AISTech 2019 — Proceedings of the Iron & Steel Technology Conference

6–9 May 2019, Pittsburgh, Pa., USA

DOI 10.1000.377.006

Crystallization Behavior of CaO-SiO2-MgO-Al2O3-Based Slags and Its Potential Application in

P-Bearing Steelmaking Slags

Zhanjun Wang, Il Sohn*

Materials Science and Engineering, Yonsei University

262 Seongsanno, Seodaemun-gu, Seoul, Korea, 120-749
Phone: +82-2-2123-5837
Email: ilsohn@yonsei.ac.kr

Keywords: Al2O3/SiO2, Crystallization, Ca2Al2SiO7, P-enriched phase

INTRODUCTION
It’s well known that the CaO-SiO2-MgO-Al2O3 slag system is widely applied in various industries, including ironmaking,
steelmaking, glassmaking, ceramic manufacturing and construction industry[1,2]. Extensive research on the structure and
physical properties of this quaternary slag system has been conducted by the researchers using experimental and modeling
methods for achieving the stable operation of blast furnaces, the optimal lubrication and refining abilities of high Al-
containing steel mold fluxes, the selective crystallization and phase separation of valuable elements, ect[3-5]. Among them, the
formation of the crystal phase involved in these processes, the ratio of the crystal volume to the amorphous volume of the
slag, and the morphology of the crystal phase are all particularly important[6]. However, as far as the authors are aware, the
crystallization behavior of CaO-SiO2-MgO-Al2O3 slag having a wide range of Al2O3/SiO2 mass ratios has not been fully
understood.
In addition, some studies based on selective crystallization and phase separation method to enhance the phosphorus solubility
in P-enriched phase in CaO-SiO2-MgO-Al2O3-FetO-P2O5 steelmaking slags by adding different additives have also been
carried out[7]. However, how the additives introduction into the steelmaking slags influence the structure and further affect the
phase transformation has not been studied.
The present work mainly investigated the crystallization behavior of CaO-SiO2-MgO-Al2O3 slags with varying Al2O3/SiO2
mass ratios. In addition, its potential application on selective enrichment of phosphorus in P-enriched phase in CaO-SiO2-
MgO-Al2O3-FetO-P2O5 steelmaking slag were also studied.

EXPERIMENTAL
Sample preparation
The raw materials of the synthetic slags were analytical grade CaO, SiO2, MgO, Al2O3, where CaO was used in the form of
CaCO3 due to its stability in air. The weighed samples with different compositions were thoroughly mixed in a glass vial and
premelted in a Pt-10wt pct Rh crucible at 1823 K under 0.3 L/min of high purity Ar (99.999%) to obtain a uniform CaO-
SiO2-MgO-Al2O3 quaternary slag. After 4 hours, the molten slag was quenched on a water-cooled copper plate, then the
quenched slags were pulverized and ground into powder less than 200 mesh. Then the premelted slag was analyzed using X-
ray fluorescence spectrometer (XRF, S4 Explorer, Bruker AXS GmbH, Germany) and the chemical compositions is shown in
Table 1.

CLSM observation
The crystallization behaviors of the slags were evaluated with CLSM (Confocal Laser Scanning Microscopy, SVF-SP;
Yonekura MFG. Co. LTD, Japan), which combines the advantages of confocal optics and a He-Ne laser to enable high-
resolution evolution of samples at high temperatures. This technique allows high-resolution images to be obtained directly at

© 2019 by the Association for Iron & Steel Technology. 49

high temperatures and the detail of the equipment has been described in previous studies in our research group[6,8]. During
CLSM experiment, about 60 mg slags were heated at a constant heating rate of 400 K/min in a platinum crucible with a
diameter of 5 mm and a height of 5 mm under an argon atmosphere (High purity, >99.999%) in the CLSM isolated
observation chamber. The slags were hold 2 minutes at 1823 K to guarantee the homogeneity of the slags, followed by
cooling at various cooling rates (25 K/min, 50 K/min, 100 K/min, 400 K/min and 800 K/min) for the continuous-cooling-
transformation (CCT) curves or at a cooling rate of 800 K/min to the target temperatures and then holding different time for
the time-temperature-transformation (TTT) curves. It should be pointed out that the high cooling rates was controlled by
injecting He to the CLSM isolated observation chamber. The video images of the molten slags as a function of temperature,
time, cooling rate and slag compositions can be collected during the cooling process to explore the crystallization behavior of
the slags.

