fibers

Article
Interfacial Characterization by Pull-Out Test of
Bamboo Fibers Embedded in Poly(Lactic Acid)
Quentin Viel 1,4 , Antonella Esposito 1, * ID
, Jean-Marc Saiter 2 , Carlo Santulli 3, *
and Joseph A. Turner 4
1 Normandie Univ, UNIROUEN Normandie, INSA Rouen, CNRS, Groupe de Physique des Matériaux,
76100 Rouen, France; [email protected] (Q.V.); [email protected] (A.E.)
2 AMME-LECAP EA 4528 International Laboratory, Institute for Materials Research,
Université de Rouen BP 12, 76801 Saint-Etienne du Rouvray CEDEX, France; [email protected]
3 School of Architecture and Design (SAAD), Università degli Studi di Camerino, Viale della Rimembranza,
63100 Ascoli Piceno, Italy
4 AMME-ATEAM International Laboratory, Department of Mechanical and Materials Engineering,
University of Nebraska-Lincoln, Lincoln, NE 68588-0526, USA; [email protected]
* Correspondence: [email protected] (A.E.); [email protected] (C.S.);
Tel.: +33-2-3295-5083 (A.E.); +39-334-1737527 (C.S.)

Received: 25 December 2017; Accepted: 16 January 2018; Published: 19 January 2018

Abstract: In this work, the apparent shear strength at the interface between a bamboo fiber and
the surrounding poly(lactic acid) (PLA) matrix is quantified. A method for processing pull-out test
samples within a controlled embedded length is proposed and the details of the test procedure
are presented, along with a critical discussion of the results. Two series of samples are considered:
untreated and mercerized bamboo fibers from the same batch, embedded in the same polyester
matrix. Electron and optical microscopy are used to observe the fiber–matrix interface before and
after the test, and to identify the failure mode of each sample, especially as regards the occurrence of
fibrillation in the fiber bundles. The values of apparent interfacial shear strength are calculated only
for regular fibers successfully pulled out from the matrix, and reported with their statistical variations.
Mercerization, whose efficiency was proven by Fourier transform infrared (FTIR) spectroscopy, did
not appear though to improve the quality of the interface (τ app = 7.0 ± 3.1 MPa for untreated fibers
and τ app = 5.3 ± 2.4 MPa for treated fibers).

Keywords: bamboo biomass; biodegradable composites; pull-out; surface treatments; mercerization

1. Introduction
Processing 100% green composites implies that biosourced (biodegradable) polymeric resins can
be conveniently reinforced by natural materials, such as plant-based fibers, for example jute, hemp,
flax and bamboo fibers [1–5]. Bamboos are one of the most abundant ligno-cellulosic plants produced
in the world [6]. There are so many different species of bamboos, and some of them grow so fast
(up to 120 cm per day), that no other source of vegetable fibers could be considered more renewable.
On the other hand, it is not obvious how to control from a botanical point of view the supply of
bamboo from tropical forests, due to their degradation, especially when classified as “ambiguous
lands”, i.e., in principle state-owned yet used by low income people for harvesting, e.g., bamboo
shoots [7]. For this reason, a possibility which has been explored is for example the extraction of lignin
from steam exploded bamboo for the production of epoxy resins [8].
A more valuable yet sustainable perspective is nonetheless the possibility to produce composites
by using bamboo fibers as the reinforcement for biodegradable matrices [9]. In this regard, the use of
bamboo fibers, also due to the variable quality of supply, cannot always be recommended, because

Fibers 2018, 6, 7; doi:10.3390/fib6010007 www.mdpi.com/journal/fibers

Fibers 2018, 6, 7 2 of 15

the difficult predictability of their properties has an effect also on those of composites produced with
them. For example, due to the variable presence of defects in the fibers, introducing longer fibers in
the load direction does not always result in substantial and repeatable improvement of composite
performance, as, e.g., reported in a study on bamboo fiber/starch-based composites [10]. A further
issue, which heavily contributes to the variability of bamboo fibers properties, is that, as it is the case
for all ligno-cellulosic fibers, their morphology can be very variable in terms of diameter, hollow size
and geometry, elliptical shape of the section, etc. [11–13].
Polymers synthesized from naturally sourced monomers, such as poly(lactic acid) (PLA), have
in contrast quite controllable properties and are therefore very suitable for the production of fully
sustainable composites with vegetable fibers: a significant amount of literature does exist on these
materials [14]. A major aspect to be controlled is therefore the quality of the fiber–matrix interface,
that can be measured on fiber composites by a number of possible methods, among which is pull-out
testing [15].
An early study on flax fiber pull-out from polyethylene matrix proposed that the same methods
used in the case of traditional fibers, such as glass or carbon fibers, could work as well, despite the
peculiar structural characteristics of lignocellulosic fibers [16]. Following this, pull-out testing proved
suitable to offer sufficiently reliable values of the apparent interface shear strength on a number of
different lignocellulosic fibers [17]. Pull-out tests of sisal fibers embedded at three-millimeter depth in
polyester blocks of 10-mm side and then stretched to failure confirmed, despite a very large standard
deviation, the effectiveness of mercerization in improving fiber–matrix interface strength [18].
As for bamboo fibers, the significant influence of environmental factors on the adhesion strength
between fiber and matrix has already been highlighted [19]. However, in general, the measurement of
interface strength has found so far only quite limited coverage in the literature, despite the fact that
substantial issues are still perceived in the achievement of sufficient properties for PLA/bamboo fiber
composites [2,6,11,20]. Recent work pointed out that information about practical adhesion of bamboo
fibers with thermoplastic polymer matrices could be obtained from different parameters from pull-out
tests, such as interfacial shear stress, radial tensile stress and theoretical work of adhesion: the study
indicated a better interface for bamboo fibers with poly(vinylidene fluoride) (PVDF) rather than with
polypropylene (PP), although much weaker than for glass fibers [21].
The measurement of apparent shear strength can be not completely accurate, since the pull-out
process may be friction-dominated in bamboo fiber systems, and friction is not considered by this
parameter [22]. Accurate measurements of interfacial adhesion in bamboo fibers are also cumbersome
for other reasons, such as the variable adhesion of filaments to form bundles (which makes them easily
prone to fibrillation) and the need to account also for cross-sectional complex shapes and variable sizes
(which requires multiple measurements of the diameter across the same section). Notwithstanding
these limitations, it is worth considering whether the application of a simple method for measuring the
apparent interfacial shear strength with values of diameter obtained under reasonable assumptions
would supply any suitable indication for the improvement of composite properties. This approach
may be simplistic in comparison with other approaches, such as local analysis and computational
predictions [23], well adapted when both the matrix and the fibers have quite regular and predictable
properties. However, when it comes to natural materials, whose supply is not subjected to a rigorous
quality control from the producer as for synthetic ones, but only possibly to some selection of the most
suitable samples, predictability is a real issue: for this reason, experimental approaches, which give
access to the average properties of the entire population under sensible assumptions, can provide
reasonably good estimates of the properties. In spite of this, the positive influence of maleinisation and
silane treatment on polypropylene/bamboo composites interfacial shear strength was highlighted [24].
In this work, measurements of the apparent interfacial shear strength were carried out by
performing pull-out tests on bamboo technical fibers embedded in thin PLA matrices. Fibers belonging
to the same batch were used either as received or after mercerization, embedded in the same polymeric
Fibers 2018, 6, 7 3 of 15

matrix. A procedure was used to obtain samples with an improved control over the embedded length,
and a critical approach to the experimental results was used to select and interpret them.

