Composites: Part B 30 (1999) 309–320

Effect of fiber surface treatment on the fiber–matrix bond strength of

natural fiber reinforced composites
A. Valadez-Gonzalez a, J.M. Cervantes-Uc a, R. Olayo b, P.J. Herrera-Franco a,*
a
Centro de Investigación Cientı́fica de Yucatán, A.C., Apartado Postal 87, Cordemex, C.P. 97310, Mérida, Yucatán, México
b
Universidad Autónoma Metropolitana-Iztapalapa, Departamento de Fı́sica, Apartado Postal 55-534, 09340 México City, México D.F.
Received 2 January 1998; accepted 28 May 1998

Abstract
The interfacial shear strength (IFSS) between natural fibers and a thermoplastic matrix has been improved by the morphological and silane
chemical modification of the fiber surface. An alkaline treatment was used to enhance both the matrix fiber wetting and the chemical surface
modification in order to improve the physicochemical interactions at the fiber–matrix interphase. For characterization of the mechanical
properties of such interphase, a modification of the micromechanical techniques commonly used in the characterization of the IFSS for
circular-cross-section smooth fibers is proposed. The relationships developed for circular fibers were modified to incorporate the natural fiber
perimeter instead of an equivalent fiber diameter. From the micromechanical test’s results it was found that both surface modifications,
preimpregnation and chemical, improves the fiber–matrix IFSS. Finally, the results obtained from the single fiber fragmentation test seem to
better agree with the effective mechanical properties measured for the laminated material than those obtained with the pull out test. 䉷 1999
Elsevier Science Ltd. All rights reserved.
Keywords: A. Fibres; B. Mechanical properties; Interfacial shear strength

1. Introduction Joseph et al. [2] reported that hard fibers have been success-
fully incorporated into elastomers and thermoplastics.
The performance and properties of composite materials Herrera-Franco et al. [3] deposited a silane coupling agent
depend on the properties of the individual components and to henequén fibers and have shown that adhesion between
their interfacial compatibility. To ensure appropriate inter- the natural hard fibers and matrix plays an important role on
facial interactions their surface properties must be modified the final mechanical properties of the composite. Since the
accordingly. Also, the use of thermoplastic polymers with interface plays a major role in transferring the stress from
particulate fillers or short-fiber reinforcements has grown the matrix to the fiber, it is important to be able to charac-
rapidly because of their good processability and ability to terize the interphase and the level of adhesion to properly
be recycled. Fillers are added to the polymeric matrix with understand the performance of the composite.
the aim of improving its thermal and mechanical properties. There are several methods available to quantify the inter-
There are, however, some adverse effects, i.e. toughness, facial adhesion in composite materials. In the case of single
and ultimate elongation that polymers often suffer because fiber model composites, techniques such as the pull-out test
of the addition of fillers. A properly selected interface has a and the single-fiber fragmentation test (SFFT) are
significant effect on the dispersion quality and adhesion commonly used [4–8]. The SFFT test offers several impor-
between the polymer and the filler. tant practical advantages such as simplicity in sample
Natural hard fibers are gaining attention as a reinforcing preparation and the possibility of obtaining a large number
agent in thermoplastic matrices [1–3]. Low density and a of fragments from a single specimen. Then, a statistically
highly reduced wear of the processing machinery may be valid distribution can be obtained from a limited number of
mentioned as attractive properties, together with their abun- test samples. These methods have been successfully used to
dance and low cost. Cazaurang et al. [1] pointed out that characterize the interfacial shear strength (IFSS) of both
these hard fibers posses mechanical properties that make thermoplastic and thermosetting resins reinforced with a
them a suitable candidate to reinforce thermoplastic resins. rigid, constant diameter and smooth surface fibers such as
carbon, glass, kevlar etc. In the case of natural hard fibers
* Corresponding author. Fax: ⫹00 52-99-81-3900. such as henequén, sisal, coconut, etc., however, they can be
1359-8368/99/$ - see front matter 䉷 1999 Elsevier Science Ltd. All rights reserved.
PII: S1359-836 8(98)00054-7
310 A. Valadez-Gonzalez et al. / Composites: Part B 30 (1999) 309–320

