Calcium modification
of alumina and spinel inclusions
in aluminum-killed steel
Chris Pistorius, Neerav Verma and Richard Fruehan
Center for Iron and Steelmaking Research
Carnegie Mellon University
Pittsburgh, PA, USA
Topics considered
Transient reaction products upon Ca treatment:
CaS & CaO
Modification of spinel (MgO.Al2O3) inclusions
Size & matrix effects on SEM/EDX inclusion analysis
Solid Oxide Inclusions in Al-killed steel
Alumina Spinel
From Al deoxidation • MgAl2O4-Al2O3 solid solution
2[Al] + 3[O] Al2O3 (s) • Mg source: mainly ladle slag
Clustered alumina inclusion Spinel
Solid inclusions tend to clog
submerged-entry nozzle (etc.) in continuous caster
Tundish nozzle plug
(Al-killed steel)
(Pielet, Tsai & Gass, ISSTech 2003 Proceedings, pp. 241-255, 2003)
Why calcium treat?
Liquidus temperatures of Al2O3-CaO (-MgO) mixtures
CaO:
• more stable than Al2O3
• lowers liquidus temperature
MgO:
FactSage • contributes to liquefaction
Possible reactions upon injection of Ca into liquid steel
Injected Ca
Majority: evaporates
Dissolution +[S] +[O] +<Al2O3> +<MgAl2O4>
[Ca] <CaS> <CaO> Ca aluminate ?
Extent of Ca dissolution in steel: unknown
Proposed Ca-O-<CaO> relationships in liquid steel (JSPS, 2010)
(Hanna Pistorius)
Current best guess:
Dissolved calcium in Ca-treated steel: ~ppm
Total calcium content: ~20 ppm
Most calcium present as reaction products.
What are these?
- studied by sampling steel immediately after
Ca treatment
- laboratory and industrial samples
- steel samples examined by SEM/EDX
automated analysis of polished sections
manual SEM:
inclusions in polished sections
inclusions extracted by dissolving steel matrix
Experimental Procedure
Off Gas
Pyrometer
Power
Supply Sampling
tube
CaSi2
Vacuum Al/Al-Mg
System MgO crucible
Ar cylinder
VACUUM INDUCTION FURNACE SAMPLING TOOL
Evacuation + Deoxidation of Calcium Treatment
Melting of Iron
Ar backfilling Steel (Al-Mg alloy) (CaSi2)
Inclusion detection and analysis
using polished cross-sections
Backscattered electron image:
inclusions dark; steel bright Quantified composition
Detected inclusions
Analyzed X-ray spectrum
Hundreds of inclusions
analyzed in tens of
minutes
Displaying results: proportional symbol plot
Traditional scatter plot Proportional symbol plot
(each inclusion composition plotted)
Area of triangle in the modified plot is proportional to
number of inclusions
(similar to a "bubble plot")
"Bubble chart" example
(bubble size annual CO2 emissions)
Visualization from Gapminder World, powered by Trendalyzer from www.gapminder.org.
Previously proposed initial reactions upon Ca injection
Lu, Irons & Lu: "A kinetic study of calcium wire injection into steel"
First International Calcium Treatment Symposium, 1988
This work: initial formation of CaS / CaO confirmed;
CaS and CaO react further to modify Al2O3
Al2O3 CaS
Alumina Cluster Transient state Calcium aluminate
Before Immediately after 4 min after
treatment Ca treatment Ca treatment
These images: inclusions extracted / exposed by dissolving steel matrix
in bromine-methanol
This work: initial formation of CaS / CaO confirmed
INCA Feature analysis, 10 kV
Industrial sample: Ladle
(immediately after Ca treatment)
CaS
Molar ratios
Al2O3
Proportional symbol map:
distribution of inclusion compositions found in polished sections
This work: initial formation of CaS / CaO confirmed
INCA Feature analysis, 10 kV
Industrial sample: Caster mold
(long after Ca treatment)
Proportional symbol map:
distribution of inclusion compositions found in polished sections
Expected inclusion
composition changes:
3<CaS> + <Al2O3>
3(CaO) + 2[Al] + 3[S]
Modification of spinel inclusions
• Composition: MgAl2O4-Al2O3 solid solution
• Formation: reduction of MgO from slag
• Cause clogging, like alumina
• If Ca modified, MgO contributes to liquefaction
Spinel cluster
(extracted with bromine-methanol)
Spinel inclusions in deoxidized steel
Proportional symbol map:
distribution of inclusion compositions found in polished sections
Ca treatment partially removes MgO from inclusions
Proportional symbol map:
distribution of inclusion compositions found in polished sections
Modification of spinels: initial formation of CaS;
MgO removed from spinel during Ca treatment
CaS
Al2O3 partially
liquid
spinel
low-MgO
liquid
fully
spinel CaS liquid
Before Immediately after 4 min after
treatment Ca treatment Ca treatment
These images: inclusions extracted / exposed by dissolving steel matrix
in bromine-methanol
Modification of spinel inclusions
Readily modified to liquid / partially liquid inclusions
Partial removal of MgO (Mg enters liquid steel)
upon calcium treatment
Similar transient path to alumina
(CaS forms first, then reacts to give modification)
[Mg] returned to solution upon Ca treatment:
spinels can reappear upon reoxidation
Analysis of micron-sized inclusions:
sources of inaccuracy
Not all inclusions detected
(<1 µm inclusions not analyzed)
Matrix distorts analysis
Significant proportion of inclusions
is not detected by SEM/EDX
Comparison of total O and Ca of
steel, with O and Ca contained in
detected inclusions
Sample: 2 min after Ca
Size distribution of detected inclusions (cross-sections)
(only inclusions 1 µm analyzed)
Matrix effect:
X-rays pass through inclusion and steel matrix
Matrix effect:
Steel matrix filters Al & Mg X-rays
Matrix effect:
Analyzed Ca content too high; varies with size & kV
DTSA-II simulations
Matrix effect:
Depends on kV (size of interaction volume)
CASINO simulations
Predicted matrix effect
confirmed by simulation and measurements
Inclusion geometries considered:
a) Cube
b) Truncated sphere
c) Hemisphere
d) Spherical cap
Line scan across inclusion in two directions
Line scans across
inclusions:
predicted effect
PENEPMA simulations
Line scans across
inclusions:
measured effect
Acceleration voltage:
predicted effect
PENEPMA simulations
Acceleration voltage: measured effect
Conclusions
Transient reaction products form upon Ca treatment:
CaS & CaO
CaS & CaO react further with alumina & spinel
to yield modified inclusions (calcium aluminates)
Spinel (MgO.Al2O3) inclusions modified readily;
MgO partially removed from inclusions
upon Ca treatment
Analyses affect by:
- matrix
- non-analysis of <1 µm inclusions
