Investigation of Dealumination in Phosphate-Based Geopolymer Formation Process: Factor Screening and Optimization
Abstract
:1. Introduction
2. Materials and Methods
2.1. Raw Material Characterization and Geopolymer Preparation
2.2. Methods
2.2.1. Chemical Experimental Methods
2.2.2. Experimental Designs
- Plackett–Burman design
- Central composite designs
- A 23 complete factorial design (NF = 8 experiments carried out at the corners of the cube);
- Six axial points at a distance of ±α from the center. The distance a is calculated so as to obtain rotatability. A three-variable central composite design is rotatable if:A = ±(NF)1/4 = ±1.6818
- Six replicates at the center point in order to estimate pure error.
3. Results and Discussion
3.1. Screening of Factors Influencing Phosphate-Based Dealumination Process Based on Plackett-Burman Design
- The curing time factor predominates, and the relatively high sensitivity of the response to this factor (41.32%) shows that the % of the released Al is highly dependent on this factor. This is well expected and justified. Indeed, when the reaction time is prolonged, the probability of protonating the bonds increases, and dealumination becomes more favored [13,38]. Subsequently, the different stages of geopolymerization will have the necessary time to take place successively.
- The P/Al molar ratio factor contributes 36.53% to the sensitivity of the response. Indeed, the increase in this factor means, firstly, the increase in the concentration of phosphoric acid as an activating solution and, secondly, the decrease in the pH of the reaction medium. These two conditions favor the dealumination process as well as the other stages of geopolymerization.
- The curing temperature factor contributes 11.27% to the sensitivity of the response. Indeed, dealumination, like any breakage of chemical bonds, requires energy [39]. Thus, by providing heat, the % of released Al increases systematically.
3.2. Optimization of Selected Variables by Using Central Composite Design
Evaluation of Model Adequacy and Validation
- Model Adequacy
- Validation of the Model
- Exploitation of the Model
- P/Al molar ratio close to 2;
- Curing temperature ≈ 70 °C.
- P/Al molar ratio between 1.5 and 2.5;
- Curing time close to 5 h.
3.3. Study of the Optimal Path
- P/Al molar ratio = 2.0;
- Curing temperature ≈ 70 °C;
- Curing time = 4.76 h.
4. Conclusions
Author Contributions
Funding
Data Availability Statement
Conflicts of Interest
References
- Pierrehumbert, R. There is no Plan B for dealing with the climate crisis. Bull. At. Sci. 2019, 75, 215–221. [Google Scholar] [CrossRef]
- Xu, H.; Van Deventer, J.S. Geopolymerisation of multiple minerals. Miner. Eng. 2002, 15, 1131–1139. [Google Scholar] [CrossRef]
- Essaidi, N.; Samet, B.; Baklouti, S.; Rossignol, S. Feasibility of producing geopolymers from two different Tunisian clays before and after calcination at various temperatures. Appl. Clay Sci. 2014, 88, 221–227. [Google Scholar] [CrossRef]
- Škvára, F.; Kopecký, L.; Nemecek, J.; Bittnar, Z. Microstructure of geopolymer materials based on fly ash. Ceram. Silik. 2006, 50, 208–215. [Google Scholar]
