Bioresource Technology 98 (2007) 5868

Study of banana and coconut Wbers

Botanical composition, thermal degradation and textural observations
Ketty Bilba , Marie-Ange Arsene, Alex Ouensanga
Universit des Antilles et de la Guyane, UFR Sciences Exactes et Naturelles Laboratoire COVACHIMM, Chimie des Matriaux,
BP 250, 97157 Pointe Pitre Cedex, France

Received 9 September 2003; received in revised form 21 November 2005; accepted 22 November 2005
Available online 25 January 2006

Abstract

Four Wbers from banana-trees (leaf, trunk) and coconut-tree (husk, fabric) were examined before their incorporation in cementitious
matrices, in order to prepare insulating material for construction. Their botanical compositions have been determined following a method
described previously. Thermal degradation of these Wbers were studied between 200 and 700 C under nitrogen gas Xow. Temperature of
pyrolysis was the experimental parameter investigated. The solid residues obtained were analyzed by classical elemental analysis, Fourier
Transform Infra Red (FTIR) spectroscopy and were observed by Scanning Electron Microscopy (SEM). This study has shown (1) the
relation between botanical, chemical composition with both localization of Wbers in the tree and type of tree; (2) the rapid and preferential
decomposition of banana Wbers with increasing temperature of pyrolysis and (3) the rough samples are made of hollow Wbers.
2005 Elsevier Ltd. All rights reserved.

Keywords: Banana Wbers; Coconut Wbers; Carbonization; Thermal degradation

1. Introduction have also been suggested (Coutts et al., 1994) or eucalyptus

Asbestos Wbers had been used historically for insulating
houses. However, since January 1997, to provide protection
of workers and consumers, the manufacture and transfor-
mation of asbestos Wbers even if they are or are not incor-
porated in materials became forbidden in France (Journal
OYciel no. 300).
The introduction of an insulating material in cement
should improve the insulation characteristics of building
material. In order to obtain insulating low cost materials
for construction (Aziz et al., 1981), the mixing of cement
with vegetable Wbers (VF)as banana (Zhu et al., 1994),
coir and sisal (Savastano and Agopyan, 1999; Savastano
et al., 1999), malva (Savastano and Agopyan, 1999), sugar-
cane bagasse (Bilba et al., 2003)has been proposed to pre-
pare composites. Mixtures of cement and pulps as bamboo
*
Corresponding author. Tel.: +33 590 938709; fax: +33 590 938787.
E-mail address: Ketty.Bilba@univ-ag.fr (K. Bilba).
(Coutts, 1987; Savastano et al., 1999).
Macroscopic behavior of VF reinforced cement, mortar
or concrete have been studied by various authors (Aziz
et al., 1981; Savastano et al., 2000; Savastano, 2001). Mech-
anical characteristics such as compressive and tensile
strength, fracture toughness, are the most widely studied
(Coutts et al., 1994; Zhu et al., 1994; Savastano and Ago-
pyan, 1999; Al Rim et al., 1999; Savastano, 2001; Smaoui
et al., 2005). Physical properties of composites such as
density, porosity, setting, have also been investigated (Cou-
tts et al., 1994; Zhu et al., 1994; Al Rim et al., 1999; Savast-
ano, 2001; Arsne et al., 2001). Research eVorts have been
focused on thermal behavior of VF reinforced cement
(VFRC), they have been published by Al Rim et al. (1999),
Khedari et al. (2001), Chung (2001), Kim et al. (2003),
Mangal et al. (2003), Cerny et al. (2003) and Khedari et al.
(2005).
The incorporation of vegetable Wbers mostly residues of
agriculture and agro-industries, allows a valorization of
these wastes and a limitation of environmental damages.

