Journal of Solid Mechanics and Materials Engineering

Vol. 5, No. 5, 2011

Production of High-Strength Glass-Ceramics from Industrial Wastes Using Phase Equilibrium Diagram of CaO-Al2O2-SiO2 System*
Kiyohiko IKEDA**, Hiroyuki KINOSHITA**, Ryusuke KAWAMURA**, Akira YOSHIKAWA***, Osami KOBORI*** and Akira HIRATSUKA****
**Department of Mechanical Systems Engineering University of Miyazaki 1-1Gakuenn Kibanadai Nishi, Miyazaki 889-2192, JAPAN ***Department of Mechanical Engineering, Osaka Sangyo University ****Department of Civil Engineering, Osaka Sangyo University 3-1-1Nakagaito, Daito-shi, Osaka 574-8530, JAPAN

Abstract The production of new materials by mixing together more than two raw materials is a useful method from the viewpoint of waste disposal. However, a number of trials and errors are required to produce the desired material. It is therefore important to clarify the target to improve the efficiency of production. In this study, as targets of production, glass-ceramics with anorthite, wollastonite, and gehelenite crystals are used, and inorganic wastes of fly ash, concrete sludge, and glass cullet are used as raw materials. The mixing ratios of these inorganic wastes are determined on the basis of the phase equilibrium diagram of CaO-Al2O3-SiO2. The XRD profiles and SEM observations showed that the crystallized phase of the glass ceramic samples produced were identified as anorthite, wollastonite, and gehelenite, respectively. Moreover, the strength, hardness, Young’s modulus, fracture toughness, and acid resistance were measured. From the results, it is considered that glass-ceramics with wollastonite crystals are excellent in terms of mechanical properties, but those with anorthite are excellent in terms of chemical resistance. Key words: Glass-Ceramics, Industrial Wastes, Fly Ash, Glass Cullet

1. Introduction
Increasing accumulation of inorganic waste has become one of the most serious problems from the viewpoint of environmental burden (1). As a useful means of solving the problem, the development of the recycle technique has been required. In particular, the production of new materials by mixing together more than two raw materials is a more useful method, and many production methods have been developed (2)-(6). In many cases, some samples produced with an arbitrary mixing ratio are prepared, and by experimental tests on the production, it is confirmed whether or not the mixing ratio is suitable. A trial and error to produce desired materials by this method is under way. This can be made more efficient if the target of production can be clarified and the most suitable mixing ratio can be determined by tracing production backward from the target. The purpose of this study is to produce glass-ceramics with anorthite,wollastonite, and

*Received 11 Jan., 2011 (No. 11-0019) [DOI: 10.1299/jmmp.5.209]

Copyright © 2011 by JSME

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gehelenite crystals from inorganic wastes of fly ash, concrete sludge, and glass cullet. There are only a few studies (7)-(10) that examined the mixing ratios of the wastes using the phase equilibrium diagram. In this study, the phase equilibrium diagram of CaO-Al2O3-SiO2 is effectively used to determine the mixing ratios of these inorganic wastes. Some batches are prepared by mixing the wastes at the respective weight ratios. Glass samples could be produced by melting the batches at high temperatures and then quenching the melt. The amorphous glasses produced are reheated in the range of crystallization temperatures to make them transform into glass-ceramics. Whether the produced material is a glass-ceramic with the desired crystal phase could be determined by XRD analysis and SEM. For recycling, it is useful to obtain glass-ceramics that have many advantages in terms of mechanical and chemical properties. Thus, the strength, hardness, Young’s modulus, fracture toughness, and acid resistance are also investigated.

