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Cellulose acetate treatment of sisal fiber for cement based composites

SANTOS, Heni Mirna cruz, 1, a , LIMA, Paulo Roberto Lopes 1, b, * , CAMILLOTO,

Geany Peruch 2, 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 b c d e

* corresponding author


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.


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


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 fibrematrix 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/ dm 3 , 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/dm 3 and 2.28 kg/dm 3 , 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.

in immersing the fibers in CAP gel and drying for 24h. Figure 1. Treatment of fiber:

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, w 0 and after, w t absorption as follows: Abs = 100(w t - w 0 )/w 0 (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.

capacity of 500 N and a displacement speed of 0.03 mm/s. Figure 2 . Fiber tensile

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.L f ) (2), where F is the maximum load, d is the average fiber diameter and L f 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 CO stretching vibration of acyl group present in the lignin [26, 27]. The broad peak in the range of 33003500 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 CO stretching vibration of acyl group present in the lignin, is shifted after treatment.

group present in the lignin, is shifted after treatment. Figure 3. Fourier transform infrared (FTIR) spectrum

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

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


Tensile strength





Elastic modulus




639,01 (118,58)

0,041 (0,01)

21,44 (2,39)

475,42 (102,90)

0,034 (0.01)

15,20 (4,87)

*Coefficient of variation between parentheses

Figure 5. Effect of treatment on stress-strain behavior of sisal fiber Pull out test. Table

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.

increase of bond stress for all fibers, natural or treated. Figure 6. Tension-pull out curves of

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

Table 2. Mean values of the pull out test


Lf (mm)

F (N)

τ (MPa)


3.24 (0.54)

0.15 (0.03)

Natural Sisal Fiber


7.32 (3.02)

0.19 (0.04)

Treated Fiber



2.00 (0.66)

5.20 (1.05)

0.09 (0.01)

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






FT 150

FT 60

Sisal Natural




3,07 (0,30)

3,29 (0,15)


Acetato de Celulose


2,44 (0,17)

2,45 (0,22)

Sisal Natural

10 ciclos


3,70 (0,70)

3,75 (1,09)

Acetato de Celulose


2,05 (0,05)

1,82 (0,41)

e l u l o s e 2,92 2,05 (0,05) 1,82 (0,41) Figure 7. Effect of
e l u l o s e 2,92 2,05 (0,05) 1,82 (0,41) Figure 7. Effect of

Figure 7. Effect of the wetting and drying cycles of composite and fiber treatment on

the bending behavior of sisal fiber cement composite


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.


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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