Table 1 Table 3
Chemical composition of the henequén fibers [18] Different fibers treatments applied to the henequén fibers

Component Percent (w/w) TAPPI a Standard Keyword Surface treatment

Cellulose 60 TAPPI T9 m-54 FIB No treatment

Hemicellulose 28 TAPPI T9 m-54 FIBNA Treated with an aqueous alkaline solution
Lignin 8 TAPPI T9 m-54 FIBNASIL Treated first with alkaline solution and then with
Extractives 4 TAPPI T12 m-59 a silane coupling agent
Ashes 0.5 TAPPI T15 m-58 FIBNAPRE Treated with alkali and then impregnated with a
dilute matrix solution
a
Technical Association of pulp and paper industry.

considered to be flexible, they have a diameter that varies 2.2. Fiber surface treatments
along their length and a rough surface [1,9–12].
The aim of this work was to explore the possibility of In order to improve the adhesion between the fiber and the
improving the effective mechanical properties of a thermo- matrix, the fibers were subjected to one or several surface
plastic matrix reinforced with natural fibers enhancing the treatments (see Table 3) which are described hereafter.
fiber–matrix interphase physicochemical interactions. The
fiber surface area was increased by means of an alkaline 2.2.1. Treatment with alkaline solution
treatment and then preimpregnated with a diluted matrix The fibers were treated with a NaOH aqueous solution
solution or treated with a silane coupling agent to promote (2% w/v) for an hour at 25⬚C, then they were washed with
a chemical interaction between the fiber and the matrix. distilled water until all the sodium hydroxide was elimi-
Such interactions were characterized using two micro- nated, that is until the water used for washing the fibers
mechanical methods, the single-fiber fragmentation test no longer gave any alkalinity reaction. Subsequently, the
and the pull-out test. The results of the micromechanical fibers were dried to 60⬚C for 24 h. 1
characterization were compared with the effective mechan-
ical properties of the natural-fiber reinforced composite. 2.2.2. Surface treatment with silane
For the surface treatment of the fiber, 1% silane and 0.5%
dicumyl peroxide (Polyscience), weight percentage regard-
ing the fiber, dissolved for their hydrolysis in a mixture of
2. Experimental methanol–water (90/ 10 w/w) were used. The pH of the
solution was adjusted to 3.5 with acetic acid and stirred
2.1. Materials continuously during 10 min. Then, the fibers were immersed
in the solution and left for 1 h under agitation. At last, the
High density polyethylene (HDPE–Petrothene) extrusion fibers were dried at 60⬚C for 24 h.
grade, was supplied by Quantum Chemical Inc. with a melt
flow index (MFI) of 0.33 g/10 min., a density of 0.96 g/cm 3
2.2.3. Surface preimpregnation with polyethylene dilute
and a melting point of 135⬚C. The MFI was determined
solution
following the ASTM standard D-1238-79 at 190⬚C with a
The henequén fibers were preimpregnated with a 1.5% w/
weight of 2160 g. The ASTM standard D-792-86, with
w HDPE–Xylene solution as follows: HDPE in powder
benzene as the immersion liquid, was used to determine
form was added to Xylene at 110⬚C in a Pyrex beaker and
the density. The melting point was determined in a DSC-7
stirred continuously with a magnetic bar to dissolve the
Perkin Elmer calorimeter. The natural hard fiber used was
polyolefin. The natural fibers were put in a stainless-steel
henequén (Agave fourcroydes) supplied by DESFIYUSA.
basket and carefully immersed in the hot solution and stirred
The chemical composition and mechanical properties of
continuously for 5 min. Then, the basket was removed and
the henequén fibers are shown in Tables 1 and 2.
the lumps of fibers were transferred to a flat tray and kept in
Sodium hydroxide and xylene, reactive grade from
an oven at 60⬚C for 24 h to allow the solvent to evaporate.
Técnica Quı́mica S.A., were used for the various surface
The lumps of impregnated fibers were dispersed before
treatments. As a coupling agent, the vinyltris (2-methoxy-
blending them with the matrix.
ethoxy) silane (Silane A-172) from Union Carbide was
used.
2.3. Micromechanical characterization
Table 2
Mechanical properties of the henequén fibers One of the techniques most frequently used to measure
the interfacial shear strength (IFSS) is the so-called pull-out
Tensile strength (MPa) 500 ^ 70 test. In this test, one end of the fiber is embedded in a block
Strain at break (%) 4.8 ^ 1.1
Tensile modulus (GPa) 13.2 ^ 3.1
of a polymer matrix, Fig. 1(a), and a force is applied to the
free end to pull it out off the matrix while the force is
 A. Valadez-Gonzalez et al. / Composites: Part B 30 (1999) 309–320 311

