Use of Bamboo Organosolv Pulp as Reinforcement for Cementitious Matrices

Viviane C. Correia1*; Alessandra E. F. S. Almeida1; Dbora Caroline G. de Oliveira1; Holmer Savastano Jr.1
1

Faculdade de Zootecnia e Engenharia de Alimentos, Universidade de So Paulo, Avenida Duque de Caxias Norte, 225, Pirassununga, 13635-900 , Brasil. *vivianecostcor@usp.br

Abstract The consideration of natural fibers as reinforcement for brittle cement matrices is supported by the low cost, high availability, especially in countries like Brazil, which has developed agriculture, good soil and climatic conditions and large areas for cultivation. However, due to the high alkalinity of the cement paste the reinforced matrix has its durability affected by the fiber degradation. One approach to minimize this alkaline attack is to remove the excess of lignin and the hemicellulose from the fibers, that are the less resistant components under the high pH conditions. It can be achieved by chemical pulping, a process that individualizes the cellulosic fibers, that can be used afterwards as a reinforcement of cementitious composites and in partial replacement of synthetic fibers. The pulps applied for this purpose in industrial scale (in fiber cement corrugated sheets, e.g.) are commonly produced by the kraft pulping process. An interesting alternative is the organosolv pulping that is based on organic reagents for cooking and allows the solvent recovery at the end of the process. The purpose of this study was the use of bamboo organosolv pulp as reinforcement in blended cementitious matrices by following their physical and mechanical behavior under accelerated aging conditions. The composites were produced by the method of slurry dewatering followed by pressure with partial replacement of cement by metakaolin and tested the levels of 6, 8, 10 and 12% by mass of bamboo pulp. The pads were produced with partial substitution of cement by 25% of metakaolin. The composites containing metakaolin were subjected to accelerated ageing through 50, 100 and 200 soak and dry cycles for durability evaluation. The optimum amount of organosolv pulp was defined as 8%, in agreement with prior studies for bamboo Kraft pulp. The physical properties of the composites were modified with the ageing cycles, refining the porosity by the migration of the cement hydration products to the transition zone around the fibers and, consequently, improving the mechanical properties of the material for partial replacement of cement by metakaolin. The decrease in the tenacity of the fibrous composites subjected to the soak and dry cycles was due to the higher adhesion between the fiber and the cement matrix that reduced the pullout mechanism with the consequent predominance of the fractured fiber. The achieved results show a promising behavior of the organosolv bamboo pulp produced in the conditions of the present experiment for the reinforcement of inorganic matrices. Key words: organosolv pulp, reinforcement, cementitious composites. 1. Introduction The use of renewable resources such as vegetable fibers and other agricultural resources by the construction industry can contribute to the achievement of more sustainable building materials (Pacheco-Torgal & Jalali, 2011). Fiber cement composites have been mainly reinforced by short or pulped cellulose fibers. For example, softwood (mainly Pinus radiata) fiber has been extensevely applied as the sole reinforcing element in commercial autoclaved cement products (Tonoli et al., 2009a).

These materials provide an exciting opportunity to the housing construction and may generate economic incentives particularly in developing countries since the production of reinforced composites may require a low degree of industrialization. Furthermore, in comparison to the most common synthetic reinforcing fibers, such as polyvinyl alcohol (PVA) and polypropylene (PP), natural fibers require less energy to their fabrication and can be considered as green products (Silva et al., 2009). The fibers tend to increase the tensile strength in and toughness of the hardened composite when submitted to bending tests. This increase in the mechanical behavior depends on the volume fraction, aspect ratio and mechanical properties of the fibers. Although the satisfactory performance at early ages, the composites reinforced with natural fibers present as major disadvantage the low durability, due to their chemical degradation under the aggressive effect of the high alkalinity of the cement based matrix. A route to minimize the alkaline attack is the partial removal of the lignin and hemicellulose of the fibers, that are less resistant at high pH conditions. The reduction of lignin and hemicellulose content can be achieved by chemical pulping, a process that is well known by the pulp and paper industry (Li et al., 2012). Another way of improving the fiber durability in the composite is thru the modification of the cementitious matrix, adding pozzolanic by-products to Portland cement. Previous results show that the use of ternary blends containing slag/metakaolin and silica fume are effective in preventing fibre degradation (Mohr et al., 2007). This study presents the physical-mechanical behavior of cementitious composites reinforced with different levels of 6, 8, 10 and 12% by mass of bamboo organosolv pulp and followed by the assessment of the effects of degradation of the fibers and matrix after submission to the accelerated aging conditions. 2. Experimental The bamboo pulp was manufactured in laboratory scale by organosolv pulping process, according to preceding work developed by Joaquim et al. (2009). Fibres morphological properties wereanalyzedbyaPulptecMFA-500 Morphology Fibre and Shive Analyser MorFiTrac according to methodology adopted by Tonoli et al. (2009a). Chemical characteristics were determined according to Silva and Queiroz (2006). Chemical and morphological characteristics of the organosolv pulp are presented in Table 1. TABLE 1. Chemical and morphological characteristics of bamboo organosolv pulp Lignin Cellulose Hemicellulose Average Average (%) (%) (%) lengh (mm) width (m) Bamboo organosolv pulp 2.52 89.77 4.52 0.80 19.8 The content of bamboo organosolv pulp varied from 6, 8, 10 and 12% by mass in relation to the solid raw materials. The range of fiber content under consideration was based on previous study by Dos Anjos et al. (2003). The matrix was composed of Portland cement type V (according to Brazilian Standard NBR 5733, 1983) and metakaolin 40 HP, provided by Metakaolin do Brasil, as pozzolanic material for partial replacement (25% by mass) of the cement. The composites were produced in thin pads with thickness of approximately 6 mm at laboratory scale using a slurry vacuum dewatering followed by pressing technique as adopted by Savastano Jr. et al. (2000) and subjected to thermal curing in water bath at a temperature of 70oC. Eight test specimens were produced for each formulation in order to guarantee a sufficient number of repetitions taking in account the variations in the raw material and in the adopted method of fabrication. In the completion of eight days of age under the thermal curing conditions the composites were subjected to non-destructive physical tests of water absorption (WA), bulk density (BD) and apparent void volume (AVV) according to ASTM C-948-81 (1982). Mechanical tests were performed using the universal 2

