Proceedings of the 7th International Symposium on East Asian Resources Recycling Technology November 10~14, 2003, Tainan, Taiwan

Production geopolymer materials by coal fly ash

J. W. Wang* and T.W. Cheng**
*Department of Environmental Engineering, National Cheng Kung University, bhww.tw@yahoo.com.tw **Department of Materials & Mineral Resources Engineering, National Taipei University of Technology, twcheng@ntut.edu.tw

Abstract : Coal ash is the main waste from power plant. It is estimated that the consumption of the coal for power plant will increase to 240 million tons each year and the coal ash wastes will produce more than 2 million tons per year. Although the utilization of coal fly ash can be reached 74.1%, large amount of coal fly ash and bottom ash still cannot be utilized. The purpose of this research is to develop a process to manufacture geopolymer using coal fly ash waste. The test results show that the characteristics of waste coal fly ash-based geopolymer have great physical/mechanical properties for fire resistance test. A 10 mm thick geopolymer panel was exposed to a 1100 flame, with the measured back-side temperatures reaching less than 470 after 30 minutes. The products can be fabricated for construction purposes and have great application potential. Keyword: coal fly ash, geopolymer, fire resistances

Introduction
Throughout the world, the amount of coal fly ash from power plant is increasing. The production of coal fly ash from Tai-Power Company (TPC) is about two million tons per year and the quantity of fly ash is four times of bottom ash in Taiwan (Kuo, 1991 Kuo, 1994 Lee et al., 1998Wang et al., 1996). For the purpose of energy, economic developing, and environmental ecosystem conserving, many research works and development investigations have been conducted in its utilizations as a starting material, such as using coal fly ash to produce artificial reef (Kuo, 1994), as an addition materials for concrete (Kuo, 1994; Lai, 1994 Yang, 1997), raw materials of ceramic (Wang et al., 1994), etc. The reuse amount of fly ash is still limited. However, due to the coal fly ash in Taiwan is classified as Class F (Yen, 1996), and it could be a good raw material for making geopolymer. Geopolymers, an inorganic polymer, firstly developed by Joseph Davidovits in 1978 (Comrie and Davidovits, 1988; Davidovits et al., 1990), have been gradually attracting world attention as potentially revolutionary materials. It is a class of three-dimensionally networked alumino-silicate materials, similar to natural zeolite minerals. Unlike conventional organic polymers, glass, ceramic, or cement, geopolymers are non-combustible, heat-resistant, formed at low temperatures, and fire/acid resistant. The bond of geopolymer is chemical bonding the mechanism is different to cement hydration. While using fly ash as cement addition, between fly ash and Ca(OH)2 occurred during cement hydration, will appear secondary reaction, then forming hydrated materials (Ke, 1994). However, the geopolymerisation including the following step: (1) the dissolution of alumino-silicate oxide in MOH solution (M=Na or K); (2) the diffusion of dissolved Al and Si complexes, from particle surfaces to the interparticle space; (3) the formation of a gel phase resulting from the polymerization between an added silicate solution and Al and Si complexes; (4) hardening of the gel phase by the exclusion of spare water to form geopolymeric product (Xu et al., 2001). According to previous studies (Hua et al., 1999 Swanepoel et al., 2002), geopolymerisation involves a chemical reaction between various aluminosilicate oxides with silicates under highly alkaline conditions, which can be presented schematically as follow:
n(Si2O 5,Al2 O2) + 2nSiO2 + 4nH2O + NaOH/KOH (Si-Al materials) Na+ ,K + + n(OH)3-Si-O-Al-O-Si-(OH) 3 (OH)2 (Geopolymer precusor) (1)

n(OH) 3-Si-O-Al -O-Si-(OH) 3+NaOH/KOH (OH)2

(Na +,K +) - (-Si-O-Al -O-Si-O-) + 4H2O O O O

(2)

(Geopolymer backbone)

The aim of this research is to try to fabricate a coal fly ash-based geopolymer for fire -resistance purposes that has the potential for using coal fly ash in Taiwan.

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Table1. The composition of fly ash and metakaolinite Composition (Wt. %) SiO2 Al2 O3 Fe2 O3 CaO MgO Na 2 O K2 O TiO2 PbO ZnO Cr2 O3
1800 1600 1400

Fly ash 59.95 22.35 3.65 1.45 0.77 0.62 1.07 0.99 0.04 0.02 0.02

Metakaolinite 52.26 42.83 1.01 0.02 0.09 0.02 1.56 0.13 0.06 < 0.01 < 0.01

with slightly amorphous phase. Fig.2 shows the particle size distribution of the coal fly ash. The D50 of the fly ash is around 19.3m. Sodium silicate (weigh ratio SiO2 /Na 2 O = 3.3, wt. % Na 2 O= 6-7 % and SiO2 = 23-25%) and KOH (analytical grade) were obtained from L.K. chemical CO., Ltd., Taiwan. Kaolinite was obtained from the standard Reagent Co. Ltd., USA. Metakaolinite was prepared by calcining the above kaolinite at 750 for 6 hours as described by Davidovits ((1999a). The particle size of the metakaolinite is also shown in Fig.2, and the D50 of the metakaolinite is 6m. The chemical composition of the metakaolinite is also shown in Table 1. All experiments were kept the mole ratio of Al2 O3 /SiO2 =0.22; Na 2 O+K2 O/SiO2 =0.2 by using 10 N KOH, and carried out using the same batches of starting materials and reagents. Methods

Q M-Mullite Q-Quartz

Intensity(Counts)

1200 1000 800 600 400 200 0 0 10 20 30 40 50 60 70 80 90

Q M MM M M Q

2-Theta(deg)