Analysis of as-quenched slags

After CLSM, the slags were examined by SEM (JSM-6700F, JEOL). Then the slags were ground into powders and identified
by XRD (Ultima, Rigaku, Japan) with a scanning range between 10o and 70o. Additionally, the quenched slags were
structurally detected by solid state 27Al MAS-NMR recorded at a resonance frequency of 130.318 MHz (11.7 T) using a 500
MHz FT-NMR (Fourier transform nuclear magnetic resonance; Bruker Avance II, Bruker, Germany) spectrometer.

Table 1. The chemical compositions of the samples. (wt%)

Weighted XRF
Slag
Al2O3/SiO2 CaO SiO2 MgO Al2O3 CaO SiO2 MgO Al2O3
S1 0.03 45.00 45.00 8.5 1.50 45.57 44.57 8.13 1.73
S2 0.15 45.00 40.43 8.5 6.07 45.90 40.10 8.12 5.88
S3 0.30 45.00 35.77 8.5 10.73 45.80 35.10 8.30 10.80
S4 0.70 45.00 27.35 8.5 19.15 45.46 27.29 8.27 18.98
S5 1.10 45.00 22.14 8.5 24.36 45.67 21.91 8.19 24.23

RESULTS AND DISCUSSION

CCT and TTT diagrams of the slags
The collected CLSM images can be used to construct the CCT and TTT diagrams during the initial crystallization behavior of
CaO-SiO2-MgO-Al2O3 slag with varying Al2O3/SiO2 ratios in a wide range of 0.03 to 1.10. The CCT and TTT diagrams of
the slags with different Al2O3/SiO2 ratios are shown in Figure 1. It can be observed from Figure 1(a) that the initial
crystallization temperature of the slags during continuous cooling increased with higher Al2O3/SiO2 ratios. It was also
noteworthy in Figure 1(a) that the crystallization temperature increased significantly with the Al2O3/SiO2 ratios increased
from 0.03 to 0.15, while the increasing trend became less pronounced at higher Al2O3/SiO2 ratios. This may be attributed to
the primary phase of current slag samples locating in different regions of the equilibrium phase diagram. In addition, the
crystallization temperature of the slags gradually decreases and the decreasing tendency presents more pronounced with
higher cooling rate. Figure 1(b) shows the isothermal cooling TTT diagrams for CaO-SiO2-MgO-Al2O3 slag with varying
Al2O3/SiO2 ratios. It was indicated that S1, S4 and S5 exhibited one and a half “C”-shaped curves, which may be signify that
different crystal precipitated, while only one half “C”-shaped curve can be detected for S2 and S3 during the isothermal
crystallization process. The slope of these curves rapidly increased with decreasing temperature, indicating that less time was
need to the precipitation of the primary crystal. At the same temperature, the decreasing incubation time with higher
Al2O3/SiO2 ratios implied that the tendency of the crystallization was accelerated.

Figure 1. (a) Non-isothermal CCT diagram and (b) isothermal TTT diagram of the slags with different Al2O3/SiO2 ratios.

50 © 2019 by the Association for Iron & Steel Technology.

Crystal morphology of the slags
The CLSM and SEM images of the slags collected during continuous cooling at the cooling rates of 25 K/min and 800 K/min
with various Al2O3/SiO2 ratios were shown in Figure 2, where the morphology of the primary phase varied from the rod-like
faceted crystal to the star-like dendritic crystal.

