A study of the mechanical properties of short natural-ber

reinforced composites
P.J. Herrera-Franco
*
, A. Valadez-Gonzalez
Centro de Investigacion Cient ca, de Yucatan A.C., Division de Materiales, Calle 43 # 130, Col. Chuburna de Hidalgo, C.P. 97200 Merida, Yucatan, Mexico
Received 10 January 2005; accepted 10 April 2005
Available online 22 June 2005
Abstract
The degree of bermatrix adhesion and its effect on the mechanical reinforcement of short henequen bers and a polyethylene matrix was
studied. The surface treatments were: an alkali treatment, a silane coupling agent and the pre-impregnation process of the HDPE/xylene
solution. The presence of SiOcellulose and SiOSi bonds on the lignocellulosic surface conrmed that the silane coupling agent was
efciently held on the bres surface through both condensation with cellulose hydroxyl groups and self-condensation between silanol groups.
The bermatrix interface shear strength (IFSS) was used as an indicator of the bermatrix adhesion improvement, and also to determine
a suitable value of ber length in order to process the composite with relative ease. It was noticed that the IFSS observed for the different ber
surface treatments increased and such interface strength almost doubled only by changing the mechanical interaction and the chemical
interactions between ber and matrix.
HDPE-henequen ber composite materials were prepared with a 20% v/v ber content and the tensile, exural and shear properties were
studied. The comparison of tensile properties of the composites showed that the silane treatment and the matrix-resin pre-impregnation
process of the ber produced a signicant increase in tensile strength, while the tensile modulus remained relatively unaffected. The increase
in tensile strength was only possible when the henequen bers were treated rst with an alkaline solution. It was also shown that the silane
treatment produced a signicant increase in exural strength while the exural modulus also remained relatively unaffected. The shear
properties of the composites also increased signicantly, but, only when the henequen bers were treated with the silane coupling agent.
Scanning electron microscopy (SEM) studies of the composites failure surfaces also indicated that there is an improved adhesion between
ber and matrix. Examination of the failure surfaces also indicated differences in the interfacial failure mode. With increasing bermatrix
adhesion the failure mode changed from interfacial failure and considerable ber pull-out from the matrix for the untreated ber to matrix
yielding and ber and matrix tearing for the alkaline, matrix-resin pre-impregnation and silane treated bers.
q 2005 Elsevier Ltd. All rights reserved.
Keywords: (C)Resin; Fibermatrix
1. Introduction
Cellulosic bers, like henequen, sisal, coconut ber
(coir), jute, palm, bamboo, wood, paper in their natural
condition, as well as, several waste cellulosic products such
as shell our, wood our and pulp have been used as
reinforcement agents of different thermosetting and thermo-
plastic resins [18].
During the decortication of the henequen leaves, and also
during the transformation of the raw bers into cordage,
approximately a 10% of waste is produced. These waste
bers could be protably used in the manufacture of short-
ber polymer reinforced composites because they posses
attractive physical and mechanical properties [9]. These
waste bers are composed of w60% of cellulose pulps
which are easily obtained and could also be used to
reinforce polymeric materials.
Unlike the traditional engineering bers, e.g. glass and
carbon bers, and mineral llers, these lignocellulosic bers
are able to impart the composite certain benets such as low
density, less machine wear during processing than that
produced by mineral reinforcements, no health hazards, and
a high degree of exibility. The later is especially true
because these bers, unlike glass bers, will bend rather
than fracture during processing. Whole natural bers
Composites: Part B 36 (2005) 597608
www.elsevier.com/locate/compositesb
1359-8368/$ - see front matter q 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.compositesb.2005.04.001
* Corresponding author.
E-mail address: pherrera@cicy.mx (P.J. Herrera-Franco).
undergo some breakage while being intensively mixed with
the polymeric matrix, but this is not as notorious as with
brittle or mineral bers. Also, natural bers impart the
composite high specic stiffness and strength, a desirable
ber aspect ratio, biodegradability, they are readily
available from natural sources and most important, have a
low cost per unit volume basis. It should also be mentioned
that the hollow nature of vegetable bers may impart
acoustic insulation or damping properties to certain types of
matrices.
One difculty that has prevented a more extended
utilization of the henequen bers is a lack of a good
adhesion to most polymeric matrices. The hydrophilic
nature of natural bers adversely affects adhesion to a
hydrophobic matrix and as a result, it may cause a loss of
strength. To prevent this, the ber surface has to be modied
in order to promote adhesion.
