FIRST STEP OF VALORIZATION OF DICTAME FIBERS BY

ELABORATION OF CEMENTITIOUS COMPOSITES

K.Bilba, M-A. Arsène, A.Ouensanga

Laboratoire COVACHIMM - Chimie des Matériaux, UFR Sciences Exactes et Naturelles

Université des Antilles et de la Guyane - BP 250
97159 Pointe à Pitre Cedex - Guadeloupe French West Indies

ABSTRACT

In order to restrict electric consumption due to building air-conditioning, cement/vegetal

fibers composites have been prepared , as materials for construction. Fibers, wastes of the
ground extraction of dictame (Maranta arundinacée), vegetal coming from South America,
are studied. In a first part of this paper, (a) chemical composition of raw dictame fibers, (aa)
structural and textural evolutions of fibers after pyrolysis are studied by Fourier Transform
Infrared (FTIR) spectroscopy and Scanning Electron Microscopy (SEM). In a second part,
hydration of composite materials is carried out. The influence of (b) fibers amounts, (bb)
temperature of pyrolysis of fibers and (bbb) water amount, on setting of composites are
investigated.

KEYWORDS

Vegetal fibers, dictame, Maranta arundinacée, cement, composites.

INTRODUCTION

In French West Indies Islands (FWII) especially in Guadeloupe, to prevent hurricane

disasters, construction of houses made of cement has started. Unfortunately the consequences
of these new buildings on electricity consumption become more and more important. Indeed,
in these houses made of cement, residents endure heat during all the year. So, the use of air-
conditioning grows regularly and in Guadeloupe the production of electricity is very
expensive.

The aim of the present study is to elaborate an insulating compound to add to cement, this
material allowing good mechanical behavior and thermal comfort. Our grandparents used to
live in houses made of wood, in which some thermal comfort existed. We planned that the
additional thermal insulating compound should be wood or an other lignocellulosic material.
We particularly interested in vegetal fibers/cement composites materials, because by using
vegetal fibers (1) cost of materials for construction should be lower, (2) searchers and master-
builders should contribute to environment protection thanks to the use and valorization of
wastes or agro-industrial by-products and (3) saving of energy should be realized.

In our group, previous works on bagasse fibers and bagasse fibers/cement composites have
been realized (Bilba et al., 1996, Arsène et al., 2001, Bilba et al., 2003). Other fibers coming
from coconut and banana trees have been also studied (Bilba et al., 2002). In this paper, we
propose to deal with dictame fibers (Maranta arundinacée), interesting because length of the
latter could be longer than those of fibers previously studied.

EXPERIMENTAL

Dictame (Maranta arundinacée) is a vegetal originated from South America, cultivated in

FWII for children feeding because it is rich in vitamin A, calcium and iron (Fournet, 2002).
Dictame is a tuberous rhizome tapered, with very long fibrous roots. Dictame fibers are
wastes of the ground extraction. They are dried in air, crunched then sieved. Only particles
which diameter varies from 0.125 to 0.4 mm were kept for this first step of our study.

The amounts of principal botanical components of raw fibers, cellulose, hemicellulose, lignin
were determined according to methods described by one of us (Ouensanga, 1989). Chemical
compositions of raw dictame fibers samples coming from two drying seasons shifted six
months, noted Type1 and Type2, were determined.

Evolution of chemical linkages was studied after a pyrolysis (200 to 700°C) under a nitrogen
gas flow (2L/h) of raw fibers during 2 hours, to determine optimal pyrolysis temperature
before addition to cement. This analysis was performed thanks to a Fourier Transform
Infrared spectrometer provided by Nicolet instrumental manufactory. Study of textural
changes after pyrolysis was realized thanks to a Scanning Electron Microscope Hitachi
S-2500.

The incorporation of dictame pyrolyzed fibers in cement was realized. Portland cement CEM
II/A-P 32,5 NCE PM CP2 NP supplied by Les ciments LAFARGE manufacture, usually used
in our tropical zone was chosen. In order to know influence of fibers amount, pyrolysis
temperature and water amount on setting of composites, various materials samples were
prepared (Table 1). The mixtures cement + fibers + water were homogenized with a spatula
then placed in an adiabatic bottle. The maximal hydration temperatures versus hydration were
followed for the different composites with Hanna Instruments HI 92804C recorder controller
(± 0.1°C).
 TABLE 1. VARIOUS COMPOSITE MATERIALS PREPARED