2. Materials and Methods

2.1. Materials
A commercial grade of poly(lactic acid) (PLA) denoted PLI 003, with density ρ = 1.25 ± 0.05 g/cm3
and melting temperature around 145–155 ◦ C, was purchased from NaturePlast (Caen, France). Bamboo
Fibers Technology (Lahontan, France) imports bamboo fibers and fillers from Thailand, and proposes
different grades (G1 to G6, from short fibers to extremely fine particles). Only short fibers belonging to
grades G1 and G2 were considered in this work (fibers 5–150 mm long). Their tapped density is 90 kg/m3
and their humidity is comprised between 8% and 15% in normal ambient conditions. The batch of fibers
used in this work was extracted from plants grown in the wild forests of northern Thailand, Province of
Lamphun. Several genera and species of bamboos are recorded in Thailand [25], but the major type of
bamboos found throughout the country is tropical bamboo, also referred to as sympodial bamboo [26].
Unfortunately, there has been no systematic survey of the vegetation in Thailand so far, so that in
particular, no assessment of the bamboo resources from Thailand has been made [27]. Thailand lacks
a proper vegetational system because the myriad of nomenclature have never been sorted and even
ecologists are often unable to get reliable names for their studies [28]. In Thailand, wild bamboos can be
found in three of the four subtypes of forest, i.e., dry evergreen forests (DEF), mixed deciduous forests
(MDF) and dry dipterocarp Forests (DDF). The fibers used in this work were extracted from plants
grown in MDF where, according to Prachayo [29], only one species is found (Dendrocalamus strictus).
It is worth mentioning, however, that Thailand’s MDF are a form of degraded forest comprising
a mixture of evergreen and deciduous trees organized in three layers, with the middle layer typically
dominated by bamboos, and that it has been recently found that all bamboos in MDF are sympodial,
but not necessarily belonging to the same species [30]; one may occasionally encounter clustered
Gigantochloa albociliata, Bambusa tulda and Cephalostachyum pergracile [31]. The fibers were mechanically
extracted from the bamboo stem by hatching, and then their size was gradually reduced from G1 to
G6 by mechanical grinding. Several fibers belonging to the same batch were used either as received or
after mercerization. Mercerization was performed with sodium hydroxide (NaOH) (Sigma-Aldrich,
St. Louis, MI, USA, ACS reagent ≥ 97.0%).

2.2. Methods

2.2.1. Preparation of the Samples

A preliminary naked-eye inspection allowed separating regularly-sized from clearly distorted
and/or defective fibers. A typical cross-section of bamboo fiber bundles inside the culm presents
an irregular form (bean shape) with a size variation depending on their position across the bamboo
wall. Once extracted, each technical fiber, irrespective of its initial position, contains many elementary
fibers (whose cross-section is either pentagonal or hexagonal) arranged in honeycomb patterns [32].
Whatever the process of extraction, natural fibers have variable cross-sectional shape, even throughout
the same batch. Indeed, when the fibers are extracted, they are partially broken resulting in different
cross-sectional shapes and sizes [12]. Optical microscopy revealed that the fibers selected from the
batch used in this work were statistically dispersed, both in shape and size, with a cross-sectional
shape mostly intermediate between circular and elliptical (Figure 1). Initially, the apparent diameters
of the technical fibers used in this work (estimated from a side view by optical microscopy) were found
to range from 200 µm to 1 mm. Some of the fibers out of the batch were also mercerized; mercerization
is likely to help loosening the bundles and separating them into elementary filaments without inducing
any significant modification of their structural components (crystallinity index and amount of native
cellulose) [33]. For mercerization, the fibers were immersed in a water solution containing 5 wt % sodium
 Fibers 2018, 6, 7 4 of 15
Fibers 2018, 6, 7 4 of 15
(crystallinity index and amount of native cellulose) [33]. For mercerization, the fibers were immersed
in a water solution containing 5 wt % sodium hydroxide (NaOH) for 24 h at room temperature: the
hydroxide (NaOH) for 24 h at room temperature: the long period of exposure to sodium hydroxide at
long period of exposure to sodium hydroxide at a not very high concentration is expected to allow
a not very high concentration is expected to allow obtaining fibers with modified surfaces but equivalent
obtaining fibers with modified surfaces but equivalent structural properties (this will be dealt with
structural properties (this will be dealt with in Section 3). After the treatment, the fibers were recovered
in Section 3). After the treatment, the fibers were recovered by a plastic tray with filter paper and
by a plastic tray with filter paper and washed with filtered water in a Büchner flask. Finally, the fibers
washed with filtered water in a Büchner flask. Finally, the fibers were placed on a plate coated with
◦ C for 24 h.
were placed on a plate coated with an aluminum
an aluminum foil and oven dried at 80 °C for 24 h.foil and oven dried at 80

Figure 1. Cross-section of two bamboo fibers randomly extracted from the batch used in the study
Figure 1. Cross-section of two bamboo fibers randomly extracted from the batch used in the study and
and imaged by optical microscopy.
imaged by optical microscopy.

Thin PLA disks were created by melting a given amount of dried pellets and then compressing
Thin
them with PLA disks were
a hydraulic created
manual by melting
press (Specac a25T,
given amount of
Orpington, dried
UK). Thepellets
thicknessand ofthenthecompressing
PLA disks
them with a hydraulic manual press (Specac 25T, Orpington, UK).
was carefully controlled, as it represents a key parameter for pull-out tests (length of fiber The thickness of the PLA disks was
embedded
carefully controlled,
in the polymer as it The
matrix). represents
controlaoverkey parameter
the thickness forwas
pull-out
ensured testsby(length
(1) usingof fiber
round embedded in the
washers with
polymer
known matrix).
thicknesses The(h)control over thediameters
and internal thickness(D was ensured
i), and by (1) usingthe
(2) determining round
masswashers with known
of PLA required to
thicknesses
fill the volume(h) and internal
inside diameters
each washer (Di ), and
(Equation (1)).(2) determining the mass of PLA required to fill the
volume inside each washer (Equation (1)).
=
 2 2ℎ
(1)
Di
The procedure to obtain the PLA disks m is= the
π following: hρ (1) two Teflon films and two aluminum (1)
2
foils are cut to the internal diameter of the washer; (2) both the Teflon films and the first aluminum
foilThe procedure
are used in theirtopristine
obtain form,
the PLA disks the
whereas is the
secondfollowing:
aluminum (1) two foilTeflon films and as
is hole-punched two aluminum
many times
foils are cut to the internal diameter of the washer; (2) both the Teflon
as the number of samples to be prepared; (3) a sandwich is obtained by stacking (in order) one films and the first aluminum foil
are usedfilm,
Teflon in their
the pristine form, whereas
first aluminum the second
foil, the washer filled aluminum
with the PLA foil is hole-punched
pellets, the second asaluminum
many times foilas
the
andnumber
anotherofTeflon
samples filmto(Figure
be prepared;
2a). The(3) a sandwich
first aluminumisfoil obtained
acts as aby stacking
support for (in
the order)
polymer one Teflon
sample
along
film, thewith
firstthe second aluminum
aluminum foil, which
foil, the washer fillediswith
hole-punched to expose
the PLA pellets, thethe PLA matrix
second aluminum in thefoil
areas
and
where the
another Teflonbamboo fibers will
film (Figure 2a).beTheinserted. The sandwich
first aluminum is inserted
foil acts between
as a support forthe
thehot plates sample
polymer of the
hydraulic
along with thepress (temperature
second aluminum controller set tois 200
foil, which °C, with thetopolymer
hole-punched expose the not PLAexceeding
matrix170–175 °C)
in the areas
and a force of 2 tons (10 to 30 MPa depending on the external diameter
where the bamboo fibers will be inserted. The sandwich is inserted between the hot plates of the of the washer) is applied for 2
min. After
hydraulic cooling
press down to room
(temperature temperature,
controller set to 200 ◦
the thickness
C, with the of the disks is
polymer notchecked
exceedingusing170–175 ◦
a caliper.C)
Four
and washers
a force of 2 with different
tons (10 thicknesses
to 30 MPa depending (0.84,on0.15,
the 0.65 and 0.55
external diametermm) of andtheinternal
washer) diameters
is applied (34.0,
for 2
38.2, 44.6 and 44.0 respectively) were used. The PLA disks were cut
min. After cooling down to room temperature, the thickness of the disks is checked using a caliper. to produce as many samples as
the number of holes punched in the second aluminum foil. In the meantime,
Four washers with different thicknesses (0.84, 0.15, 0.65 and 0.55 mm) and internal diameters (34.0, the fibers were held in
the 44.6
38.2, ovenand at 44.0
80 °Crespectively)
to avoid any water
were used.uptake,
The PLAas the presence
disks were cut of to
water is known
produce as many to weaken
samples their
as the
interface with polymers [20]. The fibers were embedded,
number of holes punched in the second aluminum foil. In the meantime, the fibers were one by one, in every PLA precut
held indiskthe
heated between
◦ the hot plates of the press. Attention was paid to
oven at 80 C to avoid any water uptake, as the presence of water is known to weaken their interface keep them as perpendicular as
possible with respect to their surface and to force them to the bottom of the layer.
with polymers [20]. The fibers were embedded, one by one, in every PLA precut disk heated between
the hot plates of the press. Attention was paid to keep them as perpendicular as possible with respect
to their surface and to force them to the bottom of the layer.
Fibers 2018, 6, 7 5 of 15
Fibers 2018, 6, 7 5 of 15

