Composites: Part B 36 (2005) 597–608

www.elsevier.com/locate/compositesb

A study of the mechanical properties of short natural-fiber

reinforced composites
P.J. Herrera-Franco*, A. Valadez-González
Centro de Investigación Cientı́fica, de Yucatán A.C., Division de Materiales, Calle 43 # 130, Col. Chuburná de Hidalgo, C.P. 97200 Mérida, Yucatán, México

Received 10 January 2005; accepted 10 April 2005

Available online 22 June 2005

Abstract
The degree of fiber–matrix adhesion and its effect on the mechanical reinforcement of short henequen fibers 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 Si–O–cellulose and Si–O–Si bonds on the lignocellulosic surface confirmed that the silane coupling agent was
efficiently held on the fibres surface through both condensation with cellulose hydroxyl groups and self-condensation between silanol groups.
The fiber–matrix interface shear strength (IFSS) was used as an indicator of the fiber–matrix adhesion improvement, and also to determine
a suitable value of fiber length in order to process the composite with relative ease. It was noticed that the IFSS observed for the different fiber
surface treatments increased and such interface strength almost doubled only by changing the mechanical interaction and the chemical
interactions between fiber and matrix.
HDPE-henequen fiber composite materials were prepared with a 20% v/v fiber content and the tensile, flexural 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 fiber produced a significant increase in tensile strength, while the tensile modulus remained relatively unaffected. The increase
in tensile strength was only possible when the henequen fibers were treated first with an alkaline solution. It was also shown that the silane
treatment produced a significant increase in flexural strength while the flexural modulus also remained relatively unaffected. The shear
properties of the composites also increased significantly, but, only when the henequen fibers 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
fiber and matrix. Examination of the failure surfaces also indicated differences in the interfacial failure mode. With increasing fiber–matrix
adhesion the failure mode changed from interfacial failure and considerable fiber pull-out from the matrix for the untreated fiber to matrix
yielding and fiber and matrix tearing for the alkaline, matrix-resin pre-impregnation and silane treated fibers.
q 2005 Elsevier Ltd. All rights reserved.

Keywords: (C)Resin; Fiber–matrix

1. Introduction approximately a 10% of waste is produced. These waste

Cellulosic fibers, like henequen, sisal, coconut fiber
(coir), jute, palm, bamboo, wood, paper in their natural
condition, as well as, several waste cellulosic products such
as shell flour, wood flour and pulp have been used as
reinforcement agents of different thermosetting and thermo-
plastic resins [1–8].
During the decortication of the henequen leaves, and also
during the transformation of the raw fibers into cordage,
* Corresponding author.
E-mail address: pherrera@cicy.mx (P.J. Herrera-Franco).
1359-8368/$ - see front matter q 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.compositesb.2005.04.001
fibers could be profitably used in the manufacture of short-
fiber polymer reinforced composites because they posses
attractive physical and mechanical properties [9]. These
waste fibers are composed of w60% of cellulose pulps
which are easily obtained and could also be used to
reinforce polymeric materials.
Unlike the traditional engineering fibers, e.g. glass and
carbon fibers, and mineral fillers, these lignocellulosic fibers
are able to impart the composite certain benefits such as low
density, less machine wear during processing than that
produced by mineral reinforcements, no health hazards, and
a high degree of flexibility. The later is especially true
because these fibers, unlike glass fibers, will bend rather
than fracture during processing. Whole natural fibers
598 P.J. Herrera-Franco, A. Valadez-González / Composites: Part B 36 (2005) 597–608

