Journal of Non-Crystalline Solids 356 (2010) 1554–1558

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Journal of Non-Crystalline Solids

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / j n o n c r y s o l

Crystallization behavior of glass ceramics prepared from the mixture of nickel slag,
blast furnace slag and quartz sand
Zhong-jie Wang ⁎, Wen Ni, Yan Jia, Li-ping Zhu, Xiao-yan Huang
State Key Laboratory of High-Efficient Mining and Safe of Metal Mines (University of Science and Technology Beijing) Ministry of Education, Beijing 100083, China

a r t i c l e i n f o a b s t r a c t

Article history: The purpose of this paper was to investigate the crystallization process of glass ceramics prepared from a
Received 10 January 2010 mixture which was composed of nickel slag, blast furnace slag and a small amount of quartz sand. First, the
Received in revised form 4 May 2010 parent glass of the mixture was prepared. Then, the glass ceramics were obtained by heat-treating for the
Available online 16 June 2010
parent glass. The crystallization behavior was studied by differential scanning calorimetry (DSC), X-ray
diffraction (XRD) and field emission scanning electron microscope (FESEM). A large number of tiny spherical
Keywords:
Glass;
crystals were observed when the glass was heated up to 700 °C. Subsequently, the radial crystals were
Glass ceramics; observed when the glass was heated up to 820 °C. By XRD analyzing, the spherical crystals and radial crystals
Wastes; were likely to be the crystals of diopside (CaMg(Si,Al,Fe)2O6) and hedenbergite (CaFe(Si,Al,Fe)2O6). The
Crystallization crystallization temperature was 860 °C and the final crystalline phases were identified to be diopside and
hedenbergite. In addition, the activation energy of crystallization was evaluated by Kissinger method.
© 2010 Elsevier B.V. All rights reserved.

1. Introduction
Metallurgical industry generates huge amounts of slag. In Europe,
for example, nearly twelve million tons of steel slag is produced every
year [1]. At present, some of metallurgical slag is used to prepare slag
cement, slag bricks and so forth [2–4]. However, most of metallurgical
slag is mainly piled up in the slag plants without utilization. The
accumulation of metallurgical slag affects the environment and is a
burden to metallurgical enterprises as well. Therefore, other methods
for utilizing metallurgical slag should be investigated.
It is possible to prepare glass ceramics from metallurgical slag.
Several results of preparing glass ceramics from metallurgical slag
have been widely reported. Francis researched on the conversion of
blast furnace slag into glass ceramics and found that the crystalline
phases were identified as gehlenite, diopside pyroxene and barium
aluminium silicate [5]. Khater conducted an investigation into the use
of Saudi slag for the production of glass ceramics and found that the
phase of diopside formed at about 1120 °C [6]. Wang and Liang
studied the glass ceramics prepared from fly ash and titanium slag [7].
In addition, it is well known that these glass ceramics prepared from
the metallurgical slag usually have excellent mechanical properties as
well as chemical properties [8–10]. Therefore, the technology to reuse
metallurgical slag is critically important not only to protect the
environment but also to provide useful materials.
⁎ Corresponding author. Tel.: +86 10 62332662; fax: + 86 10 82385795.
E-mail address: wangzhongjie1983@163.com (Z. Wang).
Here we show a method for glass ceramics prepared from the
mixture of nickel slag (NS), blast furnace slag (BFS) and a small
amount of quartz sand. We also investigated the crystallization be-
havior of these glass ceramics by differential scanning calorimetry
(DSC), X-ray diffraction (XRD) and field emission scanning electron
microscope (FESEM).
2. Experimental
NS and BFS were obtained from Jinchuan Group Co., Ltd. and
Beijing Shougang Co., Ltd. respectively. The chemical compositions of
NS and BFS were determined by X-ray fluorescence analysis. As
shown in Table 1, the major chemical compositions of NS are FeO,
SiO2, Al2O3, CaO and MgO with its loss on ignition (L.O.I.) 2.71; the
major chemical compositions of BFS are SiO2, Al2O3, CaO and MgO
with the L.O.I. 2.30. Therefore, the system composed of NS and BFS is
mainly a system of SiO2–CaO–MgO–Al2O3–FeO. In the system, FeO and
MgO can be regarded as a group component since Fe2+ and Mg2+ take
the same role in the crystallization process. Therefore, the system can
be simplified as a system of SiO2–CaO–MgO(FeO)–Al2O3. The SiO2–
CaO–MgO(FeO)–Al2O3 phase diagram in which the content of Al2O3
has a mass percentage of 15% (Fig. 1) was selected in our inves-
tigation. By analyzing we found that the pyroxene-based glass ce-
ramic can be prepared with adding a small amount of quartz sand
into the system of NS and BFS. Finally, the mixture was prepared
containing NS, BFS and quartz sand at a mass ratio of 22:68:10. In
addition, the melting temperature of the mixture may be at 1300 °C
according to the phase diagram (Fig. 1). The composition of the mix-
ture is shown in Table 1.