Several methods to modify the natural ber surface such
as: graft copolymerization of monomers onto the ber
surface, the use of maleic anhydride copolymers, alkyl
succinic anhydride, stearic acid, etc. have been proposed. It
is also known that the use of coupling agents such as silanes,
titanates, zirconates, triazine compounds, etc. also improves
bermatrix adhesion [1014]. Furthermore, is has been
proven that pre-impregnation of the ber with the polyolen
solution will also improve bermatrix adhesion [15]. The
mechanical properties of a ber-reinforced polymer com-
posite depend not only on the properties of constituents, but
also on the properties of the region surrounding the ber
known as the interphase. Stress transfer from the matrix to
the ber takes place at such interphase and, therefore, it is
important to characterise its properties to better understand
the performance of the composite. In this paper, the degree
of mechanical reinforcement for a thermoplastic matrix that
can be achieved with short-natural bers by modifying the
ber surface by different treatments and the optimization of
the composite material properties is studied. The chemical
surface modication of henequen bres was carried out
using an organofunctional silane coupling agent in a
methanol/water medium. Heat treatment (curing) was
applied after reaching the equilibrium adsorption of the
pre-hydrolysed silane onto the lignocellulosic substrate. The
modied bers were then characterised by diffuse reec-
tance infrared spectroscopy (DRIFT).
1.1. Characteristics of the henequen bers (Agave
fourcroydes)
Depending on their origin, natural bers can be grouped
into bast (jute, banana, ax, hemp, kenaf, mesta), leaf
(pineapple, sisal, henequen, screw pine) and seed or fruit
bers (coir, cotton, oil palm). Cellulose is the main
component of the henequen bers and the elementary unit
of a cellulose macromolecule is anhydro d-glucose, which
contains three hydroxyl (OH) groups. These hydroxyl
groups form hydrogen bonds inside the macromolecule
itself (intramolecular) and between other cellulose macro-
molecules (intermolecular).
The characteristics of henequen bers have been studied
by several authors. The chemical analysis of the bers
indicated that their main component is cellulose (60%),
hemicellulose (28%), lignin (8%), extractives (4%). The
structural arrangement of these components in the ber, as
in other natural hard bers, is in such a way that lignin acts
as a cementant matrix for the cellulosic bers, which posses
their own structure. The mechanical properties of the
henequen bers are a consequence of such structural
arrangement. The mechanical properties of the henequen
bers are: tensile strength, 500G70 MPa, strain at break,
4.8G1.1% and Youngs modulus, 13.2G3.1 GPa.
2. Materials and experimental procedures
High density polyethylene, HDPE (Petrothene) extrusion
grade, was supplied by Quantum Chemical Inc. A melt ow
index (MFI) for the HDPE of 0.33 g/10 min was determined
following the ASTM standard D-1238-79 at 190 8C and
using a weight of 2160 g. A density for the HDPE of
0.96 g/cm
3
was determined following the ASTM standard
D-792-86, using benzene as an immersion liquid. The
melting point (135 8C) was determined in a DSC-7 Perkin
Elmer calorimeter.
Henequen bers with an average diameter of 180 mm,
approximately, were used in the form of short bers (6 mm
long) and it was supplied by Desbradora Yucateca, S.A.
(DESFIYUSA Co.) of Merida, Yucatan, Mexico.
Sodium hydroxide and xylene, reagent grade from
Tecnica Qu mica S.A., were used for the various surface
treatments. As a coupling agent, vinyltris (2-methoxy-
ethoxy) silane (Silane A-172) from Union Carbide was
used. Dicumyl Peroxide from Polyscience was used as
catalyst to the reaction between the silane coupling agent
and the polymer.
2.1. Fiber surface treatments
The nomenclature for the different henequen ber
surface treatments used is shown in Table 1.
Table 1
Nomenclature used for the different bre surface treatments
Keyword Description
Fib Fiber without treatment
FIBNA Fiber treated with a NaOH aqueous solution
FIBPRE Fiber pre-impregnated with dissolved HDPE
FIBNAPRE Fiber treated with a NaOH aqueous solution and then
pre-impregnated with dissolved HDPE
FIBSIL Fiber treated with a silane coupling agent
FIBNASIL Fiber treated with a NaOH aqueous solution and then
with a silane coupling agent
P.J. Herrera-Franco, A. Valadez-Gonzalez / Composites: Part B 36 (2005) 597608 598
2.2. Treatment with NaOH
The bers were treated with a NaOH aqueous solution
(2% w/v) for 1 h at 25 8C, then, they were washed with
distilled water until all the sodium hydroxide was
eliminated, that is, until the water no longer indicated any
alkalinity reaction. Subsequently, the bers were dried at
60 8C for 24 h.
2.3. Treatment with a silane coupling agent
For the ber surface treatment with the coupling agent,
1% silane and 0.5% dicumyl peroxide (Polyscience), weight
percentage with respect to the ber, were dissolved for their
hydrolysis in a mixture of methanolwater (90/10 w/w) at
25 8C. The pH of the solution was adjusted to 3.5 with acetic
acid with continuous stirring for 10 min. Then, the bers
were immersed in the solution and left for 1 h under
agitation. Afterwards, the bers were dried at 60 8C for 24 h
and at 120 8C for 2 h.
