Geopolymer comprises a family of mineral binders with similar chemical composition of the zeolite, but with a mixed microstructure: amorphous - semi crystalline. Geopolymers are also called polysialates, formed by a large molecular chain (poly) consisting of silicon, oxygen and aluminum.
Geopolymer comprises a family of mineral binders with similar chemical composition of the zeolite, but with a mixed microstructure: amorphous - semi crystalline. Geopolymers are also called polysialates, formed by a large molecular chain (poly) consisting of silicon, oxygen and aluminum.
Geopolymer comprises a family of mineral binders with similar chemical composition of the zeolite, but with a mixed microstructure: amorphous - semi crystalline. Geopolymers are also called polysialates, formed by a large molecular chain (poly) consisting of silicon, oxygen and aluminum.
EFFECT OF THE ALKALINE ACTIVATOR ON THE REFRACTORINESS OF A
GEOPOLYMER CONTAINNING METAKAOLIN AND FLY-ASH
The term geopolymer comprises a family of mineral binders with similar chemical composition of the zeolite, but with a mixed microstructure: amorphous - semi crystalline. The geopolymers are also called polysialates, formed by a large molecular chain (poly) consisting of silicon, oxygen and aluminum. Sialate is an abbreviation for silicate-oxide- aluminate. From the literature, the materials obtained by alkaline activation (or geopolymerization) are mechanically resistant and exhibit high thermal and chemical stability. These characteristics are reached faster than those of Portland cement manufactured materials. Furthermore, the different relationships SiO 2 /Al 2 O 3 allow the application of these materials in different areas, such as bricks, thermal insulation, and encapsulation of radioactive and toxic waste, foundry equipment and composites. It seems therefore evident the importance of promoting the development of alternative materials, complying with the same performance objectives. In addition, these new materials could be considered sustainable, because they reach their final properties at temperatures not exceeding 100C and can be produced from industrial wastes. The influence of alkaline activators (Na and K) in the refractoriness of a geopolymer derived from metakaolin with additions of fly ash was evaluated in this work by XRD and empirical refractoriness tests, in order to determine the final behavior of compositions, related to different activators and fly ash content.
The term geopolymer was created by Davidovits [1] in 1978 to point out a family of mineral binders with similar chemical composition of the zeolite, but with a mixed microstructure (from amorphous to semi crystalline), where the silica (SiO 2 ) and alumina (Al 2 O 3 ), constituents of aluminosilicates, react each other in a highly alkaline, organizing themselves alternately in three dimensions by sharing of oxygen atoms forming bonds of the type Si-O-Al-O, SiO-Al-O-Si-O or Si-O-Al-O -Si-O-Si-O. The geopolymers are also known polysialates (large molecular chain consisting of silicon, oxygen and aluminum). Sialate is an abbreviation for silicon-aluminate-oxide. Since 1972 Davidovits [2] worked with kaolinite as a raw material together with alkalis such as NaOH and KOH for the production of geopolymers. However, he changed later (1978) to kaolinite calcined at 750C for 6 hours, metakaolin, as a raw material which gave the best performance geopolymer. The geopolymeric binders allow applications in virtually all fields of industry, because among its properties, have high mechanical strength, resistance to freeze-thaw, high chemical inertness and excellent fire behavior, may be considered as refractory materials [3]. Thus, in principle, aluminosilicates such as slag, fly ash, volcanic ash and dust from tile or brick are potential starting materials for alkaline activation, because they have a previous heat treatment [4, ]. It has been observed in several studies, a high degree of thermal stability of geopolymers, especially in K-polysialates with melting point in the range of 1400C [6]. However, geopolymers for applications at temperatures between 1000 and 1200C were also obtained with Na activators for applications such as thermal insulation [7]. Another factor mentioned in the literature that may partially explain the superior behavior of geopolymers, obtained with the addition of fly ash when exposed to high temperatures, is related to the sintering of unreached particles of fly ash during the geopolymerization [8].
2. Materials and methods
The experimental development of this work used as raw materials: metakaolin HP (HPMK), supplied by Metacaulim do Brasil Company, metakaolin obtained from the calcination of Minasolo kaolin (MSMK) at 750C for 6 hours in a muffle EDG 3000, fly ash class F (FA) provided by Tractebel Energia, alkaline activators NaOH (commercial), KOH supplied by Dinmica Qumica, sodium silicate alkaline (SSA) and potassium silicate (PS), both provided by Unaprosil.
2.1 Alkaline activators and molar ratios between components
The alkaline activators more used to obtain geopolymeric materials are sodium or potassium hydroxide, sodium carbonate, sodium or potassium silicates, and especially mixtures thereof.
