Composites: Part B xxx (2014) xxx–xxx

Contents lists available at ScienceDirect

Composites: Part B
journal homepage: www.elsevier.com/locate/compositesb

The effect of surface modifications on sisal fiber properties and sisal/poly

(lactic acid) interface adhesion
A. Orue, A. Jauregi, C. Peña-Rodriguez, J. Labidi, A. Eceiza, A. Arbelaiz ⇑
‘Materials + Technologies’ Group, Chemical & Environmental Engineering Dep., Polytechnic College of San Sebastian, University of the Basque Country UPV/EHU, Pza. Europa 1,
20018 Donostia-San Sebastián, Spain

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

Article history: The main aims of this work were to study the effect of surface modifications on sisal fiber properties as
Received 15 July 2014 well as on fiber/poly (lactic acid) (PLA) interface adhesion. For this purpose, alkali, silane and combination
Received in revised form 31 October 2014 of both treatments were applied to sisal fiber. The effects of treatments on fiber thermal stability, fiber
Accepted 11 December 2014
wettability, morphology, tensile properties and on fiber/PLA interfacial shear strength (IFSS) were stud-
Available online xxxx
ied. After treatments IFSS values improved at least 120%, however, tensile strength of sisal fibers
decreased. Alkali treatment removed some non-cellulosic components (hemicelluloses, lignin) as con-
Keywords:
firmed by Fourier transform infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA). The
A. Fibers
B. Fiber/matrix bond
removal of non-cellulosic materials led to fibrillated and rough morphology as observed by optical
B. Mechanical properties microscopy (OM). FTIR spectrum of silane treated fibers showed a band related to silane amino group
D. Mechanical testing and contact angle measurements confirmed that fibers became more hydrophobic. All treatments used
improved fiber/PLA adhesion.
Ó 2014 Elsevier Ltd. All rights reserved.

1. Introduction interfacial adhesion leads to an inefficient stress transfer under

Environmental awareness and scarcity of fossil resources have
caused an interest in the development of composite materials
based on renewable resources with comparable properties to syn-
thetic polymers in order to reduce petroleum consumption and
pollution [1–4]. For example, PLA which is obtained from renew-
able agricultural raw materials is commercially available and fully
biodegradable polymer [1,3]. PLA is one of the most promising bio-
degradable polymers for industrial plastic applications due to its
high mechanical properties and good processability [3]. However,
PLA polymer has some drawbacks such as brittleness, low impact
strength and low ability in resisting thermal deformation [1,3].
To overcome all these disadvantages, natural fibers can be used
as reinforcement [2–4]. They are abundant around the word and
they exhibit many advantages, for example, the biodegradability,
acceptable specific mechanical properties due to their low density
and its easy processability [2–4]. However, the main disadvantages
of lignocellulosic fibers are the low compatibility and poor interfa-
cial adhesion with polymeric matrices [3,4]. Poor fiber/polymer
⇑ Corresponding author. Tel.: +34 943018585; fax: +34 943017200.
E-mail address: aitor.arbelaiz@ehu.es (A. Arbelaiz).
load, resulting in low mechanical strength. Therefore, fiber surface
has to be modified and several methods to modify the natural fiber
surface were proposed in the literature [5–12]. In this study the
effects of alkali, silane and combination of both treatments on sisal
fiber tensile properties and on sisal fiber/PLA interfacial shear
strength were investigated. Untreated and treated sisal fibers were
characterized using different techniques (FTIR, TGA, contact angle
measurements and optical microscopy).
2. Experimental
2.1. Materials
PLA (Ingeo™, 2003D) was provided in pellet form by Nature
Works LLC (Minnetonka, USA). According to the supplier, the D-
isomer content of PLA was 4%, with a melt flow index of 6 g/
10 min at 210 °C and a density of 1.24 g/cm3. The sisal fibers used
in this work were kindly supplied by Celulosa de Levante S.A.
(Tortosa, Spain). Sodium hydroxide pellets supplied by Panreac
(Castellar del Vallés, Barcelona, Spain) and 3-(2-aminoethylamino)
propyltrimethoxysilane (supplied by Sigma–Aldrich (San Luis,
USA)) were used as fiber surface modifiers. Other reagent
employed was glacial acetic acid supplied by Panreac.

http://dx.doi.org/10.1016/j.compositesb.2014.12.022
1359-8368/Ó 2014 Elsevier Ltd. All rights reserved.