up until the fiber tensile strength is reached and the fiber

fractures at some point where the stress concentration is
high enough. This loading process continues until the
fiber-fragment lengths are so small because the tensile stres-
ses that are induced in the fiber can no longer reach the fiber
tensile strength and the fiber fragmentation process ceases.
This final fiber fragment length is referred to as the fiber
critical length. It is now commonly accepted that this final
fiber fragment length is a good indicator of the ability of the
interphase to transmit loads between the two constituents
and a measure of (lc/d) can be used as an indicator of the
fiber–matrix bond strength. From this value of the critical
length, the IFSS is calculated according to the equation
developed by Kelly and Tyson [4]
 
sf d
tˆ …2†
2 lc
where d is the diameter of the fiber, lc is the critical length of
the fiber and sf is its maximum tensile strength. Drzal et al.
[5] recognized that the distribution of fiber fragments fits
well a two-parameter Weibull distribution and rearranged
the Kelly and Tyson equation proposing the following
modification to calculate the IFSS:
 
sf 1
tˆ G 1⫺ …3†
2b a
where a, b are the shape and scale parameters of the
Weibull distribution, respectively, and G is the gamma func-
tion.
Several authors have reported on the physical and
mechanical properties of natural hard fibers such as sisal
(Agave Sisalana) and henequén (Agave Fourcroydes).
Cazaurang et al. [1], Mukherjee et al. [10] and Barkakaty,
[11] have shown that the cross-section and apparent
diameter of these fibers vary considerably along their
length. From photomicrographs of the cross-section of
these natural hard fibers [1,10], it was shown that they are
Fig. 1. Schematic representation of the micromechanical techniques. (a) not circular. From these reports, it can be concluded that the
pull-out test; and (b) single fiber fragmentation test.
cross-section of the natural fibers can not be considered as
circular, smooth and rigid rods but like very flexible beams.
continuously monitored and recorded. The average interfa- In order to measure the average area and perimeter of the
cial shear strength can be calculated from the force at which henequén fibers they were embedded in an epoxy resin,
debonding occurs using the following equation: cured in an air convection oven and then microtomed at
several points along the fiber. The microtomed films were
F
tˆ …1† photographed and the geometrical parameters, such as peri-
pdl meter and cross-sectional area were calculated using a stan-
where F is the maximum load measured prior to debonding dard image analysis software. The typical cross-section of
of the fiber, d is the fiber diameter and l is the fiber the henequén fibers used in this study are shown in Fig. 2(a).
embedded length. It was observed that the variability of the perimeter, equiva-
Another well-established technique, also commonly used lent diameter and cross-section area of the henequén fibers,
to calculate the IFSS, is the single fiber fragmentation test. shown in Fig. 2((b)–(d)), fit well the two-parameter Weibull
In this test, a single fiber is embedded in a dumbbell shaped distribution
tensile coupon, which in turn is subjected to a tensile load,   a 
x
Fig. 1(b). Depending on the level of fiber–matrix adhesion, F…x† ˆ 1 ⫺ exp ⫺ x⬎0
b
such tensile forces are transferred from the matrix to the
fiber. These tensile stresses in the fiber continue to build The maximum likelihood method was employed to estimate
312 A. Valadez-Gonzalez et al. / Composites: Part B 30 (1999) 309–320

