Composite Structures 167 (2017) 20–29

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Composite Structures
journal homepage: www.elsevier.com/locate/compstruct

Biodegradable polycaprolactone-based composites reinforced with

ramie and borassus fibres
Fabrizio Sarasini a,⇑, Jacopo Tirillò a, Debora Puglia b, Franco Dominici b, Carlo Santulli c, Kristom Boimau d,
Teodoro Valente a, Luigi Torre b
a
Sapienza-Università di Roma, Department of Chemical Engineering Materials Environment & UdR INSTM, via Eudossiana 18, 00184 Roma, Italy
b
Università di Perugia, Department of Civil and Environmental Engineering & UdR INSTM, Strada di Pentima 4, 05100 Terni, Italy
c
Università degli Studi di Camerino, School of Architecture and Design, Viale della Rimembranza, 63100 Ascoli Piceno, Italy
d
University of Nusa Cendana, Department of Mechanical Engineering, Kupang, NTT, Indonesia

a r t i c l e i n f o a b s t r a c t

Article history: In this work, two natural fibres extracted from fruit (borassus) and from bast (ramie) were mechanically
Received 27 December 2016 characterized and investigated as potential natural reinforcements in biocomposites based on polycapro-
Revised 17 January 2017 lactone (PCL). The PCL-based biocomposites with content of natural fibres from 10 wt% to 30 wt% were
Accepted 28 January 2017
prepared via low-temperature melt-compounding. The influence of fibre content on hardness, tensile
Available online 1 February 2017
and thermal properties of the neat matrix was investigated. The results have shown that ramie fibres
exhibited an overall brittle failure with fibrillation, while higher elongation at break and ductile fracture
Keywords:
was detected for borassus fibres. Tensile behaviour and crystallinity of the neat matrix were significantly
Polymer-matrix composites
Hybrid
improved by introducing both fibres. In addition, the different ductility and strength of bast and fruit
Mechanical properties fibres has been exploited in hybrid formulations, confirming the possibility of tailoring the properties
Thermal analysis of the ensuing composites for a specific application.
Natural fibres Ó 2017 Elsevier Ltd. All rights reserved.

1. Introduction (PCL). The use of these polymers results in a significant reduction

In quest of more environmentally friendly materials for reduc-
ing the energy-intensive and unsustainable production processes
of synthetic fibres and polymers while increasing the recyclability
of polymer matrix composites, the last two decades have wit-
nessed a resurgent interest in biocomposites based on natural
fibres [1–6]. Up to now, applications for natural fibre reinforced
plastics have been limited to less demanding and cosmetic areas
mainly in the automotive and construction industries, though
interest to expand their applications is perceived as a new and
stimulating challenge. In this framework, a potential and profitable
market is the one of orthotic devices which are specifically tailored
to meet diverse functions, from enabling to limiting the motion of
extremities [7]. According to a research conducted by IndustryARC
[8], orthotic devices market was valued at $3.0 billion in 2014 and
is forecast to reach $4.3 billion by 2020. In particular, the market
for custom-made orthoses is expected to reach $2.7 billion by
2020. This growth has been triggered by the use of low-melting
temperature thermoplastics, in particular polycaprolactones
⇑ Corresponding author.
E-mail address: fabrizio.sarasini@uniroma1.it (F. Sarasini).
of both time and cost related to the splint fabrication as they can
be conveniently formed on body segments. However, these
biodegradable polymers exhibit limited strength and fatigue resis-
tance [9,10] which make them most suitable for upper-limb
orthoses that are not subjected to repetitive loading of high stres-
ses. Another perceived disadvantage is the high price of PCL, a fac-
tor that is still hindering its large scale application despite the
growing development of bioplastics, whose global production is
set to grow 400% by 2017 [11].
Two main strategies can be implemented to face and solve the
problems related to biopolymers, namely blending [12] or reinforc-
ing with natural fibres, with the twofold objective of decreasing
the price without impairing their biodegradability [13–16]. The
latter approach has been successfully used also for PCL, as sup-
ported by a recent work by the same authors [17], where sisal,
hemp and coir fibres were reported to affect significantly the ther-
mal and mechanical properties of the resulting biocomposites.
In the wake of these promising results, the present work inves-
tigates the suitability of two additional natural fibres originating
from two different crop plants, namely borassus and ramie, for
the production of composites based on PCL still having in mind
their use as custom-made orthoses. In addition, hybrid formula-
tions were investigated with a view to exploiting the different