(a) (b)
Figure 2. Procedure to obtain and test pull-out-samples. (a) creating poly(lactic acid) (PLA) thin
Figure 2. Procedure to obtain and test pull-out-samples. (a) creating poly(lactic acid) (PLA) thin disks.
disks.
BetweenBetween
the hotthe hot plates
plates of the of the hydraulic
hydraulic press press (stacked
(stacked from from the bottom
the bottom to thetotop):
the top): a Teflon
a Teflon film,
an aluminum foil, a washer filled with PLA pellets, a hole-punched aluminum foil and anotheranother
film, an aluminum foil, a washer filled with PLA pellets, a hole-punched aluminum foil and Teflon
Teflon
film. (b)film. (b) samples
placing placing samples on device:
on the Bose the Bose
(A)device:
clamp,(A) clamp, (B) (C)
(B) cardboard, cardboard,
free tip of(C)
thefree tip offiber,
bamboo the
bamboo
(D) washer,fiber,
and(D)
(E)washer,
PLA thinanddisk.
(E) PLA thin disk.

2.2.2. Characterization of the Fibers and Pull-Out Tests

2.2.2. Characterization of the Fibers and Pull-Out Tests
The bamboo fibers were characterized by Fourier transform infrared (FTIR) spectroscopy before
The bamboo fibers were characterized by Fourier transform infrared (FTIR) spectroscopy before
the alkali treatment, right after the alkali treatment (without washing) and after washing in filtered
the alkali treatment, right after the alkali treatment (without washing) and after washing in filtered
water. Prior to measurement, the fibers were dried and compacted into pellets (16 mm Ø) by the
water. Prior to measurement, the fibers were dried and compacted into pellets (16 mm Ø) by the
hydraulic manual press (Specac 25T). Several spectra were recorded on different areas of each pellet
hydraulic manual press (Specac 25T). Several spectra were recorded on different areas of each pellet
by a Varian 4100 FTIR device (Excalibur Series, Agilent, Santa Clara, CA, USA) in attenuated total
by a Varian 4100 FTIR device (Excalibur Series, Agilent, Santa Clara, CA, USA) in attenuated total
reflection (ATR) mode with a mono-reflection diamond crystal (Pike MIRacle). Qualitative
reflection (ATR) mode with a mono-reflection diamond crystal (Pike MIRacle). Qualitative comparisons
comparisons were made to evaluate the consequences of the alkali treatment on the chemical
were made to evaluate the consequences of the alkali treatment on the chemical composition of the
composition of the fibers. As the cross-sectional dimensions of a given bamboo fiber can vary along
fibers. As the cross-sectional dimensions of a given bamboo fiber can vary along its length, each
its length, each fiber candidate for pull-out testing was placed between two glass slides and
fiber candidate for pull-out testing was placed between two glass slides and observed by optical
observed by optical microscopy (Olympus BX51/BX52). Several measurements (at least 5) were
microscopy (Olympus BX51/BX52). Several measurements (at least 5) were performed to determine
performed to determine the variation of the apparent diameter along the length of interest at
the variation of the apparent diameter along the length of interest at distances of around 200 µm from
distances of around 200 μm from each other. The average of the apparent diameters measured for
each other. The average of the apparent diameters measured for each bamboo fiber was considered as
each bamboo fiber was considered as its equivalent diameter, i.e., the diameter of a virtual fiber
its equivalent diameter, i.e., the diameter of a virtual fiber having a circular cross-section and the same
having a circular cross-section and the same mechanical behavior (in terms of pull-out response).
mechanical behavior (in terms of pull-out response).
The pull-out tests were performed using a Bose ElectroForce 3200 device (TA Instruments, New
The pull-out tests were performed using a Bose ElectroForce 3200 device (TA Instruments,
Castle, DE, USA) with titanium T/C grips (maximum applied force 22.5 N). The locking system was
New Castle, DE, USA) with titanium T/C grips (maximum applied force 22.5 N). The locking system
ensured by hex drive nuts, which facilitated the placement of the samples in the clamps. For each
was ensured by hex drive nuts, which facilitated the placement of the samples in the clamps. For each
sample, the free tip of the fiber was fixed with MultiTemp® glue on a cardboard tab, which was
sample, the free tip of the fiber was fixed with MultiTemp® glue on a cardboard tab, which was
clamped more easily than the fiber itself. As for the PLA thin disk, a washer was placed between the
clamped more easily than the fiber itself. As for the PLA thin disk, a washer was placed between
clamps to prevent sliding. The load vs. displacement curves were recorded by the software WinTest
the clamps to prevent sliding. The load vs. displacement curves were recorded by the software
(TA Instruments, New Castle, DE, USA). All the tests were performed with a loading rate of 0.005
WinTest (TA Instruments, New Castle, DE, USA). All the tests were performed with a loading rate of
mm/s. The sample placement on the Bose device is sketched in Figure 2b.
0.005 mm/s. The sample placement on the Bose device is sketched in Figure 2b.
A preliminary evaluation of the possibility to perform successful pull-out tests led to the
A preliminary evaluation of the possibility to perform successful pull-out tests led to the
observation of two ineffective outcomes of the test: either the fibers broke before the interface failed
observation of two ineffective outcomes of the test: either the fibers broke before the interface failed
or, less frequently, the fiber tip and/or the matrix thin disk slid between the grips. The experimental
or, less frequently, the fiber tip and/or the matrix thin disk slid between the grips. The experimental
results were classed as regular or non-regular depending not only on the global shape of the curve
results were classed as regular or non-regular depending not only on the global shape of the curve
recorded during the pull-out test, but also on the aspect of the fiber tip after extraction from the
recorded during the pull-out test, but also on the aspect of the fiber tip after extraction from the matrix
matrix and the aspect of the hole left behind. Systematic observations of the fiber tip and the holes by
and the aspect of the hole left behind. Systematic observations of the fiber tip and the holes by scanning
scanning electron microscopy (SEM) were carried out after each pull-out test to decide whether the
electron microscopy (SEM) were carried out after each pull-out test to decide whether the test was
test was successful or not, therefore helping with selection and interpretation of the curves. The
inspection of the fractured samples was carried out using an FEI Quanta 200 FEG high resolution
field emission scanning electron microscope (FEI Company, Hillsboro, OR, USA). The results classed
Fibers 2018, 6, 7 6 of 15

successful or not, therefore helping with selection and interpretation of the curves. The inspection of
the fractured samples was carried out using an FEI Quanta 200 FEG high resolution field emission
scanning electron microscope (FEI Company, Hillsboro, OR, USA). The results classed as regular,
where no obvious fibrillation occurred, were used to estimate the apparent interfacial shear strength,
as described and discussed in Section 3.