Fig. 2. (a) Typical cross-sections of henequén fibers at different points along their length; and histograms of the geometrical parameters (b) perimeter, (c)
diameter, and (d) cross-sectional area.

the parameters of the Weibull distribution. These para- observed for the equivalent diameter or the cross-section
meters are solutions to area. This suggests that the perimeter could be a better para-
P a P meter for calculation of the interfacial shear strength. Dong
X lnX 1 lnXi
Pi a i ⫺ ⫺ ˆ0 and Sapieha [12], in a study concerning the characterization
Xi a n of the interfacial adhesion between cellulose and a thermo-
plastic matrix composite, modified the Kelly and Tyson
 1
1X a a equation by using the ratio of the cross-section to perimeter
bˆ Xi of the fibers instead of the apparent diameter to calculate the
n
interfacial shear strength, however, they did not report any
where a and b have the same meaning indicated earlier, that of their geometrical parameters. Karlsson et al. [13] using
is, they are the shape and scale parameters of the Weibull the Wilhelmy plate method measured the apparent peri-
distribution [5]. meter of regenerated cellulose and used this parameter to
It is observed from these figures that the perimeter of the calculate the IFSS.
fiber cross-section shows a lower dispersion than that In order to take into account the inherent variability of the
 A. Valadez-Gonzalez et al. / Composites: Part B 30 (1999) 309–320 313

2.3.1. Sample preparation

2.3.1.1. Pull-out test The pull-out specimens used to eval-

uate the IFSS were made using the following procedure: the
henequén fibers were cut in 20 cm long fragments and
attached to a frame using high temperature adhesive tape.
Then, they were placed between two sheets of HDPE and
the mold was subjected to a constant pressure (1 ton), at
180⬚C, in a Carver laboratory press for 10 min and then
cooled to room temperature. The specimens were cut in
rectangles of 3 × 1 cm in such a way that one fiber was
embedded along the main axis of the rectangle. The sample
was then perforated to produce the nominal fiber embedded
length. The actual embedded length and the apparent
diameter of the fiber of each probe were recorded with a
Specwell M820-SM optical microscope.
The specimens were subjected to a tensile force using an
universal testing machine equipped with a PC computer and
the load–displacement curve was recorded. A cross-head
speed of 1.2 mm/min was used in all the experiments.

2.3.1.2. The single fiber fragmentation test The coupons

needed to carry out the single fiber fragmentation
experiments were prepared according to the following
procedure. The henequén fibers were carefully aligned and
attached to a frame and then they were placed between two
sheets of polyethylene and pressed at 180⬚C in a Carver
laboratory press for 10 min and then cooled to room
temperature. Type IV specimens were cut using a Ceast
Co. pneumatic hollow die punch, according to the ASTM
Fig. 3. SEM photomicrographs of henequén fibers for: (a) FIB; and (b)
standard D-638, in such a way that one henequén fiber
FIBNA, showing their surface features. remained oriented along the central axis of the coupon.
The coupons were subjected to a tensile load in an Instron
1125 Universal testing machine at 25⬚C and a cross-head
henequén fibers, eqns (2), (3) were rearranged to use the speed of 2 mm/min. The application of load was stopped
perimeter Pf instead of the diameter to calculate the IFSS. before yielding of the polyethylene matrix when the
Following this approach the IFSS was calculated for the fragmentation process had ceased. The length of the
pull-out test with the expression: formed fragments was recorded with an optical
microscope coupled to a calibrated TV camera and
Ff monitor system.
tˆ …4†
Pf l e