testing machine Emic DL-30,000 equipped with 1 kN load cell. A 135 mm span and a deflection rate of 1.5 mm/min were applied in the bending tests. Four-point bending configuration was adopted to evaluate the limit of proportionality (LOP), the modulus of rupture (MOR), the modulus of elasticity (MOE) and the toughness of the specimens. The calculations of mechanical properties were performed using the equations described in Tonoli et al. (2009b). After the definition of the optimum amount of bamboo organosolv pulp in cement matrices in the initial age (eight days) additional specimens of such a formulation have been produced for the study of degradation, based on the accelerated aging cycles adapted from the procedures presented at EN 494 (1994), by the adoption of 50, 100 and 200 soak and dry cycles (Tonoli et al., 2009b). The specimens were subsequently subjected to the same physical and mechanical tests as previously described. 3. Results and Discussion 3.1 Determining the optimum fiber content in the composite Table 2 shows the average results of four replications of the physical properties of water absorption (AA), apparent void volume (AVV) and bulk density (BD) and the flexural test results of modulus of rupture (MOR), limit of proportionality (LOP), modulus of elasticity (MOE) and toughness, of the composites reinforced with 6, 8, 10 and 12% bamboo organosolv pulp. TABLE 2. Physical and mechanical properties of composites reinforced with 6, 8, 10 and 12% bamboo organosolv pulp in the initial age after thermal curing.
Fiber content (%) 6 8 10 12 WA (%) 25.42 1.26 26.48 0.29 30.32 1.64 30.93 2.72 AVV (%) 38.75 0.92 39.05 0.23 42.10 2.57 39.59 2.31 BD (g.cm-3) 1.53 0.04 1.48 0.02 1.39 0.03 1.28 0.04 MOR (MPa) 6.39 0.92 7.51 0.07 6.78 1.38 5.79 1.49 LOP (MPa) 3.84 1.54 5.44 0.62 3.22 1.17 2.30 0.97 MOE (GPa) Toughness (kJ.m-2) 1.25 0.10 1.92 0.35 2.10 1.04

10.63 0.48 0.76 0.15 9.57 0.82 6.16 1.27 4.50 0.65

The composite reinforced with 6 and 8% of bamboo organosolv pulp presented water absorption and apparent void volume lower if compared to the other composites. Although the limit of 37% of water absorption admitted for fiber cement products by the Brazilian Standards NBR 5640 (1995), the high incidence of capillary voids is often connected to the dimensional variation, cracking and reduced durability of cement based products (GRAM, 1983). The level of 8% of pulp to the composite provided the best performance both at the rupture and before the cracking stage (limit of the elastic phase). This can be attested respectively by the higher values of the modulus of rupture (MOR) and limit of proportionality (LOP). In post-cracking condition, the toughness best performance was associated to the composites reinforced with 10 and 12% of fiber, however, with a high dispersion of the results, indicating the great variability of the specimens extracted from the same pad. This behavior can be explained due to the difficulty in dispersing the high amount of fibers in the matrix during the production of the composite. There was a significant decrease of approximately 50% in the results of the modulus of elasticity with increasing the amount of the pulp to 6 and 8% by mass. This behavior is attributed to the greater porosity of the matrix by increasing the level of reinforcement. It is due to the air entrapment during the mixing procedure and also to the higher porosity associated to the fiber-matrix transition zone (SAVASTANO Jr. & AGOPYAN, 1999).