http://dx.doi.org/10.1016/j.compstruct.2017.01.071
0263-8223/Ó 2017 Elsevier Ltd. All rights reserved.
 F. Sarasini et al. / Composite Structures 167 (2017) 20–29
mechanical properties and reinforcing efficiency of a bast fibre
(ramie) and a fruit one (borassus) previously determined by exten-
sive single fibre tensile tests. In the present work, ramie fibres were
subjected to a mild alkali treatment aimed at promoting fibrillation
during the subsequent extrusion process, thus increasing the
fibre/matrix interface strength through the removal of hemicellu-
lose and improved fibre aspect ratio [18]. Borassus fibres were
not surface treated because the effects of alkali treatment on their
mechanical properties are usually limited [19–21], and the
increase in tensile strength that can be achieved does not allow
borassus to be comparable to ramie in terms of strength and stiff-
ness. In addition, borassus fibres have been chosen for their high
ductility and not for their strength, therefore the use of a chemical
treatment was not deemed to be appropriate and environmentally
friendly.
Whilst ramie fibres have been thoroughly investigated in liter-
ature as reinforcement for both thermoset [22–24] and thermo-
plastic [25–31] matrices, borassus fibres have received
considerably less attention [32–35] and to the best of authors’
knowledge, no composites based on PCL as well as hybrids with
ramie fibres can be found in literature.
2. Materials and methods
2.1. Materials
A commercial grade of PCL (CapaTM 6500) provided by Perstorp
was used as matrix, while the two natural fibres were Borassus fla-
bellifer (B) and ramie (Boehmeria nivea) (R). Ramie fibres were trea-
ted in a sodium hydroxide solution (5%w/v) for 4 h at room
temperature. Then the fibres were washed with distilled water
containing acetic acid until complete removal of NaOH. After
washing, the fibres were dried at 80 °C for 12 h. Borassus fibres
were used in the as-received state and both fibres were dried at
98 °C in a vacuum oven for 24 h prior to composite manufacturing.
2.2. Compounding and processing
After a drying step in a vacuum oven at 30 °C for 24 h, PCL pel-
lets and natural fibres were fed in a twin-screw microextruder by
DSM (Explore 5&15 CC Micro Compounder). The following param-
eters were used throughout the whole experimental campaign:
30 rpm screw speed, 2 min mixing time, and temperature profile:
60–75–90 °C. The tensile specimens were obtained by injection
moulding using a mini-injection mould. Mould temperature was
kept at 30 °C, while the injection temperature was equal to
110 °C with the following pressure cycle: Pinjection = 9 bar (hold
time = 4 s), 9 bar (hold time = 4 s) and 9 bar (hold time = 10 s).
Three different amounts of natural fibres were investigated,
namely 10, 20 and 30 wt% which were obtained by diluting a mas-
terbatch containing 30 wt% of each reinforcement.
2.3. Characterization
2.3.1. Single fibre tensile tests
To discriminate the reinforcing efficiency of the two plant
fibres, each natural fibre type was tested according to ASTM
C1557 at room temperature on a Zwick/Roell Z010 equipped with
a 200 N load cell at a crosshead speed of 1 mm/min. Single fibres
were carefully separated from the fibre bundles by hand and glued
onto card tabs with a central window cut-out equal to the intended