where Ff is the force of debonding, Pf is the measured peri- 2.4. Elaboration of the composite
meter of the henequén fiber and le is the fiber embedded
length. In the case of the single fiber fragmentation test A 20% in volume fiber composite was elaborated to
the IFSS was calculated with determine the effect of the henequén fiber surface treatments
on the tensile properties of the material. Henequén fibers
2Ff (6 mm long) were incorporated to the polyethylene matrix
tˆ   …5†
1 using a BRABENDER intensive mixer at 180⬚C; the result-
bG 1 ⫹ P
a f ing material was laminated at a temperature of 180⬚C and a
pressure of 1 ton using a Carver laboratory press. From
where Ff is the tensile load at break for the henequén fiber, these laminates, type IV tensile tests specimens were
Pf is the perimeter; a, b are the shape and scale parameters obtained according to the D638 ASTM standard. The tensile
of the fragment length Weibull distribution and G is the tests were carried out in an INSTRON Universal Testing
gamma function. machine model 1125 using a cross-head speed of 5 mm/min.
314 A. Valadez-Gonzalez et al. / Composites: Part B 30 (1999) 309–320

Fig. 4. Fourier transform infrared (FTIR) spectra for FIB and FIBNA.

3. Results (FIBNA), respectively; it can be seen that FIBNA possesses

more imperfections on its surface than FIB. As a direct
3.1. Surface treatments result, there are more crevices on the surface of FIBNA
than on the surface of FIB. The change in the surface
3.1.1. Alkaline treatment composition can be appreciated in the infrared spectra for
The treatment of the henequén fibers with a diluted alka- FIB and FIBNA shown in Fig. 4. It can be noted that there is
line solution promotes the partial removal of the hemicellu- a strong absorption in FIB at 1750 cm ⫺1 which no longer
loses, waxes, and lignin present on the surface of the fiber, exists in FIBNA. Several authors [14–17] reported that
and leads to some changes in their morphology and chemi- hemicelluloses contain groups that absorb in the carbonyl
cal composition [11,14]. region and that they are soluble in aqueous alkaline solu-
The change in the surface morphology of the treated fiber tions. Furthermore, if these solutions are acidified and
was studied by scanning electron microscopy (SEM). Fig. brought in contact with ethanol, the hemicelluloses precipi-
3(a) and (b) show a fiber without treatment (FIB) and one tate [15]. This procedure was carried out and it was
that has been treated with the NaOH aqueous solution observed that a precipitate flocculated. The precipitate was
analyzed in a FTIR spectrometer and a spectrum with a very
intense band at 1750 cm ⫺1 that corresponds to the carbonyl
group was obtained. The alkaline treatment also removes
other compounds like waxes and partially dissolves the
lignin present in the henequén fiber. In addition, the removal
of hemicelluloses with the alkaline treatment was corrobo-
rated using a thermogravimetric analysis (TGA). Fig. 5
shows the thermogram of FIB and FIBNA, and it can be
appreciated that both curves suddenly decrease approxi-
mately a 10% at 100⬚C corresponding to water evaporation
and also at 250⬚C where the decomposition of the fibers
begins. However, there is an inflection in the FIB curve
that is not present in FIBNA that corresponds to a weight
loss of 20% approximately, which is similar to the hemi-
celluloses content in the henequén fibers as can be seen in
Table 1 [18].

3.1.2. Silane treatment

Fig. 6(a) shows the SEM micro photographs correspond-
Fig. 5. Thermogravimetric analysis (TGA) decomposition thermograms for ing to the silane treated fiber. It can be seen that there is no
FIB and FIBNA. dramatic change in the surface morphology of FIBNASIL
 A. Valadez-Gonzalez et al. / Composites: Part B 30 (1999) 309–320 315

fiber as compared to FIBNA. However, these fibers were

analyzed in a Nicolet FTIR spectrophotometer and in a
Perkin Elmer X-ray photoelectron spectrometer with the
aim of verifying the efficiency of the silane treatment.
From these results, it could be seen that the silane was
effectively deposited on the fiber surface and that the alka-
line treatment enhanced the efficiency of deposition. Details
of this study are described in a forthcoming paper [19].

3.1.3. Preimpregnation treatment

The change in the surface morphology of the preimpreg-
nated fiber, FIBNAPRE, was followed by scanning electron
microscopy (SEM) and it is shown in Fig. 6(b). It can be
appreciated that there are lumps of the polyolefin deposited
on the fiber. The preimpregnated fibers were subjected to a
soxhlet extraction with xylene to determine the amount of
resin deposited on it. This determination was carried out by
triplicate and approximately a 5% (w/w) of HDPE with
respect to the fiber was found to be deposited on the fiber
surface.