0960-8524/$ - see front matter 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2005.11.030
 K. Bilba et al. / Bioresource Technology 98 (2007) 5868
Previously, it has been demonstrated that natural Wbers can
reinforce concrete and exhibit the same performance
behavior as that of conventional Wber reinforced concrete
produced from steel and other inorganic/synthetic Wbers
(Aziz et al., 1981). Other authors have indicated that the
performance of tiles made with composites of blast furnace
slag based cement mortar reinforced with vegetable Wbers
(malva, sisal, coir) was in accordance with international
requirements (Savastano and Agopyan, 1999). Khedari
et al. (2001) have shown that the addition of Wbers of Wber
from young coconut and durian in mortar reduced thermal
conductivity specimen and yield a lightweight of the com-
posite, this decrease being inversely related to the amount
of pores. The addition of wood aggregates (wastes from
joiners workshops) to a mixture claycement improves
insulation characteristics of composites (Al Rim et al.,
1999). Khedari et al. (2003) indicated that the manufactur-
ing particleboards with a low thermal conductivity is an
economic and interesting option for speciWc applications as
an insulating ceiling and walls. Finally apart from energy
consumption for the building, the proposed VF reinforced
cement, mortar or concrete oVer an alternative option to
dispose biomass wastes.
However, the VF composites are facing durability limi-
tations (Al Rim et al., 1999; Toldo Filho et al., 2003). The
knowledge of chemistry and texture of VF should establish
a correlation between the microscopic behavior of Wbers
and the macroscopic performances of composites including
durability considerations.
Results on the chemical nature of VF are reported else-
where. A chemical study of Coreido et al. (2004) on annual
plants, a banana pseudo-stem of Portugal, has shown that
these Wbers have high ash and low levels of lignin so the
deligniWcation is relatively easy. They also possess high
holocellulose (cellulose + hemicellulose) contents meaning
a hemicellulose/cellulose ratio of 1.2 which is very impor-
tant if one considers the primary role which hemicellulose
plays in papermaking (Coreido et al., 2004). The thermal
degradation of sugarcane bagasse has been examined,
demonstrating that the lignin is more thermally stable and
hemicellulose the less stable (Ouensanga and Picard, 1988;
Bilba and Ouensanga, 1996). Bourgeois et al. (1989) also
reported the thermal treatment of torriWed wood, showing
that the chemical structure of wood was strongly altered
by thermal treatment (temperature, duration of heat).
Fekadu and Ledin (1997) have studied a banana-like
perennial herbaceous plant collected in Ethiopia, showing
that there was a substantial diVerence in the content of dry
matter, crude protein of the corm and lignin of the sheath
of the plant parts (leaf, pseudo-stem and other compo-
nents). The eVect of various chemical treatments as NaCl
(Low and Morterra, 1985) and KHCO3 (Morterra and
Low, 1985) on cellulose pyrolysis in vacuum and char oxi-
dation, corresponding to a chemical activation of the char,
have been analyzed. The chemical composition of mari-
time pine bark with or without alkaline extraction has
been investigated by Frandinho et al. (2002) from trees
59
grown in Portugal. They have shown that the bark was
composed of lignin and polyphenolics (44 wt%), polysac-
charides (39 wt%), dichloromethane, ethanol and water
extractives (17 wt%) and ashes (1 wt%). Sun et al. (2004)
proposed procedures for isolation of cellulose of bagasse.
A one-step treatment of sugarcane bagasse with acetic
acid and nitric acid were relatively free of associated lig-
nin. The use of pyrolysis assisted with hydrogen pressure
on oak wood has been described as a potentially rapid
procedure for obtaining lignin-enriched residues from
wood (Beramendi-Orosco et al., 2004). Mosier et al. (2005)
proposed an experimental investigation of physical
changes and chemical reactions that occur during pretreat-
ment of lignocellulosic biomass.
The research presented involves determination of botan-
ical composition, thermal degradation and textural studies
of banana and coconut Wbers, which are abundant in Gua-
deloupe.
2. Experimental
Banana and coconut Wbers were obtained from banana-
trees (Musa acuminata) and coconut-tree (Cocos nucifera
L.) collected in Guadeloupe. Banana is a high herbaceous
plant (216 m high), composed of long Wbers strongly over-
lapping forming a pseudo-stem. Banana-trees produce gen-
erally 30 large leaves (almost 2 m long and 3060 cm wide).
Two parts of a banana-tree were studied, leaves (BL) and
the pseudo-stem core (BC). The coconut-tree is a very high
monocotyledon (2030 m), plant containing 2526 leaves.
Two parts of a coconut-tree were also studied, the husk of
the fruit shell (CH) and the fabric located at the bottom
of the leaves (CF), coming from the young leaves sheaths.
After cutting, the samples were dried in air during a week,
then at 50 C in an oven two days for banana Wbers. The
four samples were crushed, and only particles from 0.125 to
0.400 mm diameter, the recommended size for botanical
analysis (Ouensanga, 1989), were retained for analysis and
experiments.
The method used for determination of botanical com-
positions of the samples has been described previously
(Ouensanga, 1989). Four to six samples were used for this
work, those four to six values allowed us to calculate the
average values, the standard deviation (SD) and the 95%
probability conWdence intervala normal distribution of
resultsfor each botanical component quantiWed. Those
calculations were performed with the help of Statistica 6
software (Statsoft Incorporation, Tulsa, OK 74104).
An alumina crucible with approximately 0.25 g of Wbers
was placed in the homogeneous temperature zone of a reac-
tor, consisting of a laboratory quartz tube heated from
room temperature to the holding temperature under a
nitrogen gas Xow of 2 L/h, at a heating rate of 10 C/min.
The inXuence of the maximum temperature of pyrolysis
(200700, 900 C for BC samples) was studied. After each
experiment, the samples were cooled down to room temper-
ature under a nitrogen gas Xow.
 60

