Upload
others
View
5
Download
0
Embed Size (px)
Citation preview
Database Selection for Ferrous Applications 1
DATABASE SELECTION FOR
FERROUS APPLICATIONS
Database Selection for Ferrous Applications 2
Contents
Topics Slide #
FactSage databases for steelmaking:
History and important solution phases
3
Steelmaking chemistry and availability of database 10
Important phase diagrams for steelmaking processes 12
Slag viscosity database 33
Database Selection for Ferrous Applications 3
FactSage databases for steelmaking applications
Brief History of Database Development
Important Solution Phases for Steelmaking Applications
Ref. : I.-H. Jung, “Overview of the applications of thermodynamic databases
to steelmaking processes”, Calphad, 2010, vol. 34, pp. 332-362.
Database Selection for Ferrous Applications 4
Databases in FactSage
Brief History of FactSage Database Development
1976~2001: FACT 2001~present: FactSage (a fusion of FACT + ChemSage)
< 1998 : FACT database (before 1998)
1999~2003 : FACT53 database
2000~2004 : FACT Consortium project (2000~2004): 16 companies
pyrometallurgy (ferrous, non-ferrous), hydrometallurgy-corrosion, glassmaking
- FACT53 database FToxid, FTmisc, FThall, FTsalt, FThelg,..
- New alloy databases: FSstel, FSlite, FScopp, SGTE, ….
2004~2010 : Mini-consortiums
- Al consortium (Alcoa, Alcan, and Norsk-Hydro)
- Glass consortium (Corning, Schott, and Saint-Gobain)
- Light alloy (Al, Mg) consortium (Al consortium, GM, MagNET): FTlite
2009~present : Mini-consortiums
- Al consortium (3 companies), Glass consortium (3 companies)
- Steelmaking consortium: 11 companies Consortium database (‘CON1 or CON2’)
Database Selection for Ferrous Applications 5
Databases in FactSage for Steelmaking Applications
FactPS (pure substances database): All gaseous species, stoichiometric solid and
liquid species (organic, inorganic) Similar to thermodynamic tables like JANAF,
Barin-Kubaschewski. (When you need a “Gas” phase you always have to select this
database).
FToxid: Frequently updated oxide database containing
- many solution phases (slag, spinel, monoxide, olivine, etc.)
- pure solid and liquid oxides, no gas phase
FTmisc: FeLq solution
- most reliable liquid steel database for steelmaking calculations
(slags/refractories/gases/molten iron)
FSstel: solid and liquid steel phases
(also includes a small number of gases, oxides, sulfides, nitrides, etc.)
- for steel solidification and alloy design.
- liquid steel: reasonable calculations for steelmaking applications
For steelmaking calculations:
priority: FToxid > FeLq > FactPS
(In the FactSage 6.4 and later versions, the best selections of compounds among
multiple compound databases are provided automatically. But solutions must be
selected carefully.)
Database Selection for Ferrous Applications 6
FToxid database Main solution phases when T > 1550oC (steelmaking)
Slag (I option): CaO-MgO-Al2O3-SiO2-FeO-Fe2O3-MnO-Mn2O3-Ti2O3-TiO2…
+ Gas solubility such as S (SO2), P, H (OH), N, C, F, …
- All oxide components + sulfides: valid for liquid oxy-sulfide solution over a wide range
- (Ca,Al,Mg,Si,Na//O,F): liquid oxy-fluoride valid up to ~ 50% fluoride content.
Spinel (I option) (SPIN): (Mg,Fe,Mn,Co,Ni,Zn)(Al,Fe,Cr,Co,Mn,Va)2O4, extensive solid solution
containing MgAl2O4, MgCr2O4, MgFe2O4, FeCr2O4, Fe3O4, FeAl2O4, Cr3O4, MnAl2O4, MnCr2O4,
MnFe2O4, etc.
Al spinel (AlSp): (Fe,Mg,Mn)Al2O4-Al2O3 solution
a-, a’-Ca2SiO4 (aC2S, bC2S): Ca2SiO4 (C2S)-rich solution with limited solubility of Mg2SiO4,
Fe2SiO4, Mn2SiO4,etc.
Olivine (Oliv): Mg2SiO4, Fe2SiO4, etc. (Mg,Fe,Ca,Mn,Ni,Zn,Co,Cr,etc.)2SiO4, covering forsterite
(Mg2SiO4), fayalite (Fe2SiO4), -Ca2SiO4, monticellite CaMgSiO4, tephroite Mn2SiO4.