gauge length for the test, namely 20, 30, and 40 mm. For increasing
data statistical reliability, twenty fibres were tested for each gauge
length and type. An optical microscope (Nikon Eclipse 150L) was
used to determine fibre diameter by averaging five apparent diam-
21
eter measurements taken at different positions along the fibre.
Assuming a circular cross-section, the apparent cross-sectional
area of each fibre was then evaluated from the average fibre diam-
eter [36,37]. The cross-head displacement, once corrected accord-
ing to ASTM C1557 [17] in terms of system compliance (0.031
and 0.014 mm
N1 for borassus and ramie fibres, respectively),
was used to calculate the actual strain in the fibres.
A common two-parameter Weibull distribution (Eq. (1)) was
employed to investigate the mechanical properties, namely
Young’s modulus and tensile strength, obtained from single fibre
tensile tests:
  a 
n
FðnÞ ¼ exp  ð1Þ
n0
where F(n) is the probability of survival of the parameter n, a is a
dimensionless shape parameter and n0 is a scale parameter. The
probability of failure was estimated using Eq. (2):
i  0:3
F¼ ð2Þ
n þ 0:4
where i is the rank of the ith data point and n is the number of data.
Scale and shape parameters for each mechanical property were
obtained from the slope and intercept of the plot ln(ln(1F)) ver-
sus ln(n).
2.3.2. Mechanical properties of composites
Type 1BA samples (l0 = 30 mm) in accordance with UNI EN ISO
527-2 were used for tensile tests, which were carried out in dis-
placement control using a crosshead speed of 10 mm/min on a
Zwick/Roell Z010. The results reported in the work are the average
of at least five tests for each material type. A Digital Durometer
Model S1 by Instron allowed the measurement of Shore D hardness
in accordance with ASTM D-2240. The hardness value reported for
each sample is to be intended as the average of 30 measurements
performed at room temperature.
2.3.3. Thermal properties of composites
The thermal behaviour of neat polymer and composites was
investigated by differential scanning calorimetry (DSC) on three
samples for each material type. Specimens were analyzed in a Met-
tler Toledo 822e according to the following thermal program: heat-
ing from 30 °C to 100 °C (5 min hold), cooling to 30 °C and
heating to 100 °C, all steps at 10 °C/min. The measurements were
performed in nitrogen flow. The degree of crystallinity (XC) of the
samples was calculated according to Eq. (3):
DH m
XC ¼
100 ð3Þ
DH0m ð1  wfibre Þ
where DHm represents the experimental enthalpy of melting of the
sample (J/g), DH0m the enthalpy of melting for 100% crystalline PCL
(J/g), taken as 139.5 J/g [38] and wfibre is the weight fraction of nat-
ural fibres.
2.3.4. Morphological analysis
Both the fibre microstructure and composite fracture morphol-
ogy were investigated by scanning electron microscopy (SEM)
using a Philips XL40. All specimens were sputter coated with gold
prior to examination.
3. Results and discussion
Typical morphological features of the natural fibres investigated
in the present study are reported in Fig. 1 at different magnifica-
tions. Ramie fibres are clearly characterized by a smooth surface
enriched with defects, known as dislocations, typical of some bast
22 F. Sarasini et al. / Composite Structures 167 (2017) 20–29

