Characterization of modified fibers
Analysis by infrared spectroscopy FTIR
The wood fiber modified in this study obtained by heterogeneous esterification with C12 anhydride. The modified wood fiber was analyzed by FTIR and solid state NMR.
FTIR spectra, shown in Fig. 2, exhibits the presence of an ester carboxyl absorption band at 1732 cm−1, methylene peak at 2855 cm−1 and 1450 cm−1. The other characteristic peaks of acyl moiety are hidden by the overlapping of wood fiber bundles.
Analysis by CP/MAS 13C solid state NMR
The NMR spectra of fiber wood and fiber wood modified are shown in Fig. 3. In the spectrum of fiber wood, all signals, i.e., those at 104.7 ppm (C-1), 89.8 ppm (C-4 of crystalline cellulose), 74.7 ppm (C-5), 72 ppm (C-2 and C-3), and 69.5 ppm (C-6 of crystalline cellulose) [33], are attributed to six carbon atoms of the glucose unit. However, there is no signal of C-4 and C-6 of amorphous cellulose in the spectrum, suggesting the complete disruption of the cellulose amorphous structure during the acid hydrolysis of cotton. Notably, two more intense signals appear in the spectrum of fiber wood modified (Fig. 3) in addition to those of fiber wood, due to the carbon atoms of carboxylic groups C-7 at 173.8 ppm and methylene carbon in the alkyl moiety at 20–40 ppm.
Contact angle measurement
By analyzing the result concerning the evolution of contact angles as a function of time, a clear difference can be seen in the variation of these angles (Fig. 4). In fact, the alkaline treatment of the fibers with sodium hydroxide increases the hydrophilic appearance, and reveals the contact angle recorded for this sample, which remained stable around 20°. The same is noticed from the fibers handled by soda/EDTA, the contact angle varies from 45° at the beginning. From the obtained curves, we notice that the wood modified by grafting of hydrocarbon chain possesses the highest angle (70°), it suggests that the evolution of character of surface is bound to the presence of chain alkyls which are going to paper the surface while adopting a perpendicular configuration on the surface to that this.
The value of the contact angle of a drop of water onto the surface of the grafted fibers with increasing level of esterification is depicted in Fig. 5. Results show that the angle ϴ increased with increasing aliphatic chain length and the esterification extent. For modified wood fibers having an acylation degree higher then DS = 0.43, ϴ exceeded 90°, indicating that the surface became totally hydrophobic.
Recovery of pores
The hydration of cement favors the liberation of a very important quantity of calcium ions, the addition of a low concentration by adjuvant anionic (anionic surfactant SDBS) can assure the electrostatic neutralization. If we add a higher concentration of this additive, we shall have in this case an excess of the molecules of SDBS in the mixture. By arriving at the CMC (critical micellar concentration), the molecules of the additive group together by forming micelles responsible for the superficial cover of complex Ca2+/pectin, and as a result of recovery of pores in composites.
Electrokinetic study of the fiber wood suspensions handled by SDBS in the presence of a cement matrix
Every surfactant possesses a certain concentration molar called “critical micellar concentration” (CMC), from which it will be capable of forming micelles grouping together on the superficial part of the composite. This operation gives birth to a phenomenon of emulsion (Fig. 6). The addition of an anionic additive (SDBS) in the water by mixing improves of more the surface of samples by minimizing the size of pores by emulsifying effect, from where the absorption of water reduces (Fig. 7).
According to the curve of the potential Zeta, we notice that the addition of the additive in the manufacturing of composites, pass by several stages. Indeed, for a low concentration of the SDBS ~ (0.1 mmol L−1), the potential Zeta is of the order of 35 mV, this value results from the ionization of calcium during the hydration of cement. The more the concentration by adjuvant increases, the more the potential Zeta decreases; this relation informs us about the role of the molecules of the anionic additive in the neutralization of the ions Ca2+. By arriving at a certain concentration of the additive ~ (1.1 mmol L−1), the total neutralization was made and we have negative values of the potential Zeta. These show that the molecules of the additive are in excess, where from the formation of micelles from the CMC (Fig. 8).
Characterization physical appearance
In this part, we have solved one of the major concerns about our subject, namely the problem of water absorption. This last factor is responsible for the decarbonization of steels in cementitious materials and therefore negatively affects their life expectancy.
Absorbance in water
*Effect of the treatment processing of the wood on the absorbance: the results obtained in Fig. 9 show that treatments processing made on wood fibers have certain effects on the absorbance in water of samples.
*Alkaline treatment: the dumping of fibers in a basic solution of NaOH can engender the ionization of the group hydroxylate OH on the surface of fibers [26]:
$$ ({\text{Fiber}} - {\text{OH}}) + {\text{NaOH}} \to ({\text{Fiber}} - {\text{O}}^{ - } + {\text{Na}}^{ + } ) + {\text{H}}_{2} {\text{O}} . $$
This anionic structure of fibers favors the collision of water molecules through electrostatic interactions. This justifies then the fact that the wood handled by the present soda a rate of absorbance raised with regard to compared with the only cement (Fig. 10).
*Treatment processing by the EDTA: concerning the chemical interaction fibers–matrices, wood fibers seem capable of getting an important quantity of calcium on their surfaces. This fixation of the ions Ca2+ by pectin inhibits the growth of silicate of calcium hydrated (C-S-H), and is probably responsible for delays of taking observed in the dough of cement (Fig. 11). Give a complex to Ca2+/EDTA (effective chelate) with the aim of solving this problem; we tried to prevent the fixation of the ions Ca2+ on the surface of fibers by a treatment processing in the EDTA. In fact, the EDTA by its strong chelating power (or having complexes) can train (form) a very stable complex with the calcium ions, where from we can say that this substance contributes to the destruction of complex Ca2+/pectin.
