 0.45 0.115 2.30
PBS/MBF (95/5) 2.30
76 3.25 0.308 0.049 2.27
78 4.88 0.205 0.020 2.25
72 1.27 0.787 0.420 2.36
74 1.75 0.571 0.201 2.28
PBS/MBF (90/10) 2.26
76 2.57 0.389 0.088 2.23
78 3.82 0.262 0.039 2.16
72 1.18 0.847 0.499 2.26
74 1.52 0.658 0.293 2.16
PBS/MBF (85/15) 2.16
76 2.18 0.459 0.137 2.12
78 3.34 0.299 0.058 2.09

The obtained t1/2 values for PBS and its composites are listed in Table 1. As expected, with increasing
crystallization temperature Tc , the t1/2 value of all the samples correspondingly increased, suggesting
a slower crystallization rate. In the presence of untreated and silane-treated basalt fiber, the t1/2 values
became shorter, exhibiting a heterogeneous nucleating effect. Moreover, by increasing the content of
silane-treated fiber, the values of t1/2 further decreased, indicating an accelerated crystallization rate.
For example, at a given Tc of 78 ◦ C, the t1/2 values of neat PBS is 11.4 min, whereas PBS/BF (95/5) and
PBS/MBF (98/2, 95/5, 90/10, and 85/15) completed the crystallization within 5.33, 7.53, 4.88, 3.82,
and 3.34 min, respectively.
Figure 7 illustrates the variation of 1/t1/2 with Tc for all of the samples. Conveniently, the reciprocal
of t1/2 represented the crystallization rate. Both PBS and its composites exhibited an increase of
1/t1/2 values with the reduction of Tc due to a greater super-cooling at lower Tc , which accelerated
the crystallization rate. These enhanced crystallization rates with decreasing Tc further confirm that
the initial nucleation dominated the isothermal crystallization rate of the samples. On the other
hand, the 1/t1/2 value of silane-treated fiber-reinforced PBS composites was greater than that of
untreated samples. In particular, the 1/t1/2 values further prolonged with the increase content of
silane-treated basalt fiber. During the crystallization process, the presence of pristine and silane-treated
basalt fiber served as nucleating agent for PBS. Furthermore, the silane-treated one presented a better
heterogeneous nucleation effect.
 Polymers 2017, 9, 351 10 of 14
Polymers 2017, 9, 351 10 of 14
Polymers 2017, 9, 351 10 of 14

1.0
1.0 PBS
PBS/MBF(98/2)
PBS
0.8 PBS/BF(95/5)
PBS/MBF(98/2)
0.8 PBS/MBF(95/5)
PBS/BF(95/5)

) )
-1
PBS/MBF(95/5)
PBS/MBF(90/10)

(min
-1
0.6 PBS/MBF(90/10)
PBS/MBF(85/15)

(min
0.6 PBS/MBF(85/15)

1/2
1/2
1/t1/t 0.4
0.4

0.2
0.2

0.0
0.0
72
72 74
74 76
76 7878
TTcc (°C)
(°C)

Figure 7. 7.Variation
Figure
Figure ofof
7.Variation
Variation 1/t
of 1/t
1/2
1/t 1/2 with T
1/2 with T
forPBS,
Tccc for
for PBS,PBS/BF
PBS, PBS/BF
PBS/BF and
and
and PBS/MBF
PBS/MBF
PBS/MBF composites.
composites.
composites.

3.4.
3.4. Tensile
Tensile
3.4. Properties
Propertiesof
Properties
Tensile ofofPBS/MBF
PBS/MBFBiocomposites
PBS/MBF Biocomposites
Biocomposites