3.2. Interfacial shear strength measurement

3.2.1. Pull-out
The typical load–displacement curves for the native
(FIB), alkali treated (FIBNA), silane treated (FIBNASIL)
and preimpregnated henequén (FIBNAPRE) fibers from the
pull-out test are shown in Fig. 7. It can be noted that all the
curves exhibit the non-linear behavior characteristic of a
ductile matrix [20–22]. However, once the load reaches
its maximum value there are clearly significant differences
Fig. 6. SEM photomicrographs of henequén fibers for: (a) FIBNASIL; and
in the way these curves drop. For the native henequén it can
(b) FIBNAPRE. be seen that the load increases gradually and when it reaches
a maximum value there is a smooth transition and it begins
to decrease in a linear fashion until the total embedded
length of the fiber is pulled-out. This behavior agrees well
with the behavior of a poor interphase that results because of
the incompatibility between the hydrophilic fiber and the
hydrophobic matrix. This behavior shows a slight change
in the case of FIBNA, because the higher the roughness of
the alkali treated fiber, the better the fiber–matrix mechan-
ical interlocking, i.e. the fiber–matrix interaction is
improved. For the silane treated fiber, the load–displace-
ment curve depicts a weakly bonded interphase; after the
interphase has failed, the fiber can be extracted in a
controlled way and friction was measured until the fiber
was completely pulled-out [20]. The load displacement
curve for FIBNAPRE resembles a very strongly bonded
interphase: the interface fails immediately after fiber extrac-
tion, as reported by Désarmont et al. [20]
On the other hand, it can be seen in Fig. 8 that the depen-
dence of the force of debonding with the embedded length
follows linear behavior with a different slope for all treat-
ments. This seems to indicate some bond ductility [21,22]
Fig. 7. Typical pull-out test load–displacement curves for HDPE and and that the surface treatments increase the fiber–matrix
henequén fibers subjected to different surface treatments. interaction [20]. The slope of these curves indicates that
316 A. Valadez-Gonzalez et al. / Composites: Part B 30 (1999) 309–320

mechanical interlocking. However, the preimpregnated

fiber (FIBNAPRE) gave clearly better results than FIBNA
and even FIBNASIL. This seems to indicate that the wetting
of the fiber plays a key role in the fiber–matrix adhesion
because it increases the mechanical interlocking. Thus, the
high viscosity of the matrix in the molten state that does not
allow a proper fiber wetting could explain the small incre-
ment on the IFSS for FIBNA.
The silanization of the fiber surface also enhances the
fiber–matrix interaction as can be observed from the incre-
ment of the IFSS although such increment is somewhat
lower than that observed for the preimpregnated fiber.
Several authors [3,23–25] have pointed out that the silani-
zation of natural fibers modifies the surface properties and
that it increases the fiber matrix interaction. The silane used
in this work to modify the fiber, has two functional groups: a
hydrolyzable alkoxy group able to condense with the hydro-
xyls of the henequén surface fiber and a organofunctional
(vinyl) group capable of interacting with the thermoplastic
Fig. 8. Debonding force versus embedded length for non-treated and trea-
ted henequén fibers. matrix. The hydrolyzed alkoxy silanes can undergo conden-
sation and the bond-formation stage under base- and acid-
catalyzed mechanisms. Besides these reactions of the silanol
fiber matrix interaction increases in the order FIB ⬍ and the fiber surface hydroxylic groups, the formation of
FIBNA ⬍ FIBNASIL ⬍ FIBNAPRE. polysiloxanes structures can also occur [26]. A schematic
The IFSS calculated using the equivalent diameter (Eq. 1) picture of the various interphases formed for the non-treated
and the measured perimeter (Eq. 4) of the henequén and treated fibers are shown in Fig. 10. It can be seen in this
fiber for the pull out test is presented in Fig. 9. It can figure that for FIBNAPRE the matrix penetrates into the
be appreciated that the fiber surface treatments increased the fiber whereas in the case of FIBNASIL the silane groups
IFSS in the order FIB ⬍ FIBNA ⬍ FIBNASIL ⬍ are chemically attached to the fiber surface on one side and
FIBNAPRE. As can be seen, the alkali treatment shows a bonded with some chains of the matrix in the other one.
sligth increment in the fiber–matrix interaction mainly due
to the higher fiber surface roughness that allows certain 3.2.2. Single fragmentation test
The calculated IFSS from the SFFT test results using the
equivalent fiber diameter (Eq. 3) and the measured peri-
meter (Eq. 5) are shown in Fig. 11. It can be seen that all
treatments improve the fiber–matrix interactions, and it is
observed in this case that the silane treated fibers yielded
better results. It should be noted that Eq. (5) always yields
lower values than Eq. (3) but the same trend is observed.
These results can easily be explained because as it was
mentioned before, the treatment with NaOH removed
some lignin and hemicelluloses from the surface of the
fiber, thus, the fiber surface area also increased. Such fiber
surface increase resulted in a larger area of contact between
the fiber and the matrix. Therefore, the hydroxyl groups on
the cellulose fibers were able to better interact with the
silane-coupling agent because of the availability of a larger
number of possible reaction sites. It is interesting to note
that the pull-out test also yielded values of IFSS lower than
the fragmentation test as it has been observed from the
literature for high performance fiber reinforced polymers
[6,27].