2.4. Surface pre-impregnation with a polyethylene dilute
solution
The henequen bers were pre-impregnated with a
1.5% w/w HDPE/xylene solution as follows: HDPE in
powder form was dissolved in xylene at 110 8C in a Kettle
reactor by continuously stirring it with a magnetic bar. The
natural bers were placed in a stainless-steel basket and
carefully immersed in the hot solution and stirred continu-
ously for 1 h. Then, the basket was removed and the lumps
of bers were transferred to a at tray and kept in an oven at
60 8C for 24 h to allow evaporation of the solvent. The
lumps of impregnated bers were dispersed before blending
them with the matrix.
2.5. Composites processing
A 20% v/v ber content HDPE-henequen ber compo-
site was chosen in order to determine the effect of the
different surface treatments on its mechanical properties.
The henequen bers were incorporated into the HDPE
matrix, at 180 8C using a Brabender Plasticorder intensive
mixer, model PL330. The mixing process was performed in
the following order. First, one half of the HDPE was placed
inside the mixing chamber for about 1 min at 30 rpm; then
henequen bers were added over a period of 3 min. Then,
the other half of the HDPE was placed inside the mixing
chamber and the mixing speed was increased to 60 rpm for
5 min. The total mixing time process was 10 min. The
resulting material was compression molded at a pressure of
1 ton using a Carver laboratory press and a temperature of
180 8C. The specimens for the mechanical test were
obtained from these laminates according to ASTM
standards.
2.6. Fibermatrix adhesion characterization
2.6.1. Fiber pull-out
Is a direct method used for the characterization of the
bermatrix interphase and relies on the use of single ber
matrix adhesion and detection of failure modes. In this test
the ber is pulled out of the matrix (Fig. 1), which can be
Fig. 1. Schematic representation of the micromechanical techniques used
for the determination of the interfacial shear strength measurement: (a)
pull-out test; and (b) single ber fragmentation test.
P.J. Herrera-Franco, A. Valadez-Gonzalez / Composites: Part B 36 (2005) 597608 599
a block of resin, a disc, or a droplet [16]. In this case, one
end of the ber was embedded in the middle plane of a plate
made from the resin. The bers were rst aligned on a plate
and a second one was used to complete the assembly. The
samples were made using compression molding at a
pressure of 1 ton using a Carver laboratory press and a
temperature of 180 8C. The load and displacements were
monitored continuously and upon ber pull-out, the load (P)
registered at debonding was converted into an average
interfacial shear strength (t) by
t Z
P
pdL
where d is the ber diameter, L is the embedded length of
the ber. The force was applied by holding one end of the
resin plate xed and pulling from the free end of the ber
using an Instron Universal Testing Machine Model 1125,
equipped with a 50 kg load cell, after conditioning at 25 8C
and a loading speed of 0.02 mm/min was used.
2.6.2. Single ber fragmentation
In this method, a single-ber coupon is loaded in tension
to determine the stress transfer efciency at the bermatrix
interphase. Upon load application, the tensile stress on the
ber (s
f
) increases and fragmentation occurs at points where
its tensile strength is reached. This fragmentation process
continues as the applied stress is continuously increased. At
some point, the ber fragments become so short that stress
transferred to the ber though the interface is no longer high
enough to cause any further ber breakage. When this
occurs, it is said that a critical ber fragment length (l
c
) has
been reached [16]. To a rst approximation, the interface
shear strength (t) is calculated from a simple relationship
obtained from a force balance on a ber fragment and the
recognition of the random nature of the ber-fragmentation
process as:
t Z
s
f
2b
G 1 K
1
a

here G is the gamma function, a and b are Weibull shape
and scale parameters.
2.7. Mechanical properties
Both, tensile and exural tests were performed using an
Instron Universal Testing Machine Model 1125, equipped
with a 500 kg load cell, after conditioning at 25 8C
according to ASTM standards D638 and D790, respectively.
The cross-head speed used for the type IV tensile specimens
was 5 mm/min. For the Flexural test (three point bending) a
specimen with nominal dimensions of 50!25!2 mm
3
, a
span of 32 mm and a cross-head of 1 mm/min were used.
The Iosipescu Shear Test was carried out following the
ASTM D-5379 standard using a Wyoming Shear Test
Fixture adapted to the Instron machine, after conditioning at
25 8C. The Iosipescu shear test specimens were cut from the
laminates obtained previously, and the dimensions of
specimens were 76 mm of length, 19 mm of wide, 2 mm
of thickness and the distance between the two 908 notches
was 12 mm. The cross-speed used was 0.5 mm/min.
2.8. Infrared spectroscopy (FTIR)
The FTIR analysis was performed using a Nicolet model
Protege 460 Magna IR spectrometer. Diffuse reectance
spectroscopy (DRIFTS), with a deuterated triglycine
sulphate (DTGSKBr) detector, was used. In order to
obtain a good resolution spectra it was necessary to mill the
henequen bers to an average length of 0.2 mm. The milled
bers were then mixed with an analytical grade KBr and the
spectra were recorded with a 2 cm
K1
resolution and 200
scans.
