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Cellulose acetate treatment of sisal fiber for cement based

composites
SANTOS, Heni Mirna cruz,1, a, LIMA, Paulo Roberto Lopes1, b, *, CAMILLOTO,
Geany Peruch2, c, CRUZ, Renato Souza 2, d, ESPELETA, ALexandre F. 3, e
1
Post-graduate Program of Civil and Environmental Engineering, Department of
Technology, State University of Feira de Santana, Av. Transnordestina, S/N – Novo
Horizonte, Feira de Santana, Bahia 44036-900, Brazil
2
Food Laboratory, Department of Technology, State University of Feira de Santana,
Av. Transnordestina, S/N – Novo Horizonte, Feira de Santana, Bahia 44036-900, Brazil
3
LAPRON, Department of Exact Sciences, State University of Feira de Santana, Av.
Transnordestina, S/N – Novo Horizonte, Feira de Santana, Bahia 44036-900, Brazil
a
henimirna@hotmail.com blima.prl@pq.cnpq.br c geanyperuch@yahoo.com.br
d
cruz.rs@gmail.com eespeleta@uefs.br
* corresponding author

ABSTRACT

Sisal fibers were modified using resin produced from corn starch and cassava. The
objective is to verify the possibility of reduction of the fiber water absorption without to
affect the adherence with cement matrix using a sustainable resin . A combination of
Fourier-transform infrared (FTIR) spectroscopy, water absorption and tensile tests were
used to investigate the effects of chemical treatment on sisal fibers. The pull-out tests of
sisal fibers with 20 mm and 40 mm were carried out to define the influence of
treatments on bond stress with cement mortar. Composites with 4% of short fiber were
produced and tested on flexion. The results indicated that the layer of polymeric film
formed on the fiber surface reduced the hydrophilicity and didn´t affect of tensile
strength. Experimental tests on composites indicate little effect of resin treatments on
average bond stress and flexural behavior.