Table 1
Elemental analysis (wt% of dry solid) of the raw and pyrolyzed Wbers obtained as a function of pyrolysis temperature
Sample C H N O Sum Dry residue General formula Relative ratio (Rr)
(C + H + N + O)
C/sum H/sum N/sum O/sum
BL 44.01 0.22 6.10 0.03 1.360 0.007 38.84 0.19 90.31 0.45 6.56 0.03 CH1.66O0.66N0.03 0.487 0.067 0.015 0.430
[0.4780.497] [0.0660.069] [0.01470.0153] [0.4220.438]
BC 36.83 0.18 5.19 0.02 0.930 0.005 43.62 0.22 86.57 0.43 6.43 0.03 CH1.69O0.89N0.02 0.425 0.060 0.011 0.504
[0.4170.433] [0.0590.061] [0.0100.011] [0.4930.509]
CH 46.22 0.23 5.44 0.03 0.360 0.002 40.47 0.20 92.49 0.46 1.660 0.008 CH1.41O0.66N0.007 0.499 0.059 0.004 0.437
[0.4890.509] [0.05760.0600] [0.00380.0039] [0.4290.446]
CF 42.23 0.21 5.69 0.03 0.440 0.002 45.57 0.23 93.93 0.47 4.31 0.02 CH1.62O0.81N0.009 0.449 0.060 0.005 0.485
[0.4410.454] [0.0590.062] [0.00460.0048] [0.4750.495]
Bagasse 45.50 5.60 0.30 45.20 96.60 CH1.48O0.78N0.006 0.471 0.058 0.003 0.468
(Ouensanga,
1989)
BC (300 C) 38.01 0.19 3.11 0.01 28.36 0.14 1.080 0.005 70.56 0.35 16.70 0.08 CH0.98O0.02N0.60 0.539 0.044 0.401 0.0153
[0.5280.546] [0.04330.0447] [0.3940.410] [0.01500.0156]
BC (700 C) 39.89 0.20 1.570 0.008 23.63 0.12 0.670 0.003 65.76 0.33 21.82 0.11 CH0.47O0.01N0.47 0.606 0.024 0.359 0.0102
[0.5950.618] [0.02340.0243] [0.3520.366] [0.01000.0104]
CF (300 C) 51.29 0.26 4.40 0.02 29.70 0.15 1.020 0.005 86.41 0.43 11.66 0.06 CH1.03O0.01N0.46 0.593 0.051 0.344 0.0118
K. Bilba et al. / Bioresource Technology 98 (2007) 5868

[0.5810.605] [0.05000.0519] [0.3370.350] [0.0110.012]

CF (700 C) 65.36 0.33 1.470 0.007 9.60 0.05 0.460 0.002 76.89 0.38 20.61 0.10 CH0.27O0.005N0.12 0.850 0.019 0.125 0.006
[0.8330.858] [0.01870.0195] [0.1220.127] [0.00580.0061]
Between brackets, 95% probability conWdence intervals assuming a normal distribution of the results.
 K. Bilba et al. / Bioresource Technology 98 (2007) 5868 61

0.6

0.5

0.4

C/Sum
0.3
H/Sum
N/Sum
0.2 O/Sum

0.1

0.0
BL BC CH CF

Fig. 1a. Elemental relative ratios of studied Wbers. Fig. 1b. Bar diagrams of botanical components of studied Wbers.

The structure of the diVerent solid residues obtained
were studied by Fourier Transform Infra Red (FTIR) spec-
troscopy. Spectra were recorded in air by use of a FTIR
Nexus spectrometer (Thermo Optek, Division Thermo Nic-
olet, ZA du Pas du lac, Montigny le Bretonneux, France).
The analysis software used was Omnic 5.2 provided by
Thermo Nicolet (ZA du Pas du lac, Montigny le Breton-
neux, France). Elemental analysis were performed by the
Service Central dAnalyse du CNRS Vernaison (France).
Measurement precision was approximately 0.5%. Fibers
were coated with gold before SEM observations. The
microscope used was an Hitachi-S2500 model (Elexience,
BP 61, Verrires Le Buisson, France).
3. Results and discussion
3.1. Chemical analysis of raw Wbers
The results of elemental analysis, with the corresponding
standard deviations (SD), were listed in Table 1. In this
table, the relative ratioselement amount/sum amount
and general formulas were calculated in order to make
comparisons. In the square brackets are also presented the
relative ratios for 95% probability interval conWdence and
reported in Fig. 1a. According to the relative ratios, the
general formulas and the distance between the various
square brackets, we noted some diVerences in the composi-
tion. For banana raw Wbers, the contents of O appeared to
decrease from trunk to leaves while the amounts of C, H, N
appeared to increase. For coconut Wbers, H, O and N con-
tents seemed to decrease from the bottom of the leaves
sheaths (CF) to fruits (CH). In fact, the contents of C, H, O
and N elements vary with the localization of the studied
sample in the tree. When we performed statistical analysis,
it was conWrmed that banana and coconut raw Wbers did
not have similar elemental composition. For both species,
the highest relative ratio in mass was obtained for carbon
and oxygen; particularly for BL and CH in case of carbon,
BC and CF for oxygen. The upper part of the trees con-
tained more carbon (leaves and fruits) while more oxygen
was located in the lower part of the tree (trunk and leaves
sheaths), it is in the core that the nutrients Xow. In fact, the
contents of C, H, N, O elements vary with localization in
the tree, as shown by Marquez Montesino et al. (2003) for
eucalyptus.
For banana-tree Wbers, the relative amounts of nitrogen
were always higher than in the coconut-tree Wbers and this
may be due to the fact that banana Wbers derive from green
precursors. Indeed Lttge et al. (1992) showed that dry
green wood, wheat seed, can contain up to 14.3% of organic
nitrogen. It is the reason why banana-tree, which is rich in
nitrogen element, can be used as a fertilizer in banana-tree
plantations after cutting the banana branch (Lttge et al.,
1992; Demeyer et al., 1981).