0022-3093/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.jnoncrysol.2010.05.063
 Z. Wang et al. / Journal of Non-Crystalline Solids 356 (2010) 1554–1558 1555

Table 1 and 25 °C min− 1 and the corresponding crystallization temperatures

Chemical composition of NS, BFS and the mixture (wt.%). were also detected by DSC analysis. Then, the activation energy of
Oxide NS BFS Mixture crystallization (EC) was evaluated by Kissinger equation [12]:
FeO 42.01 0.60 9.87 !
SiO2 34.61 36.70 42.57 α EC
ln =− + constant ð1Þ
MgO 8.86 5.97 6.00 Tp2 RTp
CaO 3.37 37.76 26.41
Al2O3 8.26 16.46 13.01
where Tp is the crystallization exothermal peak temperature, α is the
NiO 0.12 0.01 0.03
CuO 0.04 0.06 0.09 heating rate and R is the gas constant. A linear relationship between ln
Na2O 0.02 0.14 0.10 (α/T2p) and 1/Tp for the crystallization temperatures was obtained in
L.O.I. 2.71 2.30 2.13 according with Eq. (1) and then the activation energy of crystalliza-
tion can be evaluated.

The mixture (200 g) composed of NS, BFS and quartz sand was
firstly mixed by a planet ball milling with a speed of 120 rpm for
30 min. Then, the milled mixture was transferred into an alumina
crucible and melted in an experimental furnace at 1300 °C for 2 h.
After that, the melt was poured into five steel moulds with each size
40 mm (length) × 30 mm (width) × 20 mm (thickness). The moulds
with the cooled melts was put into another furnace with its
temperature 650 °C and held for 15 min. After the annealing process,
the parent glass prepared from the mixture was obtained.
Glass powder with grain size below 200 mesh was prepared for
the DSC analysis. DSC analysis was conducted using a simultaneous
thermal analyzer (STA 409C/CD Netzsch Gerätebau GmbH, selb,
Germany) with the heating rate 10 °C min− 1. Based on the results of
DSC analysis, some temperature points were selected in order to
investigate crystallization behaviors of glass ceramics at different
temperatures. They were T 1 = 700 °C, T2 = 740 °C, T 3 = 780 °C,
T4 = 820 °C and T5 = 860 °C. After the parent glass was re-heated up
to the selected temperature in the furnace and held for 15 min, the
glass samples were removed from the furnace in order to prevent the
development of crystallization.
The structures of samples heat-treated at the selected tempera-
tures were observed by field emission scanning electron microscope
(FESEM, SUPRA 55, Carl Zeiss, Germany). Inner parts of samples were
selected and etched in 1% HF solution for 30 s at room temperature for
FESEM observation. Simultaneously, the X-ray diffraction (XRD)
spectra of the powder of samples were recorded with a Mac M21X
diffractometer.
Based on the principle that the crystallization temperature varied
with the heating rate, the activation energy of crystallization can be
evaluated. The heating rates were selected as 5 °C, 10 °C, 15 °C, 20 °C
3. Results
Fig. 2 shows the DSC plot of parent glass. It can be seen that the
glass transition temperature (Tg) and crystallization temperature (Tc)
are 700 °C and 860 °C respectively, recorded at 10 °C min− 1. In
addition, the temperatures of T1 = 700 °C, T2 = 740 °C, T3 = 780 °C,
T4 = 820 °C and T5 = 860 °C were selected.
Fig. 3 shows the FESEM images of glass heated at different
temperatures: (a) T1 = 700 °C for 15 min, (b) T2 = 740 °C for 15 min,
(c) T3 = 780 °C for 15 min and (d) T4 = 820 °C for 15 min. From Fig. 3
(a) it can be seen that a great number of crystals, in the form of
sphericity, distribute throughout the glass matrix when the sample
was heated at 700 °C for 15 min. Sizes of spherical crystals are mostly
less than 100 nm except for several ones whose sizes are about 100–
200 nm. As shown in Fig. 3(b) and (c), the number of tiny spherical
crystals increases with temperature increasing. Simultaneously, the
phenomenon of agglomeration for these tiny spherical crystals can be
observed. Fig. 3(d) shows that there is a new crystal—the radial crystal
in the sample. When the temperature was up to 820 °C, the radial
crystals appeared. Each radial crystal has six prisms with the size
8 μm. The prism presents a symmetric distribution with a shared
point. In addition, the former tiny spherical crystals can also be
recognized in Fig. 3(d). The tiny spherical crystals can be found in the
some plane surfaces which are surrounded by prisms. On the other
hand, the tiny spherical crystals cannot be observed on the prisms.
Fig. 4 shows the FESEM image of glass heated at T5 = 860 °C for
15 min. The sample has well crystallized with compact structure from
Fig. 4. It can be seen that the radial crystals embed in the crystalline
matrix and staggered with each other, which probably contributes to
the high mechanical strength for the crystalline sample.
Fig. 5 shows the XRD patterns of glass heated at temperatures:
(a) 700 °C for 15 min, (b) glass heated at 780 °C for 15 min and (c)
glass heated at 860 °C for 15 min. From Fig. 5, we can see that the XRD