undergo some breakage while being intensively mixed with itself (intramolecular) and between other cellulose macro-
the polymeric matrix, but this is not as notorious as with molecules (intermolecular).
brittle or mineral fibers. Also, natural fibers impart the The characteristics of henequen fibers have been studied
composite high specific stiffness and strength, a desirable by several authors. The chemical analysis of the fibers
fiber aspect ratio, biodegradability, they are readily indicated that their main component is cellulose (60%),
available from natural sources and most important, have a hemicellulose (28%), lignin (8%), extractives (4%). The
low cost per unit volume basis. It should also be mentioned structural arrangement of these components in the fiber, as
that the hollow nature of vegetable fibers may impart in other natural hard fibers, is in such a way that lignin acts
acoustic insulation or damping properties to certain types of as a cementant matrix for the cellulosic fibers, which posses
matrices. their own structure. The mechanical properties of the
One difficulty that has prevented a more extended henequen fibers are a consequence of such structural
utilization of the henequen fibers is a lack of a good arrangement. The mechanical properties of the henequen
adhesion to most polymeric matrices. The hydrophilic fibers are: tensile strength, 500G70 MPa, strain at break,
nature of natural fibers adversely affects adhesion to a 4.8G1.1% and Young’s modulus, 13.2G3.1 GPa.
hydrophobic matrix and as a result, it may cause a loss of
strength. To prevent this, the fiber surface has to be modified
in order to promote adhesion.
2. Materials and experimental procedures
Several methods to modify the natural fiber surface such
as: graft copolymerization of monomers onto the fiber
High density polyethylene, HDPE (Petrothene) extrusion
surface, the use of maleic anhydride copolymers, alkyl
grade, was supplied by Quantum Chemical Inc. A melt flow
succinic anhydride, stearic acid, etc. have been proposed. It
index (MFI) for the HDPE of 0.33 g/10 min was determined
is also known that the use of coupling agents such as silanes,
following the ASTM standard D-1238-79 at 190 8C and
titanates, zirconates, triazine compounds, etc. also improves
using a weight of 2160 g. A density for the HDPE of
fiber–matrix adhesion [10–14]. Furthermore, is has been
0.96 g/cm3 was determined following the ASTM standard
proven that pre-impregnation of the fiber with the polyolefin
D-792-86, using benzene as an immersion liquid. The
solution will also improve fiber–matrix adhesion [15]. The
melting point (135 8C) was determined in a DSC-7 Perkin–
mechanical properties of a fiber-reinforced polymer com-
Elmer calorimeter.
posite depend not only on the properties of constituents, but
Henequen fibers with an average diameter of 180 mm,
also on the properties of the region surrounding the fiber
approximately, were used in the form of short fibers (6 mm
known as the interphase. Stress transfer from the matrix to
long) and it was supplied by Desfibradora Yucateca, S.A.
the fiber takes place at such interphase and, therefore, it is
(DESFIYUSA Co.) of Mérida, Yucatán, México.
important to characterise its properties to better understand
Sodium hydroxide and xylene, reagent grade from
the performance of the composite. In this paper, the degree
Técnica Quı́mica S.A., were used for the various surface
of mechanical reinforcement for a thermoplastic matrix that
treatments. As a coupling agent, vinyltris (2-methoxy-
can be achieved with short-natural fibers by modifying the
ethoxy) silane (Silane A-172) from Union Carbide was
fiber surface by different treatments and the optimization of
used. Dicumyl Peroxide from Polyscience was used as
the composite material properties is studied. The chemical
catalyst to the reaction between the silane coupling agent
surface modification of henequen fibres was carried out
and the polymer.
using an organofunctional silane coupling agent in a
methanol/water medium. Heat treatment (curing) was
applied after reaching the equilibrium adsorption of the 2.1. Fiber surface treatments
pre-hydrolysed silane onto the lignocellulosic substrate. The
modified fibers were then characterised by diffuse reflec- The nomenclature for the different henequen fiber
tance infrared spectroscopy (DRIFT). surface treatments used is shown in Table 1.

1.1. Characteristics of the henequen fibers (Agave Table 1

fourcroydes) Nomenclature used for the different fibre surface treatments

Keyword Description
Depending on their origin, natural fibers can be grouped
Fib Fiber without treatment
into bast (jute, banana, flax, hemp, kenaf, mesta), leaf
FIBNA Fiber treated with a NaOH aqueous solution
(pineapple, sisal, henequen, screw pine) and seed or fruit FIBPRE Fiber pre-impregnated with dissolved HDPE
fibers (coir, cotton, oil palm). Cellulose is the main FIBNAPRE Fiber treated with a NaOH aqueous solution and then
component of the henequen fibers and the elementary unit pre-impregnated with dissolved HDPE
of a cellulose macromolecule is anhydro d-glucose, which FIBSIL Fiber treated with a silane coupling agent
FIBNASIL Fiber treated with a NaOH aqueous solution and then
contains three hydroxyl (OH–) groups. These hydroxyl
with a silane coupling agent
groups form hydrogen bonds inside the macromolecule
 P.J. Herrera-Franco, A. Valadez-González / Composites: Part B 36 (2005) 597–608 599