Introduction
The use of natural fiber as reinforcement of composites had advanced in last decades
due capacity of this fiber in provide stiffness, strength and/or toughness [1]. Sisal fiber,
which is extracted from the Agave sisalana leaf, is one of the most important fibers used
as reinforcement due excellent mechanical properties [2]. The classification of patents
associated with sisal fiber documents, extracted of Derwent Innovation Index database,
between the years 1960 to 2009, indicated the presence of 1373 records, with about
7,4% associated with the use of this fiber as reinforcement of composites [3]. Compared
with other natural fiber, the sisal fiber has the advantage of having a commercial
production in many countries which facilitates the immediate use for the production of
building elements on a large scale. In cement based composites, the sisal fiber had been
used as pulp, short fiber, long fiber or fabrics [4-7].
However, the most serious concern with natural fibers is their hydrophilic nature due
to the presence of pendant hydroxyl and polar groups in various constituents, which can
lead poor adhesion between fibres and matrix [8-9]. The sisal fiber show a great water
absorption [10], thus the swelling and shrinking of the fibers due wetting and drying of
composites in use may lead to cracking in fiber-matrix interface. How the loads are
applied directly to the matrix, it is necessary to have an effective load transfer from the
matrix to the fibers for the ensuing composites to have good mechanical behavior. As a
result, the mechanical properties of the composite reinforced are very sensitive to
moisture content and an increase of this property is associated with reductions in
modulus of elasticity and strength [11-13]. In addition, the dimensional changes of the
cement composites due loss of water is modified by the presence of the hygroscopic
natural fibres, which intensify the extent of shrinkage strain compared cement matrix
[14].
Two major types of fiber treatment had been used to reduced of the hydrophilicity of
the fiber: bulk and surface treatments. The fundamental difference between these
treatments is not to be found in the underlying chemistry, but instead in the fact that the
first leads to a radical transformation of the entire fiber, which almost always modified
its morphology and semi-crystalline phase, whereas the second maintains these features
virtually intact, except for a very thin outer layer [15].
Heat treatments applied of sisal fibers, using wetting-drying cycles [16] or
mechanical pression [17] result in reduction of the fiber area and lumen dimension and,
consequently, reduce moisture absorption.
Surface treatment of the fibers with various coupling agents is the more used method
aiming to improve the fiber-matrix interaction. Coupling agents are molecules
possessing two functions: the first is to react with OH groups of cellulose (pore sealing)
and the second is to react with functional groups of the matrix (increase of chemical
links) [18]. Coupling agents usually improve the degree of crosslinking in the interface
region and offer a perfect bonding [19]. The effect of surface treatment of the sisal
fibers with various coupling agents to enhance the durability of fiber and fibre–matrix
interaction was reported in several studies. Silane coupling agents were found to be
effective in modifying the natural fiber-matrix interface; silane treatment of sisal fibers
changes the surface topography, surface chemical structure, and thermal degradation of
sisal fibers [20]. Canovas et al. [21] used timber extracts (colophony, tannin and
vegetable oil) to impregnation of sisal fiber which shown good results in the reduction
of water absorption (more than 50%) despite a small reduction of tensile strength of
fiber. Flexural tests indicate a better durability behavior in mortar reinforced by
impregnated than in those with unimpregnated fibers. Toledo Filho et al. [22] available
the effect of treatment of aligned long sisal fibre with slurried silica fume on durability
of cement based composites and verified that this treatment represents an effective
method to improve the strength and toughness of the composites with time.
Despite the relative success of the surface treatment on reduction of water absorption
of fiber and improve of fiber-matrix interface there is an apparent contradiction between
the use of synthetic polymer and natural fiber. In this condition, the main environmental
advantages such as biodegradability and renewal reduce or cease to exist. The aim of
this study was to evaluate the effect of fiber treatment with cellulose acetate, an polymer
from renewable resource, on the properties of sisal fiber and cement based composite.
Water absorption and mechanical tests were carried out on sisal fiber. Pull-out tests
were carried out to evaluated the interface bond. For characterization of composites
reinforced with 4% of treated sisal fibers (Lf = 40 mm) flexural test were carried out.
Material and Methods
Sisal fiber were collected in city of Valente, state of Bahia – Brazil. Initially, the
fibers were washed in hot water (50 °C) to remove surface residues, such as mucilages
from the extraction process, and cut to the length of 40 mm.
Cement. For the composite preparation portland cement of initial high strength CPV
ARI (ASTM Type III), with a specific mass of 3.06 kg/ dm3, was used.
Mineral additions. For the creation of the cementitious matrix, silica of fume and
fly ash were used - the specific mass being 2.11 kg/dm3 and 2.28 kg/dm3, respectively.
The use of pozzolans in cementitious matrices causes the consumption of calcium
hydroxide, thereby avoiding fiber mineralization [23].
Sand. As fine aggregate, quartz sand with a specific mass of 2.62 kg/dm 3 was used.
The maximum dimension was 1.18 mm and the thinness modulus of 1.79.
Fiber treatment. Cellulose Acetate Polymer (CAP) is an environmentally
degradable material made from a modified natural polymer (cellulose). Cellulose, acetic
acid, and acetic anhydride are mixed together and reacted to form cellulose acetate
polymers. With the use of additives, the physical properties of cellulose acetate films
can be modified to accommodate a wide range of film applications. Fiber treatment
(Figure 1) consisted in immersing the fibers in CAP gel and drying for 24h.

Figure 1. Treatment of fiber: a) gel of cellulose acetate; b) immersion of fiber; c)