Table 2
Botanical composition of studied Wbers (wt%)
Sample BL BC CH CF
Cellulose 25.75 1.42 [22.9728.53] 31.27 3.61 [24.1938.34] 21.22 1.44 [18.4024.04] 30.57 2.88 [24.9236.21]
Hemicellulose 17.08 1.11 [14.9019.25] 14.98 2.03 [11.0018.96] 12.69 2.34 [8.1017.28] 19.45 3.46 [12.6726.23]
Lignin 24.84 1.32 [22.2527.43] 15.07 0.66 [13.7816.36] 46.50 1.73 [43.1149.89] 29.38 4.36 [20.8337.92]
Partial amount, PAa 67.67 3.85 61.32 6.30 80.41 5.51 79.40 10.70
Extractives 9.84 0.11 [9.6210.05] 4.46 0.11 [4.244.67] 8.77 0.39 [8.009.53] 1.74 0.71 [0.353.13]
Moisture 11.69 0.03 [11.6311.75] 9.74 1.42 [6.9612.52] 13.68 0.05 [13.5813.78] 5.90 1.84 [2.299.51]
Ashes 7.02 0.79 [5.478.57] 8.65 0.10 [8.458.84] 1.05 0.90 [02.81] 8.39 0.48 [7.459.33]
Suma 96.22 4.78 [91.44101.00] 84.77 7.93 [76.8492.70] 103.91 6.85 [97.06110.76] 95.43 13.73 [81.70109.16]
Between brackets, 95% probability conWdence intervals assuming a normal distribution of the results conWdence.
a
Cumulative standard deviation (SD).
62 K. Bilba et al. / Bioresource Technology 98 (2007) 5868
The gaps between the relative amounts H/sum ratios were
not signiWcant for BC, CH and CF while it was for BL Wbers;
this showed that BL samples contained more hydrogen than
other Wbers. This may be because banana-tree leaves contain
more water than coconut-tree leaves. This assumption was
true only for BC and CF because in Table 2, the moisture of
BL is higher than that of BC and CF. However, it was not
veriWed for CH samples. BL Wbers contained more hydrogen
possibly because BL had less double linkages than other
samples but it was not conWrmed in Table 2. Comparison of
relative ratios of BL, BC, CH, CF and bagasse samples, par-
ticularly the (C + O)/sum ratios, showed that CH, CF and
bagasse possess similar compositions.
The amounts of dry solid residues of banana and coco-
nut Wbers were not comparable, banana Wbers deriving
from green wood contain higher amounts than coconut.
For banana Wbers, the contents of dry solid residue in
leaves and in the core were equivalent and seemed to be
independent of the localization in the tree. However, for
coconut Wbers, the amount of dry solid residue varied with
localization in the tree, it was higher in CF than in CH. The
amounts of dry solid residues (Table 1) and ashes (Table 2)
were comparable only for BL and CH, the banana leaves
and coconut husk.
The botanical compositions of the four studied Wbers
were presented in Table 2, with their corresponding stan-
Fig. 2. FTIR spectra of raw Wbers.
dard deviation and 95% probability conWdence intervals
(Fig. 1b). The precision of the measurements varied from
0.2% for the moisture of BL samples for example up to 86%
for the ash content of CH samples. These results show that
the method used leads to a large variability of the botanical
composition of studied Wbers. The square brackets values
and Fig. 1b showed that the gaps between the various
amounts were signiWcant for cellulose only for CH samples;
for lignin with regards to BC and CH, for extractives and
moisture in the four Wbers and for ashes only for CF. For
the primary botanical components, this showed that (1) CH
samples contained less cellulose than other Wbers, (2) the
amount of hemicellulose were comparable for the four sam-
ples and (3) BC Wbers contained less lignin. The values of
PAmajor components (cellulose, hemicellulose, lignin)
presented in square brackets, calculated according to the
standard deviations showed that there were no signiWcant
diVerences of the PA values of banana Wbers (BL, BC) and
coconut Wbers (CH, CF). This observation indicated that the
diVerences between values were not signiWcant and therefore
no conclusion could be drawn for Wbers of the same tree.
Also the contents of dry solid residue and hemicellulose of
banana Wbers were not dependent of localization in the tree.
With lignin being responsible for mechanical strength
and compactness of wood as proposed by Dumon and
Glus (1982), then banana Wbers BL samples should be
 K. Bilba et al. / Bioresource Technology 98 (2007) 5868
more rigid than BC. BL samples exhibited equivalent 95%
probability conWdence intervals for cellulose and lignin.
For BC Wbers, the relative amounts of hemicellulose and
lignin were similar.
For coconut, although partial amounts were equal,
repartition of cellulose, hemicellulose and lignin was not
