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School of Materials Science and Engineering, Wuhan University of Technology, Wuhan 430070, China
State Key Laboratory of Silicate Materials for Architectures, Wuhan University of Technology, Wuhan 430070, China
a r t i c l e
i n f o
Article history:
Received 27 March 2012
Accepted 19 May 2012
Available online 5 June 2012
Keywords:
A. Fabrication and characterization
B. Crystalline phase
D. Glassceramic
Steel slag
a b s t r a c t
In this study, glassceramic materials were produced from SS (steel slag) obtained from Wuhan Iron and
Steel Corporation in China. The amount of SS used in glass batch was about 3141 wt.% of the total batch
mixture. On basis of differential thermal analysis (DTA) results, the nucleation and crystallization temperature of the parent glass samples were identied, respectively. X-ray diffraction (XRD) revealed that
multiple crystalline phases coexisted in the glassceramics, and the main crystalline phase was wollastonite (CaSiO3). SEM observation indicated that there was an increase in the amount of crystalline phase
in the glassceramics when the CaO content and crystallization time increased. It was also found that the
glassceramics with ne microstructure enhance mechanical properties and erosion wear resistance. The
obtained glassceramics showed a maximum bending strength of 145.6 MPa and very nice wear resistance. Therefore, it is feasible to produce nucleated glassceramics materials for building and decorative
materials from SS.
2012 Elsevier Ltd. All rights reserved.
1. Introduction
The accumulation of industrial wastes not only occupies a great
deal of land but also causes pollution, which has become a serious
problem in many countries. Waste utilization is an attractive disposal in that disposal costs and potential pollution problems are
reduced or even eliminated while increasing resource conservation. Steelmaking slag (SS), a by-product of steel production, is
one of the most common industrial wastes. The production of steel
was over 650 million tons in 2010 in China, and about 90 million
tons SS was produced. Only 1520% of the SS was utilized, with
the remainder discarded which was very harmful to environment.
SS can be used to produce many kinds of materials, such as cement,
glassceramics and paving materials. The SS has very high hardness and strength, so it can be used in concrete as aggregate [1],
in paving materials [2], and in the raw meal for Portland cement
[3]. Glassceramic materials have a number of outstanding characteristics in comparison with the traditional ceramics and glasses,
which make them favorable for wear and corrosion resistant applications in advanced technology [4]. These can be produced by
melting [5] or glass powder sintering [6] methods.
Recently, glassceramics based on silicate structures have been
investigated [7,8], including research on the wollastonite (CaSiO3),
Corresponding author. Address: School of Materials Science and Engineering,
Wuhan University of Technology, 122 Luoshi Road, Wuhan 430070, Hubei Province,
China. Tel./fax: +86 27 87871643.
E-mail addresses: he-feng@whut.edu.cn, he-feng2002@163.com (F. He).
0261-3069/$ - see front matter 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.matdes.2012.05.033
199
Table 2
Compositions of base glasses.
Chemical composition (g)
A1
A2
A3
A4
SiO2
Al2O3
CaO
MgO
ZnO
BaO
Fe2O3
TiO2
P2O5
Na2O
58.00
6.20
18.00
4.20
1.50
3.90
4.50
0.25
0.64
2.81
58.00
6.20
20.00
4.20
1.50
3.90
4.50
0.25
0.64
2.81
58.00
6.20
22.00
4.20
1.50
3.90
4.50
0.25
0.64
2.81
58.00
6.20
24.00
4.20
1.50
3.90
4.50
0.25
0.64
2.81
Table 1
Original composition of SS.
Chemical composition
(mass%)
SS
SiO2
Al2O3
CaO
MgO
BaO
FeO
Fe2O3
TiO2
P2O5
Undetermined
21.36
4.62
50.56
8.86
0.27
3.16
6.35
0.53
1.32
2.97
200
m0 m1
S
F=2.0 h
808
T Exotherm
810
813
818
965
969
978
Endotherm
982
A4
A3
A2
A1
400
600
20
30
40
50
60
70
80
2 (degree)
G=3.0 h
Wollastonite
Anorthite
10
20
30
40
50
60
70
80
2 (degree)
200
10
800
1000
1200
Temperature ( oC)
Fig. 1. DTA results of the investigated glass samples.
Fig. 2. XRD of glassceramics samples with different crystallization time (F: 2.0 h,
G: 3.0 h).
tonite. The reaction equation can be shown as: CaO + SiO2 ? CaSiO3 in these materials. It shows that with the amount of CaO
increasing, the conjoint probability of CaO and SiO2 also increases.