Please cite this article in press as: Orue A et al. The effect of surface modifications on sisal fiber properties and sisal/poly (lactic acid) interface adhesion.
Composites: Part B (2014), http://dx.doi.org/10.1016/j.compositesb.2014.12.022
2 A. Orue et al. / Composites: Part B xxx (2014) xxx–xxx

2.2. Fiber surface treatments Table 1

Total, dispersive and polar surface energy components of test liquids.

2.2.1. Alkali treatment Liquid cL (dyne cm1) cdL (dyne cm1) cpL (dyne cm1)
In order to swell raw sisal fibers, they were treated with 2 wt%
Ethylene-glycol 48.0 29.0 19.0
NaOH solution for 12 h at room temperature using a fiber/NaOH Diiodomethane 50.8 48.5 2.3
solution ratio of 1:20 (w/v). After this, fibers were treated with HPLC water 72.8 21.8 51.0
7.5 wt% NaOH solution under reflux for 90 min to remove more lig-
nin amount and separate fiber bundles into smaller fibers. Finally,
fibers were washed to pH 6 and dried at 100 °C for 12 h [13].
Surface energy values were calculated by using Owens–Wendt for-
2.2.2. Silane treatment mula [14,15] as shown in Eq. (1):
To improve the accessibility of silane chemical agent to the j 0:5  p p 0:5 k
hydroxyl groups of cellulose, firstly sisal fibers were sonicated for ð1 þ cos hÞcL ¼ 2 cdL cdS þ cL cL ð1Þ
3 h. Sonicated fibers were soaked in silane aqueous solution
(2% v/v) under continuous stirring for 3 h. The pH of solution was where h is the contact angle of the fibers with the test liquid, cdL ; cpL
adjusted to 3–4 with glacial acetic acid and fiber and silane ratio and cL are dispersive, polar and total surface energy of the test
used was 1:2 (w/v). Wet fibers were kept in air for 3 days before liquid, respectively, and cdS ; cpS are dispersive and polar components
to dry at 100 °C for 12 h. of the surface energy of fibers, respectively. Plotting cL ð1þ
 0:5  0:5
cos hÞ= 2 cdL versus cpL =cdL the polar and dispersive compo-
2.2.3. Alkali and silane treatment nents of fibers were determined by the slope and intercept of the
When a combination of both treatments was applied to sisal resulting graph, respectively [16].
fibers, alkali treated sisal fibers were further modified by silane
chemical agent. Alkali and silane treatments conditions were the 3.5. Fiber bundle tensile test
same used previously.
Tensile tests of untreated and treated fibers were performed
3. Characterization of fibers using a Minimat 2000 tester (Rheometric Scientific, Piscataway,
USA) at a testing speed of 1 mm/min. Fiber bundles were mounted
3.1. Fourier transform infrared spectroscopy and glued on a paper tab with a drop of glue before measurement.
The paper tab with the sample was mounted in the grips and then
Attenuated total reflection-Fourier transform infrared (ATR- the middle portion of the papers was cut by means of scissors, so
FTIR) spectroscopy was used to analyze the characteristic functional that only the fiber carried the load [17]. Clamping length used
groups of natural fibers and also to investigate changes in treated was of 5 mm and at least 10 specimens were tested. Fiber diameter
fibers. Measurements were performed with a Nexus spectrometer was measured by optical microscopy and the minimum diameter
(Nicolet, Madison, Wisconsin, USA) equipped with a MKII Golden value measured at three different locations along the fiber length
Gate accessory (Specac, UK), which uses diamond crystal at a nomi- was taken for calculating the cross section area. The cross section
nal incident angle of 45° with a ZnSe lens. Single beam spectra of the of natural fibers is polygonal and has a cavity inside fiber, the
samples were obtained after averaging 32 scans in the range from lumen. However, the fiber cross section area was calculated
600 to 4000 cm1 with a resolution of 4 cm1. assuming that fibers have a round cross section without lumen.
Taking into account these assumptions, the cross section area of
natural fibers could vary along the fiber length more than 70%.
3.2. Optical microscopy
Mechanical properties obtained should be analyzed with caution
due to the assumptions used and the high dispersion of cross sec-
Optical images of untreated and treated fibers surfaces were
tion area values. The strength values were fitted to a two parame-
taken using an Eclipse E600 microscopy (Nikon, Tokyo, Japan) with
ters Weibull distribution function (Eq. (2)):
software analysis of Soft Imaging SystemÒ.
  a
r
3.3. Thermogravimetric analysis FðrÞ ¼ exp  ð2Þ
ro
To study the thermal stability of untreated and treated sisal where the cumulative probability of failure is related to the applied
fibers, thermogravimetric analysis was carried out using a TGA/ stress (r) and the parameters a and ro are the shape and scale
SDTA 851 (Mettler Toledo, L’Hospitalet de Llobegrat, Barcelona, parameter, respectively.
Spain). Samples between 5 and 10 mg were placed in ceramic cru-
cibles and tests were carried out in nitrogen atmosphere between 3.6. Pull-out test
30 and 600 °C at a rate of 10 °C/min.
Force and displacement values of pull-out samples were
3.4. Contact angle and surface energy measurements acquired with a Minimat 2000 tester (Rheometric Scientific, Piscat-
away, USA).The maximum force (Fmax) was used to calculate the
Contact angles of untreated and treated sisal fibers were mea- apparent interfacial shear strength between fiber and matrix
sured with OCA 20 (Data Physics Instruments, Germany). Three according to the Kelly/Tyson formula [14,17,18] as shown by Eq.
different test liquids, HPLC water, ethylene-glycol and diiodometh- (3):
ane were used and their dispersive, polar and total surface energy
F max
components are given in Table 1. A controlled amount of sisal s¼ ð3Þ
fibers was compressed in a mould to obtain disc geometry and a
pDL
droplet of liquid was deposited on the surface and contact angle where D and L are fiber diameter and embedded length, respec-
was measured. Five samples were used to measure contact angles tively. Interfacial shear strength (IFSS) values were obtained using
and the average values and standard deviation were calculated. the assumption that the shear stress at the interface was uniformly