- Pu, S.; Zhu, Z.; Song, W.; Huo, W.; Zhang, C. A eco-friendly acid fly ash geopolymer with a higher strength. Constr. Build. Mater. 2022, 335, 127450. [Google Scholar] [CrossRef]
- Pu, S.; Zhu, Z.; Song, W.; Huo, W.; Zhang, J. Mechanical and microscopic properties of fly ash phosphoric acid-based geopolymer paste: A comprehensive study. Constr. Build. Mater. 2021, 299, 123947. [Google Scholar] [CrossRef]
- Pacheco-Torgal, F.; Castro-Gomes, J.; Jalali, S. Investigations about the effect of aggregates on strength and microstructure of geopolymeric mine waste mud binders. Cem. Concr. Res. 2007, 37, 933–941. [Google Scholar] [CrossRef]
- Komnitsas, K.; Zaharaki, D. Geopolymerisation: A review and prospects for the minerals industry. Miner. Eng. 2007, 20, 1261–1277. [Google Scholar] [CrossRef]
- Ismail, I.; Bernal, S.A.; Provis, J.L.; San Nicolas, R.; Hamdan, S.; van Deventer, J.S. Modification of phase evolution in alkali-activated blast furnace slag by the incorporation of fly ash. Cem. Concr. Compos. 2014, 45, 125–135. [Google Scholar] [CrossRef]
- Carreño-Gallardo, C.; Tejeda-Ochoa, A.; Perez-Ordonez, O.I.; Ledezma-Sillas, J.E.; Lardizabal-Gutierrez, D.; Prieto-Gomez, C.; Valenzuela-Grado, J.A.; Robles Hernandez, F.C.; Herrera-Ramirez, J.M. In the CO2 emission remediation by means of alternative geopolymers as substitutes for cements. J. Environ. Chem. Eng. 2018, 6, 4878–4884. [Google Scholar] [CrossRef]
- Nuruddin, M.F.; Malkawi, A.B.; Fauzi, A.; Mohammed, B.S.; Almattarneh, H.M. Geopolymer concrete for structural use: Recent findings and limitations. In IOP Conference Series: Materials Science and Engineering; IOP Publishing: Bristol, UK, 2016; Volume 133, p. 012021. [Google Scholar]
- Provis, J.L.; Van Deventer, J.S.J. Geopolymers: Structures, Processing, Properties and Industrial Applications; Woodhead: Cambridge, UK, 2009; p. 448. [Google Scholar]
- Zribi, M.; Baklouti, S. Investigation of Phosphate based geopolymers formation mechanism. J. Non-Cryst. Solids 2021, 562, 120777. [Google Scholar] [CrossRef]
- Louati, S.; Baklouti, S.; Samet, B. Acid based geopolymerization kinetics: Effect of clay particle size. Appl. Clay Sci. 2016, 132, 571–578. [Google Scholar] [CrossRef]
- Tchakouté, H.K.; Rüscher, C.H. Influence of the molar concentration of phosphoric acid solution on the properties of metakaolin-phosphate-based geopolymer cements. Appl. Clay Sci. 2017, 140, 81–87. [Google Scholar] [CrossRef]
- Tchakouté, H.K.; Ruescher, C.H.; Kamseu, E.; Andreola, F.; Leonelli, C. Influence of the molar concentration of phosphoric acid solution on the properties of metakaolin-phosphate-based geopolymer cements. Appl. Clay Sci. 2017, 147, 184–194. [Google Scholar] [CrossRef]
- Wang, Y.S.; Dai, J.G.; Ding, Z.; Xu, W.T. Phosphate-based geopolymer: Formation mechanism and thermal stability. Mater. Lett. 2017, 190, 209–212. [Google Scholar]
- Dong, T.; Xie, S.; Wang, J.; Chen, Z.; Liu, Q. Properties and characterization of a metakaolin phosphate acid–based geopolymer synthesized in a humid environment. J. Aust. Ceram. Soc. 2020, 56, 175–184. [Google Scholar] [CrossRef]
- Zribi, M.; Samet, B.; Baklouti, S. Effect of curing temperature on the synthesis, structure and mechanical properties of phosphate-based geopolymers. J. Non-Cryst. Solids 2019, 511, 62–67. [Google Scholar]