Fig. 1. SEM micrographs at different magnifications of (a-b) ramie and (c-d) borassus fibres.

fibres, such as flax [18] and hemp [39]. These are basically regions
of the cell wall where the direction of the microfibrils differs from
the microfibril angle of the surrounding cell wall and have been
recognized as sources of both chemical degradation and loss of
fibre/matrix adhesion [40]. In addition, the fibrils are not strongly
bonded with each other due to the alkali treatment, thus suggest-
ing an increased tendency to fibrillation during the subsequent
processing steps. For untreated borassus fibres, an irregular,
rougher but much more compact surface was observed, with no
detectable fibrillation [21].
3.1. Tensile behaviour of single borassus and ramie fibres
Tables 1 and 2 summarize the tensile properties of single ramie
and borassus fibres as a function of gauge length, respectively. Both
fibres exhibit a large variability in their tensile properties due to
the inherent irregularity of the natural fibres and to various
defects, as commonly encountered in most natural fibres. The
results of the present investigation for ramie fibres, especially for
tensile strength, appear to be lower than the ones reported in liter-
ature. This is not surprising because many parameters have been
recognized to affect the mechanical properties of natural fibres,
namely testing conditions, gauge length, fibre extraction methods
and degree of maturity of plants [1,41,42]. Other studies have
reported the tensile strength of ramie fibres between 400 and
938 MPa and Young’s modulus up to 128 GPa [43,44]. Another pos-
sible explanation is related to alkali treatment that has been found
to affect the mechanical properties of single ramie fibre. Choi and
Lee [18] pointed out a slight improvement of tensile strength and
a decrease in Young’s modulus for fibres treated at 5% NaOH for
1 h, whilst Goda et al. [45] reported an increase in Young’s modu-
lus and tensile strength only for fibres with load application during
mercerization. Therefore, despite the inevitable differences, the
present results compare favourably with those in literature. A fea-
ture common to all available studies is the brittle character of
ramie fibres. Borassus fibres exhibited tensile properties consistent
with those found by other researchers with a considerable strain to
failure ranging from 30 to 50% [21,46,47]. Such high ductility is
rarely seen in natural cellulosic fibres and is mainly due to the high
microfibrillar angle, low degree of crystallinity and poor orienta-
tion of cellulose crystals along the fibre axis. Such parameters
can be interpreted and explained considering the different function
of the fibres in the living plants.
Bast fibres, such as ramie, have to meet structural requirements
in the plant and therefore are characterized by high cellulose con-
tent and cellulose cryistallinity, both directly influencing the ten-
sile strength and Young’s modulus. On the other hand, ductility
can be mainly ascribed to a low microfibrillar angle. Borassus
fibres, similarly to what happens to other fruit fibres such as coir,
do not have a supportive function in nature, instead they are

Table 1
Comparison between mechanical properties obtained in this work and data available from open literature for ramie fibres.

Gauge length (mm) Average diameter (lm) Tensile strength (MPa) Young’s modulus (GPa) Strain-to-failure (%) Weibull modulus References
50 120 ± 40 627 ± 162 31.8 ± 10.72 2.7 ± 0.4 4.16 [61]
10 34 560 – 2.5 – [45]
– 30.9 610 – 3.59 – [31]
50 48.5 ± 7.8 621 ± 296 47.5 ± 15.2 1.9 ± 0.45 2.6 [62]
20 24.27 ± 5.96 439.51 ± 114.91 37.18 ± 14.68 1.34 ± 0.51 See Table 3 This work
30 28.08 ± 7.04 429.20 ± 129.64 36.45 ± 13.70 1.91 ± 0.45 See Table 3 This work
40 27.23 ± 4.11 421.16 ± 153.29 35.89 ± 10.13 1.57 ± 0.56 See Table 3 This work
 F. Sarasini et al. / Composite Structures 167 (2017) 20–29 23

Table 2
Comparison between mechanical properties obtained in this work and data available from open literature for borassus fibres.

Gauge length (mm) Average diameter (lm) Tensile strength (MPa) Young’s modulus (GPa) Strain-to-failure (%) Weibull modulus References
*
50 120 ± 26 61.8 ± 0.304 – 25.58 ± 8.37 – [46]
50 130 65.2 ± 2.7 4.92 ± 0.10 47.2 ± 1.6 – [47]
50 140 70.8 ± 4.1 10.8 ± 4.7 34.8 ± 3.5 – [21]
20 122.78 ± 32.54 108.31 ± 32.62 3.60 ± 1.39 31.29 ± 16.91 See Table 3 This work
30 118.86 ± 50.52 97.78 ± 35.23 3.21 ± 1.00 29.07 ± 15.06 See Table 3 This work
40 129.53 ± 38.87 89.09 ± 38.60 3.09 ± 1.41 30.10 ± 15.65 See Table 3 This work
*
cN/tex.