Samples Mass Volume Pyrolysis Weight Mass of Mass of Mass

of of added temperature percent of added cellulose of
cement water fibers fibers lignin
(g) (mL) (°C) (%) (g) (g) (g)
1 62.5 25 0 0 0 0 0
2 62.5 25 200 0.5 0.3125 0 0
3 62.5 25 200 1 0.625 0 0
4 62.5 25 200 1.5 0.9375 0 0
5 62.5 25 200 2 1.25 0 0
6 62.5 25 250 1 0.625 0 0
7 62.5 37.5 0 0 0 0 0
8 62.5 37.5 200 1 0.625 0 0
9 62.5 25 0 0 0 0.625 0
10 62.5 25 0 0 0 0 0.625

RESULTS AND DISCUSSION

Dictame fibers

Chemical composition

The chemical compositions of raw fibers (Types 1 and 2) are reported in Table 2. Amount of
cellulose and lignin are different for Type 1 and Type 2. This difference can be due to the fact
that the extracts come from dictame fibers were dried at two different periods corresponding
to the two harvests of the year. Indeed Marquez et al. (2003) have shown that botanical
composition is highly dependant on physiological stage of the plant (age, localization in the
plant…) and on agro-pedological conditions (grounds composition, hydrography …). For
hemicellulose, difference between the two types is smaller (0.5%), it is still being reasonable.
The sum of principal components of both types is close to 100% showing that dictame does
not contain a lot of minerals.

TABLE 2. CHEMICAL COMPOSITION OF RAW DICTAME FIBERS (STANDARD DEVIATION 0.003%)

Weight percent (%) Type 1 Type 2

Cellulose 37,73 39,99
Lignin 26,96 22,50
Hemicellulose 31,70 31,19
Extractives 2,51 3,77
Total 98,9 97,45
Humidity 10,68 11,36

Pyrolysis and structural evolution

The picks observed were identified thanks to bagasse (Bilba et al., 1996), carbonaceous char
(Meldrum et al., 1991) and coal studies (Ibarra et al., 1991). For raw dictame fibers (Types 1
and 2), we can note (Figure 1):
1 a large pick (3600-3000 cm-1) corresponding to OH linkages of cellulose, hemicellulose
and lignin
2 a fairly intense pick (2900 cm-1) corresponding to CHn aromatic and aliphatic linkages of
cellulose, hemicellulose and lignin
3 a slightly intense pick (1730 cm-1) attributed to C=O linkage of lignin
4 at 1640 cm-1, C=C linkages of lignin
5 around 1430 cm-1, C-H aliphatic of cellulose, hemicellulose and lignin
6 a thin pick (1320 cm-1) corresponding to O-H, C-C and CO of cellulose and hemicellulose
7 a fairly intense pick (1240 cm-1) corresponding to C-O-C and CO of cellulose and
hemicellulose
8 at 1150 cm-1, C-O-C and C-OH linkages of cellulose and hemicellulose a very intense
pick at 1040 cm-1 corresponding to CO linkages of cellulose, hemicellulose and lignin.

10
Raw dictame fibers - Type 1 40.
99
0.03

12
0.02 33 16 14 13 42.
73. 17 26. 03
43. 23.
04 28.
37 57 27
16
0.01
Absorbance

0.00

Raw dictame fibers - Type 2 10

52.
0.015 60

13 12
0.010 33 17 16
14 25. 43.
53. 31. 23.
26. 54 20
69 18
0.005 70 87

0.000

-0.005
3500 3000 2500 2000 1500 1000
Wave number (cm-1)

FIGURE 1. IRTF SPECTRA OF TWO TYPES OF RAW DICTAME FIBERS

The picks 1, 2, 5 and 9 are more intense for Type 1 than for Type 2. As Type 2 contains less
cellulose+hemicellulose+lignin (93.8%) than Type 1 (96.39%), there is a good agreement
between chemical analysis and FTIR ones.

The consequences of pyrolysis for the more intensive picks, for both types are (1) a
diminution of intensity of pick 1, (2) an increase of intensity of pick corresponding to C=C
linkages of lignin (1640 cm-1), C-H aliphatic (1430 cm-1), a diminution of intensity of CO
linkages (1040 cm-1). Theses observations show that there is a rearrangement of linkages of
char, leading for high pyrolysis temperature to partial graphitic carbon. At 700°C, this
transformation is not complete.