Please cite this article in press as: Orue A et al. The effect of surface modifications on sisal fiber properties and sisal/poly (lactic acid) interface adhesion.
Composites: Part B (2014), http://dx.doi.org/10.1016/j.compositesb.2014.12.022
 A. Orue et al. / Composites: Part B xxx (2014) xxx–xxx 3

distributed along the embedded length. The strength values were

fitted to a two parameters Weibull distribution function. At least
10 specimens were tested for each fiber treatment and the typical
sisal fiber/PLA pull-out test specimen is shown in Fig. 1.

4. Results

4.1. Fourier transform infrared spectroscopy

FTIR spectra of untreated and treated sisal fibers are shown in

Fig. 2. Untreated fibers showed a broad band at 3500–3200 cm1
related to O–H stretching vibration of the hydroxyl groups in cellu-
lose molecules. The bands between 2900 and 2700 cm1 were
related to the C–H stretching vibration of alkyl groups in aliphatic
bonds of cellulose, lignin and hemicelluloses. The band around
1740 cm1 was ascribed to the acetyl and ester groups of hemicel-
luloses and aromatic components of lignin. The band around
1640 cm1 was related to the O–H bending of water absorbed into
Fig. 2. FTIR spectra of sisal fibers after different surface treatments: (a) untreated,
cellulose fiber structure and absorption bands at 1602 cm1 and (b) silane, (c) NaOH and (d) NaOH + silane.
1505 cm1 were associated with C–C in plane symmetrical stretch-
ing vibration of aromatic rings present in lignin. The band at
1430 cm1 was associated to the CH2 symmetric bending present 4.2. Thermogravimetric analysis
in cellulose. The band at 1250 cm1 was related to the C–O stretch-
ing vibration of hemicelluloses component and aryl–alkyl ether TGA and derivative TGA curves of untreated and treated sisal
compounds present in lignin. Bands observed around 1170– fibers are shown in Fig. 3a–b. Untreated and alkali treated fibers
1050 cm1 and 890 cm1 were associated with the C–O stretching showed around at 100 °C a weight loss of about 4% related to sur-
and C–H deformation vibrations of the pyranose ring skeletal of face water evaporation [19,22]. However, when fibers were treated
cellulose [19–21]. After alkali treatment, the chemical composition with silane chemical agent, the evaporation of water was not so
of fibers changed since the prominent bands of the raw fiber obvious which may indicate that after silane treatment fibers
around 1740 and 1250 cm1 were disappeared almost completely became less hydrophilic. Fibers without alkali treatment showed
indicating that alkali treatment removed hemicelluloses and a por-
tion of lignin. Valadez-Gonzalez et al. [5] and Zhou et al. [6] studied
the effect of alkali treatment on sisal fibers and they also observed
that after alkali treatment the bands which appeared approxi-
mately at 1740 and 1250 cm1 disappeared. Liu et al. [7] observed
the same changes in FTIR spectra for native grass fibers treated
with an alkali solution. Silane treated fibers showed (b and d
spectra) a new absorption band around 1560 cm1 related to –
NH2 bending vibration of organosilane agent indicating that the
silane was successfully grafted on the fiber. The band around
1560 cm1 was more appreciable when fibers were previously
alkali treated. Similar result was observed by Koga et al. [8] after
treating cellulose paper with 3-aminopropyl-trimethoxy-silane.
Zhou et al. [6] for sisal fibers treated with two different aminosil-
(a)
anes observed new bands at 1570 and 1484 cm1.