Table 3
Weibull parameters for borassus and ramie fibres.

Natural fibre Gauge length (mm) Tensile strength - a Tensile strength – n0 (MPa) Young’s modulus – a Young’s modulus – n0 (GPa)
Borassus 20 3.70 120.07 2.96 4.04
30 2.66 107.30 3.84 3.55
40 2.35 101.27 2.72 3.48
Ramie 20 3.11 480.64 2.56 41.84
30 3.49 474.28 2.87 40.82
40 3.16 470.67 3.88 39.04

basically energy absorbing fibres with a protective function
towards the fruit. There is no report on the microfibrillar angle of
borassus fibres, but it is reasonable to assume that it is high, as it
is the case for coir (45°) [44]. In addition, the low cellulose con-
tent (50%) and degree of crystallinity (38%) [20] result in boras-
sus fibres having a low strength, low modulus and a high strain to
failure. On the other hand, ramie fibres have a supporting function
in the plant and as a consequence these fibres exhibit higher cellu-
lose content (68–75%) [45], higher degree of crystallinity (58%)
[48] and lower microfibrillar angle (7.5°), thus supporting the
higher strength, stiffness and lower strain to failure of ramie fibres
compared to borassus ones.
From Tables 1 and 2 it can be also inferred that gauge length
plays a significant role in determining the values of both tensile
strength and Young’s modulus, with a much more marked ten-
dency for the former. As commonly observed, the lower the gauge
length, the higher the tensile strength [17,48–52] a tendency
which can be explained by taking into account that a longer
stressed length is likely to host a higher number of defects that
impair the structural performance of the fibre.
The wide scatter observed in tensile data of natural fibres is
ascribed to naturally occurring pre-existing flaws or process-
related defects and both determine the premature failure of fibres
under load. Due to the random nature of flaws, the tensile data
have been analyzed by a statistical model, the most widely used
being the Weibull distribution function. In particular, the tensile
data were fitted to a two-parameter Weibull distribution and the
results are summarized in Table 3 and Fig. 2. The Weibull probabil-
ity distribution does provide a good fit for the experimental tensile
data. The linear trend at each gauge length indicates that the fail-
ure of these natural fibres is dominated by a single-flaw popula-
tion. Weakest fibres exhibited a deviation from Weibull
distribution, which is likely to be due to possible defects intro-
duced during the preparation and handling of the specimens. As
reported for other natural and synthetic fibres, Weibull moduli
were not found to show any definite relationship with gauge
length [17,52,53]. Both ramie and borassus fibres exhibited Wei-
bull moduli in the range 2.35–3.70, values that compare quite
favourably with those found in literature, when available.
Typical morphological features of natural fibres once failed in
tension are shown in Fig. 3. Ramie fibres (Fig. 3a and b) exhibited
an overall brittle failure with no fibrillation, failure which mostly
occurred at the same stress level. A much more ductile type of frac-
ture was shown by borassus fibres (Fig. 3c and d) with the presence
of a localized strain in a small region of the material (similar to
necking), thus confirming the higher strain to failure of these nat-
ural fibres.
3.2. Mechanical properties of natural fibre composites
The tensile behaviour of PCL-based composites is shown in
Fig. 4 as a function of natural fibre content and type, while Fig. 5
summarizes the mechanical properties. The typical cold drawing
behaviour with the formation of a neck of neat PCL was not
observed in the case of highly filled composites (>20wt%) which
are characterized by a gradual disappearance of cold drawing. A
yield point can still be recognized but the macromolecular mobility
is hindered by fibres, thus preventing the attainment of extensive
and sustained ductility. The addition of ramie fibres results in a sig-
nificant increase in both tensile strength and Young’s modulus of
the composites compared to the neat matrix (Fig. 5). Values for
two commercial products for orthotic devices, OrfitÒ (blue dashed
line) and RolyanÒ (red dashed line), are reported for comparison
purposes in Fig. 5 [17]. A slightly different behaviour is presented
by borassus fibres that did not cause an improvement of the
strength over that of neat PCL, irrespective of the fibre content.
An almost constant value was found with increasing fibre content,
which is comparable to the one of commercial materials
(13.02 MPa for OrfitÒ and 19.46 MPa for RolyanÒ). As expected, stiff
and strong fibres caused a dramatic decrease in the ductility of the
composites, with a reduced tendency shown by the more ductile
borassus fibres (Fig. 5c).
The addition of natural fibres did not influence to a great extent
the hardness of the resulting composites, with values in the range
of 55–60, which are close to the ones of commercial materials
(54.76 for 35 OrfitÒ and 57.57 for RolyanÒ) (Fig. 6). As a general
conclusion, the present formulations exhibited comparable or even
better mechanical properties than those offered by commercially
available materials. Ramie fibres are responsible for the highest
improvements and the different reinforcing efficiency compared
to borassus fibres is linked to the single fibre performance. In fact,
non-supportive borassus fibres have the lowest mechanical values
that do not allow them to attain the high reinforcement effect
exhibited by ramie fibres, with improvements for strength and
stiffness over the neat matrix equal to 115% and 445%, respectively.
Besides single fibre mechanical properties, the mechanical
24 F. Sarasini et al. / Composite Structures 167 (2017) 20–29