Figure 2. CLSM images and SEM images of CaO-SiO2-MgO-Al2O3 slags with different Al2O3/SiO2 ratios during continuous
cooling at 25 K/min and 800K/min.
Figure 3(a) and (b) describe the primary crystal morphologies that occur during isothermal cooling of the slags with various
Al2O3/SiO2 ratios. A comparable crystal morphology was monitored with that illustrated in the continuous cooling process. In
addition, during the isothermal crystallization process, it can also be observed from Figure 3(c) and (d) that the growth rate of
the crystal increased first and then decreased with increasing isothermal temperature, which was controlled by the
competitive effect of diffusion rate and the undercooling.

Figure 3. (a)-(b) CLSM images of crystallization for isothermally cooled CaO-SiO2-MgO-Al2O3 slags at different Al2O3/SiO2
ratios, (c) The variation in the crystal growth rate of different samples at different isothermal temperatures, and (d) The
different controlling factors of the crystal growth.

© 2019 by the Association for Iron & Steel Technology. 51

XRD identification of the slags
Based on the XRD results of the slags collected during continuous cooling and the slags isothermal crystallized at target
temperatures shown in Figure 4, it can be concluded that the primary phase transformed from Ca2MgSi2O7 to Ca3MgSi2O8
and then to Ca2Al2SiO7 with the change in the Al2O3/SiO2 ratios from 0.03 to 1.10.

Figure 4 (a)-(c) XRD result of the slags with different Al2O3/SiO2 ratios obtained at cooling rates of 25K/min and 800K/min,
(d) XRD results for S5 isothermally cooled at different temperatures based on the TTT diagrams.

27
Al MAS-NMR analysis of the slags
The quantified Al-related structural units can be obtained after deconvoluting 27Al MAS-NMR spectra into isolated [AlO4]
and [AlO5] characteristic peaks[9]. It was observed from Figure 5 that the mole fraction of [AlO4]-structural units increased in
cost of [AlO5]-structural units, which in turn contributes the increasing of [AlO4]/[AlO5] ratios.
Based on the above discussion, it can be deduced that the transformation from Ca2MgSi2O7 to Ca3MgSi2O8 is due to the
relatively higher basicity, while with higher Al2O3/SiO2 ratios, some Mg2+ and Si4+ ions in Ca2MgSi2O7 can be substituted by
Al3+ to form Ca2Al(AlSi)O7, which also was accelerated by the increasing [AlO4]/[AlO5] ratios.

.
Figure 5. The mole fraction of different Al-related structural units with different Al2O3/SiO2 ratios.

Potential application in P-bearing steelmaking slags

For P-bearing CaO-SiO2-MgO-Al2O3-FetO-P2O5 steelmaking slags, the P-enriched phase nCa2SiO4-Ca3(PO4)2 will be formed
during the cooling of the slags[7]. For the slags modified with higher content of Al2O3, the [AlO4]-tetrahedra units can
copolymerize with [SiO4]-tetrahedra units derived from the early precipitated nCa2SiO4-Ca3(PO4)2 to produce higher
phosphorus solid solution (n’Ca2SiO4-Ca3(PO4)2, n’<n) and Ca2Al2SiO7. The enrichment mechanism can be expressed in
equation (1)[5] and Figure 6.

52 © 2019 by the Association for Iron & Steel Technology.

 nCa2SiO4ꞏCa3(PO4)2+mAl2O3=mCa2Al2SiO7+n’Ca2SiO4ꞏCa3(PO4)2, n’<n (1)

Figure 6. The enrichment mechanism of P in steelmaking slags.

In short, with higher Al2O3/SiO2 ratios or Al2O3 content in P-bearing CaO-SiO2-MgO-Al2O3-FetO-P2O5 steelmaking slags,
Al2O3 would capture Ca2SiO4 from the early precipitate solution nCa2SiO4-Ca3(PO4)2 to form Ca2Al2SiO7, i.e., Ca2SiO4
vanished gradually and improved the concentration of phosphorus in P-enriched phase, which is meaningful to the recovery
of valuable elements and the reclamation and reutilization of steelmaking slags.