A mechanical mixer firstly mixed KOH and metakaolinite at certain ratio for 10 minutes. After Sodium silicate solution was added, the coal fly ash was then mixed. Following a further 10 minutes of mixing, the samples were cast in 25-mm cube molds and vibrated for 5 minutes in order to release bubbles. The molds were sealed and set at room temperature and 60C for 1 to 7 days in a sample-drying oven. After being removed from the moulds, the samples were kept at room temperature for another 24-156 hours, before beginning physical and mechanical property measurements. The geopolymer setting time measurements are conducted by Vicat needle (refer to CNS 786 and ASTM C191-01 standard test methods). The testing methods and formulas for physical property were evaluated according to the Archimedes method. Compressive strength tests for all sampled were carried out after 7 days by Shimadzu UEH-30 compressive strength analysis apparatus. For fire resistance tests, a 100.5 mm thick geopolymer panel was exposed to an 1100 flame. The reverse-side temperature of the panel was measured and recoded by a thermocouple (Davidovits, 1999b).

Fig.1 The XRD pattern for the coal fly ash

100

80

%PASS

60

Metakaolinite

40

Coal fly ash

20

0
0.01 0.1 1 10 100 1000

Results and discussion

Setting Time Measurements A Vicat needle was used to measurement the geopolymer setting time. By recording the time of a 1 mm needle penetration in the softening specimen of 25 mm was determined; it is the initial setting time. The final setting time is when the needle does not sink visibly into the paste. Fig.3 shows the effect of temperature on the setting time. It is can be seen that the initial setting time and final setting time at room temperature and 60 are 531, 60 and 566, 65 min, separately. It is obvious that the geopolymer setting time at 60 is faster than that at room temperature, due to water loss increasing the

Size( m)

Fig.2 Particle size distribution of coal fly ash and metakaolinite

Experimental methods
Materials Coal fly ash is collected from Tai-Power Company in northern Taiwan. Table 1 shows the major chemical composition of the coal fly ash. The amount of SiO2 and Al2 O3 is over 80 wt. %. Fig. 1 illustrated the XRD pattern for coal fly ash. The JCPDS card shows that the reflections were mainly assigned to quartz and mullite

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setting rate.

60 . The densities are around 1.3-1.4 g/cm3 . It can be seen that the porosities and water absorption rates are higher than that of setting at room temperature, ranged of 35.9-40.4% and 226.4-30.8%, respectively. The compressive strength can be increased to 64.4 MPa at 48 hrs de-mould time. However, after 48 hrs de-mould time, the compressive strength of coal fly ash based geopolymer is decreased. Table 3 Various properties of the geopolymer materials at 60 De-mould Compressive Density Porosity time Strength (g/cm3 ) (%) (hour) (MPa) 12 42.2 57.4 64.4 43.4 43.0 1.3 1.4 1.3 1.4 1.4 40.1 40.4 36.6 36.2 35.9 Water absorption (%) 30.8 30.2 27.7 26.7 26.4

Fig.3 The effect of temperature on setting time (at room temperature and 60 , separately) Physical and mechanical Properties of the Coal Fly Ash-Based Geopolymer At room temperature, from Fig.3, it can be found that the geopolymer precursor needs about 7 hours to start to setting after casting into the mould and needs about 9.5 hrs to reach the final setting. Therefore, the de-mould time were set in 12, 24, 48, 72 and 144 hrs, respectively. Before carried out all tests, the geopolymer samples were cured at room temperature until the 7th day. Table.2 Various properties of the geopolymer materials at room temperature De-mould Compressive Water Density Porosity time strength absorption 3 (g/cm ) (%) (hour) (MPa) (%) 12 24 48 72 144 37.8 56.7 51.8 33.9 53.7 1.4 1.4 1.4 1.4 1.4 35.2 35.1 36.6 35.3 35.7 25.7 25.0 26.9 26.5 26.9

24 48 72 144

From above results, the trends of the compressive strength changing from room temperature to 60 are similar as Fig. 4 shows. Generally, the compressive strength of geopolymer setting at 60 is higher than that of setting at room temperature. This could due to setting at higher temperature promoted geopolymerization process occurring.

The effect of de-mould time on geopolymer properties at room temperature are shown in Table 2. The Density of fly ash-based geopolymer is 1.4 g/cm3 . Porosities and water absorption rates are ranged of 35.1-36.6% and 25.0-26.9%, respectively. Generally said that the geopolymers have similar characterizations. However, it can be found the sample de-mould after casting 24 hrs has the best compressive strength reaching 56.7MPa. Comparing with the setting time of geopolymer precursor at room temperature, the setting time at 60 are much faster. This attributed the higher temperature to speed up the geopolymerization occuring. Table 3 shows the effect of de-mould time on geopolymer properties at

Fig.4 The trend of compressive strength changing at different temperatures Fire-Resistance Test of the Geopolymer Using the test method described above to examine the fire-resistance of geopolymer. Fig. 5 shows that when a 10 mm thick panel of geopolymers is exposed to an 1100 flame, the measured reverse-side temperature of fly ash-based geopolymer only reaches 440-470 . Both geopolymer samples setting at room temperature and 60 have similar fire resistance characteristic. Comparing those results to calcium silicate board that was bought from market, it can be proved that the coal

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fly ash-based geopolymer is a fire resistant material that could be had potential to use in engineering applications.

Fig.6 Fire resistance test results for fly ash-based geopolymer and calcium silicate board

Conclusions
At same operation conditions, the geopolymer precursor can be completely hardened after 9.5 hrs at room temperature. However it only needs 1 hr to harden at 60 . The coal fly ash -based geopolymer have high porosity and compressive strength. On the other hand, this geopolymer also have good fire resistance characteristic and could have potential for building materials.

References
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