2.2. Treatment with NaOH 2.6. Fiber–matrix adhesion characterization

The fibers 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 fibers were dried at
60 8C for 24 h.
2.6.1. Fiber pull-out
Is a direct method used for the characterization of the
fiber–matrix interphase and relies on the use of single fiber–
matrix adhesion and detection of failure modes. In this test
the fiber is pulled out of the matrix (Fig. 1), which can be

2.3. Treatment with a silane coupling agent

For the fiber surface treatment with the coupling agent,

1% silane and 0.5% dicumyl peroxide (Polyscience), weight
percentage with respect to the fiber, were dissolved for their
hydrolysis in a mixture of methanol–water (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 fibers
were immersed in the solution and left for 1 h under
agitation. Afterwards, the fibers 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 fibers 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 fibers 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 fibers were transferred to a flat tray and kept in an oven at
60 8C for 24 h to allow evaporation of the solvent. The
lumps of impregnated fibers were dispersed before blending
them with the matrix.

2.5. Composites processing

A 20% v/v fiber content HDPE-henequen fiber compo-

site was chosen in order to determine the effect of the
different surface treatments on its mechanical properties.
The henequen fibers 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 fibers 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 Fig. 1. Schematic representation of the micromechanical techniques used
obtained from these laminates according to ASTM for the determination of the interfacial shear strength measurement: (a)
standards. pull-out test; and (b) single fiber fragmentation test.
600 P.J. Herrera-Franco, A. Valadez-González / Composites: Part B 36 (2005) 597–608
a block of resin, a disc, or a droplet [16]. In this case, one
end of the fiber was embedded in the middle plane of a plate
made from the resin. The fibers were first 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 fiber pull-out, the load (P)
registered at debonding was converted into an average
interfacial shear strength (t) by
P
tZ
pdL
where d is the fiber diameter, L is the embedded length of
the fiber. The force was applied by holding one end of the
resin plate fixed and pulling from the free end of the fiber
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 fiber fragmentation
In this method, a single-fiber coupon is loaded in tension
to determine the stress transfer efficiency at the fiber–matrix
interphase. Upon load application, the tensile stress on the
fiber (sf) 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 fiber fragments become so short that stress
transferred to the fiber though the interface is no longer high
enough to cause any further fiber breakage. When this
occurs, it is said that a critical fiber fragment length (lc) has
been reached [16]. To a first approximation, the interface
shear strength (t) is calculated from a simple relationship
obtained from a force balance on a fiber fragment and the
recognition of the random nature of the fiber-fragmentation
process as:
 
sf 1 FTIR and TGA pointed out that these lignocellulosic fibers
t Z G 1K
2b a can experience a significant weight loss due to the partial
here G is the gamma function, a and b are Weibull shape
and scale parameters.
2.7. Mechanical properties
Both, tensile and flexural 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 mm3, 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 reflectance
spectroscopy (DRIFTS), with a deuterated triglycine
sulphate (DTGS–KBr) detector, was used. In order to
obtain a good resolution spectra it was necessary to mill the
henequen fibers to an average length of 0.2 mm. The milled
fibers were then mixed with an analytical grade KBr and the
spectra were recorded with a 2 cmK1 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 fiber 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 fibers, induced variation in the physicochemical
properties of henerquén fibers. Valadez et al. using [18]
dissolution of hemicellulose, lignin and pectin. They clearly
identified that the band around 1730 cmK1, corresponding
to hemicellulose, disappears when the fiber 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 cmK1 are shown in Fig. 2. It could be appreciated
that the strong band at 1240 cmK1 disappears whereas two
bands become evident, the doublet at 1200 and 1230 cmK1.
These behavior has been associated to the mercerization of
lignocellulosic fibres [19,20]. Mercerization removes waxy
epidermal tissue, adhesive pectins and hemicelluloses that
bind fiber bundles to each other and to the pectin and
hemicellulose rich sheats of the core [21]. In Fig. 3, features
of the fibers surfaces are shown. A comparison between the
native fiber 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-González / Composites: Part B 36 (2005) 597–608 601

1060
1111
0.4

965
1161

Absorbance(a.u)

700
895
1240
0.0
Absorbance(a.u)

1370
1320

1240
1370

0.3
1600 1400 1200 1000 800 600
1430

Wavenumber(cm–1)

0.2
1230
1200

895
1

0.1

700
650
FIB
FIBNA
0.0
1500 1350 1200 1050 900 750
Wavenumber(cm–1)

Fig. 2. Fourier Transform Infrared (FTIR) spectra for untreated henequen

fibers (FIB) and a Na(OH) aqueous solution treated fibers (FIBNA).

surface. One of the consequences of the topographical

change is an increment of the surface area.