Use I option specially when Ca2SiO4 is present.
Corundum (CORU): (Al,Cr,Fe,Mn)2O3 solution, the solution of Al2O3, Cr2O3, Mn2O3 and Fe2O3. Solid
miscibility gaps exist between the constituents. I option required.
Monoxide (halite) (MeO_): solution of CaO-MgO-FeO-MnO-NiO-Fe2O3-Al2O3-Cr2O3 etc. Major
constituents: lime (CaO), periclase (MgO) and wustite (FeO). Use I option especially when CaO and
MgO are present together.
The four character in red
give the name of each
solution phase
Database Selection for Ferrous Applications 7
Mn/Ti oxides:
i) ilmenite (ILME): (FeTiO3(ilmenite)–Ti2O3–MgTiO3–MnTiO3 + Al2O3),
ii) pseudo-brookite (PSEU): (Ti3O5–FeTi2O5-MgTi2O5–MnTi2O5 ),
iii) Ti-spinel (TiSp): (Mg,Fe,Mn)[Mg,Fe,Mn,Ti,Al]2O4
iv) Rutile (TiO2):TiO2 + Ti2O3-ZrO2 solid solution
Mullite (Mull): non-stoichiometric Al6Si2O13 with possible solubility of B.
(MulF): stoichiometric Al6Si2O13 with dilute Fe6Si2O13.
Melilite (Mel_): Ca2[Mg,Fe2+,Fe3+,Al](Fe3+,Al,Si)2O7. Akermanite Ca2MgSi2O7 and gehlenite
Ca2Al2SiO7 form the melilite solid solution stable below 1590 °C.
Main additional solution phases when T < 1550oC (solidification of slag):
(Including all above phases + additional phases below)
Wollastonite (Woll): (Ca,Mg,Mn)SiO3, which is a CaSiO3-rich phase stable below 1300 °C.
Pseudo-wollastonite is stoichiometric CaSiO3 stable below 1550 °C.
Pyroxene (pPyr, oPyr, cPyr): (Mg,Ca,Fe)[Mg,Fe]Si2O6, which is a MgSiO3-rich phase stable
below 1560 °C. Proto-, ortho-, low-clino-pyroxene exist. Clino-pyroxene is a CaMg2SiO6-rich
phase, which is stable below 1390 °C.
Rhodonite (Rhod): (Mn,Ca)SiO3, a MnSiO3-rich solid stable below 1300 °C.
FToxid database
Database Selection for Ferrous Applications 8
Main additional solution phases in the CaO-Al2O3-SiO2-FetO system at high PO2
(air)
CAFS Ca2(Al,Fe)8SiO16, CAF6 Ca(Al, Fe)12O19, CAF3 Ca(Al,Fe)6O10, CAF2 Ca(Al,Fe)4O7
CAF1 Ca(Al,Fe)2O4, C2AF Ca2(Al,Fe)2O5, C3AF Ca3(Al,Fe)2O6
Main additional solution phases when T < 1550oC (mould flux, Na2O-containing
systems)
Nepheline (Neph): NaAlSiO4 with excess SiO2.
Carnegeite (Carn): NaAlSiO4 with excess SiO2.
NaAlO2 (NASl): low temperature - NaAlO2 with excess NaAlSiO4
NaAlO2 (NASh): high temperature - NaAlO2 with excess NaAlSiO4
Combeite (NCSO): Na4CaSi3O9 (bombeite) – Na2Ca2Si3O9 solid solution
Feldspar (Feld): complete solution between Anorthite(CaAl2Si2O8)-Albite(NaAlSi3O8)
NCA2: (Na2,Ca)O·Na2O·2Al2O3 solid solution
C3A1: Ca3Al2O6 dissolving Na2O, (Ca,Na2)1Ca8Al6O18 solution
FToxid database
Database Selection for Ferrous Applications 9
FTmisc (FeLq) and FSstel
FeLq Liquid Fe containing Ag,Al,B,Ba,C,Ca,Ce,Co,Cr,Cu,H,Hf,La,Mg,Mn,Mo,N,Nb,Nd,Ni,O,P,Pb,Pd,S,Si,
Sn,Ta,Th,Ti,U,V,W,Zr. This phase is better suited for calculations involving iron and steelmaking
processes (optimized for iron-rich solutions only).
