Materials and Design 42 (2012) 198203

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Materials and Design

journal homepage: www.elsevier.com/locate/matdes

Fabrication and characterization of glassceramics materials developed

from steel slag waste
Feng He a,b,, Yu Fang a, Junlin Xie a, Jun Xie b
a
b

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

diopside (CaMgSi2O6), and anorthite (CaAl2Si2O8) systems [911].

Toya et al. [10] studied on the preparation and properties of
CaOMgOAl2O3SiO2 system glassceramics, reporting diopside
and anorthite as major crystalline phases appearing over 900 C.
Banijamali et al. [11] investigated crystallization and properties
of glassceramic tiles belonging to CaF2CaOMgOAl2O3SiO2
system and found that surface crystallization was the main precipitation mechanism of the samples. The structure and character of
the crystalline phases and the microstructure of the material were
reported to be the most important factors affecting the technical
properties of the glass ceramic [8].
Steel slag contains valuable oxide such as SiO2, Al2O3, CaO, and
Fe2O3. Depending on the composition of SS, it can be used as a raw
material in the CaOAl2O3SiO2 system or the CaOMgOAl2O3
SiO2 system for producing architectural and decorative glass
ceramics [4,1214]. More generally, the use of industrial waste
materials such as SS, cement kiln dust, blast furnace slag and y
ash for the production of glassceramic materials is of great economic, technological, and scientic importance with proper adjustment of the chemical composition [4,9,1516]. Jingde Luan et al.
[17] investigated the nucleated glassceramics materials produced
from oil shale y ash with the addition of analytic reagent CaO. The
results indicated that it was feasible to produce nucleated glass
ceramics materials for building and decorative materials from oil
shale y ash. Kavouras et al. [18] studied on the microstructure
and characterization of materials from electric arc furnace dust.
Wollastonite (CaSiO3) was separated from the parent matrix as
the dominant crystalline phase, with its properties strongly

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F. He et al. / Materials and Design 42 (2012) 198203

dependent on the morphology and orientation of the separated

crystal phase.
Karamberi and Moutsatsou [19] focused on the production of
glass and glassceramics by using two y ashes and a slag from
steelmaking. Vitrication took place at 13501450 C, and crystallization was achieved by heat treatment at 900, 950 and 1000 C.
The crystalline phase depended greatly on the structure of the
by-product and the heat treatment. The slag-based glassceramics
can be obtained by the molten SS casting process and the heat
treatment process. The results show that dominant crystalline
phase is diopside and the size of the crystals is about 7 lm [20].
The present work was concentrated on the study of SS usability
for the production of glassceramic materials. In addition, mechanical properties (including bending strength, wear and tear) were
examined in order to know whether the nucleated glassceramics
produced from SS can be used as a decorative material. In this paper, a new type of SS glassceramic material was prepared by meltquenching and heat treatment. If it can be practically applied, a
large volume of raw SS can be recycled so that solid waste pollution and the consumption of natural resources will be reduced.
2. Experimental details

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

the melt was poured into 80  50  20 mm graphite molds. The

molds with the cooled melts were annealed in a mufe furnace
at 600 C for 30 min to relieve residual stress in the glass samples.
Prepared samples were then heat treated at the nucleation temperature (Tn) for 1.0 h, heated at the rate of 5 C/min to crystallization
temperature (Tc), crystallized at Tc for 2.0 or 3.0 h, and then cooled
to room temperature in the furnace.
2.3. Differential thermal analysis

2.1. Raw material

Transforming industrial residue into slag glass ceramic products
is a high quality added-value resource recovery technology. SS
used in this study was supplied by Wuhan Steel Company. The
SS was ground into particles less than 100 lm in diameter, and
atomic absorption spectroscopy was used to determine its composition (Table 1). The sample was alkalescent slag which contained
abundant CaO (about 50 wt.%). Based on the SS composition, we
chose the CaOMgOAl2O3SiO2 glass system because it should
accommodate a large quantity of slag. Table 2 shows the glass
compositions investigated (including the slag contribution). The
full CaO content was supplied by the SS, while the other components in Table 1 were necessarily included. The amounts of these
other components which came from SS were xed based on the
CaO content and in general did not correspond to the desired composition of the base glasses, so the remainder was supplied by
oxide and carbonate (analytical pure) reagents. The amount of SS
used in the glass batches was about 3242 wt.% of the total batch
mixture.
2.2. Glass preparation
The mixed batch (280 g) composed of SS and other raw materials was rst mixed by ball milling with a speed of 150 rpm for
20 min. The milled mixture was transferred into an alumina crucible and heated at 1000 C for 1 h to make carbonate decompose,
then melted at 1500 C for 3 h in the same furnace. After that,

