Composites: Part A 39 (2008) 1488–1495

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Composites: Part A
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Silane treatment of bagasse fiber for reinforcement of cementitious composites

K. Bilba, M.-A. Arsene *
Département de Chimie, EA 3592 UFR SEN, Laboratoire COVACHIMM, Université des Antilles et de la Guyane, Campus de Fouillole BP 250, 97157 Pointe-à-Pitre, Guadeloupe

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

Article history: Silane coating of fibers is a promising process for improving durability and adhesion of vegetable fibers
Received 22 September 2007 used as reinforcement material in a cementitious matrix. The work presented in this paper gives an
Received in revised form 7 May 2008 insight into the effect of combining pyrolysis treatment with silane treatment. Indeed, this study focuses
Accepted 24 May 2008
on silane treatment of unpyrolyzed and pyrolyzed sugar cane bagasse fibers with an alkyltrialkoxysilane
(RSi(OR0 )3), S1 or a dialkyldialkoxysilane (R2Si(OR00 )2), S2. The silane solutions used vary from 0.5% to 8% by
volume. This paper describes the effect of two silane compounds on parameters such as the porosity,
Keywords:
dimension, morphology and hygroscopic character of silane-coated sugar cane bagasse fibers.
A. Fibers
Bagasse fiber reinforced cement composites
Preliminary studies on natural fiber reinforced composite setting time show the importance of the silane
E. Heat treatment chemistry/structure, for fiber treatments with silane solution containing up to 6% (volume percent)
E. Surface treatment silane. In the case of composites reinforced with unpyrolyzed bagasse fibers, setting time increases with
silane coating. Combining pyrolysis and silane treatment improve the water resistance of the fibers,
which become more hydrophobic.
Ó 2008 Elsevier Ltd. All rights reserved.

1. Introduction treatment has been found to increase moisture-cycling resistance

Bagasse fiber is a by-product of the sugar cane industry whose
role is sugar, rum or biofuel production. This industry is located in
the tropical and sub-tropical regions of the world where sugar cane
(scientific name Saccharum officinarum) is cultivated. Sugar cane
bagasse is the leftover after crushing of the stalk to extract the su-
gar cane juice from which sugar is obtain by evaporation and crys-
tallization, and rum and ethanol which is used as biofuel, are
obtained by fermentation. The bagasse/stalk ratio by mass is
around 30%. Bagasse makes a sugar mill more than self-sufficient
in energy; the surplus bagasse can be used as animal feed, in paper
manufacture, or as fibers to replace asbestos in a cement matrix.
This last aspect of the use of sugar cane bagasse constitutes the
objective of this paper.
The advantage of vegetable fiber reinforced cement composites
(VFRC) lies in the improvement of mechanical [1–4] and thermal
[5,6] properties, and in the reasonable cost [7,8]. However, the
wide use of these materials is hampered by their low stability
[2,9–11]. The vegetable fiber in the porous alkaline matrix is slowly
damaged and the reinforcing effect of the fiber decreases. To im-
prove aging of the VFRC, two techniques were tested: (1) modifica-
tion of the matrix [12,13] and (2) fiber treatment [14,15]. This
second approach can have the advantage of improving the fiber–
matrix interface. In the case of VFRC with kraft or hardwood, silane
[16]. The effects of silane treatment on mechanical properties vary
with the nature of the vegetable fiber [17]: silane treatment in-
creases toughness of newspaper and kraft fiber-cement while the
modulus of rupture (MOR) and the modulus of elasticity (MOE) de-
crease for newspaper fiber-cement and increase for kraft fiber-ce-
ment [18].
Alkyltrialkoxysilanes R0 Si(OR)3 are often used in many indus-
trial application as coupling agent to improve adhesion between
a polymeric matrix and inorganic materials. They have also been
used in vegetable fiber–polymer composites [19,20] to modify fi-
ber surface. The mechanism of these coupling reactions is related
to the effect of two reactive surface groups and the reactions are
different according to the substrate in contact. On the one hand,
alkoxy groups (OR) allow the silane to bind to surface OH groups
after hydrolysis and, on the other hand, the alkyl groups R0 increase
the compatibility with organic compounds and the hydrophobic
character of the surface, thus leading to an increase in the strength
of the interface in the polymer matrix. Usually, silane treatment is
carried out with a dilute silane solution at 0.2% to 20% by weight
[17,18]. These conditions have the following advantages:
– an increase in the silane solubility,
– an improvement in the thickness of the surface film,
– the development of a uniform cover on the surface.