Based on the Unified Interaction Parameter Formalism (more advanced than classical Wagner
Interaction Parameter Formalism) with associate model for deoxidation. Many interaction
parameters between metallic elements are taken from JSPS (Japanese compilation)
FSstel database FCC/BCC: Fe / Carbide / Nitride are all treated as FCC phases
Fe with N and C : use J option (possible 3-phase immiscibility).
Fe with N or C : use I option (possible 2-phase immiscibility).
Also recommend to use I option for BCC phase See Fe-Ti-Nb-C-N example.
Liquid: O and S are treated by the associate model
FCC ordered phase (FCC_L12), BCC ordered phase (BCC_B2) normally slow down the
calculations significantly. If you are not really interested in order/disorder transitions, do not select
these phases.
Carbon: when C content is lower than ~ 1%, Fe3C (metastable) phase is normally formed instead
of C (stable). So, in the selection of solid phases, “deselect” C solid.
Database Selection for Ferrous Applications 10
The important chemical systems of non-metallic phases for steelmaking
processes can be summarized as follows. All of these are modeled in the
FactSage databases.
Database availability for general steelmaking processes: Blue: available in FactSage 6.4; Green: available in 7.0; Red: unavailable
1) Molten slag for refining processes
a) CaO-FeO-Fe2O3-SiO2-MgO-MnO-P2O5 system: BOF process
b) CaO-MgO-Al2O3-SiO2-FeO-Fe2O3 system: ladle refining process
c) CaO-MgO-SiO2-CaF2 system: stainless steel refining
d) CaO-CrO-Cr2O3-MgO-SiO2 system: AOD and VOD process for
stainless steel
e) CaO-MgO-SiO2-MnO-CrO-Cr2O3 system: high-Mn stainless steel
2) Mould flux for casting processes
a) CaO-MgO-Al2O3-SiO2-Na2O(-Li2O)-F system: conventional process
b) CaO-MgO-Al2O3-SiO2-Na2O-Li2O-B2O3 system: new candidate.
Steelmaking Chemistry and Availability of Databases
Database Selection for Ferrous Applications 11
3) Non-metallic inclusions
a) CaO-Al2O3-MgO-CaS: conventional low carbon steels
b) MnO-SiO2-Al2O3-CaO-MnS: wire steels and free cutting steels
c) MnO-SiO2-Ti2O3-TiO2-Al2O3: high strength steels
d) Al2O3-Ti2O3-TiO2: interstitial-free (IF) steels
e) Ti-Nb-C-N: high-strength low-alloy (HSLA) steels containing Ti and Nb
4) Refractories
a) MgO-C: BOF and RH vessel refractories, ladle slag line
b) MgO-Al2O3: ladle castable
c) MgO-Cr2O3-FeO-Fe2O3-Al2O3: VOD and AOD refractories
d) Al2O3-ZrO2-SiO2-C: nozzle refractories and tundish plugs
Database Selection for Ferrous Applications 12
Most common phase diagrams for
steelmaking applications
CaO-MgO-SiO2-Al2O3-FeO-Fe2O3-MnO
Na2O-CaO-Al2O3-SiO2
MnO-Ti2O3-TiO2
Database Selection for Ferrous Applications 13
Important phases and phase diagrams
Fe(liquid)+MW+Slag
Schenck and Pfaff[54]
Gokcen[69]
Fischer and Ende[72]
Taylor and Chipman[70]
Shim and Ban-Ya[74]
Fe(liquid)+MW
Fe(bcc) + MW
Fe(fcc) + MW
Fe(liquid)+Slag
Scheel et al.[73]
Fetters and Chipman[71]
molar ratio FeO/(MgO+FeO)
Tem
per
atu
re,
oC
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
1000
1200
1400
1600
1800
2000
2200
2400
2600
2800
3000
Slag
Lime
Wustite
Ca2Fe2O5 + WustiteLime + Ca2Fe2O5
Lime+Wustite
Lime + Slag
Zhao et al.[45]
Abbatista[20]
Allen and Snow[17]
Larson[21]
Takeda[22]
Timucin[23]
Ca
2F
e2O
5
1059oC
1125oC