Pyrolysis and textural evolution

For both types, the observations are similar. Each particle of dictame is formed of a mass of
unitary hollow fibers, of variable diameters (1 to 5 µm, figure 2a). Sometimes, in a mass, a
tube formed of a squared weaving is observed (Figure 2b).When pyrolysis temperature grows,
particles loose some matter and become rougher, so hanging between dictame fibers and
cement will be more efficient.
Setting of cementitious composites

Influence of fibers amount

This study has been performed from pyrolyzed dictame (200°C), because this temperature is a
compromise between mass loss, partial elimination of sugars and surface rugosity. The
hydration curves of various composites are reported in Figure 3.

5µm

(a) (b)

FIGURE 2. (a) SECTION OF A DICTAME PARTICLE (X 800)

(b) INTERNAL VIEW OF A DICTAME PARTICLE (X 400)

Three zones can be observed on the curves:

- Zone 1 is observed during the first hour of hydration, its amplitude is around 27°C for all
fibers amounts. After water addition, a part of Ca3Al2O6 (C3A) seems to react with gyps
in solution to form Ca3(Al, Fe)(OH)6.12 H2O X3, x H2O (AFt) (Taylor 1997).
- Zone 2 is located around 10 hours of setting, it corresponds to the maximum hydration
temperature. It seems that Ca3SiO5 (C3S) reacts with water to form CaO. SiO2. H2O (C-S-
H). The hydration temperature goes down from 28.2°C (sample 1) to 25.5°C when adding
2% of fibers; while, in the same time, setting duration grows from 8.5 et 10.5 hours.
- Zone 3 appears after 25 hours of hydration. It can be due to hydration of the rest of C3A.
A decrease of amplitude of picks is observed when amount of fibers grows.
 29 Sample 1 (0% fibers)

Hydration temperature (°C)

Sample 2 (0.5% fibers)
28
Sample 3 (1% fibers)
27 Sample 4 (1.5% fibers)
Sample 5 (2% fibers)
26

25

24

23
0 5 10 15 20 25 30 35

Hydration time duration (h)

FIGURE 3. INFLUENCE OF FIBERS AMOUNT ON SETTING OF COMPOSITE MATERIALS

In order to clarify the influence of botanical components on setting of composites, the

hydration of cellulose/cement, lignin/cement composites were followed. The setting
parameters are reported in Table 3.

TABLE 3. INFLUENCE OF BOTANICAL COMPONENTS ON SETTING OF COMPOSITES

Material Sample 1 Sample 9 Sample 10

(reference) (cellulose) (lignin)
Hydration temperature (°C) 28.2 25.4 27.2
Hydration duration (h) 8.5 12.5 9.0

It is for lignin/cement material that variations of hydration temperature and hydration duration
are more important. So we can conclude that it is this botanical component which influences
the most setting parameters. More, we can note that cellulose influences hydration
temperature. Indeed, the more there are fibers in composites, more amounts of lignin and
cellulose grow; the setting of composites is longer and "colder". So, we can say that dictame
fibers have a retarding effect on setting of composites.

Influence of pyrolysis temperature of fibers

Only the maximal hydration temperatures and corresponding hydration time duration of
composites containing 1% of dictame fibers (raw and pyrolyzed) are reported in Table 4, for
the three zones still being observed.

TABLE 4. INFLUENCE OF BOTANICAL COMPONENTS ON SETTING OF COMPOSITES

Material Sample 1 Sample 3 Sample 6

(reference) (200°C) (250°C)
Hydration temperature (°C) 28.2 27.3 25.6
Hydration duration (h) 8.5 9.0 12.5
When adding fibers to reference sample (sample 1), there is a competition between hydration
of cement and hydration of fibers. Indeed, maximal hydration temperature of sample 1 is
reached after 8.5 hours although for sample 3 it is reached after 9 hours and for sample 6 it is
after 12.5 hours. Samples 1 and 3 have a comparable hydration duration. This seems to show
that the addition of fibers pyrolyzed at 200°C does not influence hydration duration, while it
leads to a diminution of maximal hydration temperature, may be because of endothermicity of
the reaction between fibers and water. The behavior of sample 6 shows a limited influence of
pyrolysis treatment, indeed it is for fiber samples pyrolyzed at 250°C that we observed the
extension of setting duration and the most important fall of hydration temperature. We can
propose that, at 250°C, the hydration of hemicellulose and the retarding effect of lignin,
which is partially damaged, lead to lengthen setting and low maximal hydration temperature.

Influence of water amount

Figure 4 shows the influence of water amount on the setting of composites.