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

Glass powder was analyzed by differential thermal analysis

(DTA). After crushing annealed glasses to about 200 lm particles,
non-isothermal DTA was performed in dry nitrogen by heating
30 mg samples in a Pt crucible with Al2O3 as the reference material
within the temperature range between 20 C and 1200 C at 10 C/
min (Netzech thermal analysis system).
2.4. Structure analysis
X-ray diffraction was utilized to determine which crystalline
phases occurred. X-ray diffraction spectra were acquired by a D/
MAX-RB X-ray diffraction system (RIGAKU) at 40 kV and 30 mA
utilizing Cu Ka radiation on powder samples passed through 300
grade mesh. The detector was scanned over a range of 2h angles
from 10 to 80, at a step size of 0.02 and a dwell time of 2 s per
step.
Scanning Electron Microscopy was used to study the glassceramic morphology, grain size, and distribution in the residual glassy
matrix. The polished samples were etched with HF solution
(5 vol.%) for 30 s, immediately rinsed with distilled water and then
cleaned in ethanol for 3 min. The samples were coated with carbon
prior to examination. For SEM observations, the glassceramic
samples were gold-coated and then observed with a JSM 600
microscope operating at 25 kV.
2.5. Mechanical properties tests
The physical properties of the glassceramics samples were
investigated by three-point-bend and wear-and-tear tests. Rectangular specimens of dimensions 60  5  8 mm were used for the
three-point-bend test according to ISO 14704: 2008(E) [21]. For
each sample, ten measurements were made. The wear-and-tear
test was carried out with a CSM exactitude tribometer according
to GB/T 2611: 2007 [22]. Square specimens of dimensions
40  40  8 mm were washed and dried before the test. Each piece
of glassceramic sample was weighed carefully and the original
mass (m0) was obtained. The glassceramic samples were xed
on the test platform and ground continuously for 10, 20, 30, 40,
50 and 60 min under 50 N force applied by spherical diamond.
After grinding, samples were washed, dried and weighed again to
obtain the nal mass (m1). The area (S) of the circular grinding spot
retained on the surface of the samples was also obtained. The fol-

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F. He et al. / Materials and Design 42 (2012) 198203

lowing formula was used to calculate the wear property of the

sample, with units of mg/m2.

m0  m1
S

F=2.0 h

3. Results and discussion

3.1. Differential thermal analysis and heat treatment
The DTA results of the investigated glass samples are shown in
Fig. 1. A shallow endothermic peak with an onset of 808818 C
indicates the glass transition temperature (Tg), at which the sample changes from solid to liquid-like behavior [23]. The second
endothermic peak around 878888 C is the dilatometric softening
point of the low viscosity phase. Various exothermic effects at
965982 C indicating crystallization of the glasses are also recorded. As CaO content in the glass composition was increased,
the peak temperature of the crystallization exotherms decreased
and the endothermic effects mentioned above were slightly
displaced towards to lower temperatures. The reason for this phenomenon is that with increasing CaO content, the inter-connectivity of the structural units of the glass is reduced, and the activation
energy of crystallization is decreases.
The nucleation temperature is an important factor for nucleus
formation. Previous studies showed that the optimum nucleation
temperature usually occurred in the range from 50 to 100 C above
the glass transition temperature [17,24]. In our work, the nucleation temperatures of samples A1A4 were identied as Tn1 =
868 C, Tn2 = 863 C, Tn3 = 860 C and Tn4 = 858 C, respectively.
CaO content had an advantageous effect upon the crystalline
phases formed in glassceramics materials [25].

Fig. 2 shows X-ray diffraction (XRD) patterns of produced glass

ceramic samples with varying crystallization time. The diffraction
peaks are very distinct in Fig. 2, suggesting crystalline phases are
fully precipitated from the glass. Monoclinic or triclinic wollastonite (CaSiO3) are the main crystalline phases observed, but anorthite
(CaAl2Si2O8) also occurs. The coexistence of multiple crystalline
phases reects the complexity and uncertainty of nucleation and
crystallization in the CaOAl2O3SiO2 glass system [26].
In Fig. 2, there were notable differences in the peak intensity of
wollastonite among samples due to the different CaO content.
Independent of heat treatment time, with increasing CaO content,
the intensity of wollastonite peaks increases too. This was because
the increase of CaO could efciently increase the amount of wollas-

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)

3.2. Microstructure of glassceramics

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

F. He et al. / Materials and Design 42 (2012) 198203

201

Fig. 3. SEM micrographs of glass ceramics samples at 2.0 h.

Fig. 4. SEM micrographs of glass ceramics samples at 3.0 h.

sample, SEM micrographs of glassceramics samples were in the

ascendant. Previous studies indicated that the number and the size
of the crystallites in glassceramics increased with the increase of
crystallization time [28]. Therefore, both the high content of CaO in
the glass and the increase of crystallization time had a favorable
effect on the precipitation of crystalline phases in the glass
ceramics.

3.3. Bending strength and wear properties

The mechanical properties of the glassceramics are improved
with the embedded crystalline phase. From the curve in Fig. 5, it
could be found that with content of CaO increasing, the bending
strength of the samples also increases. The strength of the crystalline phase was much higher than the strength of the glass phase.

202

F. He et al. / Materials and Design 42 (2012) 198203

150

F=2.0 h

140

130

120

G
F

110

Quantity of wearing (mg/m 2)

Bending strength (MPa)

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)

Fig. 5. Relation between bending strength and the content of CaO.

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-

Quantity of wearing (mg/m 2)

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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