3. Results and Discussion

Pull-out tests consist of embedding a fiber in a matrix and then performing a tensile test by
gripping the free tip of the fiber (top) and the matrix (bottom) to pull them apart (Figure 2b). The result
typically expected for this kind of test is the fiber being pulled out of the matrix without breaking,
meaning that adhesive failure (debonding at the fiber/polymer interface) rather than cohesive failure
(either in the fiber or in the matrix) occurs. The force vs. displacement curves are used to determine
the shear strength at the interface between the fiber and the matrix using the Kelly–Tyson equation,
as suggested by Greszczuk (Equation (2)) [34] that can be written as:

Fdeb
τapp = (2)
πD f Lemb

where τ app (MPa) is the apparent interfacial shear strength, Fdeb (N) is the force required to debond the
fiber from the matrix, πDf (mm) is the perimeter of the fiber as Df (mm) is the diameter, and Lemb (mm)
is the length of fiber embedded into the matrix.
Equation (2) provides a value of interfacial shear strength that is apparent because it depends
on both the embedded length and the diameter of the fiber, which are usually assumed constant.
A number of issues can be seen in the application of Equation (2) to pull-out tests on vegetable
fibers. Major ones would concern the fact that the section of vegetable fibers is typically non-circular,
presenting at least some ellipticity if not a more complex shape, which may be not accounted for by the
method of diameter measurement. In practice, considering the diameter at five different locations along
the length of the fiber, as described in Section 2.2.2, led to measuring values with a standard deviation
between 0.7% and 7.5% and an average standard deviation of 3.1%. As a whole, the main concentration
of diameter values measured in this work reflected those reported by Rao and Rao [35], who found
that most mechanically extracted bamboo fibers have a diameter between 200 and 350 microns.
The experimental approach suggested in this work gives a reliable value for Lemb and the
debonding force Fdeb is measured directly: the consequence of this fact is that the fiber perimeter
πDf estimated with the assumption of a constant diameter is the parameter in Equation (2) with the
highest uncertainty. Each fiber is unique and has a shape that varies over its entire embedded length;
thus, estimates of fiber perimeter can be made only indirectly at best, unless the fiber is imaged while
embedded in the matrix for example using X-ray microtomography (µ-CT) [36].
At least five possibilities exist for estimating the contact perimeter, and each one of these has its
own advantages and disadvantages. For example, the perimeter of the hole left in the PLA matrix
by the pulled-out bamboo fiber could be estimated by SEM, but this approach lacks precision and
does not account for the fact that the perimeter is not uniform over the entire embedded length.
Another approach would be to cut the fiber before embedding and taking an image of the cross-section,
but cutting obviously introduces damage, which may reduce the fiber strength. Some authors assume
a density and estimate the total fiber length to evaluate the perimeter by weighing a group of fibers [12],
whereas others estimate the perimeter by the Wilhelmy method [34]. Finally, assumptions about the
fiber cross-sectional shape can be made, such as the projection of a virtual cross-section whose diameter
could be estimated from optical microscope images at several positions along the fiber length and that
would behave equivalently to the real cross-section. In this work, the final choice was made to assume
a circular equivalent fiber such that the perimeter is πDf with Df as the equivalent diameter, obtained
as the average of five values of apparent diameter measured at different places along each fiber from
a side view by optical microscopy. This approach is expected to give estimates for the perimeter that
Fibers 2018, 6, 7 7 of 15

are larger than reality, in a way that the final estimates for the apparent interfacial shear strength are
lower than reality (conservative estimate).
In Equation (2), τ app was interpreted as if the fiber was loaded until debonding and then completely
extracted 6, 7 the matrix. Fdeb was estimated as the maximum value of the experimental force
Fibers 2018, from vs.
7 of 15
displacement curves, whereas Lemb was evaluated by measuring the thickness of the PLA thin disk.
Figure 3 reports
thin disk. Figure two examples
3 reports twoofexamples
the typical ofload vs. displacement
the typical curves obtained
load vs. displacement in this
curves work. in
obtained In this
all
cases the fiber was completely extracted from the polymer without
work. In all cases the fiber was completely extracted from the polymer without clearly breaking. clearly breaking. Figure 3a shows
the ideal3a
Figure outcome
shows the for the
idealpull-out
outcome tests
forperformed
the pull-out in this
testswork (smoothinload
performed thisvs.workdisplacement
(smooth load curve vs.
until interface failure
displacement by fiber/polymer
curve until interface failure debonding). Results like
by fiber/polymer these areResults
debonding). the most appropriate
like these are the to
calculate Fdeb and τ app
most appropriate because none
to calculate of the
Fdeb and τappelementary
because none fibersofbreak during the test.
the elementary fibersOn the other
break duringhand,the
the
test.curve in Figure
On the other 3b reveals
hand, the that
curvesome intermediate
in Figure failure
3b reveals thatoccurred during the tensile
some intermediate failurepart of the
occurred
pull-out
during the test.tensile
In fact,part
whenever the test is
of the pull-out runInon
test. a technical
fact, whenever fiber,
thethetestinternal
is run on interfaces between
a technical fiber,thethe
elementary fibers may debond at lower loads with respect to the outer
internal interfaces between the elementary fibers may debond at lower loads with respect to the interface, and break the bundle
before debonding
outer interface, andit from
breakthethematrix.
bundleCurves like this cannot
before debonding it frombe the
assuredly
matrix.discarded,
Curves like but can
this neither
cannot be
be used to determine
assuredly discarded, τbut app according
can neither to Equation
be used to (2). In
determinethis τcase
app the stressed
according to interface
Equation is not
(2). In only
this the
case
one
the connecting the outer
stressed interface surface
is not onlyofthe
theone
technical
connectingfiber tothethe matrix,
outer but also
surface of the thetechnical
one connecting
fiber tothe the
elementary
matrix, butfibers to each
also the other withinthe
one connecting theelementary
same bundle. fibersFortothis
eachreason,
other even
within whenthe the
sameexperimental
bundle. For
curves seemedeven
this reason, correct,
when thethe
tip of each bamboo
experimental fiber extracted
curves seemed correct,from thethe PLA tipmatrix
of eachwasbamboo
observedfiber by
optical
extracted microscopy
from the (example
PLA matrix pictures on the top
was observed byright corner
optical of Figure(example
microscopy 3a,b) to identify
pictures theon failure
the top
mechanism
right cornerassociated
of Figure with
3a,b)the pull-out the
to identify testfailure
and to mechanism
get a deeperassociated
insight in thewithnature of the constraints
the pull-out test and to
experienced
get a deeperby the fiber.
insight in the nature of the constraints experienced by the fiber.