According to the theory of stable energy of glass forming and
structural units, the structural units of CAS system glass are [SiO4]Ca[SiO4], [AlO4]Ca[SiO4] and [AlO4]Ca[AlO4]. When heated at
nucleation temperature, the free Ca2+ was prone to join with
[SiO4] such that wollastonite was rst formed in the glassceramics. During crystallization, the structure unit [AlO4]Ca[AlO4] was
forced to rearrange and join with [SiO4] to form anorthite as the
main crystalline phase in CAS system glassceramics [17,27].
In Fig. 2, there were notable differences in the peak intensity of
wollastonite between F and G samples due to the different crystallization time. As the crystallization time increased from 2 h to 3 h,
the peak intensity increased as well. This phenomenon indicates
that the content of wollastonite in G samples was higher than that
in F samples. In Fig. 2, the maximum wollastonite content occurred
in sample A4 under the heat treatment of Tn4 = 858 C for 2.0 h and
Tc4 = 965 C for 3.0 h.
SEM micrographs of glassceramic samples with different crystallization time are shown in Figs. 3 and 4. In Fig. 3, a large number
of small, irregularly-shaped crystals are seen. With the increase of
CaO content, the quantity and the size of crystals increased. Under
the heat treatment of different Tn and Tc for 2.0 h, the average crystal size of A1 was less than 3 lm, and A4 was about more than
15 lm, (Fig. 3). With increasing crystallization time, the quantity
of crystals in the glassceramics increased (Fig. 4). Either the size
of crystals or the quantity of crystals in the relevant glassceramics
201
202
150
F=2.0 h
140
130
120
G
F
110
140
100
18
20
22
136
132
128
A4
A3
A2
A1
124
120
116
24
10
CaO (wt%)
20
30
40
50
60
Time (min)
With content of CaO increasing, more wollastonite crystals precipitate, which can effectively increase the bending strength of the
samples. In the glassceramic, the crystal can cause the crack tip
passivation and prevent the crack propagation through the interface of the crystalline phase and glass phase. As the crystallization
time increased from 2 h to 3 h, the content of wollastonite in G
samples were more than that in F samples, therefore, the bending
strength in G samples was higher than that in F samples.
Glassceramics are often used for wall or oor decoration as a
new building and furnishing material. The wear property M of
the glassceramics (Eq. (1)) as a function of heating time is shown
in Fig. 6. As time increases, the amount of wear per unit time gradually increases. Samples showed a downward trend in wear and
tear with increasing CaO content for any particular grinding time,
indicating that the wear resistance of samples increased. From
the above analysis, it showed that the increase of CaO could efciently increase the amount of wollastonite. Wear resistance of a
material relates to its hardness, the greater hardness, the stronger
wear resistance. The hardness of wollastonite phase was much
higher than the hardness of the glass phase, so with the increase
of CaO content, the wear resistance of the samples also increased.
There are few studies of the mechanisms of erosion wear because the structure of glassceramic materials is very complex.
Although glassceramics are brittle materials, resilience change
in the early period of erosion wear, and then, these cracks were
created to a larger extent in the material of the lowest fracture
toughness. The damage mechanism is reected by formation of micro-cracks at the surface. The intersection of cracks with each other
and with the surface leads to material removal [29]. With the erosion wear continuing, there were three forms crackle in the surface
of glassceramics plate, such as crackle vertical to the surface of
glassceramic plate, cone crackle and horizontal crackle. When
the defects appear on the surface of glassceramic, the taper
crackle appeared, and expended into the internal of the material.
The horizontal crackle was parallel to the erosion wear countenance, it is the main reason of erosion wear [30].
4. Conclusions
Glassceramic materials were successfully produced from steel
slag in this study. The optimal amount of SS used in the glass batch
was about 3141 wt.% of the total batch mixture. High quality
glassceramic materials were obtained when CaO content was
changed from 20 to 26 wt.%. XRD and SEM results revealed that
multiple crystalline phases coexist in the glassceramics, and the
main crystalline phase is wollastonite (CaSiO3). The samples with
higher content of CaO or longer crystallization time exhibit in-
G=3.0 h
108
104
100
A4
A3
A2
A1
96
92
88
10
20
30
40
50
60
Time (min)
Fig. 6. The curve of the wear property of the glassceramics as time changes.
creased crystallization. The glassceramics with ne microstructure showed better mechanical properties with a maximum of
145.6 MPa, as well as improved erosion wear resistance. Therefore,
steel slag waste appears to be well suited for use as batch material
for decorative architectural glassceramics.
Acknowledgment
This work was supported by Research and Test of Materials,
Wuhan University of Technology.
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