2.9. Scanning electron microscopy
The failure surfaces of shear for specimens will be used
to illustrate the effect of the different ber surface treatments
and their effect on the effective properties of the composite.
This analysis was performed using a Zeiss DSM 940A
Scanning Electron Microscope (SEM). Fracture surfaces of
the composite samples were coated with gold and then
analyzed using the SEM operated at 20 keV.
3. Results and discussion
3.1. Surface treatments
3.1.1. Alkaline treatment
Alkaline treatments, similarly as with other lignocellu-
lose bers, induced variation in the physicochemical
properties of henerquen bers. Valadez et al. using [18]
FTIR and TGA pointed out that these lignocellulosic bers
can experience a signicant weight loss due to the partial
dissolution of hemicellulose, lignin and pectin. They clearly
identied that the band around 1730 cm
K1
, corresponding
to hemicellulose, disappears when the ber is treated by a
dilute NaOH aqueous solution. The DRIFT spectra of FIB
and FIBNA and their subtraction in the region between 1500
and 650 cm
K1
are shown in Fig. 2. It could be appreciated
that the strong band at 1240 cm
K1
disappears whereas two
bands become evident, the doublet at 1200 and 1230 cm
K1
.
These behavior has been associated to the mercerization of
lignocellulosic bres [19,20]. Mercerization removes waxy
epidermal tissue, adhesive pectins and hemicelluloses that
bind ber bundles to each other and to the pectin and
hemicellulose rich sheats of the core [21]. In Fig. 3, features
of the bers surfaces are shown. A comparison between the
native ber and the alkaline treated one reveals topogra-
phical changes because of the removal of low molecular
weight compounds resulting in a formation of a rougher
P.J. Herrera-Franco, A. Valadez-Gonzalez / Composites: Part B 36 (2005) 597608 600
surface. One of the consequences of the topographical
change is an increment of the surface area.
3.2. Silane treatment
The spectra in the 1500600 cm
K1
range, for FIBSIL
and FIBNASIL and their subtraction spectra are shown in
Fig. 3. The broad intense bands around 1200 was assigned to
the stretching of the SiOcellulose and the absorption
bands at 700 and at 765 cm
K1
, were assigned to the SiO
Si bonds [18,19,2325]. It should be noted that the
intensity of these bands was more evident after the curing
at 120 8C, suggesting that both the grafting of silane onto
cellulose and the intermolecular condensation between
adjacent adsorbed SiOH groups had been substantially
enhanced. The peaks near 1060 cm
K1
are related to residual
unhydrolysed Siethoxymethoxy groups and their small
intensity, compared to those of the spectrum of the
hydrolysed A-172 (not shown), suggested that most of the
silane adsorbed under our conditions had been hydrolysed.
These peak assignments are in agreement with those
reported in other studies dealing with glass surfaces treated
with the same coupling agents [26,27]. These ndings
suggest that the condensation reaction between the hydro-
lysed silane and the henequen ber was carried out in a
greater extent in FIBNASIL than FIBSIL (see Fig. 4).
3.3. Stress transfer at the interface between the short ber
and the matrix
Generally, the best mechanical properties in a composite
depend mainly on ber orientation, but the adhesion
between the ber and the matrix is also important. This is
especially true for short ber reinforced composites. The
bers are loaded through the matrix and for good
performance, the load must be transferred effectively to
the ber, and a strong ber/matrix bond is required.
The micromechanical events that occur for a long ber
reinforced composite are not the same as those observed for
a short reinforced composite. In a short ber there are
variations in stress distribution along the bermatrix
interface, and end effects can be neglected in the case of
long bers, but they can be very important in the case of
short ber reinforced composites. Additionally, because the
bers are not oriented parallel to the applied loads, ber
matrix adhesion should be studied more carefully. Table 2
Table 2
Fiber critical length and ber aspect ratio obtained for the different surface
treatments
Fiber sur-
face treat-
ment
Critical
length (mm)
Fiber aspect
ratio (l
c
/df)
IFSS pull-
out (MPa)
IFSS SFFT
(MPa)
FIB 12.96 72 2.5 5.4
FIBPRE 11.40 63.33 4.2 5.0
FIBNA 9.25 51.38 3.5 6.0
FIBNAPRE 6.00 33.33 4.0 9.2
FIBSIL 5.45 30.27 3.75 11.9
FIBNASIL 3.50 19.44 5.0 16.0
1500 1350 1200 1050 900 750
0.0
0.1
0.2
0.3
0.4
1600 1400 1200 1000 800 600
0.0
6
5
0
1
3
7
0
7
0
0
1
3
2
0
1
4
3
0
1
0
6
0
1
1
1
1
1
1
6
1
1
2
0
0
1
2
4
0
1
2
3
0
8
9
5
A
b
s
o
r
b
a
n
c
e
(
a
.
u
)
Wavenumber(cm
1
)
FIB
FIBNA
7
0
0
1
2
4
0
1
3
7
0
9
6
5
8
9
5
A
b
s
o
r
b
a
n
c
e
(
a
.u
)
Wavenumber(cm
1
)
1
Fig. 2. Fourier Transform Infrared (FTIR) spectra for untreated henequen
bers (FIB) and a Na(OH) aqueous solution treated bers (FIBNA).