Figure 3. Typical load vs. displacement curves obtained by pull-out tests performed on bamboo fibers
Figure 3. Typical load vs. displacement curves obtained by pull-out tests performed on bamboo
embedded in a PLA matrix: (a) adhesive failure at the bamboo/PLA interface and (b) adhesive failure
fibers embedded in a PLA matrix: (a) adhesive failure at the bamboo/PLA interface and (b) adhesive
combined with cohesive failure within the bamboo fiber. The pictures on the top right corner of each
failure combined with cohesive failure within the bamboo fiber. The pictures on the top right corner
curve show the typical aspect of the fiber tips after the pull-out test: (a) regular and (b) non-regular fiber.
of each curve show the typical aspect of the fiber tips after the pull-out test: (a) regular and (b)
non-regular fiber.
Regular fibers were defined as those that did not show an obvious fibrillation, i.e., separation
of filaments,
Regularwhenfibersbeing
were extracted
defined asfromthosethe polymer
that did notmatrix
show an (Figure
obvious3a).fibrillation,
Wheneveri.e., fibrillation
separationwas of
clearly shown
filaments, whenduring
beingfiber failure sofrom
extracted that the
the tensile
polymer load could(Figure
matrix not be regarded as exclusively
3a). Whenever applied
fibrillation was
orthogonally
clearly shown to during
the fiber section,
fiber thesofibers
failure that were defined
the tensile as non-regular
load could not be (Figure 3b). as
regarded SEM images
exclusively
confirmed that successful pull-out tests were most frequently obtained from regular
applied orthogonally to the fiber section, the fibers were defined as non-regular (Figure 3b). SEM fibers, where the
fiber tip remained
images confirmedaligned with the bulk
that successful of it during
pull-out the whole
tests were loading event.
most frequently Moreover,
obtained from when thefibers,
regular fiber
behavior was non-regular, a load drop was frequently observed during loading, which
where the fiber tip remained aligned with the bulk of it during the whole loading event. Moreover, can be attributed
to the moment
when the fiberwhen the filaments
behavior started splitting
was non-regular, a loadfrom
dropeach
wasother, leadingobserved
frequently to fibrillation.
duringIn general,
loading,
fibrillation might be considered to improve fiber–matrix adhesion; as a matter
which can be attributed to the moment when the filaments started splitting from each other, leadingof fact, mechanically
induced fibrillation
to fibrillation. has beenfibrillation
In general, already used on bamboo–PLA
might be considered composites
to improve to make them more
fiber–matrix suitableastoa
adhesion;
processing techniques,
matter of fact, such asinduced
mechanically extrusion, pelletizing
fibrillation hasand subsequent
been injection
already used molding [37].composites
on bamboo–PLA However,
when fibrillation occurs, pull-out tests usually overestimate the value obtained for
to make them more suitable to processing techniques, such as extrusion, pelletizing and subsequent the interfacial shear
injection molding [37]. However, when fibrillation occurs, pull-out tests usually overestimate the
value obtained for the interfacial shear strength because mechanical interlocking could contribute to
a stronger connection of the technical fiber (through its elementary fibers) to the polymeric matrix.
Figure 4a shows the failure mode associated with non-regular pull-out-test curves; in this case,
the technical fiber partially broke instead of getting pulled out of the matrix, meaning that the
Fibers 2018, 6, 7 8 of 15

strength because mechanical interlocking could contribute to a stronger connection of the technical
fiber (through its elementary fibers) to the polymeric matrix.
Figure 4a shows the failure mode associated with non-regular pull-out-test curves; in this case, the
technical fiber partially broke instead of getting pulled out of the matrix, meaning that the bamboo/PLA
interface was
Fibers 2018, 6, 7 not necessarily stressed to failure. In contrast, Figure 4b shows the hole left in the 8matrix
of 15
by a fiber pulled out during a regular pull-out test; here, only a few elementary fibers broke, proving
fibers
that thebroke, proving
interface thatstressed
actually the interface actually
by the pullingstressed
action by
wasthe pulling action
essentially wasconnecting
the one essentially the
the outer
one
connecting
surface of thethe outer surface
technical fiber toofthe
thepolymer.
technical Itfiber to thenoticing
is worth polymer. It the
that is worth noticing
bamboo that thein
fiber shown
Figure 4a has an apparent diameter of about 200 µm, whereas the one shown in Figure 4b shown
bamboo fiber shown in Figure 4a has an apparent diameter of about 200 μm, whereas the one is much
in Figure 4b is much thicker (about 500 μm). This is quite typical and indicates that, to avoid
thicker (about 500 µm). This is quite typical and indicates that, to avoid fibrillation, fibers should not
fibrillation, fibers should not only be regularly-sized and possibly defect-free, but also rather thick.
only be regularly-sized and possibly defect-free, but also rather thick. In fact, a balance should be
In fact, a balance should be found between the cross-section resisting the uniaxial tensile stress
found between the cross-section resisting the uniaxial tensile stress (which depends exactly on the
(which depends exactly on the cross-sectional shape and size of the technical fiber) and the extent of
cross-sectional shape and size of the technical fiber) and the extent of the outer surface in connection
the outer surface in connection with the matrix (which depends essentially on the equivalent
with the matrix (which depends essentially on the equivalent diameter of the fiber and on the length
diameter of the fiber and on the length of it actually embedded in the polymeric matrix, Lemb).
of it actually embedded in the polymeric matrix, Lemb ). Considering only regular samples (12 values
Considering only regular samples (12 values out of the 39 tests reported in this work), a value τapp =
out of the 39 tests reported in this work), a value τ app = 7.0 ± 3.1 MPa was obtained.
7.0 ± 3.1 MPa was obtained.

Figure 4. SEM images of (a) a technical bamboo fiber that broke (instead of debonding) during the
Figure 4. SEM images of (a) a technical bamboo fiber that broke (instead of debonding) during the
pull-out test (apparent diameter of the fiber ca. 200 μm); (b) the hole left in the PLA matrix by a
pull-out test (apparent diameter of the fiber ca. 200 µm); (b) the hole left in the PLA matrix by a bamboo
bamboo fiber successfully pulled-out during the test (diameter of the hole ca. 500 μm); (c) the surface
fiber successfully pulled-out during the test (diameter of the hole ca. 500 µm); (c) the surface of an
of an untreated bamboo fiber (scale bar 300 μm); (d) the surface of a mercerized bamboo fiber (scale
untreated bamboo fiber (scale bar 300 µm); (d) the surface of a mercerized bamboo fiber (scale bar
bar 50 μm); (e) the loosening of a technical bamboo fiber (bundle of elementary fibers) as a
50 µm); (e) the loosening of a technical bamboo fiber (bundle of elementary fibers) as a consequence of
consequence of mercerization (scale bar 100 μm); (f) residual salts (NaOH) left behind by
mercerization (scale bar 100 µm); (f) residual salts (NaOH) left behind by mercerization in the absence
mercerization in the absence of a proper washing procedure (scale bar 50 μm).
of a proper washing procedure (scale bar 50 µm).