3.2. Silane treatment

The spectra in the 1500–600 cmK1 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 –Si–O–cellulose and the absorption
bands at 700 and at 765 cmK1, were assigned to the –Si–O–
Si– bonds [18,19,23–25]. It should be noted that the
intensity of these bands was more evident after the curing Fig. 3. SEM photomicrographs of henequen fibers for (a) untreated
at 120 8C, suggesting that both the grafting of silane onto henequen fibers (FIB) and (b) Na(OH) aqueous solution treated fibers
(FIBNA), showing their surface features.
cellulose and the intermolecular condensation between
adjacent adsorbed –Si–OH groups had been substantially
enhanced. The peaks near 1060 cmK1 are related to residual The micromechanical events that occur for a long fiber
unhydrolysed Si–ethoxy–methoxy groups and their small reinforced composite are not the same as those observed for
intensity, compared to those of the spectrum of the a short reinforced composite. In a short fiber there are
hydrolysed A-172 (not shown), suggested that most of the variations in stress distribution along the fiber–matrix
silane adsorbed under our conditions had been hydrolysed. interface, and end effects can be neglected in the case of
These peak assignments are in agreement with those long fibers, but they can be very important in the case of
reported in other studies dealing with glass surfaces treated short fiber reinforced composites. Additionally, because the
with the same coupling agents [26,27]. These findings fibers are not oriented parallel to the applied loads, fiber–
suggest that the condensation reaction between the hydro- matrix adhesion should be studied more carefully. Table 2
lysed silane and the henequen fiber was carried out in a
greater extent in FIBNASIL than FIBSIL (see Fig. 4).
Table 2
Fiber critical length and fiber aspect ratio obtained for the different surface
3.3. Stress transfer at the interface between the short fiber treatments
and the matrix Fiber sur- Critical Fiber aspect IFSS pull- IFSS SFFT
face treat- length (mm) ratio (lc/df) out (MPa) (MPa)
Generally, the best mechanical properties in a composite ment
depend mainly on fiber orientation, but the adhesion FIB 12.96 72 2.5 5.4
between the fiber and the matrix is also important. This is FIBPRE 11.40 63.33 4.2 5.0
especially true for short fiber reinforced composites. The FIBNA 9.25 51.38 3.5 6.0
fibers are loaded through the matrix and for good FIBNAPRE 6.00 33.33 4.0 9.2
FIBSIL 5.45 30.27 3.75 11.9
performance, the load must be transferred effectively to
FIBNASIL 3.50 19.44 5.0 16.0
the fiber, and a strong fiber/matrix bond is required.
602 P.J. Herrera-Franco, A. Valadez-González / Composites: Part B 36 (2005) 597–608

shows fiber critical lengths and fiber aspect ratios obtained 300
for the different fiber surface treatments, obtained using the fib
fibna
single fiber fragmentation test.

PULL-OUT STRESS (MPa)

250 fibnapre
For all the surface-treated fibers there was a noticeable fibnasil
decrease of the fiber critical length as compared to that
200
measured for the untreated fibers. For the untreated fibers
(FIB), an average critical length value of 12.96 mm was
150
obtained, 6 mm for the pre-impregnated fiber (FIBNAPRE)
and 3.5 mm for the silane treated fiber (FIBNASIL). The
dimension of the fiber critical length is important from 100
several points of view. First, it is convenient to select a
suitable fiber length in order to allow for an adequate flow of 50
the molten composite material during processing. This will
avoid the development of excessive temperature in the 0
composite. Especially during injection or extrusion, extre- 0.0 0.2 0.4 0.6 0.8

