Quantitative Comparison of Binary Mix of Agro-Industrial Pozzolanic Additions for Elaborating Ternary Cements: Kinetic Parameters
Abstract
:1. Introduction
2. Materials and Methods
2.1. Materials
2.1.1. Binary System SCBA and SCSA
2.1.2. Binary System SCBA and BLAsh
2.1.3. Binary System PS and FA
2.1.4. Lime
2.2. Test Methodologies
2.2.1. Pozzolanic Activity Methods
2.2.2. Mathematical Model
- −
- The spherical form of the granule is retained, and the densities of F and B are the same. Consequently, the total radius of the granule rs (considering the reaction product layer and the nucleus without reacting) does not change with time and an intermediate region does not exist between the nucleus and the layer of product [54].
- −
- The movement rate of the reaction interface, drc/dt, is small in comparison to the diffusion speed of A through the product layer (pseudo-stable state) [55]. This is valid when the density of the fluid in the pores of F is smaller than the density of the solid reactant, which is certain in general.
- −
- Taking into account the pseudo-stable conditions, where the speed equations, expressed as a mole of solution A (CH solution) that disappears per unit of time per particle, are identical, the rate equation is obtained by handling these equations and considering well-founded physical hypotheses. It is determined by the control regime or by the rate-limiting step which can be [56,57]: (i) diffusive control and (ii) kinetic control.
- −
- In accordance with all the above, Villar-Cociña et al. [36,37] proposed a kinetic-diffusive model that allows the characterization of the pozzolanic activity in the sugar cane straw-clay ash/CH solution. Subsequently, the model was perfected in the characterization of the reaction kinetics in the sugar cane straw ash/CH and sugar cane bagasse ash/CH systems, where a correction term Ccorr was incorporated. This term is related to the remaining concentration of CH, which in some systems is not consumed totally. The corrected model is [38]:
3. Results
3.1. Chemical Characterization
3.1.1. SCBA/BLAsh System
3.1.2. SCBA/SCSA System
3.1.3. Paper Sludge/FA System
3.2. Pozzolanic Activity
3.3. Application of the Mathematical Model and Determination of the Kinetic Parameters
4. Conclusions
- –
- Chemically, all the binary samples are formed by the same oxides but with different contents. The main oxides are silica and alumina (although PSLSFA and POISFA shows a 47% and 54% of CaO respectively), whose contents are: 71.6% (SCSA), 70.5% (BLAsh), 69.79% (2SCBA), 60.10% (SCWI), 55.70% (FA), 75.39% (LS), 72.13% (SCSA), 49.79% (2SCBA50SCSA50) and 36.20% (1SCBA).
- –
- The values of the reaction rate constant, obtained in the fitting process of the kinetic-diffusive model, show that the binary blends 1SCBA60BLAsh40 (6.18 · 10−1 h−1), 1SCBA50BLAsh50 (1.72 · 10−2 h−1), 1SCBA70BLAsh30 (2.89 · 10−1 h−1) have a very high pozzolanic reactivity followed by PSLSFA (6.26 · 10−2 h−1), 2SCBA50SCSA50 (1.72 · 10−2 h−1), PSISFA (5.51 · 10−3 h−1) and SCWI (9.32 · 10−4 h−1).
- –
- Analyzing the three binary systems we can point out that the 1SCBA + BLAsh system is, in general, the one that shows the greatest pozzolanic reactivity, showing the highest values of the reaction rate constant K (order of 10−1 h−1) for all the binary mixtures, the highest being 1SCBA60BLAsh40 (the same order of silica fume), followed by the PS + FA system, specifically the PSLSFA binary mixture, and by the 2SCBA + SCSA system, specifically the 2SCBA50SCSA50 binary mixture. In all these cases, there is a good synergy between the basic and complementary pozzolans, and the mentioned binary mixtures have greater reactivity than the basic pozzolans (1SCBA, 2SCBA and LS).