Tokoro et al. [20] used short bamboo fiber bundles (diameter 39.2 μm and length 215 μm before
fabrication)ettoal.
Tokoro [20] used
obtain PLA short bamboo
composites by fiber bundles
injection (diameter
molding. They 39.2 µm andmicro-droplet
performed length 215 µm before
tests to
fabrication)
evaluate τapp according to Equation (2) and found an average value of about 4.3 MPa (estimating thatto
to obtain PLA composites by injection molding. They performed micro-droplet tests
evaluate
processing according
τ appreduced bothto the
Equation (2) and
diameter and found an average
the length to 21.3 value of about
μm and 86.3 μm 4.3respectively),
MPa (estimating that
but no
processing reduced both
statistical variations werethe diameter
given and the
about these length
values. to 21.3
A clear µm and 86.3
comparison µm respectively),
is difficult but no
to make, because
statistical variations
the samples were
used for thisgiven
studyabout these values.
have larger A clear
Df (200–480 μm)comparison is difficult
and Lemb (423–790 μm)to make,
and because
the results
obtained for regular samples spread over a range going from 2.1 to 13.6 MPa. Fuentes et al. [38]
performed fiber pull-out tests on technical bamboo fibers embedded in poly(vinylidene fluoride)
(PVDF) and polypropylene (PP). The diameter of the fibers was not given, but their perimeter was
estimated by the Wilhelmy equation applied to dynamic contact-angle measurements. They
considered different Lemb (0.6 to 5 mm) and fit the experimental data with Greszczuk’s model [35],
Fibers 2018, 6, 7 9 of 15

the samples used for this study have larger Df (200–480 µm) and Lemb (423–790 µm) and the results
obtained for regular samples spread over a range going from 2.1 to 13.6 MPa. Fuentes et al. [38]
performed fiber pull-out tests on technical bamboo fibers embedded in poly(vinylidene fluoride)
(PVDF) and polypropylene (PP). The diameter of the fibers was not given, but their perimeter was
estimated by the Wilhelmy equation applied to dynamic contact-angle measurements. They considered
different Lemb
Fibers 2018, 6, 7(0.6 to 5 mm) and fit the experimental data with Greszczuk’s model [35], finding 9aofvalue 15
of ultimate interfacial shear strength of about 7.5 MPa for PVDF (polar) and 3.4 MPa for PP (non polar).
Asfor
a comparison,
PP (non polar). theAsvalue obtained the
a comparison, here is quite
value closehere
obtained to the value
is quite obtained
close for PVDF,
to the value which
obtained for is
PVDF, which
consistent is consistent
considering that PLAconsidering
is a fairlythat
polar PLA is a fairly
polymer. polar polymer.
Le Duigou et al. [39]Le Duigou etmicrobond
performed al. [39]
performed
tests microbond
on flax fibers and polytests(L-lactic
on flax acid)
fibers (PLLA),
and polyand (L-lactic acid)a (PLLA),
reported value ofand reported
interfacial a value
shear of
strength
interfacial shear strength of 15.3 ± 3.3 MPa calculated according to Equation
of 15.3 ± 3.3 MPa calculated according to Equation (2) for fibers having an aspect ratio (Lemb /Df ) of (2) for fibers having an
1.3aspect
± 0.1. ratio
Wong(Let /Df)[40]
embal. of 1.3
also± used
0.1. Wong et al.(2)[40]
Equation also usedthe
to evaluate Equation (2) to
interfacial evaluate
strength the interfacial
between flax fibers
andstrength
PLLA. between
They obtainedflax fibers and in
values PLLA. They obtained
the range 8–17 MPavalues in the out
by pulling range 8–17having
fibers MPa by Dfpulling out
in the range
fibers having D f in the range 100–160 μm and Lemb in the range 200–500 μm. The comparison of all
100–160 µm and Lemb in the range 200–500 µm. The comparison of all these values, especially when it
thesetovalues,
comes especially
Df , would when
be even it comes
more to Diff, the
difficult would be even(or
ellipticity more
even difficult
higherifgeometrical
the ellipticitycomplexity)
(or even
higher geometrical complexity) of bamboo fiber sections were, as it should be, taken into account. In
of bamboo fiber sections were, as it should be, taken into account. In fact, this would require the
fact, this would require the measurement of the exact diameter of the fractured section, an example
measurement of the exact diameter of the fractured section, an example of which is reported in Figure 5.
of which is reported in Figure 5. Such a procedure was not systematically pursued due to the
Such a procedure was not systematically pursued due to the difficulty of getting a section with obvious
difficulty of getting a section with obvious edges and as flat as possible, and may be the object of
edges and as flat as possible, and may be the object of dedicated work in the future.
dedicated work in the future.

Figure 5. SEM image of fractured section of a bamboo fiber with tentative measurement of diameter.
Figure 5. SEM image of fractured section of a bamboo fiber with tentative measurement of diameter.
The values of maximum load (Fmax) recorded during the pull-out tests of untreated bamboo
Theare
fibers values of maximum
shown in Figure 6load
as a (F max ) recorded
function during
of Df (39 the12pull-out
values, regular tests
plus of
27 untreated bamboo
non-regular). Figurefibers
6
areprovides
shown inan Figure 6 as a function
additional criterion offorDfthe
(39initial
values,selection
12 regular
of plus 27 non-regular).
the fibers: Figure
they should not 6only
provides
be
regularly-sized, defect-free and thick enough to resist the tensile stress applied to pull them out, but
on the other side also thin enough to minimize the proportion of internal interfaces (connecting the
elementary fibers and the fibrils to each other) with respect to the outer interface (connecting the
fiber to the polymer). Thicker technical fibers have more extended outer surfaces, but also many
more internal interfaces, which increases the probability of extraction by structural telescoping. The
Fmax values in Figure 6 are spread over a range of equivalent diameters from about 250 μm to almost
Fibers 2018, 6, 7 10 of 15

an additional criterion for the initial selection of the fibers: they should not only be regularly-sized,
defect-free and thick enough to resist the tensile stress applied to pull them out, but on the other
side also thin enough to minimize the proportion of internal interfaces (connecting the elementary
fibers and the fibrils to each other) with respect to the outer interface (connecting the fiber to the
polymer). Thicker technical fibers have more extended outer surfaces, but also many more internal
interfaces, which increases the probability of extraction by structural telescoping. The Fmax values in
Fibers 2018, 6, 7 10 of 15
Figure 6 are spread over a range of equivalent diameters from about 250 µm to almost one millimeter,
but regular
diameter lesstests
thanwere obtained
500 μm, only the
whatever for value
samples of Lprocessed with fibers having a diameter less than
emb. As a matter of fact, Da Costa et al. [41] already
500 µm, whatever the value of L . As a matter
observed that, when performing tensile tests on bamboo fibers
emb of fact, Da Costa et al.
with the[41]
aimalready observed
of Weibull that,
analysis,
when performing tensile tests on bamboo fibers with the aim of Weibull analysis,
thinner fibers showed a more uniform fracture associated with lesser fibrils, while fibers with larger thinner fibers showed
a more uniform
diameters would fracture associated
display with lesser
a relatively fibrils, while
non-uniform fiberswith
fracture with larger diameters
participation of would
more display
fibrils.
a relatively non-uniform fracture with participation of more fibrils. Statistically,
Statistically, the probability that one of the many fibrils of the thicker bamboo fiber would the probability that one
of the many fibrils of the thicker bamboo fiber would prematurely break and then
prematurely break and then act as a flaw to cause the fiber rupture at a lower stress is higher, when act as a flaw to cause
the fiber rupture
compared to theatthinner
a lowerfiber.
stressAs
is ahigher, when compared
consequence, it is moreto the thinner
likely fiber. As
that larger a consequence,
diameter it is
fibers have
more likely that larger diameter fibers
lower interfacial shear strength than the opposite. have lower interfacial shear strength than the opposite.