Fig. 3. SEM photomicrographs of henequen bers for (a) untreated
henequen bers (FIB) and (b) Na(OH) aqueous solution treated bers
(FIBNA), showing their surface features.
P.J. Herrera-Franco, A. Valadez-Gonzalez / Composites: Part B 36 (2005) 597608 601
shows ber critical lengths and ber aspect ratios obtained
for the different ber surface treatments, obtained using the
single ber fragmentation test.
For all the surface-treated bers there was a noticeable
decrease of the ber critical length as compared to that
measured for the untreated bers. For the untreated bers
(FIB), an average critical length value of 12.96 mm was
obtained, 6 mm for the pre-impregnated ber (FIBNAPRE)
and 3.5 mm for the silane treated ber (FIBNASIL). The
dimension of the ber critical length is important from
several points of view. First, it is convenient to select a
suitable ber length in order to allow for an adequate ow of
the molten composite material during processing. This will
avoid the development of excessive temperature in the
composite. Especially during injection or extrusion, extre-
mely high pressures are developed, and consequently, very
shear stresses can produce ber breakage or splitting.
The increase in the respective calculated IFSS values
were 5.4 MPa (FIB), 9.2 MPa for FIBNAPRE and 16.0 MPa
in the case of FIBNASIL. The initial treatment with the
aqueous solution of NaOH removed some lignin and
hemicelluloses from the ber surface, thus, the ber surface
area also increased. Such ber surface increase resulted in a
larger area of contact between the ber and the matrix.
Then, the hydroxyl groups on the cellulose bers could
better react with the silane-coupling agent because a larger
number on possible reaction sites were available. It is
interesting to note that even though a pre-impregnation of
the ber with a solution of the matrix ensures a better ber
wetting, there was a decrease of the measured ber critical
length, and the corresponding increase of the IFSS, does not
seem to improve considerably.
Typical curves of average interfacial shear stress versus
displacement are shown in Fig. 5. It can be noted that all the
curves shown in this gure exhibit the non-linear behavior
characteristic of a ductile matrix. However, once the load
reaches its maximum value there are clearly signicant
differences in the way of these curves drop. It can be seen
that during the pull-out process the debond force follows a
linear behavior but the slope differs between them
depending on the bermatrix interactions. For the
untreated and the alkaline solution treated henequen bers,
it can be seen that after reaching the maximum force value,
then, there is a smooth transition and a decrease in a linear
fashion until the total embedded length of ber is pulled-out.
This behavior agrees well with the behavior of a poor
interphase that results as a consequence of the incompat-
ibility of the hydrophilic ber and hydrophobic matrix.
In the case of a combination of the alkaline solution and
the matrix-pre-impregnation treatment, the pull-out force
was higher than that observed for the previous ber
treatments. After reaching a maximum the pull-out process
takes place more rapidly but some frictional effects could be
mentioned. That is, after failure of the interphase, the ber
can be extracted in a controlled way and the friction
measured up to the nal point [14]. In the case of the ber
treated with the alkaline solution and the silane coupling
agent, the pull-out force was higher that the previous
treatments, but the interphase failed and pull-out process
occurred catastrophically.
From the load-embedded length curve two character-
istics should be noted: the initial portion of the curve is
linear only in a very small portion and that the slope varies
for each surface treatment. The rst is indicative of a ductile
interphase behavior and the second that the interaction
between ber and matrix is different for each treatment.
Several authors [15,28,29] have pointed out that the
silanization of the natural bers modies the surface
properties and increases the bermatrix interaction. The
silane used in this study has two functional groups: an
ethoxymethoxy group able to react with hydroxil groups of
1500 1350 1200 1050 900 750
0.0
0.1
0.2
0.3
0.4
1500 1350 1200 1050 900 750 600
0.1
0.0
0.1
1
1
0
0
1
0
6
1
1
3
7
0
1
3
3
0
1
2
4
0
8
4
0
7
0
0
7
6
5
A
b
s
o
r
b
a
n
c
e
(
a
.
u
)
Wavenumber(cm
1
)
FIBSIL
FIBNASIL
1
1
0
0
7
6
5
7
0
0
6
6
5
1
2
4
0
1
2
0
0
1
3
3
09
6
5
1
0
6
1
A
b
s
o
r
b
a
n
c
e
(
a
.u
)
Wavenumber(cm
1
)
Fig. 4. Fourier Transform Infrared (FTIR) survey spectra for (a) silane
coupling agent solution treated henequen bers (FIBSIL) and (b) silane
coupling agent solution plus NaOH aqueous solution treated henequen
bers FIBNASIL.