2. Experiments
2.1 Material The fly ash used for the experiments was obtained from the Kyushu Electric Power Co. Inc. Japan. The fly ash, concrete sludge, and glass cullet were used as raw materials. The chemical compositions of the raw materials analyzed by X-ray fluorescence spectroscopy (Rigaku 3270) are shown in Table 1, in which some materials contain un-measurable amounts of components such as nitric anion, carbon anion and organic compounds. The Na2O content contained in glass cullet decreases the viscosity of melt(2). Thus the melt could be rapidly poured into water in the formation of quenched glass. Table 1 Chemical composition (wt.%) of the raw materials used.
Composition SiO2 Al2 O3 CaO Fe2 O3 P2 O5 TiO2 SO3 K2 O MgO Na2 O Others Fly ash 50.3 21.6 6.36 4.4 1.57 1.54 1.04 0.913 0.587 0.192 11.498 Concrete Sludge 19 6.37 43.6 1.54 0.116 0.282 1.51 0.306 1.61 0.179 25.487 Glass cullet 55.7 1.84 9.97 0.253 0.014 0.055 0.041 1.08 0.25 8.39 22.407

2.2 Production of sintered samples The ranges in which the anorthite, wollastonite, and gehelenite crystals could be precipitated in the phase equilibrium diagram of CaO-Al2O3-SiO2 system are shown in Fig.1 (11), respectively. Some batches were prepared by mixing the raw materials in various weight ratios so as to satisfy the chemical components within the range. The mixing ratio is predicted by the following method. First, it is assumed that the raw materials are composed of only three oxides, i.e., CaO, Al2O3, SiO2, as shown in Table 2. For example, the position A is selected to obtain anorthite crystal in the phase equilibrium diagram of the CaO-Al2O3-SiO2 system, as shown in Fig.1. It is seen that the chemical composition of position A is CaO=18%, Al2O3=21%, and SiO2=61%. The mixing ratio in mass%, x:y:z, of the fly ash, concrete sludge and glass cullet can be obtained by solving the following simultaneous equations.

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0.64x+0.28y+0.83z=61 0.28x+0.09y+0.03z=21 0.08x+0.63y+0.14z=18

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(1)

Table 3 shows the mixing ratios in mass% of the raw materials, determined by the above method, required to precipitate the respective crystal phases, in which mixture A is selected to obtain anorthite, mixture W to obtain wollastonite, and mixture G to obtain gehelenite. An amorphous glass was obtained by melting a mixture of fly ash, concrete sludge, and glass cullet in an alumina crucible at 1450℃ in an electric furnace for about 2 h and then quenching the melt in water. The glass was machine-ground in a disk-type ball mill. After milling, the glass was sieved to obtain particles of uniform sizes. In this study, glass powder with a grain size smaller than 63 µm was produced. Such powder was packed in rectangular metal mold of with a width of 5 mm and a length of 40 mm, and molded at a pressure of 150 MPa for 1 min using an inverter hot press (Motoyama Co., Ltd. NPS-5001). On the basis of the DTA data, the glasses formed were reheated at different temperatures of 900-1100℃ for 1 h. The samples were then slowly cooled down to room temperature, and glass-ceramics were prepared. Table 2 Main components of the respective wastes (wt. %).

Composition SiO2 Al2 O3 CaO

Fly ash 64 28 8

Concrete Sludge 28 9 63
0% 100%

Glass Cullet 83 3 14

18%
Wollastonite (1400℃, atmosphere)

31% W A 61% 58%

CaO

45%

Anorthite 2 (1400℃, atmosphere)

SiO

G
Gehlenite (1400℃, atmosphere)

40%

100% 11% 0% 15%21%

Al2O3

0% 100%

Fig.1 Chemical compositions corresponding to position A in phase equilibrium diagram of CaO-Al2O3-SiO2 system. Table 3 Mixing ratios of wastes for the respective mixtures (wt %).
Fly ash Mixture A Mixture W Mixture G 69.3 23.7 31.9 Concrete Sludge 16.3 36.7 66.8 Glass Cullet 14.4 39.7 1.3