Water produces moderate hydrolysis of the silane and leads to

* Corresponding author. Tel.: +590 590 48 30 59; fax: +590 590 48 30 72. silanol. This behavior allows the adhesion of silanes onto the OH
E-mail address: maarsene@univ-ag.fr (M.-A. Arsene). groups of the fiber substrate.

1359-835X/$ - see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.compositesa.2008.05.013
 K. Bilba, M-A.M.-A. Arsene / Composites: Part A 39 (2008) 1488–1495 1489

After solvent evaporation, the residual silanol groups can condense
with the hydroxyl groups of the substrate, or can lead, by ‘‘self-conden-
sation” reactions, to a polysiloxane network on the surface. In aqueous
media, partially or totaly hydrolyzed silanes are reactive molecules
that change with time by self-condensation of silanol groups or con-
densation of silanol with alkoxy groups to form dimers or oligomers.
They are commonly used as commercial water repellents.
2. Materials
Sugar cane bagasse, the fibrous solid residue left over after juice
extraction from Sugar cane (S. Officinarum) – designated ‘‘B” – was
supplied by the Montebello distillery (Petit-Bourg, Guadeloupe).
Sugar cane bagasse fibers were obtained by milling using a labora-
tory blender.
Two commercial alkylalkoxysilanes provided by Sigma-Aldrich
company, commonly termed silanes S1 and S2 in the text, were
used. S1 is in fact an alkyltrialkoxysilane (RSi(OR0 )3) while S2 is a
dialkyldialkoxysilane (R2Si(OR00 )2).
The commercial ordinary portland cement (OPC) used was supplied
by Ciment Antillais (Lafarge Group). CIMABAT NF P 16-102 was com-
posed of 53.6% imported clinker, 42% local pozzolan and 4.4% gypsum.
3. Methods
3.1. Fiber treatment
Pyrolysis was performed on milled and sieved fibers in a tubular lab-
oratory furnace at 200 °C for 2 h under a nitrogen stream (grade U pro-
vided by Air Liquid, Bergevin, Guadeloupe) (2 l/h – at atmospheric
pressure). The pyrolyzed sugar cane bagasse fibers are designated ‘‘PB”.
Silane coating was performed by stirring an immersion of 5 g of fiber in
an emulsion of silane for 2 h. These treatments were performed on
unpyrolyzed and pyrolyzed fibers, for both alkylalkoxysilanes S1 and
S2 and with various volume fractions ‘‘X” of silane. Fiber treated in a
solution with X % of silane Si is designed ‘‘PBXSi” for pyrolyzed fibers
and ‘‘BXSi” for unpyrolyzed fibers.
3.2. Composite preparation and setting
VFRCs with 2% (by weight relative to cement weight) of short fibers
(0.4–1 mm diameter), with random fiber orientations, were prepared
from the untreated and treated fibers. The fibers were soaked for 2 h
in water. The wet fibers and the cement matrix were mixed with a spat-
ula to obtain a homogeneous paste. The mixture was then poured into a
plastic bag in order to be introduced into an adiabatic bottle.
The matrices, treatments and weight fractions of silanes are as
follows:
(1) control: CIMABAT paste matrix (the water/cement ratio by
weight is 0.42:1);
(2) cement reinforced with 2% by weight of unpyrolyzed (CB) or
pyrolyzed bagasse fiber (CPB);
(3) cement reinforced with 2% by weight of bagasse fiber B trea-
ted with solutions of X% (0.5 to 8%) of silanes S1 or S2, respec-
tively, CBXS1 or CBXS2;
(4) OPC reinforced with 2% by weight of pyrolyzed bagasse fiber
PB then treated with solutions of X% (0.5–8%) of silanes S1 or
S2, or CPBXS1 or CPBXS2, respectively.
3.3. Morphological and physical characteristics of the fibers
For these six treatments, 90–200 samples were studied in order
to perform a statistical analysis of the results.
3.3.2. Texture
After coating with gold, the cross-section and the surface of the
fibers, as well as the fracture surface of the composites were exam-
ined using scanning electron microscopy (SEM) in secondary elec-
tron mode (SE).
3.3.3. Porosity
Porosity of the fibers was studied by mercury intrusion porosi-
metry from 0.1–200 MPa with THERMOFINNIGAN Pascal 140 and
Pascal 240 mercury porosimeters. This range of pressure corre-
sponds to pore radius from 3.7 to 58 000 nm.
3.3.4. X-Ray photoelectron spectroscopy (XPS) analysis
A structural analysis of the chemical bond present on the fiber
surface and 1 nm under the surface was performed by XPS. The
surface area analysed was 150 lm in diameter and the thickness
was 1–2 nm.
3.3.5. Water sorption
The hygroscopic character of the fibers was estimated by intro-
ducing 100–180 mg of fibers into a closed container under con-
trolled static pressure of water. Partial pressure of water was
regulated at 0.83 P0 using a saturated solution of potassium chlo-
ride KCl, at a temperature of 35 °C [21]. Water uptake was mea-
sured at 24-h intervals until weight stabilization was obtained.
3.4. Composite setting
As the composite mix was prepared and poured into a plastic
bag, a thermocouple was introduced into the mix before placing
it in an adiabatic bottle. The setting temperature versus setting
time was monitored using HANNA Instruments HI92804C recorder
controller with a frequency of 15 min.
4. Results and discussion
4.1. Dimensional, morphological and structural study of the fibers
4.1.1. Dimensional analysis
The results in Fig. 1 show an increase in the dimensions of the
fibers after silane treatment. This trend is not significant consider-
ing the standard deviation of the results. This is observed for the
three dimensions of the fibers.
9
8 B
7 B6S1
B6S2
6
PB
5
PB6S1
4 PB6S2
3
2
1
0
)