Fig. 1 shows the typical stress versus strain curves of the composites reinforced with the levels of 6, 8, 10 and 12% bamboo organosolv pulp undergoing thermal curing for eight days. The tenacity (associated to the area under the curve) is significantly greater in the case of the composites produced with 10 and 12% of fiber clearly showing the strain hardening aspect of the curves and with the continuous increasing of the stresses after the occurrence of the first cracking point. Such a behavior demonstrates that the organosolv bamboo pulp fiber plays a remarkable role in the mechanical strength and total specific deformation of the composites in continuation of the limit of proportionality.
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6% organosolv bamboo pulp 8% organosolv bamboo pulp 10% organosolv bamboo pulp 12% organosolv bamboo pulp

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FIGURE 1. Typical stress x strain curves of the composites at under flexure tests, with 6, 8, 10 and 12% of bamboo organosolv pulp and after 8 days of thermal cuiring. The fiber content of 8% showed the best mechanical behavior if considering the results for MOR and LOP and also a reasonable combination of results for MOE and toughness. That compromise of strain hardening and strengthening of the composite worked out as the main reason for choosing this level of reinforcement for the second phase of accelerated aging tests. 3.2 Performance of the composite subjected to accelerated aging Table 3 shows the physical properties of water absorption (AA), apparent void volume (AVV) and bulk density (BD) and the mechanical properties of modulus of rupture (MOR), limit of proportionality (LOP), modulus of elasticity (MOE) and toughness for the composites reinforced with 8% bamboo organosolv pulp after submitted to 50, 100 and 200 of soak and dry cycles. TABLE 3. Physical and mechanical properties of composites reinforced with 8% bamboo organosolv pulp after 50, 100 and 200 of soak and dry cycles.
Number of aging cycles 50 100 200 WA (%) 23.57 2.70 21.11 1.36 19.04 1.55 AVV (%) 33.71 3.06 30.86 1.27 28.36 1.53 BD (g.cm-3) 1.43 0.05 1.46 0.04 1.49 0.04 MOR (MPa) 8.14 0.38 8.24 0.82 8.28 0.75 LOP (MPa) 7.04 0.64 7.14 0.91 7.19 1.00 MOE (GPa) 10.95 1.36 10.59 1.00 11.17 2.09 Toughness (kJ.m-2) 0.57 0.11 0.50 0.13 0.58 0.17

With the increasing number of the aging cycles there was a decrease in water absorption and apparent void volume of the composite and a correspondent increase in the bulk density. This is attributed to the filling of the voids of the matrix and the fiber-matrix interface with the hydration products of the cementitious matrix, which are responsible for the decrease of porosity, and consequently, the densification of the matrix. With the increase of the aging cycles there was an increase in modulus of rupture, limit of proportionality and modulus of elasticity of the composite, which indicates the improvement in the mechanical behavior of the matrix and in the fiber-matrix interfacial bonding. This behavior indicates that the adhesion between fiber and matrix were improved after accelerated aging, as the result of re-precipitation of the cement hydration products into and around the fibers and consequently filling the pores in the fiber-matrix interface.

The toughness has dramatically decreased to 50 cycles of accelerated aging, which can be basically attributed to the mineralization of the cellulose fibers and better adhesion of the fibers with the matrix. Mohr et al. (2005) showed that the degradation of mechanical properties is not linearly correspondent with increasing numbers of cycles of aging. Most of the loss in mechanical strength and toughness of the composite occurs in the initial aging cycles. Fig. 2 shows the typical stress x strain curves of the composites subjected to 50, 100 and 200 accelerated aging cycles in comparison this the composites in the early age. There is a clear decrease of toughness in the composite after the accelerated aging cycles, and a markedly increase in the LOP of the matrix with a slight increase in the strength of the composite.
10 9 8
8 Days 50 Cycles 100 Cycles 200 Cycles

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7 6 5 4 3 2 1 0 0,00 0,01 0,02 0,03 0,04 0,05 0,06

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FIGURE 2. Typical stress x strain curves of the composites at under flexure tests, reinforced with 8% of bamboo organosolv pulp after 8 days of thermal curing followed by 50, 100 and 200 of soak & dray cycles. Conclusion The physical-mechanical behavior of composites reinforced with 8% by mass of bamboo organosolv pulp demonstrates that it is possible to apply this non-conventional non-wood fiber in combination with inorganic matrices based on Portland cement with partial substitution of metakaolin. There is a significant decrease in the water absorption and apparent void volume of the composite followed by the increase in bulk density with the increase of the accelerated aging cycles. The increase in modulus of rupture, limit of proportionality, and modulus of elasticity of the aged composites indicates the improvement in the mechanical performance of the matrix and the improved adhesion between the fiber and the matrix, as a result of the reprecipitation of the cement hydration products into and around the fibers and consequently filling the pores in the interface between the fiber and matrix. Acknowledgments The authors were supported by grants offered by Capes, Brazil, through the Pro-Engineering Project (Process no 103/2008), CNPq (Process no 305792/2009-1) and Fapesp (Process no 2001/01128-5). The authors also thank Dr. Pescatori Fernando Henrique Silva, Fibria, Brazil, for the technical contribution. References ASTM. American Society for Testing and Materials. ASTM C 948-81: Dry and wet bulk density, water absorption and apparent porosity of thin sections of glass-fiber-reinforced concrete, test for - Annual Book of ASTM Standards Philadelphia, 1982.

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