- Mathivet, V.; Jouin, J.; Gharzouni, A.; Sobrados, I.; Celerier, H.; Rossignol, S.; Parlier, M. Acid-based geopolymers: Understanding of the structural evolutions during consolidation and after thermal treatments. J. Non-Cryst. Solids 2019, 512, 90–97. [Google Scholar] [CrossRef]
- Zribi, M.; Samet, B.; Baklouti, S. Screening of Factors Influencing Phosphate-Based Geopolymers Consolidation Time, Using Plackett-Burman Design. In Advances in Materials, Mechanics and Manufacturing; Springer: Cham, Switzerland, 2020; pp. 115–122. [Google Scholar]
- Zribi, M.; Samet, B.; Baklouti, S. Mechanical, microstructural and structural investigation of phosphate-based geopolymers with respect to P/Al molar ratio. J. Solid State Chem. 2020, 281, 121025. [Google Scholar] [CrossRef]
- Cao, D.; Su, D.; Lu, B.; Yang, Y. Synthesis and structure characterisation of geopolymeric material based on metakaolinite and phosphoric acid. Guisuanyan Xuebao (J. Chin. Ceram. Soc.) 2005, 33, 1385–1389. [Google Scholar]
- Sadangi, J.K.; Muduli, S.D.; Nayak, B.D.; Mishra, B.K. Effect of phosphate ions on preparation of fly ash based geopolymer. IOSR J. Appl. Chem. 2013, 4, 20–26. [Google Scholar]
- Khan, M.I.; Azizli, K.; Sufian, S.; Siyal, A.A.; Man, Z.; Ullah, H. Sodium silicate free geopolymer as coating material: Adhesion to steel. In Proceedings of the 1st International Electronic Conference on Materials, Online, 26 May–10 June 2014; Volume 26. [Google Scholar]
- Bui, D.D.; Hu, J.; Stroeven, P. Particle size effect on the strength of rice husk ash blended gap-graded Portland cement concrete. Cem. Concr. Compos. 2005, 27, 357–366. [Google Scholar]
- Buffat, P.; Borel, J.P. Size effect on the melting temperature of gold particles. Phys. Rev. A 1976, 13, 2287. [Google Scholar]
- Louati, S.; Hajjaji, W.; Baklouti, S.; Samet, B. Structure and properties of new ecomaterial obtained by phosphoric acid attack of natural Tunisian clay. Appl. Clay Sci. 2014, 101, 60–67. [Google Scholar] [CrossRef]
- He, Y.; Liu, L.; He, L.; Cui, X. Characterization of chemosynthetic H3PO4–Al2O3–2SiO2 geopolymers. Ceram. Int. 2016, 42, 10908–10912. [Google Scholar]
- Djobo, J.N.Y.; Stephan, D. The reaction of calcium during the formation of metakaolin phosphate geopolymer binder. Cem. Concr. Res. 2022, 158, 106840. [Google Scholar]
- Murat, M.; Barchioni, A. Corrélation entre l’étatd’amorphisation et l’hydraulicité du métakaolin. Bull. Minéral. 1982, 105, 543–555. [Google Scholar] [CrossRef]
- Amara, A.A.; Salem-Bekhit Mounir, M.; Alanazi, F.K. Plackett-Burman randomization method for Bacterial Ghosts preparation form E. coli JM109. Saudi Pharm. J. 2013, 6, 273–279. [Google Scholar]
- Czyrski, A.; Sznura, J. The application of Box-Behnken-Design in the optimization of HPLC separation of fluoroquinolones. Sci. Rep. 2019, 9, 19458. [Google Scholar] [CrossRef]
- Samghouli, N.; Bencheikh, I.; Azoulay, K.; Abahdou, F.Z.; Mabrouki, J.; Hajjaji, S.E. Study of Piroxicam Removal from Wastewater by Artichoke Waste Using NemrodW® Software: Statistical Analysis. In IoT and Smart Devices for Sustainable Environment; Springer: Cham, Switzerland, 2022; pp. 29–42. [Google Scholar]