Figure 6. Values
Figure 6. Valuesofof maximum
maximum loadload (Fmax)
(Fmax) (N) recorded
(N) recorded by pull-out
by pull-out test on made
test on samples samples made of
of untreated
untreated bamboo
bamboo fibers fibers embedded
embedded in a PLA
in a PLA matrix. Thematrix.
valuesThe
are values
plottedare
as aplotted as of
function a function
the fiberof the fiber
equivalent
equivalent diameter (μm) for both regular and non-regular
diameter (µm) for both regular and non-regular samples. samples.

Pull-out tests were also performed on mercerized bamboo fibers from the same batch. Figure 4c
Pull-out tests were also performed on mercerized bamboo fibers from the same batch. Figure 4c
shows the surface of an untreated bamboo fiber. Mercerization modified the surface of the fibers
shows the surface of an untreated bamboo fiber. Mercerization modified the surface of the fibers both
both topographically and chemically. Figure 4d shows that roughness changed and Figure 4e proves
topographically and chemically. Figure 4d shows that roughness changed and Figure 4e proves that the
that the removal of the lignin loosened the bundles. The literature reports that NaOH solutions make
removal of the lignin loosened the bundles. The literature reports that NaOH solutions make the fibers
the fibers swell by attacking and destroying their non-cellulosic structure [42]. Having the
swell by attacking and destroying their non-cellulosic structure [42]. Having the elementary fibers
elementary fibers loosened is good when the objective is dispersing the bamboo fibers within a
loosened is good when the objective is dispersing the bamboo fibers within a matrix to obtain the final
matrix to obtain the final green composite; however, in terms of pull-out tests, this condition is
green composite; however, in terms of pull-out tests, this condition is probably the most complicated
probably the most complicated to interpret. Unless the elementary fibers are completely isolated
to interpret. Unless the elementary fibers are completely isolated from each other, it is hard to quantify
from each other, it is hard to quantify the extent of fiber surface actually interacting with the
the extent of fiber surface actually interacting with the polymer and efficiently stressed during the
polymer and efficiently stressed during the pull-out test. In addition, Figure 4f shows that
pull-out test. In addition, Figure 4f shows that mercerization, if not followed by a thorough washing
mercerization, if not followed by a thorough washing procedure, leaves residual salts on the surface
procedure, leaves residual salts on the surface of the fibers, which is a drawback of the treatment.
of the fibers, which is a drawback of the treatment.
The chemical effects of mercerization were investigated by FTIR spectroscopy. Figure 7A shows
The chemical effects of mercerization were investigated by−1FTIR spectroscopy. Figure 7A shows
the FTIR spectra of bamboo fibers between 2000 and 600 cm : (a) before the treatment; (b) right
the FTIR spectra of bamboo fibers between 2000 and 600 cm−1: (a) before the treatment; (b) right after
after the treatment (without washing); and (c) when the treatment was followed by careful washing
the treatment (without washing); and (c) when the treatment was followed by careful washing and
and filtering. Figure 7B reports the relative FTIR spectra between 4000 and 2000 cm− 1 , where only
filtering. Figure 7B reports the relative FTIR spectra between 4000 and 2000 cm−1, where only
−1
stretching vibration peaks of =C-H and –C-H are observed around 3300 and 2900 cm .
stretching vibration peaks of =C-H and –C-H are observed around 3300 and 2900 cm−1.
The absorption bands were assigned on the basis of the data reported in the literature about
different ligno-cellulosic materials (hemp hurds [43] and fibers [44], wheat straw nanofibers [45], oil
palm fibers [46], bamboo fibers [47], wood [48,49]). In the range between 1800 cm−1 and 800 cm−1 it is
possible to find evidence of the chemical modification of the fibers, mostly consisting of the removal
of lignin and hemicellulose and the purification of crystalline cellulose. The inset zooms in a range
showing a reduction of the bands typically assigned to hemicellulose (1740 cm−1) and lignin (1725
and 1595 cm−1, vibrations of the carbonyl groups and of the aromatic rings of phenyl propane,
 due to crystalline cellulose (COC asymmetrical stretching). The peak between 1150 cm−1 and 950 cm−1
contains many contributions: it is particularly noteworthy the slight shift of the main peak from 1031
cm−1 (in-plane deformation of CH bonds from lignin) to 1023 cm−1 (stretching vibration of CO bonds
in crystalline cellulose), which could be a further sign of successful mercerization. Additionally, the
Fibers 2018, 6, FTIR
smoothest 7 11 of 15
spectra were recorded on the fibers that were carefully washed and filtered (Figure
7Ac), which is in agreement with the comment about Figure 4f.

(A)

(B)
Figure7.7.(A)
Figure (A)FTIR
FTIRspectra
spectrabetween
between2000 2000and
and600
600cm cm−−1 obtained for
1 obtained for (a)
(a) bamboo
bamboo fibers
fibersin
intheir
theirpristine
pristine
state (untreated), (b) mercerized bamboo fibers (treated unwashed) and (c) mercerized
state (untreated), (b) mercerized bamboo fibers (treated unwashed) and (c) mercerized bamboo fibers bamboo fibers
after washing plus filtering (treated washed filtered). The inset shows a zoom of
after washing plus filtering (treated washed filtered). The inset shows a zoom of the absorption bands the absorption
bands
from from
1800 1800 cm
to 1550 to 1550 cmFTIR
− 1 . (B) −1. (B) FTIR spectra between 4000 and 2000
spectra between 4000 and 2000 cm− 1 obtained cm−1 obtained
for (a) for (a) bamboo
bamboo fibers
fibers
in their in their pristine
pristine state (untreated);
state (untreated); (b) mercerized
(b) mercerized bamboo
bamboo fibers fibers
(treated (treated unwashed)
unwashed) and (c)
and (c) mercerized
mercerized
bamboo bamboo
fibers fibers after
after washing pluswashing
filteringplus filtering
(treated (treated
washed washed filtered).
filtered).

A total of 17 pull-out tests were performed on mercerized bamboo fibers; seven of them were
The absorption bands were assigned on the basis of the data reported in the literature about
considered as regular and interpreted, resulting in a value of τapp = 5.3 ± 3.3 MPa (lower than the
different ligno-cellulosic materials (hemp hurds [43] and fibers [44], wheat straw nanofibers [45], oil
value obtained for the untreated fibers). It appears that mercerization does not necessarily improve
palm fibers [46], bamboo fibers [47], wood [48,49]). In the range between 1800 cm− 1 and 800 cm− 1
the interface between ligno-cellulosic fibers and polymers, even though previous literature suggests
it is possible to find evidence of the chemical modification of the fibers, mostly consisting of the
removal of lignin and hemicellulose and the purification of crystalline cellulose. The inset zooms in
a range showing a reduction of the bands typically assigned to hemicellulose (1740 cm− 1 ) and lignin
(1725 and 1595 cm− 1 , vibrations of the carbonyl groups and of the aromatic rings of phenyl propane,
respectively). The hatched area on the inset identifies the absorption bands assigned to the bending
vibration of the hydroxyl groups of water absorbed by holocellulose. The first hatched area on the main
graph includes the stretching vibrations of the hydroxyl groups of water absorbed by holocellulose,
but also the bending and stretching vibrations of CH and CO bonds in the aromatic rings of crystalline
cellulose. The second hatched area contains the out-of-plane stretching vibrations of CH bonds in the
Fibers 2018, 6, 7 12 of 15