InIn
In order
order
order totoexplore
explorethe therelationship
relationship between
relationship between the the transcrystalline
transcrystallinestructure
transcrystalline structure
structure and
and
andmacro
macro
macro mechanical
mechanical
mechanical
performance,the
performance,
performance, thetensile
tensileproperty
property of of composites
composites in
composites in accordance
accordancewith
accordance withASTM
with ASTMstandards
ASTM standards
standards was was
was tested
tested
tested
(Figure
(Figure 8a).
(Figure 8a). The The typical
Thetypical stress-strain
typicalstress-strain
stress-strain curves
curves
curves of neat
of of
neat PBS
neat and
PBSPBS untreated
andand and
untreated
untreated silane-treated
and and basalt
silane-treated
silane-treated fiber
basaltbasalt
fiber
reinforced
fiber reinforced
reinforced composites
composites
composites are shown
are shown
are shown in Figure
in Figure
in Figure 8b and
8b 8bandandTable 2.2.2.
Table
Table PBSPBS
PBS exhibited
exhibited
exhibited a ayielding
a yielding behavior
behavior
behavior
followed
followed
followed byby
by acold
colddrawing,
aa cold drawing,which
drawing, whichis
which is typical
is typical for
typical for ductile
ductilepolymers.
ductile polymers.On
polymers. Onthetheother
otherhand,
hand,thethe
stress-strain
stress-strain
stress-strain
behavior
behavior
behavior of of basalt fiber-reinforced
of basalt fiber-reinforced composites
fiber-reinforced composites altered
composites altered considerably
altered considerably
considerably fromfrom the
from the neat
the neat PBS.
neat PBS. The elongation
PBS. The elongation
elongation
at at break
break decreaseddramatically
decreased dramaticallywithwith almost
almost linear tensile behavior. As can be inferred from Table
linear tensile behavior. As can be inferred from Table Table2,
2,
untreated BF and silane-treated BF with same mass loading showed some difference in enhancement
untreated
untreated BF BF and
and silane-treated
silane-treated BF BF with
with same mass loading showed some difference difference in enhancement
enhancement
in tensile properties. For the PBS matrix, the tensile strength and modulus was 23.2 and 140.6 MPa,
in tensile
tensile properties.
properties. For the PBS matrix, the tensile strength and modulus was 23.2 and 140.6 MPa,
respectively. For composites reinforced with pristine basalt fiber (PBS/BF (95/5)), the tensile strength
respectively.
respectively.For Forcomposites
compositesreinforced
reinforcedwith withpristine
pristinebasalt
basaltfiber
fiber(PBS/BF
(PBS/BF(95/5)),
(95/5)), the tensile strength
strength
and modulus was enhanced by 7.3 and 126.8 MPa, respectively, which was about 31.5% and 77.7%
and modulus
modulus was enhanced by 7.3 and 126.8 MPa, respectively, which was about 31.5% and 77.7%
higher than that of PBS matrix. However, for the PBS/MBF (95/5) biocomposites, tensile strength and
higher
higher than
modulus that
that of
thanwere of PBS
34.5PBS
andmatrix.
290.0 However,
matrix. However,
MPa, which for
for the
thePBS/MBF
PBS/MBF
significantly (95/5) biocomposites,
(95/5) biocomposites,
increased by 48.7% and 144% tensile strengthtoand
in contrast and
modulus
modulus
neat PBS,were
were 34.5 and 290.0
34.5 and 290.0
respectively. MPa, which
MPa, which
At a higher significantly
significantly
silane-treated increased
increased
BF loading, by 48.7%
by 48.7%
the tensile and 144%
and 144%
strength in contrast
in contrast
and modulus to neat
of to
PBS,
neat respectively. At a higher silane-treated BF loading, the tensile strength
PBS/MBF composites were further boosted. For example, as the MBF content increased to 15%, the of
PBS, respectively. At a higher silane-treated BF loading, the tensile and modulus
strength and of PBS/MBF
modulus
composites
PBS/MBF were further
composites
tensile strength andwere boosted.
further
modulus wereForincreased
example,
boosted. as 93.1%
the MBF
For example,
by as
and content
the increased
MBF content
281.3%, compared towith
15%,neat
increased the15%,
to tensile
PBSthe
strength
tensile and modulus
strength
accordingly. Accordingly, weresurface
and modulus increased
were by 93.1%
increased
modification and 281.3%,
by 93.1%
could and
contribute compared
to281.3%, with
an improved neat PBS
compared
PBS/MBF with accordingly.
neat PBS
interfacial
Accordingly,
accordingly.
compatibility,surface
Accordingly,modification
preventing surface could contribute
modification
microvoids and todebonding
could
fiber-PBS an improved
contribute into PBS/MBF
theaninterface
improved interfacial
PBS/MBF
region. compatibility,
interfacial
preventing
compatibility,microvoids
preventing andmicrovoids
fiber-PBS debonding
and fiber-PBS in the interface in
debonding region.
the interface region.