)
m

2
)
m
(m

(m

(m

(m
ss
th

th

ne

ea
ng

id

3.3.1. Dimensions
W

ick

ar
Le

Th

ce

The length, width, and thickness of unpyrolyzed and pyrolyzed

rfa
Su

bagasse, uncoated or coated with 6% silane S1 or S2 solutions, were

measured using an optical microscope NIKON SMZ1000 (Japan). Fig. 1. Fibers dimensions.
1490 K. Bilba, M-A.M.-A. Arsene / Composites: Part A 39 (2008) 1488–1495

A direct consequence of the increase in the external surface area
that could be valuable, if the strength of the interface is preserved,
is the improvement in composite properties due to a better contact
between matrix and fiber.
4.1.2. Texture
While silanes cannot be directly identify by SEM, their effect
on bagasse fiber morphology is substantial. Silane treatment of
unpyrolyzed (Fig. 2a) or pyrolyzed bagasse fibers (Fig. 2b) change
the surface aspect of the fibers. After a 6% silane S1 treatment, the
surface of the fiber appears rougher with striations (Fig. 2c and
d). After treatment with a 6% silane S2 solution, surface texture
of fibers looks ‘‘granular” (Fig. 2e and f). We suggest that either
silane S2 partly covers the surface or causes, upon drying, crack-
ing of the surface microfibrils. In addition we noted a densifica-
tion of the fibers: the hollow structure of the pyrolyzed fibers
(Fig. 2b) disappears after treatment with a 6% silane S1 solution
(Fig. 2d).
4.1.3. XPS analysis
In Fig. 3, XPS spectra of unpyrolyzed fiber (Fig. 3a), unpyrolyzed
fiber treated by silane S1 (Fig. 3b) and unpyrolyzed fiber treated by
silane S2 (Fig. 3b), exhibit O, C, and Si peaks [22–25]. From the
experimental Si electron energy bonds (Table 2), according to
various authors [22–29], the following observations can be
deduced:

Fig. 2. Scanning electron micrography of bagasse fibers: (a) unpyrolyzed fiber; (b) pyrolyzed fiber; (c) unpyrolyzed fiber treated with silane S1; (d) pyrolyzed fiber treated
with silane S1; (e) unpyrolyzed fiber treated with silane S2; (f) pyrolyzed fiber treated with silane S2.
 K. Bilba, M-A.M.-A. Arsene / Composites: Part A 39 (2008) 1488–1495 1491

Fig. 3. XPS spectra of bagasse fibers: (a) unpyrolyzed fiber; (b) unpyrolyzed fiber treated with silane S1; (c) unpyrolyzed fiber treated with silane S2.