aromatic rings of crystalline cellulose, as well as the stretching vibrations of CH and COC bonds in
the β-(1,4)-glycosidic linkages between the anhydroglucose units. Polymorphism has already been
documented for NaOH-treated cellulose [50]. The absorption band at 1160 cm− 1 is due to crystalline
cellulose (COC asymmetrical stretching). The peak between 1150 cm− 1 and 950 cm− 1 contains many
contributions: it is particularly noteworthy the slight shift of the main peak from 1031 cm− 1 (in-plane
deformation of CH bonds from lignin) to 1023 cm− 1 (stretching vibration of CO bonds in crystalline
cellulose), which could be a further sign of successful mercerization. Additionally, the smoothest FTIR
spectra were recorded on the fibers that were carefully washed and filtered (Figure 7Ac), which is in
agreement with the comment about Figure 4f.
A total of 17 pull-out tests were performed on mercerized bamboo fibers; seven of them were
considered as regular and interpreted, resulting in a value of τ app = 5.3 ± 3.3 MPa (lower than the
value obtained
Fibers 2018, 6, 7 for the untreated fibers). It appears that mercerization does not necessarily improve 12 the
of 15
interface between ligno-cellulosic fibers and polymers, even though previous literature suggests the
opposite. An attempt
the opposite. to evaluate
An attempt the influence
to evaluate of mercerization
the influence on the quality
of mercerization on the of quality
the interfaceof thewas made
interface
by interpreting the statistics of the two populations of data via the student’s
was made by interpreting the statistics of the two populations of data via the student’s t-test. The t-test. The test gave a valuetest
of p = 0.22,
gave a valuemeaning
of p = that
0.22,inmeaning
this casethat mercerization
in this case has no significanthas
mercerization impact on the results
no significant impact(theon limitthe
being
resultsat (the
0.05).limit
Scatter
beingplots of the Scatter
at 0.05). values of the of
plots apparent interfacial
the values of the shear strength
apparent τ app asshear
interfacial a function
strength of
the equivalent diameter D
τapp as a function of the equivalent
f and the embedded length
diameter Df and theemb L are provided in Figure 8 for
embedded length Lemb are provided in Figure 8both untreated
and
for treated bamboo fibers.
both untreated No obvious
and treated bamboo mathematical
fibers. No relationships can be pointed
obvious mathematical out. Figure
relationships can 8a be
shows
pointed that,
out. except
Figurefor8atwo points,
shows that, theexcept
alkali for
treatment limitsthe
two points, data dispersion
alkali treatment by restraining
limits data the values
dispersion
ofbyboth the apparent
restraining diameters
the values of both (350thetoapparent
400 µm) diameters
and the obtained
(350 to apparent
400 μm) and interfacial
the obtainedshear strength
apparent
(3interfacial
to 5 MPa)shear to narrower
strengthranges.
(3 to 5As MPa)for the embedded
to narrower lengthAs
ranges. (Figure
for the8b), the alkalilength
embedded treatment had 8b),
(Figure no
statistical effect because
the alkali treatment had no L depends only on sample processing, and the experimental
embstatistical effect because Lemb depends only on sample processing, and the procedure
used in this work
experimental was designed
procedure used within thisthework
purpose wasofdesigned
controlling it. In
with theconclusion,
purpose of definite indications
controlling it. In
that mercerization
conclusion, is actually
definite indicationsimproving the interface between
that mercerization is actuallybamboo fibers the
improving and interface
PLA matrix were
between
not obtained
bamboo fibersin this
andwork.
PLA The matrixopposite
were result had been
not obtained inobtained
this work. on traditional
The opposite oil-based
result polyester
had been
matrices
obtaineddespite the factoil-based
on traditional that the polyester
alkali treatment
matrices reduces
despitethetheductility
fact that ofthebamboo fibers [51].
alkali treatment It is
reduces
proposed
the ductilitythat ofthebamboo
decreased ductility,
fibers [51]. together with the
It is proposed inherent
that brittleness
the decreased of PLA, together
ductility, could have withled the
to
an early pull-out
inherent brittlenessof the
of fibers, resulting
PLA, could haveinled
a weaker interface;
to an early but this
pull-out would
of the fibers,need to be confirmed
resulting in a weaker in
further studies.
interface; but this would need to be confirmed in further studies.

Figure8.8.Apparent
Figure Apparentinterfacial
interfacialshear
shearstrength
strength(MPa)
(MPa)between
betweenPLA
PLAand
andbamboo
bamboofibers
fibers(both
(bothuntreated
untreated
and mercerized)
and mercerized) as aa function
functionofof(a)(a)equivalent diameter
equivalent (μm)
diameter andand
(µm) (b) embedded length
(b) embedded (μm).(µm).
length Only
Only regular
regular samples
samples are represented.
are represented.

4.4.Conclusions
Conclusions
Inthis
In this work, aa procedure
procedurewas
wasdescribed
describedtoto
measure
measure thethe
apparent interfacial
apparent shear
interfacial strength
shear from
strength
pull-out tests on both untreated and mercerized bamboo technical fibers from
from pull-out tests on both untreated and mercerized bamboo technical fibers from the the same batch,
batch,
embedded in the same poly(lactic acid) (PLA) matrix. It was found that to acquire sufficiently
reliable measurements of interfacial shear strength on common batches of natural fibers in use in
composites, an improved control on the length of fiber embedded in the polymer matrix is needed.
The results of the pull-out tests were sorted and classified on the basis of several criteria: the shape of
the load vs. displacement curves; the aspect of the fiber tips before and after the pull-out tests; and
Fibers 2018, 6, 7 13 of 15

embedded in the same poly(lactic acid) (PLA) matrix. It was found that to acquire sufficiently reliable
measurements of interfacial shear strength on common batches of natural fibers in use in composites,
an improved control on the length of fiber embedded in the polymer matrix is needed. The results of
the pull-out tests were sorted and classified on the basis of several criteria: the shape of the load vs.
displacement curves; the aspect of the fiber tips before and after the pull-out tests; and the hole left
in the matrix by the pulled-out fiber. Data selection, treatment and interpretation were discussed by
comparing the results obtained with reference to the occurrence or not of fibrillation during pull-out.
The results showed that ideal bamboo fibers for pull-out tests should be not only regularly-sized (little or
no variation of their cross-sectional shape and size as a function of the fiber length), defect-free on the outer
surface, and thick enough to resist the tensile stress without breaking, but also thin enough to minimize
the risk of extraction by structural telescoping and the occurrence of volume defects (fiber diameter
should be in the range 250–500 µm). Mercerization modified both the surface topography and chemical
composition of the fibers, and eventually led to a finer control over the apparent fiber diameter, but did
not improve the stress transfer at the interface with the polymer (τapp = 7.0 ± 3.1 MPa and 5.3 ± 2.4 MPa
for untreated and treated bamboo fibers respectively).

Acknowledgments: The authors would like to thank Benoît Lefez for acquiring FTIR spectra and Brahim Mazian
for taking images of fiber cross-sections.
Author Contributions: Quentin Viel performed the experiments both in France and in the US, then processed
the data. Antonella Esposito conceived and designed the experiments, then coordinated the discussion of the
results within the group of collaborators. Jean-Marc Saiter obtained the raw fibers and made it possible for
Quentin Viel to go to the US. Carlo Santulli contributed to the discussion of the results and the submission of the
final manuscript. Joseph A. Turner provided the equipment and analysis tools that were used by Quentin Viel
to perform the experiments, he also supervised the experiments and contributed to the discussion of the results.
Quentin Viel and Antonella Esposito wrote the paper, which was successively proofread by all the co-authors.
English proofreading was ensured by Joseph A. Turner.
Conflicts of Interest: The authors declare no conflict of interest.

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