Fig. 2. Weibull plots for tensile strength and Young’s modulus as a function of gauge length for (a-b) ramie and (c-d) borassus fibres.

Fig. 3. SEM micrographs of (a-b) ramie and (c-d) borassus fibres fractured in tension.

response of composites is also strongly dictated by the strength of
the fibre/matrix adhesion and by the fibre aspect ratio (length/di-
ameter), which control the efficiency of load transfer and the
extension of fibre/matrix interface, respectively.
SEM analysis of the fracture surfaces (Fig. 7) confirmed the
reduced strength of the interface between borassus fibres and
PCL matrix (Fig. 7a and b), where fibre pull-out and debonding
phenomena can be easily observed. Ramie fibres (Fig. 7c and d)
appear to have a stronger interfacial adhesion compared to boras-
sus fibres, likely due to the lower content of hemicellulose [21,45]
that is responsible for the strong hydrophilic character of natural
fibres. Besides the inherent lower hemicellulose content, an
 F. Sarasini et al. / Composite Structures 167 (2017) 20–29 25

Fig. 4. Typical stress-strain curves from tensile tests for PCL-based composites as a
function of increasing content of ramie and borassus fibres. The behaviour of neat
PCL is added as reference.
additional removal of hemicellulose was also promoted by the
alkali treatment [54]. Another advantage of alkali treated ramie
fibres is their tendency to fibrillate, thus offering a higher aspect
ratio. It is in fact well known that the composite strength increases
with increasing aspect ratio of fibres, due to higher amount of
stress that can be effectively transferred.
As natural fibres extracted from different parts of the plants are
characterized by dissimilar properties, they offer the unique
opportunity to tailor the mechanical properties of the resulting
composites through hybridization with a view to meeting the
diverse requirements and functions of the splints. Although several
papers can be found on hybrid composites made from one natural
fibre combined with synthetic fibres [55], hybrid composites using
Fig. 6. Shore D hardness as a function of fibre content and type. Values for two
commercial products, OrfitÒ (blue dashed line) and RolyanÒ (red dashed line), are
reported for comparison purposes as obtained from [17] (For interpretation of the
references to colour in this figure legend, the reader is referred to the web version of
this article).
two or more natural fibres have been rarely studied. In the present
study, all hybrid composites have a fibre mass content of 30%.
Ramie/borassus fibre ratios used were 30:0, 20:10, 15:15, 10:20,
0:30 and the mechanical properties of hybrid composites are
reported in Figs. 8 and 9. From the data it is clear that the mechan-
ical properties can be tailored according to a judicious selection of
fibres to be hybridized, exploiting in the present case the higher
ductility of borassus fibres with the higher strength and stiffness
of ramie ones. In the case of PCL + 10R/20B it is possible to attain
a significant ductility (40%) still preserving higher mechanical