– mainly peaks related to SiC, SiO2C2 and SiO2 bonds are
reported on the surface,
– peaks related to Si are apparent 1 nm underneath the surface
after Silane S1 or S2 treatment,
– the signature of Si 2p apparent at 1 nm below the surface, for
unpyrolyzed and pyrolyzed fibers is present with low inten-
sity. This corresponds to the inorganic elements of the fibers
[6].
Obviously, the presence of Si atoms is more important after si-
lane treatment. Silanes are really grafted onto the surface, all sam-
ples present SiOxCy bonds due to linkages between the organic
surface and silane. The effect of pyrolysis pre-treatment is not
noticeable.
4.2. Physical characteristics of fibers
4.2.1. Water sorption
The water uptake by the different treated or untreated fibers
has been estimated under a partial water pressure equals to 0.83
P0, where P0 is the saturation vapor pressure of pure water at
35 °C according to Greenspan [21]. The experimental method is de-
scribed in Section 3.3. For pyrolyzed and unpyrolyzed fibers of ba-
gasse, silane treatment was realized with silane S1 or S2 using
1492 K. Bilba, M-A.M.-A. Arsene / Composites: Part A 39 (2008) 1488–1495

12
B (no treatment) B pyrolyzed

(Weight % of dry mass of fibers)

Table 1 B treated S1 PB treated S1
10 B treated S2 PB Treated S2
Porosity and density of treated and untreated bagasse fibers

Water absorption
B PB B6S1 PB6S1 B6S2 PB6S2 8
Total porosity (%) 69 74 87.13 83.39 91.26 85.69
Apparent density (g/cm3) 0.59 0.65 0.324 0.539 0.301 0.489 6
Bulk density (g/cm3) 1.88 2.03 2.521 3.252 3.480 3.412
4
B: untreated bagasse fiber;
PB: pyrolyzed bagasse fiber;
B6S1: unpyrolyzed bagasse fiber treated with silane solution (6% S1); 2
PB6S1: pyrolyzed bagasse fiber treated with silane solution (6% S1);
B6S2: unpyrolyzed bagasse fiber treated with silane solution (6% S2); 0
PB6S2: pyrolyzed bagasse fiber treated with silane solution (6% S2). 0% 0.5 4% 6%
Concentration of solution of silane (% by volume )

Fig. 4. Water absorption of untreated and treated sugar cane bagasse fibers.

silane solutions at 0.5%, 4%, and 6%. The main observations (Fig. 4)
are the following:

 fibers adsorb from 4% to 10% of their weight,

 unpyrolyzed fibers B are more hygroscopic than pyrolyzed fibers
PB,
 water absorption is lower after silane treatment for both unpy-
rolyzed (B) or pyrolyzed (PB) fibers,
 combination of pyrolysis and silane treatment has a cumulative
effect on water sorption,
 silane S2 usually exhibits greater repellent effect than silane S1.
 using solutions of up to 6% silane, water absorption decreases
with increasing silane content of the treatment solutions.

4.2.2. Porosity
Pore size distribution, presented in Fig. 5, is substantially the
same for unpyrolyzed and pyrolyzed bagasse fibers. There are
mainly macropores (>0.02 lm): 97.86% for unpyrolyzed and
Fig. 5. Pore size distribution in unpyrolyzed and pyrolyzed sugar cane bagasse
97.84% for pyrolyzed bagasse fibers. fibers.
The effect of pyrolysis is evident for the largest pores (50;
100 lm) obtained; they represent 15.59% from unpyrolyzed fibers
and 17.26% from pyrolyzed fibers. The total porosity measured is Regarding the botanical analysis, we noted that the increase in
69.4% from unpyrolyzed fibers and 73.70% for pyrolyzed fibers. porosity (4.27%) corresponds to the release of water and extractives
Pyrolysis causes some loss of material, which is one of the main that represent 4.65% of the total mass of fibers. As extractive com-
mechanisms involved in the creation of the largest pores. The cor- pounds that are present vary widely, this assertion cannot be based
responding density measurement is 1.88 g cm3 for unpyrolyzed on numerical data alone but is also supported by thermal degradation
fibers and 2.03 g cm3 for pyrolyzed fibers. studies of the fiber observed by DSC [20]. The lighter compounds,