the same in husk and fabric Wbers. Lignin content was
higher in CH Wbers while the relative amounts of cellulose
and lignin were similar in CF Wbers, CH Wbers should be
more rigid than CF Wbers (Lttge et al., 1992). Banana
Wbers should be less rigid than coconut Wbers because they
contained less lignin, as shown by their respective amounts.
However, as proposed by Bledzki and Gassan (1999), this
behavior depends on the degree of polymerization of the
cellulose. Indeed, Lttge et al. (1992) indicated that lignin
allowed the formation of strong cellular walls, which
allowed elaboration of high plants with independent bear-
ing. This precision can explain the diVerences of contents of
lignin in Table 2. Consequently, as expected for banana and
coconut Wbers, the highest amounts of lignin were those
from the tallest sample in the tree, the leaves for banana-
tree and the coconut fruit for coconut-tree.
3.2. Chemical analysis of pyrolyzed Wbers
The results of elemental analysis of pyrolyzed Wbers are
presented in Table 1, with those of raw Wbers for compari-
Fig. 3a. FTIR spectra of banana-trees leaves (BL) pyrolyzed Wbers.
63
son. In Table 1, the elemental analysis are presented for BC
and CF Wbers pyrolyzed at 300 C because the major diVer-
ences in the structure of the Wbers appeared at this tempera-
ture (Figs. 2 and 3). In this table, the elemental analysis of
BC and CF Wbers heat-treated at their higher pyrolysis-
temperature is shown. The sum was always smaller than
100% showing that those Wbers contained mineral elements,
in particular the BC ones which exhibited the smallest sum.
The mineral elements were mostly non-volatile elements
and they were the main constituents of the ashes of the
Wbers (Ouensanga et al., 2003). This total percentage
decreased with thermal treatment and when the tempera-
ture increased, for all samples, showing a carbon enrich-
ment from a raw Wber to the corresponding pyrolyzed
Wbers. The relative carbon ratios in the chars increased with
temperature. After pyrolysis, the relative ratios of H and O
decreased and there were no statistical diVerences, while an
increase of nitrogen relative ratios was noted. The highest
nitrogen relative amounts were observed at 300 C. The
decrease, from room temperature to maximal temperature
of pyrolysis, of hydrogen amount was linear, while oxygen
and nitrogen were not.
It appeared that the decomposition of the CF samples
was more important at lower temperature than that of the
BC samples because at 300 C the relative carbon enrich-
ment is higher in case of CF than for BC Wbers (Table 1).
This could be a consequence of the degradation of lignin
64 K. Bilba et al. / Bioresource Technology 98 (2007) 5868
Fig. 3b. FTIR spectra of banana-trees core (BC) pyrolyzed Wbers.
which starts around 250 C as shown by Ouensanga and
Picard (1988); lignin being most abundant in CF than in
BC according to Table 2. The preferential degradation of
CF was mostly related to the higher content of lignin.
At high temperature (700 C), the carbon enrichment
continued as shown by the growth of its relative amount.
The chars which contained the highest amount of carbon
and the lowest amount of H, N, O was CF samples, con-
Wrming the easier decomposition of CF than BC Wbers.
3.3. Structural study
FTIR spectra of the raw Wbers were presented in Fig. 2.
IdentiWcation of the most important peaks is based on pre-
vious studies of bagasse Wbers (Bilba and Ouensanga,
1996), carbonaceous char (Meldrum and Rochester, 1991),
coal (Ibarra and Moliner, 1991) and spectra of commercial
cellulose and lignin. The initial work enables the identiWca-
tion of the nature of the chemical linkages, while the
spectra of the commercial cellulose and lignin can identify
the contribution of these components in the spectra. Spec-
tra of BL, BC, CH and CF raw samples exhibited a strong
band at 1036 cm1 due to CAOAC symmetric stretching
dialkyl ether linkages and CAO stretching vibration in
cellulose, hemicellulose and minor lignin contribution. A
large band 36003100 cm1 characteristic of the polymeric
association of the hydroxyl groups and the bonded OAH
stretching vibration present in carbohydrates (cellulose +
hemicellulose) and lignin. A large region of absorption
involving overlapping bands in the range of 1700
1100 cm1 due to CAC, CBC, OH, CO, CHn, CAOAC,