Figure 8. (a) Standard tensile samples; (b) stress-strain curve of PBS, PBS/BF, and PBS/MBF.

Figure8.8. (a)
Figure (a) Standard
Standardtensile
tensilesamples;
samples;(b)
(b)stress-strain
stress-straincurve
curveof
ofPBS,
PBS,PBS/BF,
PBS/BF, and
and PBS/MBF.
PBS/MBF.
Polymers 2017, 9, 351 11 of 14

Polymers 2017, 9, 351 11 of 14

Figure 9 showed the tensile fracture topography of PBS, PBS/BF, and PBS/MBF composites
at a highFigure
magnification.
9 showed the For PBS/BF
tensile (95/5)
fracture biocomposites,
topography visible
of PBS, PBS/BF, andinterfacial gaps wereat found
PBS/MBF composites a
between
highthe fiber and PBS
magnification. matrix,(95/5)
For PBS/BF andbiocomposites,
fiber-PBS debonding in the interphase
visible interfacial region
gaps were found can bethe
between clearly
observed
fiber (Figure
and PBS9c), which
matrix, suggests
and fiber-PBSpoor interfacial
debonding adhesion
in the between
interphase regionthe untreated
can be clearlyfibers and PBS.
observed
For PBS/MBF composites (Figure 9b,d–f), the polymers are coated on the silane-treated
(Figure 9c), which suggests poor interfacial adhesion between the untreated fibers and PBS. For fiber surface,
PBS/MBF
and the composites
voids between (Figure
PBS 9b,d–f),
matrix and the
MBF polymers are coated onreduced,
were significantly the silane-treated fiberstrong
suggesting surface, and
interfacial
the voids
adhesion between
compared PBSuntreated
to the matrix andfiber.
MBF were significantly reduced, suggesting strong interfacial
adhesion compared to the untreated fiber.

Figure
Figure 9. Scanning
9. Scanning electron
electron microscopy(SEM)
microscopy (SEM) micrographs
micrographs ofoftensile fractured
tensile surfaces
fractured of (a)ofPBS,
surfaces (a) PBS,
(b) PBS/MBF (98/2), (c) PBS/BF (95/5), (d) PBS/MBF (95/5), (e) PBS/MBF (90/10), and
(b) PBS/MBF (98/2), (c) PBS/BF (95/5), (d) PBS/MBF (95/5), (e) PBS/MBF (90/10), and (f) PBS/MBF (f) PBS/MBF
(85/15).
(85/15).

In order to a obtain deeper understanding on the effect of interfacial crystallization on tensile

In orderand
results to ainterfacial
obtain deeper understanding
strength, a simulationonofthe effect of
material interfacial
properties wascrystallization on tensile
performed using a
results and interfacial
mathematical strength, model
Kelly-Tyson a simulation
derivedoffrom
material properties
experimental wasofperformed
data using a mathematical
PBS/MBF biocomposites, as
given by model
Kelly-Tyson Equationderived
(4) [36,37].
from experimental data of PBS/MBF biocomposites, as given by
Equation (4) [36,37]. = ⁄ + (4)
σc = τi ( L/d)Vf Co + σm Vm (4)
where σm and σc respectively represent the tensile strength of matrix and its composites, τi represents
wherethe
σminterfacial shear strength
and σc respectively (ISS), L the
represent and tensile
d are the fiber length
strength and diameter,
of matrix Co is the orientation
and its composites, τ i represents
parameter, Vm and Vf, are the fiber and matrix volume fraction, respectively. Especially, Vf is
the interfacial shear strength (ISS), L and d are the fiber length and diameter, Co is the orientation
calculated
parameter, by Equation
V m and (5) [38].
V f , are the fiber and matrix volume fraction, respectively. Especially, V f is calculated
1−
by Equation (5) [38]. = 1+ (5)
1 − Wf
  