(b)

Fig. 1. A typical sisal fiber/PLA pull-out test specimen. Fig. 3. (a) TGA and (b) derivative TGA curves of untreated and treated sisal fibers.

Please cite this article in press as: Orue A et al. The effect of surface modifications on sisal fiber properties and sisal/poly (lactic acid) interface adhesion.
Composites: Part B (2014), http://dx.doi.org/10.1016/j.compositesb.2014.12.022
4 A. Orue et al. / Composites: Part B xxx (2014) xxx–xxx
two decomposition peaks at 298 °C and 355 °C corresponding to the
thermal depolymerization of hemicelluloses and cellulose decom-
position, respectively [6]. However, in alkali treated fibers, the loss
related to hemicelluloses was not observed confirming that hemi-
celluloses were removed, in agreement with FTIR spectra obtained.
The removal of hemicelluloses and a fraction of lignin resulted in a
better thermal stability of alkali treated fibers. Other authors [6,9]
observed similar results for sisal fibers after treated with an alkali
solution. Fibers treated with silane chemical agent showed higher
percentage of char which could be related to the degradation of
grafted silane. Similar result was observed by Joseph et al. [10] for
banana fibers treated with triethoxyvinil-silane and aminopropyl-
silane. Rachini et al. [11] observed higher percentage of char for
hemp fibers treated with two different silane chemical agents and
they also attributed to the presence of grafted silane.
4.3. Optical microscopy
Fig. 4a–d shows optical images for untreated and treated sisal
fibers. Except for alkali treated fibers, no apparent changes were
observed in fiber surface morphology. After alkali treatment, fiber
surface roughness was considerably increased and created fibers
with smaller diameters probably due to the removal of hemicellu-
loses and lignin. Fernandes et al. [23] observed that alkali treatment
led to fibrillation of the sisal fiber bundles, reducing the diameter
and increasing the roughness. Bogoeva-Gaceva et al. [24] men-
tioned that alkali treatment reduced the diameter of natural fiber
and increased the aspect ratio by removing the impurities of the
fibers. Untreated sisal fibers showed diameter values between
154 and 220 lm while the diameter of alkali treated fibers was
smaller ranging from 109 to 132 lm and showed fibrils with diam-
eters around 10–20 lm. Fernandes et al. [23] observed that after
alkali treatment sisal fiber diameter values decreased from 117–
234 to 85–197 lm. Mwaikambo and Ansell [25] observed similar
changes in the morphology of hemp, sisal and jute fibers after dif-
Fig. 4. Optical microscopy images of sisal fibers after different surface treatments: (a) untreated, (b) silane, (c) NaOH and (d) NaOH + silane.
Please cite this article in press as: Orue A et al. The effect of surface modifications on sisal fiber properties and sisal/poly (lactic acid) interface adhesion.
Composites: Part B (2014), http://dx.doi.org/10.1016/j.compositesb.2014.12.022
ferent alkali treatments. Joseph et al. [10] observed by Scanning
Electron Microscopy the fibrillation of banana fibers after the alkali
treatment and they suggested that the removal of alkali soluble
hemicelluloses resulted in fibrillation of banana fibers.
4.4. Contact angle and surface energy
Contact angle values of PLA, untreated and treated sisal fibers
are reported in Table 2. After treating fibers with silane and with
a combination of NaOH + silane treatments, higher contact angles
were obtained. Le Moigne et al. [26] treated flax fibers with 3-glyc-
idyl-oxypropyl-trimethoxy-silane and they observed a decrease of
hydrophilic character of flax fibers. Park et al. [27] studied the con-
tact angle values for lignocellulosic fibers treated with a combina-
tion of NaOH and silane chemical agent using the Wilhelmy plate
technique. They observed that the contact angle became higher
after dipping fibers with silane chemical agent. Doan et al. [28]
measured the contact angle of untreated and treated jute fibers
using a tensiometer and they observed an increase in the hydro-
phobicity after silane treatment of alkali treated fibers. Total sur-
face energy cs, dispersive component cds and polar component cps
values are reported in Table 3. After silane treatment the cps =cs
value decreased as a result of polarity reduction which was in
agreement with water evaporation observed in TGA analysis. Doan
et al. [28] observed a similar reduction in cps =cs value when they
modified jute fibers with a combination of alkali and silane treat-
ments. On the other hand, comparing untreated and alkali treated
fibers, no big differences in total surface energy, dispersive compo-
nent and polar component were observed. These results were in
agreement with water evaporation observed in TGA analysis.
4.5. Fiber bundles tensile test measurements
Tensile strength values as a function of fiber surface treatments
were plotted by means of two parameters Weibull probability dis-
 A. Orue et al. / Composites: Part B xxx (2014) xxx–xxx 5