Based on the zeolits chemistry, Davidovits [9] suggests various limits and molar ratios aiming to improve the final properties of geopolymers, such as durability and strength. Activators: SiO 2 /Na 2 O =1.85 Precursors: 0.20 <Na 2 O/SiO 2 <0.48 3.30 <SiO 2 /Al 2 O 3 <4.50 0.80 <Na 2 O/Al 2 O 3 <1.60 Between activator and precursor: 10 <H 2 O/Na 2 O <25
Where is possible the replacement of Na, by K or Li.
Considering the high content of iron oxide (Fe 2 O 3 ) present in the fly ash, according to Table 1 (10.2 wt %), was taken 30 wt% as a maximum addition of fly ash on metakaolin. The iron element tends to replace the aluminum in the process of connecting the tetrahedral SiO 4 2- and it usually affects the mechanical strength [9]. Thus, and while respecting the given ranges of molar ratios, compositions were made by adding 10 and 30%wt of FA, besides on a 100% metakaolin composition. In addition, all the conditions used the HPMK and MSMK activating by the addition of Na and K activators. For both activators used, the relation between them was 2:1 by weight (silicate: hydroxide), and that for the hydroxides were prepared solutions 15 M (molar). Following this methodology, samples (cones) were made for an empirical evaluation of the refractory behavior and how different activators and addition of fly ash has direct influence on this property of the geopolymer.
3. Results and discussion
Table 1 and 2 present the results of chemical and mineralogical analysis of the precursors used, being that, the characters + (Table 2) represents a quantitative analysis of the results found by X-ray diffraction.
Table 1 Chemical analysis of precursors of the geopolymeric reaction - * supplier - ** X-ray fluorescence Raw materials (wt%) SiO 2 Al 2 O 3 Fe 2 O 3 Na 2 O K 2 O TiO 2 CaO MgO LOI HPMK* 56,2 34,8 2,2 0,0 1,9 1,3 0,0 0,2 2,6 MSMK** 49,7 35,0 0,5 0,1 1,5 0,0 0,1 0,2 2,98 FA** 55,3 19,8 10,2 0,0 2,3 1,0 1,3 0,7 2,75
Table 2 Mineralogical analysis of precursors of the geopolymeric reaction obtained by X-ray diffraction Raw materials (%) Crystalline Phases Amorphous Quartz Kaolinite Muskovite Hematite HPMK ++++ + ++ ++ MSMK ++++ +++ ++ ++++ FA ++++ +++ + +++
In order to observe how the alkaline activator and the fly ash content affect the geopolymer refractory behavior, samples (cones) of each composition were firing in a Lindenberg Blue CF56724C furnace, whereas similar firing curves: heating rate of 5 C/min., landing time of 5 min. and cooling rate of 10 C/min. Analyzing the results of the compositions with MSMK, activated with Na, it was found that the temperature peak (taken as operating temperature) which the sample maintains the structure without deformation was 1000C (Figure 1). The addition of 10 wt% of FA did not caused any damage at this temperature (Figure 2). On the other hand, the addition of 30 wt% of FA decreased this temperature to 800C (Figure 3).
Raw 700 800 900 1000 1100 (C) Fig. 1. Effect of the temperature on the refractoriness of the composition 100% MSMK (Na)
Raw 700 800 900 1000 1100 (C) Fig. 2. Effect of the temperature on the refractoriness of the composition 90% MSMK (Na)
Raw 700 800 900 1000 1100 (C) Fig. 3. Effect of the temperature on the refractoriness of the composition 70% MSMK (Na)
For samples of compositions with HPMK (also activated with Na) it was observed that the highest operating temperature was 900C (Figure 4), but the addition of 10 wt% of FA is enough to decrease the temperature to 800C (Figure 5) and 30 wt% addition maintains this behavior (Figure 6). This can be explained by the pronounced crystalline character of HPMK, as shown on Table 2, and which impairs the alkaline activation.
Raw 700 800 900 1000 1100 (C) Fig. 4. Effect of the temperature on the refractoriness of the composition 100% HPMK (Na)
Raw 700 800 900 1000 1100 (C) Fig. 5. Effect of the temperature on the refractoriness of the composition 90% HPMK (Na)
Raw 700 800 900 1000 1100 (C) Fig. 6. Effect of the temperature on the refractoriness of the composition 70% HPMK (Na) For both compositions, MSMK and HPMK, activated with K the operating temperatures found were higher compared to those activated with Na. These results are in accordance with the literature [6]. Table 3 presents the operating temperature results for pure compositions, 10 wt% and 30 wt% FA addition. Figures 7 to 12 show the samples characteristics after heat treatments.