Fig. 1. Phase diagram of the SiO2–CaO–MgO–Al2O3 with 15 wt.% Al2O3 [11]. Fig. 2. DSC plot of parent glass.
1556 Z. Wang et al. / Journal of Non-Crystalline Solids 356 (2010) 1554–1558

Fig. 3. FESEM images of glass heated at temperatures: (a) T1 = 700 °C for 15 min, (b) T2 = 740 °C for 15 min, (c) T3 = 780 °C for 15 min and (d) T4 = 820 °C for 15 min.

pattern (a) presents the glass characteristics and that there is no
crystalline peak in the glass background, which demonstrates that the
sample mainly presents glass state. However, when the glass was
heated at 780 °C for 15 min, there already exist crystalline peaks in the
glass background, which means that at 780 °C the crystal has already
appeared in the glass matrix. As shown in Fig. 5, the degree of the
crystalline peak in XRD pattern (b) is relatively low, which means that
the number of crystals is relatively small at this temperature.
Additionally, it can be found that the positions of crystalline peaks
in XRD pattern (b) are consistent with that in latter XRD pattern (c),
which belongs to the sample heated at 860 °C for 15 min. The
crystalline phases in XRD pattern (c) were identified to be diopside
(JCPDS 41-1370) and hedenbergite (JCPDS 41-1372). It demonstrates
that the crystal appeared in the glass matrix may be diopside and
hedenbergite. XRD pattern (c) demonstrates that the sample has well
crystallized at 860 °C and the crystalline phases are hedenbergite and
diopside.
Fig. 6 shows the DSC plots at different heating rates. It can be
seen that the crystallization temperature increases with the heat rate