1371oC
0.760.16
0.13
0.67
0.72
mass FeO/(CaO+FeO)
Tem
peratu
re, oC
0 0.2 0.4 0.6 0.8 1
800
1000
1200
1400
1600
1800
Monoxide; halite solution (MeO_)
Database Selection for Ferrous Applications 14
MnO
Liquid
2 Liquids
SiO2(Crist)
SiO2(Trid)
MnSiO3Mn2SiO4
1842oC
1328oC
1251oC
1347oC
1293oC
1465oC
1702oC
0.59 0.992
0.490.43
0.29
mole fraction MnO
Tem
pera
ture
(oC
)
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
1200
1300
1400
1500
1600
1700
1800
1900
Olivine: M2SiO4
MgSiO3-rich: pyroxene
MnSiO3-rich: rhodonite
Important phases and phase diagrams
Database Selection for Ferrous Applications 15
Liquid
Mullite(Al6Si2O13)
Al2O3
SiO2(Trid)
SiO2(Crist)
1890oC 1890
oC
1465oC
1596oC 0.96
0.334
2054oC
1723oC
mole fraction SiO2
Tem
pera
ture
(oC
)
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
1200
1300
1400
1500
1600
1700
1800
1900
2000
2100
2504oC
1769oC
1527oC 0.77
0.55
1842oC
MnO
Mn
Al 2
O4
Al2O3
Jacob[16]
Olsen & Heynert[17]
mole fraction MnO
Tem
pera
ture
(oC
)
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
1000
1100
1200
1300
1400
1500
1600
1700
1800
1900
2000
2100
2200
Al 2
O3
Spinel
Alper et al[22]
Viechnicki et al[23]
Saalfeld and Jagodzinski[32]
Viertel and Seifert[30]
Mori[24]
Stubican and Roy[25]
Henriksen and Kingery[27]
Whitney and Stubican[28]
Rankin and Merwin[21]
2122
(1994, 0.79)
2054
2825
0.07
Frenkel et al[26]
Roy et al[31]
Shirasuka and Yamaguchi[29]
Lejus[33]
(1985, 0.36)
(2008, 0.92)
Liquid
Mo
no
xid
e 0.90
MgO mole fraction Al2O3
Tem
pera
ture,
oC
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
1000
1200
1400
1600
1800
2000
2200
2400
2600
2800
3000
Slag
MW+Slag
SpinelMW
Slag
Spinel
Spinel + Fe2O3
MW + Spinel
MW + Slag
Roberts and Merwin[66]: phase boundaries
Willshee and White[65]: invariant points
Slag+Solid
Woodhouse and White[39]: monoxide boundary
MW+Spinel
MW
1711
Schurmann and Kolm[68]: Slag
Phillips et al.[67]
molar ratio Fe2O3/(MgO+Fe2O3)
Tem
per
atu
re,
oC
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
800
1000
1200
1400
1600
1800
2000
2200
2400
2600
2800
3000Spinel: A2+(B3+)2O4
Mullite
Important phases and phase diagrams
Database Selection for Ferrous Applications 16
Important phases and phase diagrams
Database Selection for Ferrous Applications 17
AOlivine
Fe(liq)
Fe(s)
Fe(s2)
ASlag-liq + AOlivine
Fe(s)
ASlag-liq
Mg2SiO4 - Fe2SiO4 - Fe
Fe/(Mg2SiO
4+Fe
2SiO
4) (mol/mol) = 0.001
Fe2SiO4/(Mg2SiO4+Fe2SiO4) (mol/mol)
T(C
)
0 0.2 0.4 0.6 0.8 1
1000
1100
1200
1300
1400
1500
1600
1700
1800
1900
2000
Fe saturation
Important phases and phase diagrams
Database Selection for Ferrous Applications 18
Important phases and phase diagrams
Database Selection for Ferrous Applications 19
1422
2374
1542
1349
1985
1333
1309
1597
15221344
1362
1714
1754
16902008
1778
1758
1708
1833CaO
MgO
Al2O3(2572) (2054)
(2825)
Mole fraction
2600
2400
2200
2000
1800
1600
2100
1900
1700
15001400
MgO
Spinel
CaO
Al2O3
CaAl12O19Ca3Al2O6
CaAl2O4
(1604)
CaAl4O7
(1765)
Ca3MgAl4O8
CaMg2Al16O27
Ca2Mg2Al28O46
1766
2122
MgO Al2O3
SiO2SiO2SiO2SiO2SiO2SiO2SiO2SiO2SiO2SiO2SiO2SiO2SiO2
1435
1465
1454
1575
weight percent
1381
1445
1361
1371
1558
1548
16451863
Tw
o-L
iquid
s
SiO2(Crist)
SiO2(Trid)
Cordierite
Sapphirine
2000
1900
1800
2600
2400
2200
2000
1700
1600
1500
1400
2000
1600