Table 2 Table 4
Contact angle values for PLA polymer, untreated and treated sisal fibers with different Tensile properties of sisal fibers after different fiber surface treatments.
test liquids.
Treatment ro (MPa) a Et (GPa) ebreak (%)
System Contact angle (°)
Untreated 366 2.9 9.5 ± 3.4 3.9 ± 1.3
Ethylene-glycol Diiodomethane Water Silane 341 1.9 6.4 ± 3.9 4.3 ± 1.0
NaOH 352 2.9 5.0 ± 3 9 6.1 ± 2 8
PLA 60.0 ± 1.8 48.0 ± 1.5 75.2 ± 1.6
NaOH + silane 212 1.4 5.0 ± 3.7 5.4 ± 2.2
Untreated 68.2 ± 7.2 42.7 ± 2.5 70.6 ± 2.4
Silane 77.0 ± 2.8 50.4 ± 4.8 86.7 ± 9.9
NaOH 64.8 ± 2.0 45.4 ± 4.8 74.6 ± 4.5
NaOH + silane 70.0 ± 4.4 53.1 ± 4.1 89.6 ± 7.6
fibers, Ray and Sarkar [34] observed that fibers treated with
5 wt% NaOH for 8 h showed the highest mechanical properties.
The values reported in Table 4 for alkali treated samples suggested
Table 3 that alkali treatment conditions used in this study could depoly-
Total, dispersive and polar surface energy components for PLA polymer, untreated merize the native cellulose I molecular structure, producing short
and treated sisal fibers. length crystallites [25]. However, as observed by optical micros-
System cS (mJ/m2) cdS (mJ/m2) cpS (mJ/m2) cps =cs copy, alkali treatment conditions used produced a fibrillated sur-
face that could improve fiber/polymer adhesion. The combination
PLA 34.6 26.9 7.7 0.26
Untreated 34.7 25.3 9.4 0.27 of alkali and silane treatments reduced considerably fibers proper-
Silane 28.9 25.8 3.1 0.11 ties due to the combined effect of both treatments.
NaOH 34.2 26.6 7.6 0.22
NaOH + silane 30.0 27.6 2.4 0.10
4.6. Pull-out tests

tribution function (Fig. 5) and provided a good adjustment to
experimental strength values. Tensile properties of untreated and
treated sisal fibers are reported in Table 4. Although the variability
of tensile values was very large, tensile strength and Young modu-
lus values obtained for untreated fibers were 366 MPa and 9.5 GPa,
respectively. These values were similar to those reported in the lit-
erature [23,29,30]. The variability in mechanical properties was
probably related to the variability in microstructure of natural
fibers and the possible damage suffered by the fibers during the
extraction process [29,31]. All treatments decreased the tensile
strength values of sisal fibers. However, alkali treated fibers
showed an improvement in the deformation at break values. For
silane treatment, the acid medium used could catalyze the cleav-
age of b-1,4-glycosidic bonds between two anhydroglucose units
and cellulose chain reduction might be the reason for lower
mechanical properties [14]. Similar tendency was observed by
Rong et al. [30] for sisal fibers treated with silane chemical agent.
The effects of alkali treatment on the properties of natural fibers
depend on the alkali treatment conditions (concentration, temper-
ature and time) [32]. Sydenstricker et al. [33] observed for sisal
fibers that 2 wt% NaOH treatment provided the highest fiber ten-
sile strength which decreased at higher concentrations. For jute
Fig. 6 shows typical pull-out test curves and in Table 5 are
reported the scale (so) and shape parameter (a) values obtained
using two parameters Weibull probability distribution function
for untreated fiber/PLA and treated fiber/PLA systems. A two
parameters Weibull distribution function provided a good adjust-
ment to experimental interfacial shear strength values (Fig. 7).
The IFSS value obtained for untreated fiber/PLA system was
2.4 MPa. After treatments, so value increased and the highest inter-
facial shear strength value of 6.0 MPa was obtained after alkali
treatment. This improvement can be explained by the increase of
contact surface area between fiber and PLA polymer which
improved the mechanical interlocking. Alkali treatment removed
non-cellulosic materials from fibers as observed by FTIR and TGA
techniques and increased fiber surface roughness. Moreover, after
alkali treatment, fiber bundles can be opened creating fibers with
smaller diameter, as observed by optical microscopy, and more
surface area. Another reason of adhesion improvement could be
due to the removal of the non-cellulosic materials which increase
the exposure of cellulose OH groups and might create more hydro-
gen bonds with PLA [35]. Pickering et al. [36] mentioned that the
increase in IFSS values for alkali treated fibers could be due to
the removal of non-cellulosic material allowing stronger bonding