Fig. 5. (a) Tensile strength, (b) Young’s modulus and (c) Strain at break for composites reinforced with borassus and ramie fibres. Values for two commercial products, OrfitÒ
(blue dashed line) and RolyanÒ (red dashed line), are reported for comparison purposes as obtained from [17] (For interpretation of the references to colour in this figure
legend, the reader is referred to the web version of this article).
26 F. Sarasini et al. / Composite Structures 167 (2017) 20–29

Fig. 7. SEM micrographs of the fracture surfaces of PCL-based composites reinforced with (a-b) borassus and (c-d) ramie fibres.

Fig. 8. Effect of ramie/borassus ratio on the tensile strength and modulus of hybrid
composites.
Fig. 9. Effect of ramie/borassus ratio on the strain at break of hybrid composites.

properties compared to the neat PCL in terms of strength (34%)

and stiffness (155%).
3.3. Thermal characterization of natural fibre composites
Results of thermal characterization of PCL-based composites are
reported in Fig. 10 and Table 4. Melting temperature (Tm) and asso-
ciated heat of melting (DHm) for the first and second heating scan,
crystallization temperature (Tc) and degree of crystallinity (Xc) cal-
culated in the second heating scan were obtained from the analysis
of specific thermograms.
For all the composites, the melting temperature registered dur-
ing the first heating scan did not show any appreciable variation
with respect to neat PCL: the comparison of all the different sys-
tems containing 30 wt% of fibres showed that a slight increase
can be observed only in the case of hybrid system (PCL
+ 15B/15R), with a general decrease in melting enthalpy that can
be justified by a restriction of the periodic arrangements of PCL
chains into its lattice [56]. The comparison of melting enthalpies
for PCL + 30B and PCL + 30R during the first heating scan confirmed
a reduced tendency of the latter one to recrystallize during pro-
cessing, while a substantial balance in terms of melting enthalpy
values was restored in all hybrid systems (PCL + 20B/10R, PCL
+ 10B/20R and PCL + 15B/15R).
The crystallization temperature was found to slightly increase
(4 °C) when compared to the neat PCL, regardless of fibre nat-
ure and weight content, that can be interpreted as a difficulty for
 F. Sarasini et al. / Composite Structures 167 (2017) 20–29 27

PCL a) PCL b)
PCL+10B PCL+10R
PCL+20B PCL+20R
PCL+30B PCL+30R
Heat flow (a.u.)

Heat flow (a.u.)

-20 0 20 40 60 80 100
-20 0 20 40 60 80 100
Temperature (°C)
Temperature (°C)

PCL c)
PCL+20B/10R
PCL+15B/15R
PCL+10B/20R
Heat flow (a.u.)

-20 0 20 40 60 80 100

Temperature (°C)

Fig. 10. DSC curves at second heating scan of composites reinforced with borassus (a), ramie (b) and (c) hybrid systems.

Table 4
Thermal characteristics of PCL-based composites obtained from DSC analysis.