mely high pressures are developed, and consequently, very STRAIN (mm/mm)
shear stresses can produce fiber breakage or splitting. Fig. 5. Typical average interfacial shear stress from pull-out experiments
The increase in the respective calculated IFSS values versus displacement curves for HDPE and henequen fibers subjected to
were 5.4 MPa (FIB), 9.2 MPa for FIBNAPRE and 16.0 MPa different surface treatments.
in the case of FIBNASIL. The initial treatment with the
aqueous solution of NaOH removed some lignin and reaches its maximum value there are clearly significant
hemicelluloses from the fiber surface, thus, the fiber surface differences in the way of these curves drop. It can be seen
area also increased. Such fiber surface increase resulted in a that during the pull-out process the debond force follows a
larger area of contact between the fiber and the matrix. linear behavior but the slope differs between them
Then, the hydroxyl groups on the cellulose fibers could depending on the fiber–matrix interactions. For the
better react with the silane-coupling agent because a larger untreated and the alkaline solution treated henequen fibers,
number on possible reaction sites were available. It is it can be seen that after reaching the maximum force value,
interesting to note that even though a pre-impregnation of then, there is a smooth transition and a decrease in a linear
the fiber with a solution of the matrix ensures a better fiber fashion until the total embedded length of fiber is pulled-out.
wetting, there was a decrease of the measured fiber critical This behavior agrees well with the behavior of a poor
length, and the corresponding increase of the IFSS, does not interphase that results as a consequence of the incompat-
seem to improve considerably. ibility of the hydrophilic fiber and hydrophobic matrix.
Typical curves of average interfacial shear stress versus In the case of a combination of the alkaline solution and
displacement are shown in Fig. 5. It can be noted that all the the matrix-pre-impregnation treatment, the pull-out force
curves shown in this figure exhibit the non-linear behavior was higher than that observed for the previous fiber
characteristic of a ductile matrix. However, once the load 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 fiber
1100

1061

0.4 can be extracted in a controlled way and the friction

965

0.1
1100
1061

665

measured up to the final point [14]. In the case of the fiber

1330
1240

1200
Absorbance(a.u)

treated with the alkaline solution and the silane coupling

Absorbance(a.u)

1330

0.0
0.3
1370

1240

agent, the pull-out force was higher that the previous

700
765

–0.1
1500 1350 1200 1050
Wavenumber(cm–1)
900 750 600
treatments, but the interphase failed and pull-out process
0.2
occurred catastrophically.
From the load-embedded length curve two character-
0.1 istics should be noted: the initial portion of the curve is
700
765

linear only in a very small portion and that the slope varies
840

FIBSIL
0.0
FIBNASIL for each surface treatment. The first is indicative of a ductile
interphase behavior and the second that the interaction
1500 1350 1200 1050 900 750 between fiber and matrix is different for each treatment.
Wavenumber(cm–1) Several authors [15,28,29] have pointed out that the
silanization of the natural fibers modifies the surface
Fig. 4. Fourier Transform Infrared (FTIR) survey spectra for (a) silane
coupling agent solution treated henequen fibers (FIBSIL) and (b) silane
properties and increases the fiber–matrix interaction. The
coupling agent solution plus NaOH aqueous solution treated henequen silane used in this study has two functional groups: an
fibers FIBNASIL. ethoxy–methoxy group able to react with hydroxil groups of
 P.J. Herrera-Franco, A. Valadez-González / Composites: Part B 36 (2005) 597–608
henequen fibers and a vinyl group which reacts with HDPE,
so a picture of this interphase is one with silane groups
chemically attached to fiber 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 signifi-
cant difference existed between the values of mechanical
properties as a result of the application of one or more
different fiber surface treatments, a One Way Analysis of
Varianza (ANOVA), was performed. All pairwise multiple
comparison procedures were performed following a
Student–Newman–Keuls method. Also, all strength values
for the different fiber surface modifications are related to
the strength obtained for the untreated fibers.
3.5. Tensile test results
The tensile strength of the HDPE/henequen fibers
(80:20 v/v) composites is shown in Fig. 6. When the fiber
surface was modified 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 fibers are first 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
Fig. 6. Tensile strength of a HDPE/henequen-fiber (80:20 v/v) composite,
plotted as a function of fiber surface treatment.
603
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 fiber–matrix
interface improvements of the HDPE-henequen fibers
composites (Fig. 7). Bisanda et al. [22] showed that the
mercerization of sisal fibres (0.5 N NaOH-solution for 72 h)
greatly improved the resin pick-up or wettability of the
fibres, 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/fibre interpene-
tration at the interface.
It is observed in this study, that the ratio between values
of fiber–matrix interfacial shear strength for the different
fiber surface techniques with respect to the untreated fibers
is different from the ratio of material property values
obtained from the composites using treated fibers and the
untreated fibers. It is well known that the fiber reinforcing
effect is most efficient along the fiber axis orientation.
However, the processing technique will dictate the final
fiber 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 fiber orientation
distributions: (1) when all the fibers are oriented parallel to
the test direction, (2) when all the fibers are oriented in a
transverse direction, perpendicular to the test direction and
(3) when all the fibers are randomly oriented. The formulas
developed for these different scenarios have been developed
for fibers, which because of the high stiffness will remain
straight after processing. However, in the case of natural
Fig. 7. Elastic modulus of a HDPE/henequen-fiber (80:20 v/v) composite,
plotted as a function of fiber surface treatment.
604 P.J. Herrera-Franco, A. Valadez-González / Composites: Part B 36 (2005) 597–608