- –
- The availability of pozzolanic blends with different pozzolanic reaction rates can become an important technological advantage in the manufacturing of new ternary cements that include pozzolanic binary blends. The selection of one binary system or another as the one preferred will depend on the characteristics needed for the building site.
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Conflicts of Interest
References
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Pozzolanic Binary Systems | Samples | SCBA (%) | SCSA (%) | FA (%) | BLAsh (%) | Paper Sludge | Designation |
---|---|---|---|---|---|---|---|
Sugar Cane Bagasse Ash and Sugar Cane Straw Ash (2SCBA + SCSA) | 2SCBA + SCSA (industrial) | 50 | 50 | - | - | - | SCWI |
2SCBA + SCSA (Laboratory) | 50 | 50 | - | - | - | 2SCBA50SCSA50 | |
SCSA | - | 100 | - | - | - | SCSA100 | |
2SCBA | 100 | - | - | - | - | 2SCBA100 | |
Sugar Cane Bagasse Ash and Bamboo Leaf Ash (1SCBA + BLAsh) | 1SCBA + BLAsh | 50 | - | - | 50 | - | 1SCBA50Blash50 |
1SCBA + BLAsh | 60 | - | - | 40 | - | 1SCBA60Blash40 | |
1SCBA + BLAsh | 70 | - | - | 30 | - | 1SCBA70Blash30 | |
1SCBA | 100 | - | - | - | - | 1SCBA100 | |
BLAsh | - | - | - | 100 | - | BLAsh100 | |
Paper sludge (PS) (industrial and laboratory) and Fly Ash (FA) (PS + FA) | Paper sludge (LS) +FA | - - | - | 50 | - | 50 | PSLSFA |
Paper sludge (IS) + FA | - | - | 50 | - | 50 | PSISFA | |
Paper sludge | - | - | - | - | 100 | PS |
1SCBA/BLAsh System | 2SCBA/SCSA System | Paper Sludge/Fly Ash System | |||||||
---|---|---|---|---|---|---|---|---|---|
Oxide (%) | 1SCBA 100 | BLAsh100 | 2SCBA100 | SCSA 100 | 2SCBA50SCSA50 | SCWI | PSLSFA | PSISFA | FA |
SiO2 | 36.20 | 70.5 | 69.40 | 71.6 | 49.79 | 60.10 | 13.90 | 11.02 | 55.70 |
Al2O3 | 12.30 | 0.63 | 11.26 | 0.58 | 7.53 | 12.50 | 8.30 | 9.37 | 24.00 |
Fe2O3 | 8.76 | 0.47 | 5.41 | 0.37 | 4.43 | 10.35 | 0.50 | 0.72 | 4.80 |
CaO | 7.10 | 7.86 | 2.51 | 7.47 | 11.10 | 3.11 | 47.12 | 54.36 | 2.20 |
MgO | 4.76 | 1.84 | 1.28 | 1.48 | 7.43 | 2.10 | 1.60 | 1.20 | 0.90 |
SO3 | 4.38 | 2.87 | 1.83 | 2.69 | 1.95 | 0.10 | 0.00 | 0.39 | 0.89 |
K2O | 12.80 | 5.14 | 3.45 | 4.95 | 8.45 | 6.00 | 0.30 | 0.21 | 2.18 |
P2O5 | 5.42 | 1.67 | 1.61 | 1.44 | 2.68 | 1.47 | 0.20 | 0.27 | 0.28 |
Na2O | 0.20 | <0.001 | 0.09 | <0.001 | 0.28 | 0.16 | 0.23 | 0.12 | 0.45 |
TiO2 | 1.98 | 0.06 | 1.38 | 0.07 | 0.86 | 2.73 | 0.25 | 0.50 | 0.69 |
LOI | 5.37 | 7.79 | 1.56 | 8.08 | 5.08 | 1.00 | 26.66 | 21.68 | 7.60 |