30 ciment seul + 25mlofd'eau (ech .1)

Sample 1 (25mL water)
Hydration temperature (°C)

ciment +737,5
Sample ml d'eau
(37.5mL (ech.8)
of water)
29
fibres + 3
Sample 25(25mL
ml d'eau
of(ech.3)
water)
28 Sample
fibres + 8 (37.5mL
37,5 of(ech.9)
ml d'eau water)

27

26

25

24

23
0 5 10 15 20 25 30 35
Hydration time duration (h)

FIGURE 4. INFLUENCE OF WATER AMOUNT ON SETTING OF COMPOSITE MATERIALS

We still observed the three zones already cited. For the reference material (sample 1), the
growth of water amount does not have marked effects. But for vegetal fibers/cement
composites, the growth leads to lower the maximal hydration temperature. Taylor (1997)
indicates that the minimal ratio water/cement to have a complete hydration is 0.38. For
reference sample this ratio is equal to 0.40, so this is a light excess of water compare to
optimal amount of water for setting of cement. For sample 3, dictame fibers absorb this
excess, may be thanks to Van der Waals linkages. The reaction between fibers and water
being less exothermical than between cement and water, hydration temperature of sample 3 is
lowered while setting duration is quiet the same, the excess is small. The comparison of
samples 1 and 8 shows that when the excess of water is more important setting is longer and
maximal hydration temperature is lower, may be thanks to absorption of excess of water by
dictame fibers, as shown by Bilba et al. (2003).
For higher amount of water, two phenomena can explain differences between the settings of
samples 7 and 8. On one hand water absorption by dictame fibers and on the other hand
retarding effect due to soluble sugars present in excess of water (Arsène et al., 2001).

CONCLUSION

During this work, (1) chemical composition of dictame fibers has been determined, (2) after
pyrolysis (200-700°C) evolution of linkages presented in dictame fibers has been analyzed to
determine optimal temperature of pyrolysis before their incorporation in cement, (3)
information about texture of dictame vegetal has been obtained.

The influence of various parameters on setting of dictame fibers/cement composites has been
studied. For all the studied parameters (fibers amount, pyrolysis temperature of fibers, water
amount), their growth leads to a retarding effect on setting of composites and a lowering of
maximal hydration temperature.

REFERENCES

Arsène, M.A.; Bilba, K.; Ouensanga A. (2001). Etude d’un Matériau Composite Ciment/Fibre
de Bagasse de Canne a Sucre -I Influence des Constituants de La Fibre de Bagasse sur la Prise
du Matériau Composite Bagasse/Ciment. Revue Composites et Matériaux Avancés : 11(1),
p.7-20.

Bilba, K.; Ouensanga A. (1996). Fourier Transform Infrared Spectroscopic Study of Thermal
Degradation of Sugar Cane Bagasse. Journal of Analytical and Applied Pyrolysis : 38, p.61-
73.

Bilba, K.; Arsène, M-A.; Ouensanga A. (2003). Sugar Cane Bagasse Fibre Reinforced
Cement Composites, Part I. Influence of the Botanical Components of Bagasse on the Setting
of Bagasse/Cement Composite. Cement and Concrete Composites : 25, p.91-96.

Bilba, K.; Arsène, M-A; Ouensanga A. (2002). Materials for Construction. Comparative
Study of Setting of Various Cement Based Composites Materials, Proceedings of 4th
International Conference Advanced Inorganic Fiber Composites for Structural Applications,
Florence (Italy) 14-18 july 2002.

Fournet, J. (2002). Flore Illustrée des Phanérogames de Guadeloupe et de Martinique – Tome

2, Gondwana Editions, p.2046-2048.

Ibarra, J.; Moliner, R. (1991). Coal Characterization Using Pyrolysis FTIR. Journal of
Analytical and Applied Pyrolysis : 20, p.171-184.

Marquez Montesino, F.; Arsène, M-A.; Orea Igarza, U.; Carballo Abreu, L. R.; Ouensenga,
A. (2003). Influence of Tree Trunk Part on Charcoal Elaboration: Case of Eucalyptus Wood,
Proceedings of Carbon 2003, Oviedo (Spain) 6-10 july.

Meldrum, B.J.; Rochester, C.H. (1991). Infrared Spectra of Carbonaceous Chars under
Carbonization and Oxidation Conditions, Fuel : 70, p.57-64.
Ouensanga, A. (1989). Variation of Fiber Composition in Sugar Cane Stalks. Wood and
Fiber Science : 21(2), p.105-111.

Taylor, H.F.W. (1997). Cement Chemistry, Thomas Telford Publishing, London-UK, ISBN 0
7277 2592 0, p.1-4, 113, 166-169, 189-190, 194.