fibers, they do not remain straight after processing because

they are highly flexible.
The effect of the fiber surface modifications 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 fibers (FIB)
are completely devoid of matrix material. This is a clear
indication of fiber–matrix interfacial failure followed by
extensive fiber pull-out from the matrix. Furthermore, the
matrix also shows considerable tearing. The fibers 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 fiber pull-out, but rather, it
shows massive failure of both fibers and matrix. The failure
mode observed on the fibers shows fiber 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 fibers were pre-impregnated
with the matrix in a dilute solution form, there were clear
indications and many traces of matrix material still
surrounding the fibers, thus indicating a closer contact
between the fiber and the matrix and a better wetting of the
fibers. This is also an indication that was able to fully
penetrate into the fiber and upon failure of the laminate, it
showed tearing and shearing and this explains the presence
of traces of matrix material on the fibers surface. In the case
of the silane treated fibers, the failure surface indicates a
massive matrix failure and the fibers are completely coated
with the matrix, and there are no indications of fibers 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 fiber–matrix interface increases. It can also be said
that a low fiber–matrix adhesion, results in a failure mode
dominated by fiber pull-out and matrix failure. As the
interfacial shear strength increased, the failure mode is more
like matrix tearing and flow and fiber tearing.

3.6. Flexural properties

The flexural strength of the HDPE-henequen fiber

composites plotted again as a function of the different
fiber surface treatments are shown in Fig. 9. Also, the
observations made earlier for the tensile strength on the
effect of fiber–matrix adhesion are also seen clearly here.
The fiber surface treatments had a marginal effect on the
flexural modulus, similarly to the observations made for the
tensile properties. The flexural strength improved by
"
untreated, NaOH, FIB aqueous dilute solution treated, and those subjected
to a matrix pre-impregnation and to a silane coupling agent and (b) FIBNA; Fig. 8. Photo-micrographs of a HDPE/henequen-fiber (80:20 v/v) compo-
(c) FIBNASIL and (d) FIBNAPRE. site fracture surfaces of a sample subjected to tensile stresses, for (a) the
 P.J. Herrera-Franco, A. Valadez-González / Composites: Part B 36 (2005) 597–608 605

2400
FLEXURAL STRENGTH

2000

1600

1200

800

400

0
FIB FIBNA FIBPRE FIBNAPRE FIBSIL FIBNASIL
TYPE OF FIBER SURFACE TREATMENT

Fig. 9. Flexural strength of a HDPE/henequen-fiber (80:20 v/v) composite,

plotted as a function of fiber surface treatment.

approximately a 3% just by modifying the topography of the

fiber by an alkaline aqueous solution. The increment of
interfacial area of contact was beneficial for the flexural
strength (Fig. 9). Such relative increase was doubled when
the fibers were pre-impregnated with the matrix-liquid
solution even when the fiber had no surface modification by
any alkaline treatment. When these two surface treatments
are combined, and additional increase is observed for the
flexural strength. This indicates that a better contact and the
increase in area of contact between the fiber and the matrix
are improving the level of adhesion, probably by the
incorporation of a mechanical component of adhesion for
the matrix–fiber interfacial strength. When the fiber is
treated with the coupling agent a larger increase in the
flexural 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 fiber–matrix adhesion and the flexural
strength. The specimens for FIB (Fig. 10(a) shows no trace
of matrix material on both between and around the fibers.
The fiber treated with NaOH and pre-impregnated with the
matrix (Fig. 10(b)) show traces of polymer still adhering
into and around the fiber. The fiber failure mode even shows
the cellulose microfibrils still surround by the polymer.
When the fiber was treated with NaOH and the coupling
agent, the failure mode changed to matrix failure and the
fibers are still held by the matrix (Fig. 10(c)). Considerable
amount of fibers tearing was also noticed.