1500
MgOSpinel
Al2O3
Mullite
Mg2SiO4
MgSiO3
20081985
(Mg2Al4Si5O18)
(Mg4Al10Si2O23)
(1723)
(2825) (2054)
12391328
1769
Corundum
Galaxite
Mullite
Mn2SiO4
MnSiO3
MnO
SiO2
1293
Al6Si2O13
(1890)(1347)
MnAl2O4
(2054)(1842)
(1723)
1595
1702
1890
1465
Mn2Al4Si5O18
(Mn-Cordierite)
2000
1900
1800
1700
1600
(1180)
MnO
Al2O3
1135
1119
1156
1800
1700
1600
Mn3Al2Si3O12
(Spessartite)(1200)
2 L
iquid
sCristobalite
Tridymite
1500
1400
1300
1200
1527
1251
1249
1144
1180
1157
1138
1143
1166
1194
weight percent
Tephroite
Rhodonite
1200
Important phases and phase diagrams
Database Selection for Ferrous Applications 20
Important phases and phase diagrams
Database Selection for Ferrous Applications 21
[41] Osborn and Schairer
Liquid
Liquid + Mel
Mel
[22] Buddington : rxn time not enough
Liquid
Liquid + rare mel
mel + rare L
Geh-Aker (melilite solution)
Liquid
(75, 1390oC)
L+Merw
System Ca2Al2SiO7 - Ca2MgSi2O7
wt% Ca2MgSi2O7/(Ca2Al2SiO7+Ca2MgSi2O7)
T(o
C)
0 10 20 30 40 50 60 70 80 90 100
1200
1300
1400
1500
1600
1700
Melilite solid solution
Spinel solution
‘Coru’ solution
Important phases and phase diagrams
Database Selection for Ferrous Applications 22
ilmenite Ti-spinel
Pseudo-brookite
Important phases and phase diagrams
Database Selection for Ferrous Applications 23
Important phases and phase diagrams
Database Selection for Ferrous Applications 24
CaO
SiO2
Al2O3
Na2O
C2AS CA
CAS2
C2S
CS
NAS2 NAS6
C: CaO
A: Al2O3
N: Na2O
S: SiO2
NA
NA6
NS
Na2O-containing system: Na2O-SiO2-CaO-Al2O3
Weill et al. (1980), compliation
Feldspar
Slag
CaAl2Si2O8 - NaAlSi3O8
mole NaAlSi3O8/(CaAl2Si2O8+NaAlSi3O8)
T(C
)
0 0.2 0.4 0.6 0.8 1
1000
1400
1800
* Most recently updated version: ‘CON1’ database
Database Selection for Ferrous Applications 25
ASlag-liq
ASlag-liq + NaAlO2(s2)
NaAlO2(s2) + Na2Al12O19(s)
Na2O(s) + NaAlO2(s2)
Na2O(s2) + NaAlO2(s2)
Na2O(s3) + NaAlO2(s2)
NaAlO2(s2) + NaAl9O14(s)
ASlag-liq + NaAl9O14(s)
NaA
l 9O
14(s
) +
Al 2O
3(s
4)
Na2O - Al2O3
Al2O3/(Na2O+Al2O3) (mol/mol)
T(C
)
0 .2 .4 .6 .8 1
500
700
900
1100
1300
1500
1700
1900
2100
2300
2500
Rys (2008): DTA-TG, heating
Rys (2008): DTA-TG, cooling
Na
10S
iO7
Na
4S
iO4
Na
2S
iO3
Na
6S
i 2O
7
Na
2S
i 2O
5
Na
6S
i 8O
19
Na2O mole fraction SiO2
Tem
pera
ture (
K)
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
700
900
1100
1300
1500
1700
1900
2100
Important phases and phase diagrams: Na2O-Al2O3-SiO2 system
Database Selection for Ferrous Applications 26
Important phases and phase diagrams: Na2O-Al2O3-SiO2 system
NASh
Carg
Neph
NASl
Database Selection for Ferrous Applications 27
Moir and Glasser (1974)(1:2:3)
(1:2:3) + (2:1:3)
(1:2:3) + bCS
L + (1:2:3)
(2:1:3)
L + (2:1:3)
(2:1:3) + NS
aCS
aCS + (1:2:3)
aCS + bCS + (1:2:3)
L + aCS
bCS + (1:2:3)
aCS + bCS
L
L + NS
(1:2:3)' - maybe (1:1:2)
(1:2:3)' + NS
(1:2:3) + (2:1:3) + NS
Slag
1:2:3
1:2:3 + Na2SiO3(s)
Na2SiO3(s) + Na4CaSi3O9(s)
1:2:3 + CaSiO3(s)
1:2:3 + CaSiO3(s2)
Slag + CaSiO3(s2)
CaSiO3 - Na2SiO3
mole CaSiO3/(CaSiO3+Na2SiO3)
T(C
)
0 0.2 0.4 0.6 0.8 1
0
300
600
900
1200
1500
1800
0.2
0.4
0.6
0.8
0.20.40.60.8
0.2
0.4
0.6
0.8
SiO2
Na2O CaOWeight %
(a:b:c) = aNa2O.bCaO.cSiO2
(2:0:1)
(3:0:2)
(1:0:1)
(1:0:2)
(0:1:1)
(0:2:1)
(0:3:2)
(0:4:1)
(5:0:1)
(1:1:5)
(1:3:6)
(2:1:3) (1:2:3)
(2:1:3)
(1:0:1)
(0:1:1)
(0:0:1) - Tr.