- Marzouki, M.; Samet, B.; Tounsi, H. Application of Plackett–Burman and Box-Behnken designs for the optimization of Tunisian dam sediment-based geopolymers. J. Build. Eng. 2022, 50, 104162. [Google Scholar]
- Bacaoui, A.; Dahbi, A.; Yaacoubi, A.; Bennouna, C.; Maldonado-Hódar, F.J.; Rivera-Utrilla, J.; Carrasco-Marín, F.; Moreno-Castilla, C. Experimental design to optimize preparation of activated carbons for use in water treatment. Environ. Sci. Technol. 2002, 36, 3844–3849. [Google Scholar] [PubMed]
- Elhadiri, N.; Bouchdoug, M.; Benchanaa, M.; Boussetta, A. Optimization of preparation conditions of novel adsorbent from sugar scum using response surface methodology for removal of methylene blue. J. Chem. 2018, 2018, 2093654. [Google Scholar]
- Brylewska, K.; Rożek, P.; Król, M.; Mozgawa, W. The influence of dealumination/desilication on structural properties of metakaolin-based geopolymers. Ceram. Int. 2018, 44, 12853–12861. [Google Scholar]
- Novick, S. No energy storage in chemical bonds. J. Biol. Educ. 1976, 10, 116–118. [Google Scholar] [CrossRef]
- Kamoun, A.; Samet, B.; Bouaziz, J.; Chaabouni, M. Application of a rotatable orthogonal central composite design to the optimization of the formulation andutilization of an useful plasticizer for cement. Analusis 1999, 27, 91–96. [Google Scholar] [CrossRef]
- Djobo, J.N.Y.; Stephan, D.; Elimbi, A. Setting and hardening behavior of volcanic ash phosphate cement. J. Build. Eng. 2020, 31, 101427. [Google Scholar]
Type of Aluminosilicate Precursor | Kaolin | Natural Tunisian Clay |
---|---|---|
Oxides | %mass | %mass |
Al2O3 | 47 | 31.12 |
SiO2 | 51.91 | 49.03 |
CuO | 0.01 | 3.94 |
Fe2O3 | 0.56 | 6.72 |
K2O | 0.03 | 4.57 |
MgO | 0.0.4 | 2.38 |
Cao | 0.01 | 2.15 |
P2O5 | 0.04 | 0.09 |
Factors Levels | Coded Variable | Lower Level (−1) | Higher Level (+1) |
---|---|---|---|
P/Al molar ratio | X1 | 0.5 | 2 |
Curing temperature | X2 | 25 °C | 85 °C |
Curing time | X3 | 1 day | 7 days |
Aluminosilicate particle size | X4 | ≥63 µm | ≤63 µm |
Mold’s condition | X5 | Opened | Closed |
Acidic solution | X6 | A * | B ** |
Nature of aluminosilicate precursor | X7 | Kaolin | Natural Tunisian clay |
Calcination of aluminosilicate precursor | X8 | With | Without |
pH of starting mixture | X9 | Low (between 1 and 3) | High (between 4 and 5) |
N° Exp | X1 | X2 | X3 | X4 | X5 | X6 | X7 | X8 | X9 |
---|---|---|---|---|---|---|---|---|---|
1 | 1 | 1 | −1 | 1 | 1 | 1 | −1 | −1 | −1 |
2 | −1 | 1 | 1 | −1 | 1 | 1 | 1 | −1 | −1 |
3 | 1 | −1 | 1 | 1 | −1 | 1 | 1 | 1 | −1 |
4 | −1 | 1 | −1 | 1 | 1 | −1 | 1 | 1 | 1 |
5 | −1 | −1 | 1 | −1 | 1 | 1 | −1 | 1 | 1 |
6 | −1 | −1 | −1 | 1 | −1 | 1 | 1 | −1 | 1 |
7 | 1 | −1 | −1 | −1 | 1 | −1 | 1 | 1 | −1 |
8 | 1 | 1 | −1 | −1 | −1 | 1 | −1 | 1 | 1 |
9 | 1 | 1 | 1 | −1 | −1 | −1 | 1 | −1 | 1 |
10 | −1 | 1 | 1 | 1 | −1 | −1 | −1 | 1 | −1 |
11 | 1 | −1 | 1 | 1 | 1 | −1 | −1 | −1 | 1 |
12 | −1 | −1 | −1 | −1 | −1 | −1 | −1 | −1 | −1 |
Independent Variables | Variable Symbol | Domain Center | Variation Step |
---|---|---|---|
P/Al molar ratio | X1 | 2 | 0.8 |
Curing temperature (°C) | X2 | 50 | 15.5 |
Curing time (h) | X3 | 3 | 1.6 |
N° Exp | X1 | X2 | X3 |
---|---|---|---|
1 | −1 | −1 | −1 |
2 | 1 | −1 | −1 |
3 | −1 | 1 | −1 |
4 | 1 | 1 | −1 |
5 | −1 | −1 | 1 |