Specimen Tm1(J/g) DHm1(J/g) Tc (°C) DHc (J/g) Tm2(°C) DHm2(J/g) Xc

PCL_Neat 66.5 ± 0.5 82.0 ± 0.9 29.0 ± 1.3 67.2 ± 0.3 57.8 ± 0.2 70.0 ± 1.6 50.2 ± 1.1
PCL + 10B 67.6 ± 0.8 73.3 ± 2.7 33.0 ± 0.1 60.7 ± 2.8 58.9 ± 0.9 63.8 ± 0.8 50.8 ± 0.6
PCL + 20B 67.3 ± 0.2 70.4 ± 1.9 32.0 ± 0.7 59.4 ± 1.9 62.7 ± 0.8 63.2 ± 0.7 56.6 ± 0.7
PCL + 30B 66.8 ± 0.9 69.5 ± 5.0 32.7 ± 0.2 53.7 ± 0.7 60.5 ± 1.6 57.6 ± 0.7 58.9 ± 0.7
PCL + 10R 68.4 ± 0.1 72.1 ± 0.1 32.3 ± 1.7 59.8 ± 0.7 62.2 ± 0.1 62.8 ± 0.9 50.0 ± 0.7
PCL + 20R 67.3 ± 0.2 70.4 ± 1.9 32.0 ± 0.7 59.4 ± 1.9 62.7 ± 0.8 63.2 ± 0.7 56.6 ± 0.7
PCL + 30R 66.5 ± 0.1 61.7 ± 5.1 32.2 ± 0.3 53.0 ± 0.4 61.5 ± 0.3 56.6 ± 1.0 57.9 ± 1.1
PCL + 20B/10R 67.4 ± 0.3 65.1 ± 1.9 31.6 ± 0.5 54.0 ± 0.1 62.6 ± 1.4 57.7 ± 2.9 59.1 ± 3.0
PCL + 20R/10B 66.3 ± 0.7 68.6 ± 3.0 33.2 ± 0.6 53.4 ± 1.5 61.6 ± 0.2 58.8 ± 0.6 60.2 ± 0.7
PCL + 15B/15R 68.5 ± 0.9 67.0 ± 5.0 32.3 ± 1.5 59.0 ± 1.1 59.7 ± 2.9 62.5 ± 3.5 64.0 ± 3.6

the PCL chains to rearrange themselves in presence of fibres and the lower fibre content (10 and 20 wt% for borassus and ramie
occurrence of a weak nucleating effect on the crystal growth of composites). In the second heating scan, as the concentration
PCL. The crystallization enthalpy DHc shifted to lower values of the fibres increased, the relative weight per cent of PCL in
when the fibre loading in the composites increases up to 30 wt the compound decreased, leading again to a decreased melting
%, meaning that the crystallization became more imperfect than endothermic area. Moreover, no different shapes of main melting
it is the case for the neat PCL [57]. Nevertheless, in the case of peak were detected (Fig. 10a–c), whereas it was observed that
hybrid systems, the values tend to increase again, reaching the the presence of natural fibres significantly affected the degree
crystalline content registered for neat matrix and composites at of crystallinity.
28 F. Sarasini et al. / Composite Structures 167 (2017) 20–29
These results confirmed that, even if the incorporation of the
two different fibres restrained the mobility of the polymer chains,
a larger amount of PCL crystallites, yet smaller, were formed within
the different composites and this effect was more evident in the
case of hybrid systems, proving that the ability to crystallize was
enhanced when the combination of the two fibres was considered
[58–60].
4. Conclusions
With a view to promoting the use of natural fibres in the sector
of orthotic devices, composites based on a biodegradable matrix
(PCL) reinforced with fibres extracted from two crop plants (ramie
from bast and borassus from fruit) were manufactured and charac-
terized. Significant improvements in tensile strength and modulus
due to the addition of ramie fibres were reported, while a marked
ductility without a significant decrease in strength compared to
the neat matrix was the main feature of borassus-based compos-
ites. The mechanical results of biocomposites, when compared
with those of commercially available materials used in orthotics,
proved their potential application in the fabrication of orthotic
devices. The better results offered by ramie fibres were explained
in terms of a balance of single fibre properties and favourable
aspect ratio after compounding and processing steps, ascribed to
a strong tendency to fibrillation emphasized by a mild alkali treat-
ment. Differences in reinforcing efficiency among bast and fruit
extracted fibres were used to manufacture hybrid systems able
to show significant strength and stiffness coupled with sufficient
ductility. All the fibres were found to affect the crystallization
behaviour of the neat matrix causing an increase of the overall
degree of crystallinity of polycaprolactone, with a significant syn-
ergistic effect for the hybrid composites.
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