3.3. Composite tensile strength measurement

Fig. 9. Effect of the surface treatment on the Interfacial shear strength
measured using the pull-out test. The tensile strength of the composite HDPE–henequén
 A. Valadez-Gonzalez et al. / Composites: Part B 30 (1999) 309–320 317

Fig. 10. Schematic representation of the interphases formed on the henequén fibers for: (a) FIB and fibers subjected to different surface treatments; (b) FIBNA;
(c) FIBNASIL; and (d) FIBNAPRE.

fibers (80:20 v/v) is shown in Fig. 12. It should be noted that 4. Discussion
the only modification of the fiber surface with an aqueous
solution of NaOH does not seem to be enough to improve When the fiber is preimpregnated with the matrix the
the strength of the material. Either further treatment with a resulting IFSS seems to be higher than that obtained for
silane-coupling agent to promote the adhesion by chemical fibers which are treated only with a silane coupling agent,
interactions or by enhancing the mechanical interlocking by
a preimpregnation process clearly improves the mechanical
properties of the composite.
The silane treatment of the fiber surface increases the tensile
strength of the composite material from 21 to 27 MPa whereas
the preimpregnation process yields 23 MPa. Figs. 12 and 13
show the fracture photomicrographs of the specimens
subjected to tensile loads. It can be seen in Fig. 13(a) that
for FIB fibers, the phenomenon of ‘pull-out’ occurred in a
greater extent than FIBNASIL and FIBNAPRE.
In the picture corresponding to FIBNA, Fig. 13(b), it
could be appreciated both fiber pull out and some tearing
of the fibers as a consequence of a better mechanical inter-
locking induced by the greater roughness of the fiber. The
effect of the coupling agent is shown in Fig. 14(a) where it
can easily be seen that the fibers were broken and torn and
there is no evidence of fiber pull out. In addition, it is inter-
esting to note that the fibers are completely impregnated by
the matrix. In the case of the preimpregnated fiber, Fig.
14(b), more tearing of the fibers could be observed together Fig. 11. Effect of the surface treatment on the interfacial shear strength
with some cavities left by pulled-out fibers. measured using the single fiber fragmentation test.
318 A. Valadez-Gonzalez et al. / Composites: Part B 30 (1999) 309–320

Fig. 12. Effect of the surface treatment on the tensile strength for HDPE–
henequén fiber composites.