"
(a) the untreated, NaOH, FIB aqueous dilute solution treated, and those
subjected to a matrix pre-impregnation and to a silane coupling agent and Fig. 10. Photo-micrographs of a HDPE/henequen-fiber (80:20 v/v)
(b) FIBNA; (c) FIBNASIL and (d) FIBNAPRE. composite fracture surfaces of a sample subjected to tensile stresses, for
606 P.J. Herrera-Franco, A. Valadez-González / Composites: Part B 36 (2005) 597–608

20

18

16
SHEAR STRENGTH(MPa)

14

12

10

0
FIB FIBNA FIBPRE FIBNAPRE FIBSIL FIBNASIL
TYPE OF FIBER SURFACE TREATMENT

Fig. 11. Shear strength of a HDPE/henequen-fiber (80:20 v/v) composite,

plotted as a function of fiber surface treatment.

3.7. Iosipescu shear strength

The shear strength of the HDPE-henequen fiber compo-

sites plotted again as a function of the different fiber 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 flexural
strength on the effect of fiber–matrix adhesion are evident
here. However, the effect of increased fiber 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 fiber treated with both the
aqueous alkaline solution and the silane coupling agent.
From previous observations of the tensile and flexural
properties for this fiber 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 clarifies the importance of fiber adhesion on
shear strength results. Fig. 12 shows a series of Scanning
Electron Microscope photographs for the composite for
20% v/v fiber content and tested under shear loads. In
Fig. 12(a), the untreated fibers appear to be free of any
matrix material adhering to them, thus indicating poor fiber–
matrix adhesion. In Fig. 12(b), the fibers treated with the
aqueous NaOH solution and then are pre-impregnated, more
tearing of the fibers could be observed, together with some
cavities left by the pulled-out fibers. Despite this fact, there
is some fiber pull-out but the fiber is coated with the matrix
"
(a) the untreated, NaOH, FIB aqueous dilute solution treated, and those
subjected to a matrix pre-impregnation and to a silane coupling agent and
Fig. 12. Photo-micrographs of a HDPE/henequen-fiber (80:20 v/v)
(b) FIBNA; (c) FIBNASIL and (d) FIBNAPRE.
composite fracture surfaces of a sample subjected to tensile stresses, for
 P.J. Herrera-Franco, A. Valadez-González / Composites: Part B 36 (2005) 597–608
polymer. Another feature of this fiber 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 fibers treated with
the aqueous NaOH solution and the silane coupling agent. It
can be observed that the fibers are still coated with the
matrix and that the matrix failed by shear yield flow and
tearing from the fiber. If the matrix failure mode of the
untreated fiber composite is compared to the pre-impreg-
nated fiber 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 fiber–matrix interface in the
composites with fibers 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 fiber–matrix 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 fiber reinforced
HDPE was studied. The fiber–matrix interaction was
changed by modifying the surface properties of the fiber,
first to increase the area of contact and to further expose the
cellulose microfibrils, and to improve fiber wetting and
impregnation. Also, a chemical interaction was promoted by
using a silane coupling agent. The ratio of IFSS observed
between the different fiber surface conditions and the
untreated fibers was interesting because such interface
strength almost doubled only by changing the mechanical
interaction and the chemical interactions between fiber and
matrix. The micromechanical techniques allowed the
determination of an indicator of the fiber–matrix interface
strength and also a suitable value of fiber length, both to
improve fiber matrix force interactions and to be able to
process the composite with a relative ease. One important
fact resulting from the fiber surface treatment and improved
fiber–matrix adhesion was a considerable reduction of fiber
(l/d) ratio from 72 to w20.
The mechanical properties observed did not increase in
the same ratio as those observed for the single-fiber
interfacial shear strength. This was attributed to the fact
that the random fiber orientation resulted in lower properties
that those observed for uniaxial single-fiber reinforced
composites. The increase in the mechanical properties
ranged between 3 and 30%, for the tensile and flexural
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 fiber–matrix
interaction the failure mode changed from interfacial failure
607
to matrix failure. The interface failure was mainly a
frictional type failure, and only for the pre-impregnated
and silane treated fibers, matrix tearing and shearing was
observed. The silane surface treated fibers also showed a
layer of polymer covering the fibers even after failure.
The mechanical properties determined from the tensile,
flexural and shear tests exhibit a similar behavior for each of
the different fiber surface treatments but the effect of the
fiber 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 Tecnologı́a [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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