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2.3 Experimental Procedure (1) Differential Thermal Analysis Differential thermal analysis (DTA:SII EXSTAR6000) was performed. Thermal properties such as glass transition, crystallization, and melting temperatures were determined by DTA. (2) Scanning Electron Microscopy Scanning electron microscopy (SEM: Hitachi, S-4100) was used to observe the feature and size of the precipitated crystals. (3) Power X-ray Diffraction Analysis Power X-ray diffraction (XRD: Rigaku, RINT-TTR) analysis was performed using an instrument equipped with a Cu Kα radiation operated at 40 kV-50 mA. (4) Strength Test Fracture strength was determined by the four-point bending method for 4×3×40 mm3 rectangular specimens at a cross head speed of 0.5 mm/min with an inner span of 10 mm and an outer span of 30 mm. To obtain reliable statistical data, 9-10 specimens were tested on each sample. Any heat treatment was not conducted before fracture strength test. (5) Hardness Test Hardness was measured by the indentation method using a Vickers indenter (AKASI MVK-H1). The Vickers hardness, HV, was measured with a load of 0.98 N with a loading time of 15 s. To obtain reliable statistical data, at least 10 indentations were made on each sample. (6) Fracture Toughness Test Fracture toughness was also obtained by the indentation method. The samples were indented with a load of 4.5N using a Vickers indenter. Niihara et al.(12) suggested that the fracture toughness, KIC, can be calculated from experimental values of the half diagonal, a, of the indentation and crack size, c, as follows. For the ratios of c / a ≥ 2.5 ,
H  K IC = 0.043H V a  V   3E  H  K IC = 0.012 H V a  V   3E 
−0.4

c   a l   a

−1.5

(2)

For the ratios of c / a ≤ 2.5 ,
−0.4 −1.5

(3)

Here E is the Young’s modulus, that was previously determined by the strain measurements in the bending test, and l is the dimension (c-a). To obtain reliable statistical data, 7-8 specimens were tested on each sample. Any heat treatment was not conducted before fracture toughness test. (7) Acid Resistance Test Acid resistance test was carried out by the following method. Rectangular specimens with dimensions of 10×10×5 mm3 were immersed in 50 ml of 1 vol.% H2SO4 solution at 90℃ for 24 h, and the quantity of weight loss per unit volume was measured.

3. Results and discussion
3.1 Thermal Behavior Thermal properties such as glass transition, crystallization and melting temperatures were determined by DTA . Figures 2(a) to (c) show the DTA thermo-grams of the as-cast glass samples obtained from mixtures A, W, and G. An endothermic peak occurs at about 800℃ in all the samples, which shows a glass transition temperature. An exothermic crystallization peak occurs at 970℃ in samples W and G, and at 1020℃ in mixture A. Thus, it is presumed that wollastonite and gehelenite could be precipitated at 970℃, and

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anorthite could be precipitated at 1020℃.
0 ←ENDO EXO→ DTA μV ←ENDO EXO→ DTA μV 0 -10 -20 -30 -40 -50 0
Tc

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0 ←ENDO EXO→ DTA μV -10 -20 -30 -40 0 500 1000 Temperature ℃
Tc

-20

-40

Tc

-60

0

500 1000 Temperature ℃

500 1000 Temperature℃

(a) Sample A

(b)Sample W

(c) Sample G

Fig.2 DTA curves for the respective samples (Tc: crystallization temperature)
3.2 Microstructures The results of the XRD analysis of the respective glass-ceramic samples heated to 970℃ and 1020℃ for 1 h are shown in Fig.3. It was confirmed that the main crystal phases were anorthite in samples A, wollastonite in sample W, and gehelenite in sample G. Therefore, we denote these glass-ceramics obtained from mixtures A, W, and G samples A, W, and G, respectively. Figures 4(a) to (c) show SEM images at low and high magnifications of glass-ceramic samples A, W, and G, respectively. SEM images with a low magnification show that the microstructure of samples A and W are finer and has fewer voids than that of sample G. Those with a high magnification show that all the samples are crystallized, and that many acicular grains with a long axis of about 3 µm were observed in samples A and W. The acicular characteristic, a typical morphology in wollastonite is clearer in sample W than in sample A. On the other hand, many circular grains with a diameter of about 2 µm were observed in sample G.
1000 Intensity cps Anorthite

500

0 0

10

20

30 2θ deg

40

50

60

(a) Sample A (firing temperature 1020℃,holding time 1h.)
1000 Wollastenite

Intensity cps

500

0 0

10

20

30 2θ deg

40

50

60

(b) Sample W (firing temperature 970℃,holding time 1h.)
1500 Gehlenite Intensity cps 1000

500

0 0

10

20

30 2θ deg

40

50

60

(c) Sample G (firing temperature 970℃,holding time 1h.)