*Treatment processing by grafting of alkyl chains: From a measurement of absorbance, we noticed that the linear hydrocarbon chains transplanted on wood fibers were the most effective with regard to the other treatments processing. The decrease of the content of water absorbed for the sample strengthened by modifying fibers, based on the role of chains alkyls which substitute the groupings hydroxyls on the surfaces of wood fibers. These chains thus inhibit the fixation of an important quantity of water on fibers (Fig. 12).
**Effect of the adjuvant SDBS: In this part, we added an anionic additive, SDBS (sodium dodecylbenzene sulfonates), to study its effect on the surface of samples and as a consequence on the absorbance in water. The realized measures showed that the contribution of the additive is very remarkable in the reduction of the quantity of absorbed water (Fig. 13). The decrease of the rate of water absorbed by test tubes containing modified fibers and gross fibers about 20% and 35%, respectively, with regard to the reference highlights the role of the additive in the superficial packaging of fibers. This result can be interpreted by the fact that the molecules of the used additive work as a super-plasticizing which covers the surface of fibers preventing as a consequence their contact with the water. The reactions between the various constituents of the sample containing modified fibers can be realized as indicated in Fig. 14. The molecules of the additive play the role of an intermediate element between the ions of calcium stemming from the hydration of the cement on one hand, and the alkyl chains transplanted on the surface of fibers on the other hand. They are capable of getting a significant number of Ca2+ by their hydrophilic grouping through electrostatic connections, leaving their hydrophobic part bound, by connections of hydrophobic type, in the hydrocarbon chains. The decrease in the rate of absorption, thus results from the reduction of pores within the mud samples. What justifies the superficial shine of these test tubes when one we use the additive.
**Effect of the rate of reinforcement: For this part, we made five cement-based samples white and with some wood modified with various rates (0; 0.5; 1; 1.5 and 2%), by adding a small quantity of additive to the water by mixing (Fig. 15). The measures of the absorbance showed an inversely proportional relation between the quantity of absorbed water and the percentage of wood fiber injected in the dough of cement. Indeed, if the rate of fibers increases, the content of absorbed water is reduced. For example, 2% of fibers are capable of minimizing the quantity of water absorbed about 21% to compare with a test tube containing 0.5% of the same wood. The relation between the rate of fibers and the absorbance is can be due to the phenomenon of emulsion which will be more intense by increasing the density of fibers.
Mechanical characterization
Compressive strength
The analyses of Fig. 16 examine the decrease in compressive stress with the increase in the percentage of fibers in cement. With the addition of 1% of the fibers, there is a decrease in stress up to 12.33 MPa. By exceeding the addition of 2% of the fibers, no effect is observed on the compressive strength (stress) and in this case the incorporation of the fibers in the matrix increases the vacuum and reduces the compactness during the audition. The influence of the incorporation of the wood fiber leads to a constant increase in the compression force up to a content of 1% by weight. For example, the compressive strength goes from 9.81 MPa for the pure reference cement to about 22.96 MPa, which corresponds to an improvement of about 200%. However, at 2% by weight of wood fiber, the concentration falls considerably below that of the pure cement. Three possible reasons have been put forward for the considerable improvement of the mechanical properties with the addition of wood fiber in the cement. First, because of their hydrophilic nature, hydration of the cement is accelerated and larger volumes of hydration products are formed. Second, the high surface area of wood fiber enhances the fiber–matrix interface, which improves the transfer of stress between the matrix and the fibers. Third, the high ratio of surface to wood fiber volume has favored the nucleation of the cement phases, namely CSH, providing excellent chemical reactivity to promote hydration of the cement. Finally, the application of the addition of SDBS, as a dispersing agent, also contributed to the improvement of the resistance: This improves the dispersion of wood fiber in the cement matrix. The carboxylic groups on the wood fiber surface react with the hydrated calcium silicate and result in a strong coating force between the fiber and the matrix. This reaction can provide a higher stress when the crack goes directly to the zone of the reinforced wood fiber zone and prevents the propagation of cracks. Furthermore, when the wood fiber reacts chemically with hydration products, they can behave as nucleation and form interfacial mechanical bonds. More than 1 wt% of wood fiber, a possible reason for the decrease in resistance to be due to aggregation of wood fiber, leading to inhomogeneous dispersion of the wood fiber in the cement matrix. This agglomeration is attributed to locating high wood fiber content and forming networks. These agglomerated wood fibers create fragile areas in the form of pores. After the curing process, these particles act as stress concentrators in the cement matrix and promote premature cracking. The cement reinforcement hypothesis can be mainly attributed to the wood fiber potential to improve the degree of hydration of the cement.
Young’s modulus “E”
The presence of wood fibers in a cement matrix confirms the inrease in rigidity, which is explained by the inrease of the Young's modulus at 1% of fiber addition, which increases the stress and the material also becomes more resistant. We note in Table 3 that the materials had a better maximum stress on the order of 22.96 MPa for 1% of the fibers treated with SDBS. The presence of fibers wood improves the rupture strength of composite cement; this expression was confirmed as well by the obtained results.
Table 3 Young’s modulus values of the different samples