Fig. 5. Tensile strength data fitted to a two parameter Weibull probability

distribution as a function of fiber surface treatment. Fig. 6. Pull-out test curves for untreated and treated sisal/PLA system.

Please cite this article in press as: Orue A et al. The effect of surface modifications on sisal fiber properties and sisal/poly (lactic acid) interface adhesion.
Composites: Part B (2014), http://dx.doi.org/10.1016/j.compositesb.2014.12.022
6 A. Orue et al. / Composites: Part B xxx (2014) xxx–xxx
Table 5
Sisal fiber/PLA interfacial shear strength (so) values after different fiber surface
treatments.
Treatment so (MPa)
Untreated 2.4
Silane 5.3
NaOH 6.0
NaOH + silane 5.8
Fig. 7. Apparent interfacial shear strength data fitted to a two parameters Weibull
probability distribution as a function of fiber surface treatment.
between PLA and cellulose at the interface. For silane treatment,
the increase of IFSS value may be attributed to the chemical bond
between PLA matrix and amino groups linked to the fiber surface.
Therefore, stress could be transferred from PLA chains, through
fiber bonded silane agent, to the fiber. Sawpan et al. [37] studied
the effect of different treatments on the interfacial shear strength
of hemp fiber reinforced PLA composites. They observed that IFSS
value for untreated hemp fibers/PLA system was 5.55 MPa and
when fibers were treated with an alkali solution, the highest IFSS
value was obtained (11.41 MPa) following by a combination of
alkali and silane treatments (9.87 MPa) and silane treatment
(8.22 MPa). In this work the same improvement order in IFSS value
was obtained by chemical modifications.
In the hypothetical case of a strong interfacial bond and assum-
ing that s is limited by the shear strength of the matrix, and also
assuming isotropy of the matrix, the IFFS might be estimated by
Eq. (4) [14],
r
s ¼ pmffiffiffi
3
where rm is the matrix strength. IFSS value estimated for a strong
interfacial fiber/matrix bond should be around 34 MPa. Although,
all treatments improved the so values at least 120%, the values
reported in Table 5 are far away from a strong interfacial fiber/
matrix bond which means that values obtained are related to a
weak adhesion.
5. Conclusions
Different treatments used modified sisal fibers properties as
well as sisal fiber/PLA adhesion. Alkali treatment removed some
non-cellulosic components as confirmed by FTIR and TGA. Alkali
treatment led to fibrillation of the sisal fiber bundles into smaller
fibers and surface roughness of the fibers was considerably
increased compared to untreated ones. In silane treated sisal fibers
Please cite this article in press as: Orue A et al. The effect of surface modifications on sisal fiber properties and sisal/poly (lactic acid) interface adhesion.
Composites: Part B (2014), http://dx.doi.org/10.1016/j.compositesb.2014.12.022
the presence of amino group was confirmed by FTIR analysis cor-
roborating that the silane chemical agent was successfully grafted
on the fiber. Silane treated fibers showed a polarity reduction
a which was in agreement with the amount of weight loss by water
1.3 evaporation observed in TGA thermograms. All treatments
2.2 decreased the tensile strength values of sisal fibers, especially
2.6 when the combination of NaOH + silane treatment was used. After
2.3
treating fibers, the IFSS value improved at least 120%. Alkali treat-
ment gave more surface area which can promote mechanical inter-
locking adhesion with PLA polymer. For silane treatment, the
increase of IFSS value observed could be due to the chemical bond-
ing between PLA and fibers through silane agent. However, IFSS
values obtained suggested that PLA/fiber adhesion was still weak.
Taking into account tensile properties of fibers and fiber/PLA
interfacial shear strength values, it is clear that the treatment
conditions have to optimize in order to obtain a fibrillated surface
with the highest tensile strength.
Acknowledgements