Table 2
Bending Energy (eV) of unpyrolyzed bagasse fiber

Si 2p Bending Energy (eV)

SiC SiOC3 SiO2C2 SiO3C SiO2 Si–O–Si Si(OR)x Si(O)x
Reference
99.5–100.6 [25] 100.2–100.3 [26] 101.2–101.6 [25] 102.1–102.2 [25] 102.5–103.2 [24–27] 102.7 [28] 103.7 [28] 103.8 [28] (x > 2)
100.4–100.5 [26] 104.4 [29]
101 [27] 104.7 [26] 104.8–105 [28]
Sample
B 100.94 102.88
B6S1 100 101.66 103.2
B6S2 101.47 103.59
PB 101.52 103.19
PB6S1 100.7 102.25
PB6S2 102.07 103.43 105.,14

B: unpyrolyzed bagasse fiber;

B6S1: unpyrolyzed bagasse fiber treated with silane S1;
B6S2: unpyrolyzed bagasse fiber treated with silane S2;
PB: pyrolyzed bagasse fiber;
PB6S1: pyrolyzed bagasse fiber treated with silane S1;
PB6S2: pyrolyzed bagasse fiber treated with silane S2.
 K. Bilba, M-A.M.-A. Arsene / Composites: Part A 39 (2008) 1488–1495 1493

mainly volatiles and extractives, are eliminated after the pyrolysis

step. It is also possible to suggest the creation of pores that are closed
or inaccessible to mercury intrusion. It is also interesting to note that
porosity analysis confirms previous dimensional studies.
For both unpyrolyzed and pyrolyzed fibers, a treatment with 6%
silane enhances porosity as reported in Table 1.
Pyrolyzed fibers, that are initially more porous than unpyro-
lyzed fibers, exhibit after silane treatment lower porosity than fi-
bers only subjected to silane treatment. Raw fibers are more
sensitive to the increase in porosity. Silane S2 appears to be more
efficient than S1 as regards the creation of porosity. These observa-
tions are in perfect agreement with the dimensional analysis. An
hypothesis for the increase in porosity can therefore be proposed.
When hydrated, the presence of water in the pore leads to swelling
of the fibers. Upon drying, water is released and silanes act as a
frame that maintains pores and cell walls in their hydrated config-
uration, with high pore volume, even with normal humidity. Si-
lanes are known to react with hygroscopic surface OH groups
[30]. Chemical analyses indicate that the water content also de-
creases after pyrolysis. Pyrolysis reduces the hydrophilic proper-
ties of the fibers, and consequently the number of OH groups on
the surface. This decrease in OH groups could explain the lower
sensitivity of pyrolyzed fibers treated with silanes.