Table 3 Operating temperatures of the compositions MSMK and HPMK activated with K. Composition Operating Temperature (C) MSMK 1400 MSMK +10 wt% FA 1300 MSMK+30 wt% FA 1300 HPMK 1300 HPMK+10 wt% FA 1300 HPMK+30 wt% FA 1300
Raw 1000 1300 1400 1500 (C) Fig. 7. Effect of the temperature on the refractoriness of the composition 100% MSMK (K)
Raw 1000 1300 1400 1500 (C) Fig. 8. Effect of the temperature on the refractoriness of the composition 90% MSMK (K)
Raw 1000 1300 1400 1500 (C) Fig. 9. Effect of the temperature on the refractoriness of the composition 70% MSMK (K)
Raw 1000 1300 1400 1500 (C) Fig. 10. Effect of the temperature on the refractoriness of the composition 100% HPMK (K)
Raw 1000 1300 1400 1500 (C) Fig. 11. Effect of the temperature on the refractoriness of the composition 90% HPMK (K)
Raw 1000 1300 1400 1500 (C) Fig. 12. Effect of the temperature on the refractoriness of the composition 70% HPMK (K)
Regarding to the geopolymers obtained with HPMK and activated with K, it was not possible to observe an influence so prominent in the operating temperature by the addition of the FA or the own crystalline metakaolin character as seen in the compositions of HPMK activated with Na. Taking as reference, the composition 90% MSMK activated with Na and MSMK 70% activated with K, were evaluated by XRD in order to relate the operating temperature with the melting point of the majority phase (Figures 13 and 14). In 90% MSMK activated with Na, the majority phase was considered as Faujasite; its melting point is 1300C. Leucite, which melting point is about 1690C, was considered the majority phase in MSMK 70% activated with K.
Fig. 13. X-ray diffraction patterns of the composition 90 wt% MSMK activated with Na (crude left / fired at 900C right) shown the majority phases. ( Sodium Aluminum Silicate Hydrate; + Albite; Faujasite; Corundum; Sodalite; Sodium Aluminum Silicate)
Fig. 14. X-ray diffraction patterns of the composition 70 wt% MSMK activated with K (crude left/ fired at 1300C right) shown the majority phases. ( Leucite; Corundum)
4. Conclusions
The nature of the activator, Na or K, has a direct influence on the refractoriness of the geopolymer materials as a function of the phases formed during the reaction. The amorphous character of the precursor was also an important parameter of reaction for the alkaline activation, activation being more prominent in the Na activated. The operating temperature of the geopolymer materials are directly related to the melting point temperature of the majority phases formed during the geopolymeric reaction. The development of geopolymer materials for high temperature applications is encouraging, particularly those activated by activators based K. * * *
+
Acknowledgements
The authors gratefully acknowledge the financial support of the So Paulo Research Foundation (FAPESP) and the Graduate Program on Materials Science and Engineer (PPGCEM - UFSCar) for the current work.
Bibliography
[1] T. B. Skaf, Influence of raw materials on the microstructure and strength of geopolymer composites, MSc Dissertation, Engineer Military Institute Rio de J aneiro, 2008. [2] J . Davidovits, Chemistry of Geopolymeric Systems, Terminology, Proceedings of the 2 nd Geopolymer International Conference, Saint-Quentin, 30 J une 2 J uly, 1999, pp. 9-39. [3] J . Davidovits, M. Morris, The Pyramids, an Enigma Solved, New York: Dorset Press, New York, 1988. [4] R Chang, Qumica, McGraw-Hill, Lisboa, 2005. [5] J . Davidovits, Geopolymers: Inorganic Polymeric New Materials, J ournal of Thermal Analysis, v. 37, n. 8, 1991, p. 1633-1656. [6]. V. F. F. Barbosa, K. J . D. Mackenzie, Synthesis and thermal behavior of potassium sialate geopolymers, Materials Letters, v. 57, 2003, p. 1477-1482. [7] D. S. Perera, R. L. Trautman, Geoploymers with the potencial for use as Refractory Castables, Advances in Technology of Materials and Materials Processing, v. 7, n. 2, 2006, p. 187-190. [8] D. L. Y. Kong, J . G. Sanjayan, K. Sagoe-Crentsil, Comparative performance of geopolymers made with metakaolin and fly ash after exposure to elevated temperatures, Cement and Concrete Research, v. 37, 2007, p. 1583-1589. [9] A. T. Pinto, Binder systems obtained by the alkaline activation of metakaolin, PhD Dissertation, Engineer Scholl, University of Minho, Guimares, 2004.