Fig.3 XRD profiles of the respective samples.

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300µm
(a) Sample A

3.0µm

300µ m
(b) Sample W

3.0µm

300µm
(c) Sample G Fig.4 SEM images of the respective samples.

3.0µm

3.3 Mechanical and chemical properties Figures 5(a) to (e) show the error-bar representations of measurements for mechanical properties, i.e., shrinkage, fracture strength, Vickers hardness, Young’s modulus, and fracture toughness, of glass-ceramic samples A, W, and G, respectively. For all properties, the values for samples A and W are clearly higher than those for sample G, and those for sample W are somewhat higher than those for sample A, except Vickers hardness. The highest fracture strength of about 150 MPa obtained in sample W is about 6 times as high as that of marble or granite, and is higher than that (127 MPa) of fly ash glassceramics with the addition of SiO2, MgO and TiO2(13). Furthermore, the highest fracture toughness of about 2 MPa m1/2 obtained in sample W is about 1.8 times as much as those (0.9-1.1 MPa m1/2) of commercial glass-ceramics (Neoceram N-0 and N-11: Nihon Electronic Glass Co., Ltd), also, this fracture toughness is higher than that (1.86 MPa m1/2 ) of fly ash glass-ceramics with the addition of SiO2, MgO and TiO2 (13)and that (0.9-1.6 MPa m1/2 ) of canasite glass-ceramics(14). Such high fracture toughness could be caused by the microstructure of sample W, which consists of acicular crystals with a long axis of about 3 µm, as shown in Fig. 4(b). The effect of an elongated

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grain microstructure on fracture toughness has been reported in SiC whisker reinforced alumina composites (15). As result, the SiC whisker addition caused a rising R-curve with increasing crack extension. The rising R-curve behavior is due to the bridging of SiC whiskers across the crack faces in the wake of a crack tip. Therefore, it is considered that the acicular crystal in sample W could act as an agent of the rising R-curve effect. Sample A is also an acicular type crystal. But the aspect ratios of the acicular crystal in sample A are in 3 to 5 range and the tip of the crystal is somewhat rounded, while those in sample W are in 6 to 10 range and the tip of the crystal is sharp. Furthermore, while a pullout mode fracture of the acicular crystal is observed in various places in the fracture surfaces of sample W, any pullout mode fracture is not observed in that of sample A, as described later. Such a difference in the acicular degree may cause the difference in fracture toughness between samples A and W. The highest Vickers micro hardness of about 6.0 GPa obtained in the sample A and in the sample W is the same as that in hard glass, and is comparable to those (6.73 GPa) of glass ceramics obtained by Park(13).
Fracture strength MPa
50 Shurinkage percentage 40 30 20 10 0
Sample A Sample W Sample G

150 100 50 0

Sample A

Sample W Sample G

(a) Shrinkage percentage
150
Vickers hardness HV

(b) Fracture strength

400 200 0

Young's modulus GPa

600

100

50

Sample A

Sample W Sample G

0

Sample A

Sample W Sample G

(c) Vickers hardness

(d) Young’s modulus

1/2 Fracture toughness MPam

2

1

0

Sample A

Sample W

Sample G

(e) Fracture toughness Fig.5 Mechanical properties of the respective samples. Figures 6(a) to (c) show SEM microphotographs of fracture surfaces after bending test