0.8 0.6 0.4 0.2 0.0
0
50
100
150
200
250
300

P
U
L
L
-
O
U
T

S
T
R
E
S
S

(
M
P
a
)
STRAIN (mm/mm)
fib
fibna
fibnapre
fibnasil
Fig. 5. Typical average interfacial shear stress from pull-out experiments
versus displacement curves for HDPE and henequen bers subjected to
different surface treatments.
P.J. Herrera-Franco, A. Valadez-Gonzalez / Composites: Part B 36 (2005) 597608 602
henequen bers and a vinyl group which reacts with HDPE,
so a picture of this interphase is one with silane groups
chemically attached to ber surface on one side and bonded
with some chains of the matrix in the other one.
3.4. Mechanical properties
In order to determine whether any statistically signi-
cant difference existed between the values of mechanical
properties as a result of the application of one or more
different ber surface treatments, a One Way Analysis of
Varianza (ANOVA), was performed. All pairwise multiple
comparison procedures were performed following a
StudentNewmanKeuls method. Also, all strength values
for the different ber surface modications are related to
the strength obtained for the untreated bers.
3.5. Tensile test results
The tensile strength of the HDPE/henequen bers
(80:20 v/v) composites is shown in Fig. 6. When the ber
surface was modied with an aqueous NaOH solution
(FIBNA) or with the pre-impregnation process (FIBPRE),
the tensile strength of the composite did not seem to
improve noticeably. With the pre-impregnation process
(FIBNAPRE), the tensile properties of the composite
showed a small improvement. The tensile strength increases
11% resulting from the pre-impregnation process resulted in
an enhancement of the mechanical interlocking. However,
when the silane coupling agent (FIBSIL) is used, a 19%
increase in the tensile strength was observed. Furthermore,
when the henequen bers are rst treated with alkaline
solution and then with the silane coupling agent (FIB-
NASIL) a 30% increase in the tensile strength was observed.
This increment is attributed to chemical interactions in
the case of FIBSIL and to both, mechanical and chemical
interactions in the case of FIBNASIL. No noticeable effect
on the elastic modulus was noticed from the bermatrix
interface improvements of the HDPE-henequen bers
composites (Fig. 7). Bisanda et al. [22] showed that the
mercerization of sisal bres (0.5 N NaOH-solution for 72 h)
greatly improved the resin pick-up or wettability of the
bres, which resulted in a 21% rise in the compressive
strength of the composite. It is believed that this alkali
treatment results in an improvement in the interfacial
bonding by giving rise to additional sites of mechanical
interlocking, hence promoting more resin/bre interpene-
tration at the interface.
It is observed in this study, that the ratio between values
of bermatrix interfacial shear strength for the different
ber surface techniques with respect to the untreated bers
is different from the ratio of material property values
obtained from the composites using treated bers and the
untreated bers. It is well known that the ber reinforcing
effect is most efcient along the ber axis orientation.
However, the processing technique will dictate the nal
ber orientation distribution, one of the most important
characteristics, which will determine the composite mech-
anical properties. The anisotropy expected from an injection
molded part is not the same as that found in extruded or
compression molded parts.
Furthermore, the mathematical prediction of a composite
stiffness is well established for common ber orientation
distributions: (1) when all the bers are oriented parallel to
the test direction, (2) when all the bers are oriented in a
transverse direction, perpendicular to the test direction and
(3) when all the bers are randomly oriented. The formulas
developed for these different scenarios have been developed
for bers, which because of the high stiffness will remain
straight after processing. However, in the case of natural
Fig. 6. Tensile strength of a HDPE/henequen-ber (80:20 v/v) composite,
plotted as a function of ber surface treatment.
Fig. 7. Elastic modulus of a HDPE/henequen-ber (80:20 v/v) composite,
plotted as a function of ber surface treatment.
P.J. Herrera-Franco, A. Valadez-Gonzalez / Composites: Part B 36 (2005) 597608 603
bers, they do not remain straight after processing because
they are highly exible.