drying

Cement matrix. To build the cement matrix, the proportion, by weight, of 0.5: 0.1:
0.4: 1: 0.35 (cement: silica: fly ash: sand : water) was used. The mixture were produced
in a mechanical mixer of 20 dm³, according to following procedure [24]: 30 seconds at
low speed to add the cementitious products, 30 seconds at low speed to add the sand,
90 seconds stop to scrape the walls of the bowl, 60 seconds at high speed.
Microstructural analysis. The determining of the fiber diameter was done using an
optical microscope QUIMIS model Q711FT. The fiber strands were observed in the
optical 10X lens (tenfold) and finally the mono-strand was photographed with a camera
attached to the microscope. Then, the picture was transferred to the program MOTIC
IMAGES PLUS 2.0 where the measurement of the fiber diameter was performed as
shown in Fig. 1. The analysis of the fiber morphology was carried out with an electronic
scanning microscope (JEOL JSM- 6460).
Variation in the chemical composition. The Fourier transform infrared (FTIR)
spectroscopy was used to analyze the composition change of the treated sisal. FTIR
spectrum were obtained for sisal fibers using a Perkin Elmer spectrometer.
Water absorption test. For the water absorption measurements, the specimens were
withdrawn from the waters, wiped dry to remove the surface moisture, and then
weighted using an electronic balance accurate to 10−4 g to monitor the mass during
with time t. The moisture content, M(t) absorbed by each specimen is calculated from
its weight before, w0 and after, wt absorption as follows: Abs = 100(wt - w0)/w0 (1).
Direct tension test. The tensile test of fiber was carried out according to the
procedure of [13]. For each cycle of treatment 20 fibers with a length of 50 mm were
tested. The test was performed with a TA.XT Plus Texture Analyzer (see Fig. 2) with a
load capacity of 500 N and a displacement speed of 0.03 mm/s.

Figure 2. Fiber tensile test

Fiber pull out test. The pull out test was carried out using the methodology of [22].
The embedded fiber length (Lf) varied from 16 to 44 mm according to the experiment
design. The specimens were molded using pvc tubes with a 20 mm diameter (Fig. 3a);
After filling the mold with the matrix, the top cap was fixed and the fiber stretched
slightly for alignment. The mortar was placed in plastic bags before being placed in the
mold as to facilitate the casting process. The test was carried out in the TA.XT Plus
Texture Analyzer shown in Fig. 2b with a displacement rate of 0.02 mm/s. The bond
strength was calculated using the following equation: Fd.Lf) (2), where F is the
maximum load, d is the average fiber diameter and Lf is the fiber embedded length.
Four-Point bending tests. The four-point bending tests, shown in Fig. 2c, were carried
out in the SHIMADZU testing machine. A load cell of 2 kN was used and the machine
was controlled by a displacement rate of 0.5mm/min. Three specimens with dimensions
of 400 mm x 80 mm x 1.2 mm were tested. The load and mid-span displacement, using
a LVDT, were continuously recorded using a data acquisition system. The tests were
carried out after 28 days of water immersion and after ten wetting-drying cycles of
samples, according [25]. Flexural strength and toughness index were obtained of stress-
displacement curves.

Results and Discussion

Fiber analysis
The effects of fiber treatment on the natural fiber surfaces were studied using FTIR.
Fig. 3 show the FTIR spectrum of untreated and treated sisal fiber. In natural fiber, the
carbonyl peak at 1735 cm-1 is assigned to C=O unconjugated stretching of carboxylic
acid or ester of the hemicelluloses and the peak at 1239 cm-1 is assigned to C–O
stretching vibration of acyl group present in the lignin [26, 27]. The broad peak in the
range of 3300–3500 cm-1 and a peak at 1630 cm-1 are due to the characteristics axial
vibration of hydroxyl group of cellulose (preferably from 2,3 and 6 carbon of glucose).
The peak at around 1080 cm-1 is due to the associated hydrogen group [28]. In the
cellulose acetate membrane, Zhang et al (2007) identified the IR bands at 1735 and
1035 cm-1 attributed to the C=O stretch and -C-O-C- stretch, respectively. The
evaluation of both spectra indicated a modification of sisal fiber with treatment. It is
possible to verify the decreasing intensity of characteristic bands assigned to hydroxyl
groups at 3445 cm−1, indicating a possible acylation of cellulose of sisal fiber. A
reduction of peaks between 1288 and 1500 cm-1 confirms the alteration of the fiber. In
addition, the peak at 1239 cm-1, assigned to C–O stretching vibration of acyl group
present in the lignin, is shifted after treatment.