4.3. Composite morphology

The fracture surfaces of composites were observed by SEM. In

the case of a composite with unpyrolyzed fibers (Fig. 6a), the depo-
sition of the matrix on the surface of the fiber is not very dense. In
the case of composites with pyrolyzed fibers, we note that some fi-
bers exhibit debonding from the matrix. Pith particles seem to ex-
hibit better adhesion to the matrix.
Better interface is obtained after treatment with a solution of 6%
(weight %) silane S1. Indeed, Fig. 6b represents an unpyrolyzed fi-
ber treated by silane S1, opened lengthwise when breaking the
sample for SEM analysis: the fiber is not only disconnected from
the matrix but is cut along the fracture surface of the composite.
This illustrates the good adhesion between fiber and matrix after
silane treatment (6% silane S1).
The ultrastructure of the vegetable fibers is preserved and the
lumen of the cell of the fibers is observed. These photos show fibers
still covered with matrix after fracture, confirming the good adhe-
sion obtained after 6% silane S1 treatment. Both silanes improve
adhesion between the surface of the fiber and the cement matrix.
The mechanical properties are needed in order to confirm the cor-
responding bonding strength. Also, an evaluation of surface adhe-
sion of both silanes has to be carried out both quantitatively in
terms of the percentage of coated surface and qualitatively in
terms of an estimation of the physicochemical nature and orienta-
tion of silane molecules bonded to the surface.
4.4. Composite setting
The effects of silane treatment (chemical structure of the silane
and silane content) on material setting time were studied for com-
posites reinforced with 2% unpyrolyzed or pyrolyzed vegetable fi-
ber treated by silanes S1 or S2. In this paper, the term ‘‘setting
time” refers to the time it takes to reach the maximum temperature
during composite setting. In Fig. 7a, the maximum temperature re-
corded during composites setting, here termed ‘‘setting tempera-
ture”, is reported and in Fig. 7b, the corresponding setting time.
The treatment of unpyrolyzed fiber with the 0.5% solution of silane
(S1 or S2) reduces the setting time and increases the setting temper-
ature of the composite. At this low concentration, the water repel-
lent effect of silane enhances composite setting. As demonstrated
above, water uptake by the unpyrolyzed fiber decreases after treat-
Fig. 6. Scanning electron micrography of composites: (a) composite reinforced with
unpyrolyzed bagasse fiber (CB); (b) composite reinforced with unpyrolyzed bagasse
fiber treated with silane S1 (CB6S1).
ment with silanes, thus avoiding during composite production, (1)
competition between the absorption of water by the fibers and
hydration of the cement, (2) release of sugars by the fibers [31].
After fiber treatments with 0.5% silane solution, the variation in
temperature is the same, the highest setting temperatures are ob-
served at lower silane concentrations. The maximum setting tem-
perature decreases to a minimum for 4% silanes for raw fibers and
pyrolyzed fibers treated with silane S2. In the case of pyrolyzed fi-
bers treated with silane S1, the minimum setting temperature is ob-
served after a treatment with 2% silanes. Upon increasing the silane
fraction, the setting temperature reaches a second maximum after
treatment with a 6% silane solution. The trend is mainly related to
the nature of the silanes, the effect of pyrolysis being more limited.
For concentration of up to 4% silanes, setting temperatures are high-
er after treatment with silane S2. After treatment with silane S2, the
behavior is the same, with or without pyrolysis pre-treatment, with
regard to setting temperature (Fig. 7a) and setting time (Fig. 7b).
Trends in the setting time with the concentration of silane solu-
tion are different for each silane. Treatment with silane S2, for both
pyrolyzed or unpyrolyzed fibers leads to a constant setting time
(7–8 h) for all silane concentrations. The setting time increases with
increasing content of silane S1. The effect is greater for pyrolyzed fi-
bers. Composites with pyrolyzed fibers treated with silane S1 exhibit
1494 K. Bilba, M-A.M.-A. Arsene / Composites: Part A 39 (2008) 1488–1495
Fig. 7. Composite setting, influence concentration of silane solution used for fiber treatment: (a) maximum hydration temperature of composites versus concentration of
silane solution used for fiber treatment and (b) time corresponding to this maximum hydration temperature.
setting times 4–10 h longer than the corresponding composites with
unpyrolyzed fibers. Except for fibers treated with 4% and 8% silane
S1, the setting times are substantially identical. Nevertheless, com-