Pozzolanic Binary Sistems | Material (Ash) | τ (h) | Reaction Rate Constant K (h−1) | Diffusion Coeffient De (mm2/h) | Ccorr. | Coefficient of Multiple Determination (R2) | Residual Sum of Squares |
---|---|---|---|---|---|---|---|
2SCBA + SCSA | SCWI | 152.9 ± 10.3 | (9.32 ± 0.23) · 10−4 | 0.07 ± 0.003 | 0.9775 | 0.0194 | |
2SCBA50SCSA50 | 33.1 ± 2.7 | (1.72 ± 0.25) · 10−2 | 0.051 ± 0.038 | 0.9788 | 0.0020 | ||
SCSA100 | 23.2 ± 1.8 | (8.12 ± 0.67) · 10−1 | 0.09 ± 0.01 | 0.9976 | 0.0022 | ||
2SCBA100 | 43.5 ± 3.1 | (6.91 ± 0.82) · 10−3 | 0.10 ± 0.02 | 0.9722 | 0.0125 | ||
1SCBA + BLAsh | 1SCBA50Blash50 | 5.6 ± 0.2 | (3.83 ± 0.02) · 10−1 | 0.33 ± 0.03 | 0.9863 | 0.0620 | |
1SCBA60Blash40 | 3.6 ± 0.1 | (6.18 ± 0.03) · 10−1 | 0,41± 0.02 | 0.9780 | 0.0410 | ||
1SCBA70Blash30 | 4.5 ± 0.2 | (2.89 ± 0.03) · 10−1 | 0.45 ± 0.002 | 0.9810 | 0.0420 | ||
1SCBA100 | 5.3 ± 0.06 | (1.85 ± 0.004) · 10−2 | (1.13 ± 0.005) · 10−2 | 0.74 ± 0.0006 | 0.9952 | 0.0032 | |
BLAsh100 | 2.9 ± 0.07 | (10.02 ± 0.03) · 10−1 | 0.25 ± 0.003 | 0.9873 | 0.0570 | ||
PS + FA | PSLSFA | 93.9 ± 2.07 | (6.26 ± 0.90) · 10−2 | 0.13 ± 0.030 | 0.9810 | 0.0165 | |
PSISFA | 272.1 ± 31.4 | (5.51 ± 0.12) · 10−3 | (4.71 ± 0.85) · 10−3 | 0.17 ± 0.021 | 0.9894 | 0.0072 | |
LS | 50.2 ± 2.28 | (8.28 ± 0.09) · 10−3 | 0.30 ± 0.005 | 0.9979 | 0.0006 | ||
FA | 301.6 ± 28.2 | (2.12 ± 0.47) · 10−3 | (2.21 ± 0.88) · 10−3 | 0.13 ± 0.04 | 0.9984 | 0.0012 |
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Villar-Cociña, E.; Frías, M.; Savastano, H.; Rodier, L.; Sánchez de Rojas, M.I.; Sáez del Bosque, I.F.; Medina, C. Quantitative Comparison of Binary Mix of Agro-Industrial Pozzolanic Additions for Elaborating Ternary Cements: Kinetic Parameters. Materials 2021, 14, 2944. https://doi.org/10.3390/ma14112944
Villar-Cociña E, Frías M, Savastano H, Rodier L, Sánchez de Rojas MI, Sáez del Bosque IF, Medina C. Quantitative Comparison of Binary Mix of Agro-Industrial Pozzolanic Additions for Elaborating Ternary Cements: Kinetic Parameters. Materials. 2021; 14(11):2944. https://doi.org/10.3390/ma14112944
Chicago/Turabian StyleVillar-Cociña, Ernesto, Moisés Frías, Holmer Savastano, Loic Rodier, María Isabel Sánchez de Rojas, Isabel Fuencisla Sáez del Bosque, and César Medina. 2021. "Quantitative Comparison of Binary Mix of Agro-Industrial Pozzolanic Additions for Elaborating Ternary Cements: Kinetic Parameters" Materials 14, no. 11: 2944. https://doi.org/10.3390/ma14112944