ρf
Vf = 1 + (5)
ρm Wf
Polymers 2017, 9, 351 12 of 14

where ρf and ρm are the density of polymer matrix and basalt fiber, respectively. W f is the fiber weight
fraction in the composite specimen.
Following the Kelly-Tyson model, τ i was obtained throughout Equations (4) and (5) and given in
Table 2. The average fiber diameter (d) and the fiber length (L) of composites were obtained from optical
microscopy. For short fiber reinforced composites, the empirical value of Co for random orientation of
fiber in 3D is usually 0.2 [39]. As listed in Table 2, the τ i of PBS/BF (95/5) biocomposites was 50.2 MPa,
while that of PBS/MBF (95/5) was 76.1 MPa, indicating that the silane treatment would contribute to
an improved polymer/fiber interfacial bonding. This is also supported by the observation of interfacial
crystallization from POM images as shown in Figures 3 and 4. The higher computed τ i of PBS/MBF
composites suggested better interfacial bonding between the MBF and PBS matrix. However, the τ i of
PBS/MBF composites did not increased with the increase content of MBF loading. The highest value of
τ i of PBS/MBF composites were obtained for PBS/MBF (98/2) biocomposites at a value of 100.1 MPa,
which might be due to the more effective formation of interfacial crystallization of PBS to MBF of
the composites at lower content of fiber loading. Therefore, the enhanced interfacial adhesion may
interpret the improvement of tensile strength of PBS/MBF in contrast with that of PBS/BF composites
from the perspective of interfacial crystalline structure.

Table 2. IFSS of PBS/BF and PBS/MBF composites.

σm τi
Sample σ ct (MPa) E (MPa) W f (%) V f (%) L (µm)
(MPa) (MPa)
PBS/MBF (98/2) 23.2 29.8 ± 1.1 163.2 ± 5.6 2 1 317.3 100.1
PBS/BF (95/5) 23.2 30.5 ± 0.5 267.4 ± 32.5 5 2.3 315.5 50.2
PBS/MBF (95/5) 23.2 34.5 ± 0.3 290.0 ± 19.6 5 2.3 314.2 76.1
PBS/MBF (90/10) 23.2 39.6 ± 0.7 373.9 ± 22.3 10 4.8 307.3 55.2
PBS/MBF (85/15) 23.2 45.8 ± 1.0 442.3 ± 16.8 15 7.3 303.2 51.0

4. Conclusions
Silane treatment was adopted to modify the surface of basalt fibers and improve the interfacial
adhesion between PBS matrix and basalt fibers in PBS/MBF biocomposites. It was found that the
transcrystalline structure was successfully induced and grew perpendicular to the silane-treated fiber
axis, while no TC structure was observed in neat PBS or PBS/BF composites. The overall isothermal
crystallization kinetics of PBS with varying silane-treated BF content at different crystallization
temperatures was investigated by the Avrami equation. It is observed that the crystallization half-time
(1/t1/2 ) values of PBS/MBF composites was shorter than that of PBS and its composites reinforced
by pristine BF. The silane-treated basalt fiber acted as an efficient nucleating agent and provided
abundant nucleating sites, accelerating the completion the crystallization process of PBS. Tensile results
showed that the incorporation of silane-treated BF lead to an increase in tensile strength and modulus.
The IFSS analysis verified that the interfacial crystalline structure improved PBS/BF interfacial bonding,
which was also demonstrated by SEM images. It is concluded that silane treatment of BF may provide
an effective method for preparing high-performance and biodegradable composites.

Supplementary Materials: The following are available online at www.mdpi.com/2073-4360/9/8/351/s1,

Figure S1: The growth of polymeric matrix (PBS) spherulites in the presence of pristine basalt fibers crystallized
at 89 ◦ C at different times; Figure S2: (a) Relative degree of crystallinity with time and (b) the Avrami plots of
ln[−ln(1 − Xt )] versus lnt for isothermal crystallization of PBS/BF (95/5) at different crystallized temperatures.
Acknowledgments: The work was financially supported by the National Natural Science Foundation of China
(Nos. 31500767), the China Postdoctoral Science Foundation (2015M571300), and the Fundamental Research
Funds for the Central Universities (DUT17RC(4)57).
Author Contributions: Wei Zhiyong and Sang Lin conceived and designed the experiments; Liang Qiushi and
Zhao Mingyuan performed the experiments; Zhao Mingyuan and Liang Qiushi analyzed the data; Wei Zhiyong
contributed reagents/materials/analysis tools; Sang Lin wrote the paper.
Conflicts of Interest: The authors declare no conflict of interest.
Polymers 2017, 9, 351 13 of 14

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