pared to the nature of the silanes, the effect of pyrolysis is insignifi-
cant. Further determination of the setting time of cement with either
a solution of ‘‘water + 2% silanes S1 or S2” or ‘‘water + 2% silanesS1 or
S2 + 2% fibers” indicates that the effect observed cannot be attrib-
uted to the solution of silanes in the matrix. Indeed, the setting times
for these last four experiments are similar, the exothermal hydration
reaction of the tricalcium silicate phase of cement, which usually oc-
curs 10 h after mixing, is not observed after 60 h. This observation
confirms that the behavior is related to the treatment of the fiber
and not to the presence of free silane in the cement paste that would
affect hydration of cement. These observations also suggest that
there is no free silane in the composites, and that adhesion between
silane and fiber is strong, particularly with silane S2.
To enhance the composite setting parameters, the optimal con-
centration of the silane solution for fiber treatment is less than 2%
in order to obtain the highest setting temperature and 0.5% in or-
der to obtain the shortest setting time.
5. Conclusion
5.1. Effect of pyrolysis
First of all, pyrolysis reduces the hemicellulose and extractives
content of vegetable fibers [13,20]. This leads to an increase in
porosity of 6%. If the dimensions of the fibers are not modified,
the surface morphology of the fibers changes, the surface rough-
ness increases, in theory improving adhesion and fiber/matrix
compatibility. Pyrolyzed fibers are also less hydrophilic; they can
thus potentially improve aging of fibers and composites. Their
use as reinforcement in composite materials leads to an increase
in setting time and a decrease in setting temperature.
5.2. Effect of silane coating
Silanes grafted onto the fiber surface form a network of polysi-
loxane molecules. They change the morphology of the fibers by
causing the swelling of the bagasse fibers, and they increase fiber
dimensions and porosity. Silane treatment also decreases water
adsorption by the fibers; this effect is more pronounced after silane
S2 treatment. The effects are the same for pyrolyzed fibers. Modifi-
cations are more extensive with silane S2 than with silane S1. Com-
posite setting is also better after silane S2 treatment: the setting
time is shorter and the setting temperature is higher. Silane coat-
ings are good candidates for improving the fiber–matrix interface
stability and they enhance cement adhesion onto the fibers. The fi-
bers are not pulled out after the fracture of composite.
After pyrolysis, silane grafting seems to be less extensive. The
combination of pyrolysis and silane treatments creates a lower
porosity than the corresponding silane treatment alone. Dimen-
sional changes are not influenced by additional pyrolysis. Compos-
ite setting is not modified by pyrolysis pretreatment. The only
important modification is the hydrophilic character of the fibers,
it strongly decreases with the cumulative contribution of both
pyrolysis and silane treatments.
Further work is planned to analyse the differences observed
between alkyltrialkoxysilane S1 and dialkyldialkoxysilane S2 treat-
ments and to validate the hypothesis proposed.
Acknowledgements
This research was supported by the Region Guadeloupe and
European Funds for Development project CPER-DOCUP 2000–2006
 K. Bilba, M-A.M.-A. Arsene / Composites: Part A 39 (2008) 1488–1495
project 23030 and COFECUB project 531/06. The authors would also
like to thank Florent Quiquerez (EEIGM) who did most of the exper-
imental work during his engineer training.
References
[1] Coutts RSP. Wood fibre reinforced cement composites. In: Swamy RN, editor.
Concrete technology & design, Vol. 5 Natural fiber reinforced cement and
concrete. London: Blackie; 1988. p. 1–58.
[2] Arsène M-A, Savastano Jr H, Allameh SM, Ghavami K, Soboyejo W. Cementitious
composites reinforced with vegetable fibers. In: Proceedings of the First
Interamerican conference on non-conventional materials and technologies in
the Eco-construction and Infrastructure, 13–16 November 2003, Joao-Pessoa
Brazil, IAC- NOCMAT 2003 Proceedings, ISBN 85-98073-02-4.
[3] Yue YL, Li GZ, Xu XS, Zhao ZJ. Properties and microstructures of plant-fiber-
reinforced cement-based composites. Cement Concrete Res 2000;30:1983–6.
[4] Aggarwal LK. Bagasse-reinforced cement composites. Cement Concrete
Compos 1995;17:107–12.
[5] Khedari J, Watsanasathaporn P, Hirunlabh J. Development of fibre-based soil–
cement block with low thermal conductivity. Cement Concrete Compos
2005;27(1):111–6.
[6] Bilba K, Arsène MA, Ouensanga A. Influence of chemical treatment of vegetable