6 | 1 | −1 | 1 |
7 | −1 | 1 | 1 |
8 | 1 | 1 | 1 |
9 | −1.6818 | 0 | 0 |
10 | 1.6818 | 0 | 0 |
11 | 0 | −1.6818 | 0 |
12 | 0 | 1.6818 | 0 |
13 | 0 | 0 | −1.6818 |
14 | 0 | 0 | 1.6818 |
15 | 0 | 0 | 0 |
16 | 0 | 0 | 0 |
17 | 0 | 0 | 0 |
18 | 0 | 0 | 0 |
19 | 0 | 0 | 0 |
20 | 0 | 0 | 0 |
N° Exp | P/Al Molar Ratio | Curing Temperature | Time of Heating | Particle Size | Mold’s Condition | Acidic Solution | Nature of Aluminosilicate | Calcination | pH | % of Released Al |
---|---|---|---|---|---|---|---|---|---|---|
1 | 2 | 85 | 1 day | ≤63 | Closed | B | Kaolin | With | Low | 11 |
2 | 0.5 | 85 | 7 days | ≥63 | Closed | B | Natural Tunisian clay | With | Low | 10 |
3 | 2 | 25 | 7 days | ≤63 | Opened | B | Natural Tunisian clay | Without | Low | 13 |
4 | 0.5 | 85 | 1 day | ≤63 | Closed | A | Natural Tunisian clay | Without | High | 5 |
5 | 0.5 | 25 | 7 days | ≥63 | Closed | B | Kaolin | Without | High | 5 |
6 | 0.5 | 25 | 1 day | ≤63 | Opened | B | Natural Tunisian clay | With | High | 2 |
7 | 2 | 25 | 1 day | ≥63 | Closed | A | Natural Tunisian clay | Without | Low | 9 |
8 | 2 | 85 | 1 day | ≥63 | Opened | B | Kaolin | Without | High | 7 |
9 | 2 | 85 | 7 days | ≥63 | Opened | A | Natural Tunisian clay | With | High | 16 |
10 | 0.5 | 85 | 7 days | ≤63 | Opened | A | Kaolin | Without | Low | 13 |
11 | 2 | 25 | 7 days | ≤63 | Closed | A | Kaolin | With | High | 13 |
12 | 0.5 | 25 | 1 day | ≥63 | Opened | A | Kaolin | With | Low | 2.5 |
N° Exp | P/Al Molar Ratio | Curing Temperature (°C) | Curing Time (h) | Released Al (%) |
---|---|---|---|---|
1 | 1.20 | 34.50 | 1.40 | 2 |
2 | 2.80 | 34.50 | 1.40 | 3 |
3 | 1.20 | 65.50 | 1.40 | 6 |
4 | 2.80 | 65.50 | 1.40 | 5 |
5 | 1.20 | 34.50 | 4.60 | 5 |
6 | 2.80 | 34.50 | 4.60 | 3 |
7 | 1.20 | 65.50 | 4.60 | 16 |
8 | 2.80 | 65.50 | 4.60 | 19 |
9 | 0.65 | 50.00 | 3.00 | 5 |
10 | 3.35 | 50.00 | 3.00 | 0 |
11 | 2.00 | 23.93 | 3.00 | 1 |
12 | 2.00 | 76.07 | 3.00 | 12 |
13 | 2.00 | 50.00 | 0.30 | 2 |
14 | 2.00 | 50.00 | 5.69 | 9 |
15 | 2.00 | 50.00 | 3.00 | 5 |
16 | 2.00 | 50.00 | 3.00 | 5 |
17 | 2.00 | 50.00 | 3.00 | 4 |
18 | 2.00 | 50.00 | 3.00 | 6 |
19 | 2.00 | 50.00 | 3.0 | 7 |
20 | 2.00 | 50.00 | 3.000 | 8 |
Source of Variation | Sum of Squares | Degrees of Freedom | Mean Square | F0 | Test F |
---|---|---|---|---|---|
Regression | 383.3893 | 9 | 42.5988 | 7.7227 | ** |
Residuals | 55.1607 | 10 | 5.5161 | ||
Lack of fit | 44.3273 | 5 | 8.8655 | 4.0918 | (NS) |
Pure error | 10.8333 | 5 | 2.1667 | ||
Total | 438.5500 | 19 |
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Zribi, M.; Samet, B.; Baklouti, S. Investigation of Dealumination in Phosphate-Based Geopolymer Formation Process: Factor Screening and Optimization. Minerals 2022, 12, 1104. https://doi.org/10.3390/min12091104
Zribi M, Samet B, Baklouti S. Investigation of Dealumination in Phosphate-Based Geopolymer Formation Process: Factor Screening and Optimization. Minerals. 2022; 12(9):1104. https://doi.org/10.3390/min12091104
Chicago/Turabian StyleZribi, Marwa, Basma Samet, and Samir Baklouti. 2022. "Investigation of Dealumination in Phosphate-Based Geopolymer Formation Process: Factor Screening and Optimization" Minerals 12, no. 9: 1104. https://doi.org/10.3390/min12091104