CH aromatic linkages; bands at 2910, 2850, 1416, 700
900 cm1 due to vibrations of CHn (aliphatic and aromatic)
present in carbohydrates and lignin. When comparing spec-
tra of raw Wbers and those of commercial lignin and cellu-
lose, the peak at 2910 cm1 was mostly composed of lignin
while the one at 2850 cm1 essentially consisted of cellulose.
All samples contained similar bands, but diVerences in their
intensities were noted. For all of them the strongest peak
occurred at 1036 cm1.
After pyrolysis (Figs. 3a3d), the main diVerences
appeared at 300 C, while for bagasse Wbers they usually
appear at 200 C (Bilba and Ouensanga, 1996). At this tem-
perature a decrease of intensities of OH, CAO, CBO,
CAC, CAOAC bands, an increase for CBC band and an
overlapping of peaks between 1100 and 1700 cm1 were
observed for all the samples. At 300 C (Fig. 3c), CF
samples had the strongest band at 1038 cm1; in agreement
with their highest partial amounts (Table 1). When temper-
ature increases up to 600 C, the pattern of decreasing
intensities of the bands went on and CF samples seems to
have the strongest band at 1038 cm1. When comparing
spectra of banana-trees Wbers and coconut-tree ones, it
seems that banana-trees samples decomposed more rapidly
 K. Bilba et al. / Bioresource Technology 98 (2007) 5868
Fig. 3c. FTIR spectra of banana-trees core (BC) and coconut fabric (CF) pyrolyzed Wbers.
than coconut-tree samples. Once again, the characteristic of
green wood was observed.
When comparing spectra of Wbers coming from the same
banana species (BL, BC), heat-treated between 300 and
600 C (Figs. 3a and 3b), it appeared that at 300 C for both
samples the strongest band was not the one observed at
1036 cm1 (CAOAC and CO groups) as for the raw Wbers
but approximately at 1600 cm1 for the 300 C pyrolyzed
samples. This band at 1600 cm1 corresponded to the aro-
matic skeletal modes of lignin and CBC stretching vibra-
tion of benzene ring. This behavior agreed with the
evolution of general formula. At 300 C, for BL, the two
other main peaks were at 1314 cm1 (OH groups of carbo-
hydrates) and at 778 cm1 (CH aromatic of carbohydrates
and lignin); while BC Wbers were approximately 1550 cm1
(CO and aromatic skeletal modes of carbohydrates and lig-
nin) and 778 cm1, respectively. This showed that at low
pyrolysis temperature, there was a preferential degradation
of CBO linkages for both BL and BC samples and an
increase in the amount of OH linkages present in carbohy-
drates for BC.
At 400 C, the amount of CBO linkages was still lower
for pyrolyzed Wbers than for raw samples; it was right for
BL and BC. The strongest band, for BL and BC, was at
1414 cm1, it corresponded to CAH bending of cellulose,
hemicellulose and lignin. At 400 C, peaks at 1600 and
1314 cm1 remained intense. The band at 878 cm1 due to
65
vibrations of CH species and inorganic compounds became
more intense showing that the pyrolysis led to decarbonyla-
tion and decarboxylation reactions and also to formation
of more inorganic compounds.
At 500 and 600 C, the main diVerences were a decrease
of the intensity of the band at 1600 cm1 (CBC stretching
vibrations of benzene ring, aromaticity of lignin) for BL
and BC, an important overlapping in the range 1135
1000 cm1 for BL samples, a disappearance of the broad
signal due to OAH stretching (36003000 cm1) and an
increase of the intensity of the peak at 878 cm1.
Between 300 and 600 C, (1) the localization of the Wbers
in the banana-tree (BL or BC) had no great inXuence on the
mechanism of thermal degradation of BL and BC samples,
(2) the degradation of banana samples began by a reduc-
tion of CBO linkages which led to an increase of aromatic
skeletal modes of lignin, OH, CO groups of carbohydrates
at low temperature; and at high temperature essentially
CAH bending were observed.
Spectra of the two studied species, banana and coconut,
at two temperatures (300 and 600 C) are shown in Fig. 3c.
At 300 C, most of the bands existed in both samples but
their intensities were diVerent, as expected according to
their botanical initial composition (Table 2). Indeed, for BC
Wbers, the four more intense peaks appeared at approxi-
mately 1608, 1560, 1318 and 775 cm1; while CF Wbers were
approximately 1021, 1420, 1460 and 1391 cm1. BC Wbers
66 K. Bilba et al. / Bioresource Technology 98 (2007) 5868