CONCLUSIONS
1. The crystallization of CaO-SiO2-MgO-Al2O3 slag was accelerated with higher Al2O3/SiO2 ratios by increasing
crystallization temperature and decreasing crystal incubation time.
2. The crystal growth rate was controlled by the competitive effects of undercooling and mass diffusion.
3. The primary phase transformed from Ca2MgSi2O7 to Ca3MgSi2O8 and then to Ca2Al2SiO7 with higher Al2O3/SiO2
ratios, which was due to the higher basicity and the copolymerization between [AlO4]-tetrahedra units and [SiO4]-
tetrahedra units.
4. Higher Al2O3/SiO2 ratios or Al2O3 content can enhance the enrichment of P in P-bearing steelmaking slags.

ACKNOWLEDGEMENTS
This work was supported by the Brain Korea 21Plus Project and Basic Science Research Program through the National
Research Foundation of Korea (NRF) funded by the Ministry of Science, ICT & Future Planning (2018R1A2B2006609).

REFERENCES
1. J.L. Liao, Y.Y. Zhang, S. Sridhar, X.D. Wang, and Z.T. Zhang, “Effect of Al2O3/SiO2 Ratio on the Viscosity and
Structure of Slags”, ISIJ Int. 2012;52:753-758.
2. Z. Wang and I. Sohn, “Effect of the Al2O3/SiO2 Mass Ratio on the Crystallization Behavior of CaO-SiO2-MgO-Al2O3
Slags Using Confocal Laser Scanning Microscopy”, Ceram Int. 2018;44:19268-19277.
3. X. Tang, Z. Zhang, G. Min, M. Zhang, and X. Wang, “Viscosities Behavior of CaO-SiO2-MgO-Al2O3 Slag with Low
Mass Ratio of CaO to SiO2 and Wide Range of Al2O3 Content”, J. Iron Steel Res. Int. 2011;18:1-17.

© 2019 by the Association for Iron & Steel Technology. 53

4. J.W. Cho, K. Blazek, M. Frazee, H. Yin, J.H. Park, and S.W. Moon, “Assessment of CaO-Al2O3 Based Mold Flux
System for High Aluminum TRIP Casting”, ISIJ Int. 2013;53:62-70.
5. Z. Wang, Y. Sun, S. Sridhar, M. Zhang, M. Guo, and Z. Zhang, “Effect of Al2O3 on the Viscosity and Structure of CaO-
SiO2-MgO-Al2O3-FetO Slags”, Metall Mater Trans B. 2015;46:537-541.
6. S.S. Jung and I. Sohn, “Crystallization Behavior of the CaO-Al2O3-MgO System Studied with A Confocal Laser
Scanning Microscope”, Metall Mater Trans B. 2012;43:1530-1539.
7. L. Lin, Y.P. Bao, M. Wang, and H.M. Zhou, “Influence of Al2O3 Modification on Phosphorus Enrichment in P Bearing
Steelmaking Slag”, Ironmak Steelmak. 2014;41:193-198.
8. Z. Wang and I. Sohn, “A Review of In-situ Observations of Crystallization and Growth in High Temperature Oxide
Melts”, JOM. 2018;70:1210-1219.
9. J C. Jäger, P. Hartmann, G. Kunath‐Fandrei, O. Hirsch, P. Rehak, J. Vogel, M. Feike, H.W. Spiess, K. Herzog, and B.
Thomas, “Novel Opportunities of Structural Investigations of Glasses by 2D NMR, Multiple Quantum NMR and 27Al
MAS NMR Line Shape Analysis”, Berichte der Bunsengesellschaft für physikalische Chemie. 1996;100:1560-1562.

54 © 2019 by the Association for Iron & Steel Technology.