The effect of the ber surface modications on the micro
failure mode, the surface of fractured specimens were
examined using SEM. Fig. 8 shows representative photo-
micrographs of fracture surfaces of samples subjected to
tensile stresses, for the untreated, NaOH aqueous dilute
solution treated, and those which additionally were
subjected to a matrix pre-impregnation and to a silane
coupling agent. The surfaces of the untreated bers (FIB)
are completely devoid of matrix material. This is a clear
indication of bermatrix interfacial failure followed by
extensive ber pull-out from the matrix. Furthermore, the
matrix also shows considerable tearing. The bers subjected
to the alkaline aqueous solution bath plus matrix pre-
impregnation also show interfacial failure but in this case,
there is not much indication of ber pull-out, but rather, it
shows massive failure of both bers and matrix. The failure
mode observed on the bers shows ber splitting and tearing
and it is attributed to a better interaction with the matrix, but
still such interaction is by friction and mechanical
interlocking. Also, when the bers were pre-impregnated
with the matrix in a dilute solution form, there were clear
indications and many traces of matrix material still
surrounding the bers, thus indicating a closer contact
between the ber and the matrix and a better wetting of the
bers. This is also an indication that was able to fully
penetrate into the ber and upon failure of the laminate, it
showed tearing and shearing and this explains the presence
of traces of matrix material on the bers surface. In the case
of the silane treated bers, the failure surface indicates a
massive matrix failure and the bers are completely coated
with the matrix, and there are no indications of bers pull-
out.
Then, it can be said from these failure modes that the
increase of the tensile strength of the composite is an effect
of the bermatrix interface increases. It can also be said
that a low bermatrix adhesion, results in a failure mode
dominated by ber pull-out and matrix failure. As the
interfacial shear strength increased, the failure mode is more
like matrix tearing and ow and ber tearing.
3.6. Flexural properties
The exural strength of the HDPE-henequen ber
composites plotted again as a function of the different
ber surface treatments are shown in Fig. 9. Also, the
observations made earlier for the tensile strength on the
effect of bermatrix adhesion are also seen clearly here.
The ber surface treatments had a marginal effect on the
exural modulus, similarly to the observations made for the
tensile properties. The exural strength improved by
Fig. 8. Photo-micrographs of a HDPE/henequen-ber (80:20 v/v) compo-
site fracture surfaces of a sample subjected to tensile stresses, for (a) the
untreated, NaOH, FIB aqueous dilute solution treated, and those subjected
to a matrix pre-impregnation and to a silane coupling agent and (b) FIBNA;
(c) FIBNASIL and (d) FIBNAPRE.
"
P.J. Herrera-Franco, A. Valadez-Gonzalez / Composites: Part B 36 (2005) 597608 604
approximately a 3% just by modifying the topography of the
ber by an alkaline aqueous solution. The increment of
interfacial area of contact was benecial for the exural
strength (Fig. 9). Such relative increase was doubled when
the bers were pre-impregnated with the matrix-liquid
solution even when the ber had no surface modication by
any alkaline treatment. When these two surface treatments
are combined, and additional increase is observed for the
exural strength. This indicates that a better contact and the
increase in area of contact between the ber and the matrix
are improving the level of adhesion, probably by the
incorporation of a mechanical component of adhesion for
the matrixber interfacial strength. When the ber is
treated with the coupling agent a larger increase in the
exural strength is also observed (13% approximately).
When the chemical and the mechanical components of the
adhesion are combined, a larger increase of strength is
observed (20%).
The failure modes are discussed to further clarify the
relationship between bermatrix adhesion and the exural
strength. The specimens for FIB (Fig. 10(a) shows no trace
of matrix material on both between and around the bers.
The ber treated with NaOH and pre-impregnated with the
matrix (Fig. 10(b)) show traces of polymer still adhering
into and around the ber. The ber failure mode even shows
the cellulose microbrils still surround by the polymer.
When the ber was treated with NaOH and the coupling
agent, the failure mode changed to matrix failure and the
bers are still held by the matrix (Fig. 10(c)). Considerable
amount of bers tearing was also noticed.
0
400
800
1200
1600
2000
2400
TYPE OF FIBER SURFACE TREATMENT
F
L
E
X
U
R
A
L

S
T
R
E
N
G
T
H
FIB FIBNA FIBPRE FIBNAPRE FIBSIL FIBNASIL
Fig. 9. Flexural strength of a HDPE/henequen-ber (80:20 v/v) composite,
plotted as a function of ber surface treatment.
Fig. 10. Photo-micrographs of a HDPE/henequen-ber (80:20 v/v)
composite fracture surfaces of a sample subjected to tensile stresses, for
(a) the untreated, NaOH, FIB aqueous dilute solution treated, and those
subjected to a matrix pre-impregnation and to a silane coupling agent and
(b) FIBNA; (c) FIBNASIL and (d) FIBNAPRE.
"
P.J. Herrera-Franco, A. Valadez-Gonzalez / Composites: Part B 36 (2005) 597608 605
3.7. Iosipescu shear strength
The shear strength of the HDPE-henequen ber compo-
sites plotted again as a function of the different ber surface
treatments is shown in Fig. 11. The shear strength is shown
again in a non-dimensionalized format. Similar obser-
vations made earlier for both the tensile and exural
strength on the effect of bermatrix adhesion are evident
here. However, the effect of increased ber surface area of
contact with the matrix seems to have a larger effect on the
shear strength. Fiber pre-impregnation by itself has no great
contribution to the shear strength. The largest increase in
shear strength is observed for the ber treated with both the
aqueous alkaline solution and the silane coupling agent.