Figure 3. Fourier transform infrared (FTIR) spectrum for treated and untreated sisal
fiber

The surface treatment of sisal fiber with Cellulose Acetate Polymer resulted in a
decrease in the rate of water absorption of the fibers as shown in Figure 4. It can be seen
that after 10 days of the immersion the maximum absorption of treated sisal was 88%
while natural sisal show values of 200%.
Figure 4. Water absorption of sisal fiber

The tensile test of fiber was done with the intent to investigate the influence of the
treatment on the mechanical behavior of the sisal fiber. Stress-strain curves for fibers
submitted to each cycle are shown in Fig. 5. From the curves, the tensile strength,
ultimate strain and the elastic modulus of the fibers shown in Table 1, were obtained. It
is verified a reduction of all mechanical properties after surface treatment of sisal fiber.

Table 1. Effect of the treatment on mechanical properties of the fiber


Ultimate
Tensile strength Elastic modulus
Fiber strain
(MPa) (GPa)
(mm/mm)
639,01 (118,58) 0,041 (0,01) 21,44 (2,39)
Untreated

475,42 (102,90) 0,034 (0.01) 15,20 (4,87)


Treated
*Coefficient of variation between parentheses
Figure 5. Effect of treatment on stress-strain behavior of sisal fiber

Pull out test. Table 2 shows the experimental results obtained in the pull out test for
natural and treated fibers. The maximum tension was obtained directly in the load-
displacement curves presented in Figure 6. The fiber treatment modify the pull out
behavior with reduction of interface bond and modification of load-slip stiffness in
initial branch of curve. This fact can be associated to slipping between sisal fiber and
surface film of cellulose acetate due load application. The increment of embedded
length of fiber indicate an increase of bond stress for all fibers, natural or treated.

Figure 6. Tension-pull out curves of treated and natural sisal fibers in mortar matrices

Table 2. Mean values of the pull out test


Treatment Lf (mm) F (N) τ (MPa)

20 3.24 (0.54) 0.15 (0.03)


Natural Sisal Fiber
40 7.32 (3.02) 0.19 (0.04)

20 2.00 (0.66) 0.09 (0.01)


Treated Fiber
40 5.20 (1.05) 0.10 (0.02)
Flexural test. Figure 7 shows the typical bending behavior of the composites
reinforced with treated and untreated sisal fibers in volume fractions of 4%. The natural
fiber composite presented a multiple cracking behavior with deflection hardening while
treated fiber composite shown one single crack and drop of stress after cracking. The
treatment of fiber resulted in increase of flexural strength but reduction of toughness of
composites, as shown in Table 3.
After 10 cycles of aging all composite shown reduction of stress after first cracking.
Visual inspection of fracture surface indicated the pull-out of fiber after large
displacement which indicate a reduction of interfacial bond due aging of composites.
The toughness of composites reinforced with treated fibers reduced about 51%
indicating that surface treatment doesn´t collaborate with protection of fiber in
composites submitted to environmental loads.
Table 3. Resultados do ensaio de tração flexão e indicie de tenacidade dos compósitos

Flexural Toughness
Misturas strentgh
(MPa) FT150 FT60

Sisal Natural 4,00 3,07 (0,30) 3,29 (0,15)


28 dias
Acetato de Celulose 4,16 2,44 (0,17) 2,45 (0,22)
Sisal Natural 4,58 3,70 (0,70) 3,75 (1,09)
10 ciclos
Acetato de Celulose 2,92 2,05 (0,05) 1,82 (0,41)

Figure 7. Effect of the wetting and drying cycles of composite and fiber treatment on
the bending behavior of sisal fiber cement composite

Conclusion
The treatment of sisal fibers with the applying of cellulose acetate film on your
surface resulted in the reduction of water absorption of fiber. However, it is also
observed a reduction of the tensile strength and elastic modulus, compared to the
untreated fiber. FTIR test indicated a modification of chemical structure indicating a
possible acetylation of cellulose of sisal fiber.
The use of treated fiber with cement based composite indicated a reduction of
interfacial bond strength which resulted in reduction of toughness of composites
reinforced with 4% of fiber, compared the use of natural fiber. The fiber treatment
doesn´t effective in protection of interface fiber-matrix of composites under accelerated
aging.

Acknowledgments
The authors thank: National Council for Scientific and Technological Development
(Process: 558633/2010-2; 310281/2013-0) and CAPES/PROAP for their financial
support, FAPESB for the master´s scholarship of the first author.

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