Fig. 14. Fracture surface SEM photomicrographs of: (a) FIBNASIL; and
(b) FIBNAPRE.

when it is measured with the fiber pull-out test. However,

when the single fiber fragmentation test is used, the silani-
zation results in higher IFSS values.
It should be pointed out that there are differences between
the mechanical solicitations on the specimens used for fiber
pull-out and fiber fragmentation tests. In the first case, the
fiber is subjected to an axial force and this results in a
Poisson contraction in the radial direction and the normal
radial stress on the fiber resulting from matrix shrinkage
may be reduced. As a result a decrease in the frictional
component of the interfacial strength is observed. This
may facilitate the initiation and propagation of interfacial
failure. In the fiber fragmentation test, the load is applied
directly to the matrix and the load is transferred from the
matrix to the fiber through the interphase. In this case, the
tensile forces also produce a reduction of the cross section in
both the fiber and the matrix because of the Poissońs effect.
Such cross-sectional reduction induces a radial compressive
stress component on the fiber, and the frictional component
of the adhesion should increase depending on the net cross-
Fig. 13. Fracture surface SEM photomicrographs of: (a) FIB; and (b) sectional reduction between fiber and matrix.
FIBNA. In the case of preimpregnated fibers, such cross-sectional
 A. Valadez-Gonzalez et al. / Composites: Part B 30 (1999) 309–320 319

Table 4 The mechanical characterization of such interphase was

A comparison of the interfacial shear strength (IFSS) obtained by pull-out performed using micro mechanical techniques commonly
and single fiber fragmentation test (SFFT) for several fiber treatments
used in the characterization of the interfacial shear strength
Treatment IFSS (MPa) pull-out IFSS(MPa) SFFT of circular-cross-section, smooth fibers. The interfacial
shear strength relationships developed for circular fibers
FIBNAPRE 8.0 9.0
were modified to incorporate the natural fiber perimeter
FIBNASIL 5.0 16.0
FIBNASILPRE 9.0 20.0 instead of an equivalent fiber diameter. The use of the
fiber critical aspect ratio (lc/d) in the Weibull analysis
resulted in higher values for IFSS, but the trends were the
contraction due to a Poisson effect will not take place as same as those obtained from the use of the fiber cross-
easily as in an untreated fiber because the polymeric matrix section perimeter for both the fragmentation test and the
that has penetrated into the fiber will hinder such contrac- pull-out test. The first technique, however, resulted consis-
tion. When the fiber is subjected to a silanization there is no tently in higher values of IFSS than the second one.
impediment for such contraction and the adhesion between Slight discrepancies were observed between the results
the fiber and the matrix is attributed to chemical bonds obtained from the two micro-mechanical techniques for
between the silane coupling agent present on the fiber fibers that were subjected to a preimpregnation process.
surface and the matrix. Also, in the pull out experiment, From the pull out experiment, higher interfacial shear
the fiber is completely extracted off the matrix and in the strength values were obtained than those obtained with the
case of the fragmentation the fiber is not extracted but single fiber fragmentation test. Such discrepancies were
broken inside the matrix. In order to completely extract attributed to the differences in the experimental configura-
the fiber off the matrix, it is necessary to apply a large tions and mechanical solicitations in both arrangements and
force on the fiber, because, both the frictional component to differences in the mechanical behavior of the fiber which
of adhesion has to be broken and the polymer that has pene- had been impregnated with the matrix. The results obtained
trated into the fiber has to fail either under shear or tensile from the single fiber fragmentation test seem to be in better
forces for fiber pull-out to occur. When the fibers have been agreement with the effective mechanical properties
treated with the silane coupling agent, the resulting adhesion measured for the laminated material.
between the fiber and matrix will be more efficient than for
the preimpregnated fibers only if they do not suffer a consid-
erable contraction upon load application. Then, if both fiber Acknowledgements
surface modification processes, namely the preimpregnation
and the silanization processes are combined, it is expected This work was supported by the Consejo Nacional de
that the IFSS will be higher because the load-transfer effi- Ciencia y Tecnologı́a [Grant no. 5116-A9406]. The authors
ciency at such interphase will be further enhanced by a would like to thank Ms S.M. Arce for the SEM micrographs.
synergistic effect of both treatments. This is indicated by
the results shown in Table 4 where both micromechanical
tests result in higher IFSS values. References

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