From previous observations of the tensile and exural
properties for this ber surface treatment combination,
increments of approximately a 20 and 30%, respectively,
were obtained. In the case of the shear strength, such
increase is of the order of a 25%.
Observation of failure surface of Iosipescu shear test
samples further claries the importance of ber adhesion on
shear strength results. Fig. 12 shows a series of Scanning
Electron Microscope photographs for the composite for
20% v/v ber content and tested under shear loads. In
Fig. 12(a), the untreated bers appear to be free of any
matrix material adhering to them, thus indicating poor ber
matrix adhesion. In Fig. 12(b), the bers treated with the
aqueous NaOH solution and then are pre-impregnated, more
tearing of the bers could be observed, together with some
cavities left by the pulled-out bers. Despite this fact, there
is some ber pull-out but the ber is coated with the matrix
0
2
4
6
8
10
12
14
16
18
20
TYPE OF FIBER SURFACE TREATMENT
S
H
E
A
R

S
T
R
E
N
G
T
H
(
M
P
a
)
FIBNASIL FIB FIBNA FIBPRE FIBNAPRE FIBSIL
Fig. 11. Shear strength of a HDPE/henequen-ber (80:20 v/v) composite,
plotted as a function of ber surface treatment.
Fig. 12. Photo-micrographs of a HDPE/henequen-ber (80:20 v/v)
composite fracture surfaces of a sample subjected to tensile stresses, for
(a) the untreated, NaOH, FIB aqueous dilute solution treated, and those
subjected to a matrix pre-impregnation and to a silane coupling agent and
(b) FIBNA; (c) FIBNASIL and (d) FIBNAPRE.
"
P.J. Herrera-Franco, A. Valadez-Gonzalez / Composites: Part B 36 (2005) 597608 606
polymer. Another feature of this ber treatment is on the
matrix failure mode, because appreciable shear yielding
rather than tearing is observed. It can be inferred that
mechanical interlocking and friction are responsible for the
observed composite strength increment. Fig. 12(c) shows
the failure surface for the composite with bers treated with
the aqueous NaOH solution and the silane coupling agent. It
can be observed that the bers are still coated with the
matrix and that the matrix failed by shear yield ow and
tearing from the ber. If the matrix failure mode of the
untreated ber composite is compared to the pre-impreg-
nated ber composite, it can be seen that it changes from
tearing mode to shear yielding. Then, from these matrix
failure modes, it can be said that there exists a higher force
transfer capability at the bermatrix interface in the
composites with bers treated by pre-impregnation and a
silane coupling agent. It should be pointed out that the
matrix properties are an upper bound for the composite
strength, especially when the bermatrix adhesion is
strong, in this case, such upper bound is given by the
yield strength of the matrix.
4. Conclusions
The mechanical behavior of short natural ber reinforced
HDPE was studied. The bermatrix interaction was
changed by modifying the surface properties of the ber,
rst to increase the area of contact and to further expose the
cellulose microbrils, and to improve ber wetting and
impregnation. Also, a chemical interaction was promoted by
using a silane coupling agent. The ratio of IFSS observed
between the different ber surface conditions and the
untreated bers was interesting because such interface
strength almost doubled only by changing the mechanical
interaction and the chemical interactions between ber and
matrix. The micromechanical techniques allowed the
determination of an indicator of the bermatrix interface
strength and also a suitable value of ber length, both to
improve ber matrix force interactions and to be able to
process the composite with a relative ease. One important
fact resulting from the ber surface treatment and improved
bermatrix adhesion was a considerable reduction of ber
(l/d) ratio from 72 to w20.
The mechanical properties observed did not increase in
the same ratio as those observed for the single-ber
interfacial shear strength. This was attributed to the fact
that the random ber orientation resulted in lower properties
that those observed for uniaxial single-ber reinforced
composites. The increase in the mechanical properties
ranged between 3 and 30%, for the tensile and exural
properties. In the case of the shear strength of this
composite, such increase was of the order of 25%. From
the micro-photographs, obtained from failure surfaces from
the SEM, it was observed that with increasing bermatrix
interaction the failure mode changed from interfacial failure
to matrix failure. The interface failure was mainly a
frictional type failure, and only for the pre-impregnated
and silane treated bers, matrix tearing and shearing was
observed. The silane surface treated bers also showed a
layer of polymer covering the bers even after failure.
The mechanical properties determined from the tensile,
exural and shear tests exhibit a similar behavior for each of
the different ber surface treatments but the effect of the
ber surface treatment was more noticeable for the shear
properties.
Acknowledgements
The authors would like to express the support given by
the Consejo Nacional de Ciencia y Tecnolog a [Grant #
5116-A9406]. Also, the authors would like to thank Ms S.B.
Andrade-Canto for the SEM photomicrographs and M.V.
Moreno-Chulim for the FTIR analysis.
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