Fig. 3d. FTIR spectra of banana-trees leaves (BL) pyrolyzed Wbers.

contained more lignin than CF samples, the CF pyrolyzed

Wbers contained more cellulose + hemicellulose. At 600 C,
the decrease of aromatic skeletal modes of lignin was 2-fold
more rapid for CF than for BC samples. For CF, in the
range 9001300 cm1, the broad signal from widening of
the peaks conWrmed the important degradation of the
structure.
In Fig. 3d, spectra of pyrolyzed BL Wbers were presented
in order to show the structural degradation of samples after
pyrolysis. After heat-treatment at 900 C, essentially only
bands due to aromatic hydrogen and mineral oxides vibra-
tion were still present. The comparison of structural study
of BL and bagasse (Bilba and Ouensanga, 1996) Wbers dem-
onstrated that the thermal degradation of bagasse appeared
to start at lower temperature (200 C) than that of BL sam-
ples.

3.4. Textural observations

All untreated samples were made of rough particles.

Each particle was formed of hollow not cylindrical Wbers
(Fig. 4), whose walls presented small hazardous porosities
whose size is smaller than 1 m. The walls were made of
Wbrils embedded in a homogeneous matrix (Fig. 5), the
diameter of those Wbrils was approximately 1 m. As pro-
posed by Lttge et al. (1992), Wbrils were probably com-
posed of cellulose which constitutes the skeleton of cellular
Fig. 4. SEM image of a raw particle of banana-trees core (BC).
wall, the homogenous matrix a mixture of various poly-
saccharide acids, neutral ones (hemicellulose) and lignin
(Lttge et al., 1992). In Figs. 4 and 5, Wbrils appeared to be
quite parallel, this arrangement is characteristic of second-
ary wall of plants, layers S1 or S3 (Lttge et al., 1992). After
 K. Bilba et al. / Bioresource Technology 98 (2007) 5868
Fig. 5. SEM image of a wall of a raw Wber of banana-trees core (BC).
Fig. 6. SEM image of pyrolyzed (300 C) particles of banana-trees core
(BC).
pyrolysis, surface of particles became rougher (Fig. 6) and
diameter of walls decreased by loss of vegetal material and
transformation of chars.
4. Conclusions
Four natural Wbers from banana and coconut-trees, were
studied from a chemical and textural approach. Various
results were noted: the chemical and botanical composi-
tions depend on (1) the localization of Wbers in the tree, (2)
the type of tree from which they come from (green wood or
67
not); a preferential and rapid decomposition of banana
Wbers with increasing temperature of pyrolysis. The samples
were rough and composed of hollow Wbers whose walls
were formed of microWbrils of cellulose. These studies will
allow us to choose temperature of pyrolysis of Wbers before
incorporation in cement matrix, to predict the behaviors of
elaborated composites (insulating or not) presence of large
porosity in particles.
References
Al Rim, K., Ledhem, A., Douzane, O., Dheilly, R.M., Quneudec, M., 1999.
InXuence of the proportion of wood on the thermal and mechanical
performances of claywood composites. Cement and Concrete Com-
posites 21, 269276.
Arsne, M.-A., Bilba, K., Ouensanga, A., 2001. Etude dun matriau com-
posite: ciment/Wbre de bagasse de canne sucre. Revue des Composites
et Matriaux Avancs 11 (1), 720.
Aziz, M.A., Paramasivam, P., Lee, S.L., 1981. Prospects for natural Wbre
reinforced concretes in construction. International Journal of Cement
Composites and Lightweight Concrete 3 (2), 123132.
Beramendi-Orosco, L.E., Castro-Diaz, M., Snape, C.E., Vane, C.H., Large,
D.J., 2004. Application of catalytic hydropyrolysis for the rapid prepara-
tion of lignin concentrates from wood. Organic Geochemistry 35, 6172.
Bilba, K., Ouensanga, A., 1996. Fourier transform infrared spectroscopic
study of thermal degradation of sugarcane bagasse. Journal of Analyt-
ical and Applied Pyrolysis 38, 6173.
Bilba, K., Arsne, M.-A., Ouensanga, A., 2003. Sugarcane bagasse Wbre
reinforced cement composites. Part I. InXuence of the botanical com-
ponents of bagasse on the setting of bagasse/cement composite.
Cement and Concrete Composites 25, 9196.
Bledzki, A.K., Gassan, J., 1999. Composites reinforced with cellulose based
Wbres. Progress in Polymer Science 24, 221274.
Bourgeois, J., Bartholin, M.C., Guyonnet, R., 1989. Thermal treatment of
wood: analysis of the obtained product. Wood Science and Technology
23, 303310.
Cerny, R., Totova, M., Podebradska, J., Toman, J., Drchalova, J., Rov-
nanokova, P., 2003. Thermal and hygric properties of Portland cement
mortar after high-temperature exposure combined with compressive
stress. Cement and Concrete Research 33, 13471355.
Chung, D.D.L., 2001. Cementmatrix composites for thermal engineering.
Applied Thermal Engineering 21, 16071619.
Coreido, N., Belgacem, M.N., Torres, I.C., Moura, J.C.V.P., 2004. Chemical
composition and pulping of banana pseudo-stems. Industrial Crops
and Products 19, 147154.