Authors are grateful for the financial support from the
Basque Country Government in the frame of Consolidated
Groups (IT-776-13). Technical and human support provided
by SGIker Macrobehaviour-Mesostructure-Nanotechnologie (UPV/
EHU, MINECO, GV/EJ, ERDF and ESF) is also gratefully acknowledged.
Also, the authors would like to thank Unai Unsuain for helping in
tensile properties measurements.
References
[1] Qu P, Gao Y, Wu GF, Zhang LP. Nanocomposites of poly(lactic acid) reinforced
with cellulose nanofibrils. Bioresources 2010;5(3):1811–23.
[2] Yu Y, Huang X, Yu W. A novel process to improve yield and mechanical
performance of bamboo fiber reinforced composite via mechanical treatments.
Composite Part B: Eng 2014;56:48–53.
[3] Lu T, Liu S, Jiang M, Xu X, Wang Y, Wang Z, et al. Effects of modifications of
bamboo cellulose fibers on the improved mechanical properties of cellulose
reinforced poly(lactic acid) composites. Composite Part B: Eng 2014;62:191–7.
[4] Arbelaiz A, Fernández B, Ramos JA, Retegi A, Llano-Ponte R, Mondragon I.
Mechanical properties of short flax fiber bundle/polypropylene composites:
influence of matrix/fiber modification, fiber content, water uptake and
recycling. Composite Sci Technol 2005;65(10):1582–92.
[5] Valadez-Gonzalez A, Cervantes-Uc JM, Olayo R, Herrera-Franco PJ. Effect of
surface treatment on the fiber-matrix bond strength of natural fiber reinforced
composite. Composite Part B: Eng 1999;30(3):309–20.
[6] Zhou F, Cheng G, Jiang B. Effect of silane treatment on microstructure of sisal
fibers. Appl Surf Sci 2014;292:806–12.
[7] Liu W, Mohanty AK, Drzal LT, Askel P, Misra M. Effects of alkali treatment on
the structure, morphology and thermal properties of native grass fibers as
reinforcements for polymer matrix composite. J Mater Sci 2004;39(3):1051–4.
[8] Koga H, Kitaoka T, Isogai A. In situ modification of cellulose paper with amino
groups for catalytic applications. J Mater Chem 2011;21:9356–61.
[9] Mohan TP, Kanny K. Chemical treatment of sisal fiber using alkali and clay
method. Composite Part A: Appl Sci Manuf 2012;43(11):1989–98.
ð4Þ [10] Joseph S, Sreekala MS, Thomas S. Effect of chemical modifications on the
thermal stability and degradation of banana fiber and banana fiber-reinforced
phenol formaldehyde composites. J Appl Polym Sci 2008;110(4):2305–14.
[11] Rachini A, Le Troedec M, Peyratout C, Smith A. Chemical modification of hemp
fibers by silane coupling agents. J Appl Polym Sci 2012;123(1):601–10.
[12] Arbelaiz A, Fernandez B, Cantero G, Llano-Ponte R, Valea A, Mondragon I.
Mechanical properties of flax fiber/polypropylene composites. Influence of
fiber/matrix modification and glass fiber hybridization. Composite: Part A
2005;36(2):1637–44.
[13] Mondragon G, Fernandes S, Retegi A, Peña C, Algar I, Eceiza A, et al. A common
strategy to extracting cellulose nanoentities from different plants. Ind Crops
Prod 2014;55:140–8.
[14] Arbelaiz A, Cantero G, Fernandez B, Mondragon I, Gañan P, Kenny JM. Flax fiber
surface modifications: effects on fiber physico mechanical and flax/
polypropylene interface properties. Polym Composite 2005;26(3):324–32.
[15] Gañan P, Mondragon I. Surface modification of fique fibers. Effects on their
physico-mechanical properties. Polym Composite 2002;23(3):383–94.
[16] Jamshidian M, Tehrany EA, Imran M, Akhtar MJ, Cleymand F, Desorbry S.
Structural, mechanical and barrier properties of active PLA-antioxidant films. J
Food Eng 2012;110(3):380–9.
[17] Luo S, Netravali AN. Characterization of henequen fibers and the henequen
fiber/poly(hydroxybutyrate-co-hydroxyvalerate) interface. J Adhes Sci Technol
2001;15(4):423–37.
 A. Orue et al. / Composites: Part B xxx (2014) xxx–xxx
[18] Van De Velde K, Kiekens P. Influence of fiber surface characteristics on the flax/
polypropylene interface. J Thermoplast Composite Mater 2001;14(3):244–60.
[19] De Rosa IM, Kenny JM, Puglia D, Santulli C, Sarasini F. Morphological, thermal