Fig. 5. XRD patterns of glass heated at temperatures: (a) 700 °C for 15 min, (b) glass
Fig. 4. FESEM image of glass heated at 860 °C for 15 min. heated at 780 °C for 15 min and (c) glass heated at 860 °C for 15 min.
 Z. Wang et al. / Journal of Non-Crystalline Solids 356 (2010) 1554–1558
Fig. 6. DSC plots at different heating rates.
increasing. The crystallization temperature changes from 843 °C
to 889 °C with the variation of heating rate from 5 °C min− 1 to
25 °C min− 1. According to Eq. (1), a linear relationship between ln(α/T2p)
and 1/Tp is shown in Fig. 7.
4. Discussion
Diopside is a monoclinic pyroxene mineral with composition
MgCaSi2O6. It forms variably colored but typically dull green crystals
in the monoclinic prismatic class with Mohs scale 5.5–6.5 and density
3.278 g cm− 3. Hedenbergite, CaFeSi2O6, is the iron rich end member
of the pyroxene group having a monoclinic crystal system with Mohs
scale 5.5–6.5 and density 3.56 g cm− 3.Color varies between black,
greenish back and dark brown with a resinous luster [13]. Generally,
diopside and hedenbergite usually form the completed isomorphism.
In the crystallization process, Al3+ can replace Si4+ and form [AlO4]
tetrahedrons which formed the silicate skeleton with [SiO4] tetrahe-
drons. On the other hand, Fe2+ and Mg2+ can replace each other in
the crystal lattice. This is supposedly due to the similarities of Mg2+
and Fe2+ with respect to their ionic radius and metal–oxygen bond
lengths. In addition, at high temperatures, Fe2+, Fe3+ and the phys-
ically dissolved oxygen of a melt form equilibrium [14].
þ3 2− 2þ
4Fe þ 2O ⇌4Fe þ O2
As a net gap ion, Fe2+ will destroy the [Si–O] net structure and
will decrease the viscosity of glass, similar to Ca2+ and Mg2+. Like the
Si4+ or Al3+, Fe3+ will form the [FeO4] tetrahedrons, mend the met
Fig. 7. Kissinger plot of the activation energy of crystallization.
1557
structure and increase the viscosity of the glass when it has ions of
alkali metals and alkaline-earth metals [15,16]. Therefore, the glass
ceramic with the phases of diopside (CaMg(Si,Al,Fe)2O6) and
hedenbergite(CaFe(Si,Al,Fe)2O6) can be prepared from NS and BFS
on the laboratory condition. The melting temperature was about
1300 °C, which is consistent with the result shown in phase diagram
(Fig. 1). Compared with the reported melting temperatures of glass
ceramics, it belongs to a relatively low temperature range. This is due
to the fact that there is amount of Fe2+ in the melting process, which
comes from NS. It can be seen that Fe2+ plays a very important role in
melting and crystallization for the mixture.
By analyzing, we found that the crystals of diopside and
hedenbergite appeared in the glass matrix in the spherical form.
The crystal is tiny and the size is less than 100 nm at the beginning of
the crystallization. Due to the fact that the spherical shape has the
smallest surface area compared with other shapes on the premise of
the same volumes, the interfacial energy barrier is relatively small
when the crystals appeared from the glass matrix in the spherical
form. With the temperature increasing, the spherical crystals continue
to come out from the glass matrix and agglomerate simultaneously.
The agglomeration of spherical crystals reduces the interfacial area
between glass and crystal, which results in the stability of system. It
should be noted that the spherical crystals can be found in Fig. 3(d).
Simultaneously, a new crystal can also be observed. This is due to the
general crystallographic principle: the tiny spherical crystals will
firstly agglomerate in the regions of angular points and prisms,
followed by the plane surfaces which are surrounded by prisms on the
early stage of crystallization. As shown in Fig. 4, the radial crystals can
be found in the sample, while the spherical crystals cannot be found. It
means that the sphericity of the crystal may be just a transitionary
form. From the whole crystallization process, it can be concluded that
the crystals of diopside and hedenbergite appeared from the glass
matrix in the spherical form and the finally crystalline bulk was
formed by radial crystals.
According to Eq. (1), the activation energy of crystallization can be
evaluated. It was found to be about 201.28 kJ mol− 1. The glass
ceramic prepared from the NS and BFS belongs to the iron-rich glass
ceramics because the content of FeO is 9.87% (wt.%) in the samples.
The reported activation energy from the crystallization of iron-rich
glass ceramics calculated by Kissinger method from coal ash [17],
basalt [18] and blast furnace slag [19] was 290, 238 and 329 kJ mol− 1,
ð2Þ respectively. Through a comparison, the value of activation energy of
glass ceramic prepared from NS and BFS is relatively small, which
means that the crystallization can be realized on the condition of
relatively low consumption of energy.
5. Conclusions
Glass ceramics can be prepared from NS, BFS and quartz sand. The
melting temperature, Tg and Tc were about 1300 °C, 700 °C and 860 °C,
respectively. The finally crystalline phases of glass ceramic were
diopside and hedenbergite. It was found that the crystals appeared in
the spherical form. With the temperature increasing, a large number
of spherical crystals came out from the glass matrix and agglomerated
simultaneously. At 820 °C the radial crystal was formed and the finally
crystalline bulk was formed at 860 °C. Finally, the activation energy of
crystallization was found to be about 201.28 kJ mol− 1.
Acknowledgments
The authors would like to express their thanks to Jinchuan Group
Co., Ltd. and Beijing Shougang Co., Ltd. for their assistance in the
preparation of the raw materials. Special thanks go to Mrs. Zhang
Mei and Mrs. He Jianping for their help on XRD, FESEM and DSC
measurements.
1558 Z. Wang et al. / Journal of Non-Crystalline Solids 356 (2010) 1554–1558
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