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for the respective samples. Fracture surface of sample W is remarkably rough, in which the inter-granular fracture is predominant and the pullout mode fracture of the acicular crystal is observed in various places. The pullout mode fracture seen in sample W may be the main cause of both the highest fracture strength and the highest fracture toughness shown in Fig.5(b) and Fig.5(e), respectively. On the other hand, those of samples A and G are relatively smooth, in which the trans-granular fracture is predominant and any pullout mode fracture is not observed, though the crystal of sample A is acicular. This fact shows that the aspect ratio of acicular crystal in sample A is smaller than that in sample W. Furthermore, in the fracture surface of sample G some voids are observed in various places. The occurrences of some voids in sample G seem to be the main cause of the lowest fracture strength in Fig5(b). Figures 7(a) to (c) show SEM microphotographs of crack path after indentation for the respective samples. In the crack path in sample W many grain bridgings and crack surface asperities are observed. But, in the samples A and G grain bridgings are not remarkable and a crack propagates comparatively straight. The grain bridgings obserbed in sample W seems to be due to the acicular crystal with large aspect ratio, and may be the main cause of the highest fracture toughness in Fig.5(e).

4.5μm

1.8µm
(a) Sample A

(a) Sample A
Pull out

4.5μm

4.5μm

Grain bridging
(b) Sample W

1.8µm

(b) Sample W

Void

4.5μm

1.8µm
(c) Sample G Fig.7 SEM microphotograph of crack path after indentation for respective samples.

(c) Sample G Fig.6 SEM microphotograph of fracture surfaces after bending test for respective samples.

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Figure 8 shows the error-bar representation of measurements for the acid resistance, i.e., weight loss% in H2SO4 test of the respective samples. In terms of acid resistance, little weight loss for H2SO4 solution was observed in sample A. On the other hand, the weight loss in sample W and sample G was clearly seen, and the degree was more remarkable in sample G. For samples W and G, the mass% of concrete sludge, which has CaO as its main component, is larger than that for sample A. CaO reacts with H2SO4 to generate CaSO4. The low acid resistance of samples W and G seems to be due to the decrease in mass caused by the chemical reaction.
30 Weight loss %

20

10

0

Sample A

Sample W

Sample G

Fig.8 Acid resistances for the respective samples. It was confirmed that the target material could be produced using this method, and the produced material has a high mechanical property. But, there’s still much left to be discussed about whether the produced material is the most suitable for mechanical and chemical properties or not. The future work will be focused on the comparison with the material having the different mixing ratio in the same crystal phase area in phase equilibrium diagram.

4. Conclusions
From the viewpoint of decreasing the environment load caused by industrial wastes and more effective utilization of such wastes by recycling, we tried to produce high-strength glass-ceramics from industrial wastes using the phase equilibrium diagram of CaO-Al2O3-SiO2. In particular, we determined the mixing ratios of inorganic wastes by tracing backward from the production as the target. Our findings are as follows. (1) Glass-ceramics with anorthite, wollastonite, and gehelenite crystals could be obtained by the above method. (2) Glass ceramics with anorthite and wollastonite crystals are superior in terms of mechanical properties i.e., fracture strength, hardness and fracture toughness. In particular, the fracture toughness of wollastonite was about two times that of commercial glass ceramics. (3) Glass ceramics with anorthite crystals are superior to what in chemical durability. (4) In terms of utility, glass ceramics with wollastonite crystals are suitable for industrial buildings, external and internal wall facings and pavement materials, those with anorthite crystals are suitable for crucibles that are resistant to chemicals.

References
(1) C. Ferreica, A. Ribeiro, and L.Ottosen, “Possible applications for municipal solid waste fly ash” J. Hazardous Materials B96(2003) pp.201-216 (2) L. Barbieri, A.C. Bonamartini, and I.Lancellotti , “Alkaline and alkaline-earth silicate glasses and glass-ceramics from municipal wastes” J.Eur. Ceram. Soc. 20(2000)

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(4)

(5)

(6) (7)

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(11) (12)

(13) (14) (15)

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