fibers on insulating behavior of vegetable fibers/cement composites. In:
Proceedings of the Brazilian Conference on non-conventional materials and
technologies: Affordable housing and infrastructure, Brasil NOCMAT, 29
October to 3 November 2004, Pirassununga, Brasil, ISBN 85 98073 04 0.
[7] Savastano Jr H, Warden PG, Coutts RSP. Potential of alternative fibre cements
as building materials for developing areas. Cement Concrete Compos
2003;25:585–92.
[8] Savastano Jr H, Warden PG, Coutts RSP. Performance of low cost vegetable
fibre-cement composites under weathering. In; Proceedings of the CIB world
Building Congress, April 2001, Wellington, New Zealand; 2001:1–11.
[9] MacVicar R, Matuama LM, Balatinecz JJ. Aging mechanism in cellulose fiber
reinforced cement composites. Cement Concrete Compos 1999;21:189–96.
[10] Tolêdo Filho RD, Scrivener K, England GL, Ghavami K. Durability of alkali-
sensitive sisal and coconut fibres in cement mortar composites. Cement
Concrete Compos 2000;22:127–43.
[11] Savastano Jr H, Warden PG, Coutts RSP. Ground iron blast furnace slag as a matrix
for cellulose-cement materials. Cement Concrete Compos 2001;23:389–97.
[12] De Gutiérrez RM, Diaz LN, Delvasto S. Effect of pozzolans on the performance
of fiber-reinforced mortars. Cement Concrete Compos 2005;27:593–8.
[13] Arsène MA, Bilba K, Okwo AS, Soboyejo AB, Soboyejo WO. Tensile strength of
vegetable fibers: effect of chemical and thermal treatments. Mater Manufact
Process Special Issue 2007;22(2):214–27.
[14] Tolêdo Filho RD, Ghavami K, England GL, Scrivener K. Development of
vegetable fibre-mortar composites of improved durability. Cement Concrete
Compos 2003;25:185–96.
1495
[15] Blankenhorn PR, Blankenhorn BD, Silsbee MR, DiCola M, Kessler. Temperature
and moisture effects on selected properties of wood fiber–cement composites.
Cement Concrete Res 1999;29:737–41.
[16] Blankenhorn PR, Silsbee MR, Blankenhorn BD, DiCola M. Effects of fiber surface
treatments on mechanical properties of wood fiber-cement composites.
Cement Concrete Res 2001;31:1049–55.
[17] Pehanich JL, Blankenhorn PR, Silsbee MR. Wood fiber surface treatments level
effects on selected mechanical properties of wood fiber–cement composites.
Cement Concrete Res 2004;34:59–65.
[18] Couthino FB, Costa THS, Carvalho DL, Gorelova MM, de Santa Maria JC.
Thermal behaviour of modified wood fibers. Polymer Testing 1998;17:
299–310.
[19] Pothan LA, Thomas S. Polarity parameters and dynamic mechanical behaviour
of chemically modified banana fiber reinforced polyester composites. Compos
Sci Technol 2003;63:1231–40.
[20] Arsène MA, Bilba K, Ouensanga A. Study of banana and coconut fibers:
botanical composition, thermal degradation and textural observations.
Bioressour Technol 2007;68(1):58–68.
[21] Greenspan L. Humidity fixed points of binary saturated aqueous solutions. J
Res Natl Bureau Stand A 1977;81A(1):89–96.
[22] Valadez-Gonzalez A, Cervantes-Uc JM, Olayo R, Herrera-Franco PJ. Chemical
modification of henequen fibers with an organosilane coupling agent. Compos
B 1999;30:321–31.
[23] Tserki V, Zafeiropoulos NE, Simon F, Panayiotou C. A study of the effect of
acetylation and propionylation surface treatments on natural fibres. Compos A
2005;36:1110–8.
[24] Park B-D, Wi SG, Lee KH, Singh AP, Yoon T-H, Kim YS. X-ray photoelectron
spectroscopy of rice husk surface modified with maleated polypropylene and
silane. Biomass Bioenergy 2004;27:353–63.
[25] Shimoda K, Park J-S, Hinoki T, Kohyama A. Influence of SiC nano-sized powder
analyzed by X-ray photoelectron spectroscopy on basic powder
characteristics. Appl Surface Sci 2007;253:9450–6.
[26] Balat M, Berjoan R, Pichelin G, Rochman D. High-temperature oxidation of
sintered silicon carbide under pure CO2 at low pressure: active-passive
transition. Appl Surface Sci 1998;133:115–23.
[27] Sreemany M, Ghosh TB, Pai BC, Chakraborty M. XPS Studies on the oxidation
behaviour of SiC particles. Mater Res Bull 1998;33(2):189–98.
[28] Martin HJ, Schulz KH, Bumgardner JD, Walters KB. AnXPS study on the
attachement of triethoxsilylbutyraldehyde to two titanium surfaces as a way
to bond chitosan. Appl Surface Sci 2008;254(15):4599–605.
[29] Ben Ali M, Bessueille F, Chovelon JM, Abdelghami A, Jaffrezic-Renault N,
Maaref MA, et al. Use of ultra-thin organic silane films for the improvement of
gold adhesion to the silicon dioxide wafers for (bio)sensor applications. Mater
Sci Eng C 2008;28(5–6):628–32.
[30] Bilba K, Ouensanga A. Fourrier transformed infrared spectroscopic study of
thermal degradation of sugar cane bagasse. J Anal Appl Pyrol 1996;38:61–73.
[31] Bilba K, Arsène MA, Ouensanga A. Sugar cane bagasse reinforced cement
composites. Cement Concrete Compos 2003;25(1):91–6.