Coutts, R.S.P., 1987. Eucalyptus wood Wber reinforced cement. Journal of
Materials Science Letters 6, 955957.
Coutts, R.S.P., Ni, Y., Tobias, B.C., 1994. Air-cured bamboo pulp rein-
forced cement. Journal of Materials Science Letters 13, 283285.
Demeyer, A., Jacob, F., Jay, M., Menguy, G., Perrier, J., 1981. La Conver-
sion Bionergtique du Rayonnement Solaire et les Biotechnologies.
Tech & Doc Lavoisier, France.
Dumon, R., Glus, M., 1982. Les Objectifs ScientiWques de Demain-Valori-
sation Chimique du Bois. Masson, France.
Fekadu, D., Ledin, I., 1997. Weight and chemical composition of plant
parts of enset (Ensete ventricosum) and the intake and degradability of
enset by cattle. Livestock Production Science 49, 249257.
Frandinho, D.M., Pascoal, N.C., Evtuguin, D., Jorge, F.C., Irle, M.A., Gil,
M.H., Pedrosa de Jesus, J., 2002. Chemical characterisation of bark and
of alkaline bark extracts from maritime pine grown in Portugal. Indus-
trial Crops and Products 16, 2332.
Ibarra, J., Moliner, R., 1991. Coal characterization using pyrolysis FTIR.
Journal of Analytical and Applied Pyrolysis 20, 171184.
Journal OYciel de la Rpublique Franaise n 300 du 26 dcembre 1996,
Dcret n 961133 relatif linterdiction de lamiante pris en applica-
tion du code du travail et du code de la consommation.
68 K. Bilba et al. / Bioresource Technology 98 (2007) 5868
Khedari, J., Suttisonk, B., Pratinthong, N., Hirunlabh, J., 2001. New light-
weight composite construction materials with low thermal conductiv-
ity. Cement and Concrete Composites 27, 6570.
Khedari, J., Charoenvai, S., Hirunlabh, J., 2003. New insulating particle-
boards from durian peel and coconut coir. Building and Environment
38, 435441.
Khedari, J., Watsanasathaporn, P., Hirunlabh, J., 2005. Development of
Wbre-based soilcement block with low thermal conductivity. Cement
and Concrete Composites 27 (1), 111116.
Kim, K.H., Jeon, S.E., Kim, J.K., Yang, S., 2003. An experimental study on
thermal conductivity of concrete. Cement and Concrete Research 33,
363371.
Low, M.J.D, Morterra, C., 1985. IR studies of carbonsV: eVects of NaCl
on cellulose pyrolysis and char oxidation. Carbon 23 (3), 311316.
Lttge, U., Kluge, M., Bauer, G., 1992. BotaniqueTrait Fondamental.
Tec & Doc Lavoisier, France.
Mangal, R., Saxena, N.S., Sreekala, M.S., Thomas, S., Singh, K., 2003.
Thermal properties of pineapple leaf Wber reinforced composites.
Materials Science and Engineering A 339, 281285.
Marquez Montesino, F., Arsne, M.-A., Orea Igarza, U., Carballo Abreu,
L., Ouensanga, A., 2003. InXuence of tree trunk part of char elabora-
tion: case of eucalyptus wood. In: Proceedings of Conference Carbon
2003, Oviedo, Spain, 610 July 2003.
Meldrum, B.J., Rochester, C.H., 1991. Infrared spectra of carbonaceous
chars under carbonization and oxidation conditions. Fuel 70, 5764.
Morterra, C., Low, M.J.D., 1985. IR studies of carbonsVI: the eVects of
KHCO3 on cellulose pyrolysis and char oxidation. Carbon 23 (4), 335341.
Mosier, N., Wyman, C., Dale, B., Elander, R., Lee, Y.Y., Holtzapple, M.,
Ladisch, M., 2005. Features of promising technologies for pretreatment
of lignocellulosic biomass. Bioresource Technology 96, 673686.
Ouensanga, A., 1989. Variation of Wber composition in sugarcane stalks.
Wood and Fiber Science 21 (2), 105111.
Ouensanga, A., Picard, C., 1988. Thermal degradation of sugarcane
bagasse. Thermochimica Acta 125, 8997.
Ouensanga, A., Largitte, L., Arsne, M.-A., 2003. Microporous and Meso-
porous Materials 59 (23), 8591.
Savastano Jr., H., 2001. Sustainable cement based materials and tech-
niques for rural construction. In: Proceedings of Conference Agri-
Building 2001, Campinas, Brazil, 37 September 2001.
Savastano Jr., H., Agopyan, V., 1999. Transition zone studies of vegetable
Wbre-cement paste composites. Cement and Concrete Composites 21,
4957.
Savastano Jr., H., Agopyan, V., Nolasco, A.M., Pimentel, L., 1999. Plant
Wbre reinforced cement components for rooWng. Construction and
Building Materials 13, 433438.
Savastano Jr., H., Warden, P.G., Coutts, R.S.P., 2000. Brazilian waste Wbres
reinforcement for cement based composites. Cement and Concrete
Composites 22 (5), 379384.
Smaoui, N., Brub, M.A., Fournier, B., Bissonnette, B., Durand, B., 2005.
EVects of alkali addition on the mechanical properties and durability
of concrete. Cement and Concrete Research 35, 203212.
Sun, J.X., Sun, X.F., Zhao, H., Sun, R.C., 2004. Isolation and characteriza-
tion of cellulose from sugarcane bagasse. Polymer Degradation and
Stability 84, 331339.
Toldo Filho, R., Ghavami, K., England, G.L., Scrivener, K., 2003. Devel-
opment of vegetable Wbremortar composites of improved durability.
Cement and Concrete Composites 25, 185196.
Zhu, W.H., Tobias, B.C., Coutts, R.S.P, Langfors, G., 1994. Air-cured
banana-Wbre-reinforced cement composites. Cement and Concrete
Composites 16 (1), 38.