and mechanical characterization of okra (Abelmoschus esculentus) fibers as
potential reinforcement in polymer composites. Composite Sci Technol
2010;70(1):116–22.
[20] Łojewska J, Miskowiec P, Łojewski T, Proniewicz LM. Cellulose oxidative and
hydrolytic degradation: in situ FTIR approach. Polym Degrad Stabil
2005;88(3):512–20.
[21] De Rosa IM, Kenny JM, Maniruzzaman M, Moniruzzaman Md, Monti M, Puglia
D, Santulli C, Sarasini F. Effect of chemical treatments on the mechanical and
thermal behaviour of okra (Abelmoschus esculentus) fibers. Composite Sci
Technol 2011;71(2):246–54.
[22] Arbelaiz A, Fernandez B, Ramos JA, Mondragon I. Thermal and crystallization
studies of short flax fiber reinforced polypropylene matrix composites: effect
of treatments. Thermochim Acta 2006;440(2):111–21.
[23] Fernandes EM, Mano JF, Reis RL. Hybrid cork-polymer composites containing
sisal fiber: morphology, effect of the fiber treatment on the mechanical
properties and tensile failure prediction. Composite Struct 2013;105:153–62.
[24] Bogoeva-Gaceva G, Avella M, Malinconico M, Buzarovska A, Grozdanov A,
Gentile G, et al. Natural fiber eco composites. Polym Composite
2007;28(1):98–107.
[25] Mwaikambo LY, Ansell MP. Chemical modification of hemp, sisal, jute and
kapok fibers by alkalinization. J Appl Polym Sci 2002;84(12):2222–34.
[26] Le Moigne N, Longerey M, Taulemesse JM, Bénézet JC, Bergeret A. Study of the
interface in natural fibers reinforced poly (lactic acid) biocomposites modified
by optimized organosilane treatments. Ind Crop Prod 2014;52:481–94.
[27] Park JM, Quang ST, Hwang BS, DeVries KL. Interfacial evaluation of modified
jute and hemp fibers/polypropylene (PP)-maleic anhydride polypropylene
copolymers (MAPP) composites using micromechanical technique and
Please cite this article in press as: Orue A et al. The effect of surface modifications on sisal fiber properties and sisal/poly (lactic acid) interface adhesion.
Composites: Part B (2014), http://dx.doi.org/10.1016/j.compositesb.2014.12.022
7
nondestructive acoustic emission. Composite Sci Technol 2006;66(15):
2686–99.
[28] Doan TTL, Brodowsky H, Mader E. Jute fiber/epoxy composites: surface
properties and interfacial adhesion. Composite Sci Technol 2012;72(10):
1160–6.
[29] Silva FdA, Chawla N, Filho RDdT. Tensile behavior of high performance natural
(sisal) fibers. Composite Sci Technol 2008;68(15–16):3438–43.
[30] Rong MZ, Zhang MQ, Liu Y, Yang GC, Zeng HM. The effect of fiber treatment on
the mechanical properties of unidirectional sisal reinforced epoxy composites.
Composite Sci Technol 2001;61(10):1437–47.
[31] Fidelis MEA, Pereira TVC, Gomes OdFM, Silva FdA, Filho RDdT. The effect of
fiber morphology on the tensile strength of natural fibers. J Mater Res Technol
2013;2(2):149–57.
[32] Gassan J, Bledzki AK. Alkali treatment of jute fibers: relationship between
structure and mechanical properties. J Appl Polym Sci 1999;71(4):623–9.
[33] Sydenstricker THD, Mochnaz S, Amico SC. Pull-out and other evaluation in
sisal-reinforced polyester biocomposites. Polym Test 2003;22(4):375–80.
[34] Ray D, Sarkar BK. Characterization of alkali treated jute fibers for physical and
mechanical properties. J Appl Polym Sci 2001;80(7):1013–20.
[35] Islam MS, Pickering KL, Foreman NJ. Influence of alkali treatment on the
interfacial and physico-mechanical properties of industrial hemp fiber
reinforced polylactic acid composites. Composite Part A: Appl Sci Manuf
2010;41(5):596–603.
[36] Pickering KL, Sawpan MA, Jayaraman J, Fernyhough A. Influence of loading
rate, alkali fiber treatment and crystallinity on fracture toughness of random
short hemp fiber reinforced polylactide bio-composites. Composite Part A:
Appl Sci Manuf 2011;42(9):1148–56.
[37] Sawpan MA, Pickering KL, Fernyhough A. Effect of fiber treatments on
interfacial shear strength of hemp reinforced polylactide and unsaturated
polyester composites. Composite Part A: Appl Sci Manuf 2011;42(9):1189–96.