(0:0:1) - Cr.
(0:3:2)
Morey and Bowen (1925)
(1:2:3)
(1:3:6)
(1:0:2)
(0:0:1) - Qz.
(4:3:5)
(1:1:1)
(1:2:2)
Segnit (1953)
(1:1:1)
(2:1:3)
(1:2:3)
(1:2:2)
(4:3:5)
(1:0:1)
(0:2:1)
(0:1:1)
(3:0:8)
Shahid and Glasser (1971)
(1:1:5)
(1:0:2)
(1:2:3)
(1:3:6)
(3:0:8)
(0:0:1) - Qz.
(0:0:1) - Tr.
1200 o C11
00
o C
1000
o C 1300
oC 1400
oC 1500
oC
1100
o C
SiO2 - CaO - Na2O
Important phases and phase diagrams: Na2O-CaO-SiO2 system
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
0.10.20.30.40.50.60.70.80.9
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
SiO2
Na2O CaOmole fraction
(a:b:c) = aNa2O.bCaO.cSiO2
(2:0:1)
(3:0:2)
(1:0:1)
(1:0:2)
(0:1:1)
(0:2:1)
(0:3:2)
(0:4:1)
(5:0:1)
(1:1:5)
(1:3:6)
(2:1:3) (1:2:3)
(1:2:2)
(1:1:1)
(4:3:5)
(3:0:8)
CaO-Na2O-SiO2
FactSage
?
NCSO: 1:2:3 solid solution
Database Selection for Ferrous Applications 28
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
0.10.20.30.40.50.60.70.80.90.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
Na2O
CaO Al2O3mole fraction
(a:b:c) = aNa2O.bCaO.cAl2O3
(0:1:1) (0:1:2) (0:1:6)
(1:8:3) (1:0:9)
(1:0:6)
(0:3:1)
(1:0:1)
CaO(s)
NaAlO2(s2)
1:1:2 NaAl9O14(s)
Al2O3(s4)CaAl2O4(s)CaAl4O7(s)
Na2O - Al2O3 - CaO
Projection (Slag)
FactSage
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
0.10.20.30.40.50.60.70.80.9
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
mole fraction
Slag
Na2O
CaO Al2O3mole fraction
N(a)C(b)A(c) = aNa2O.bCaO.cAl2O3
CA CA2 CA6
NC8A3 NA9NA6
C3A
NCA2s.s
NC3A8
NA
Verweij and Saris (1986), maximum solubility
Na2O - Al2O3 - CaO
1200oC
FactSage
Important phases and phase diagrams: Na2O-Al2O3-CaO system
NCA2: (Na2,Ca)O·Na2O·2Al2O3 solid solution
Database Selection for Ferrous Applications 29
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
0.10.20.30.40.50.60.70.80.9
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
MELCgNe
PW
Juan (1950)Ca2Al2SiO7
CaSiO3 NaAlSiO4mass fraction
Ca2Al2SiO7
CaSiO3 NaAlSiO4mass fraction
T(min) = 1162.95 oC, T(max) = 1594.98
oC
Melilite
CaSiO3(s2)
Ca3Si2O7(s)
Nepheline
Carnegieite
10/25/2008
D:\Work\CRCT\2007_MoldFlux_POSCO\Na2O-CaO-SiO2-Al2O3\quaternary_parameter\PD_CaSiO3-Ca2Al2SiO7-NaAlSiO4.emfCaO
SiO2
Al2O3
Na2O
Important phases and phase diagrams: Na2O-Al2O3-SiO2-CaO system
Database Selection for Ferrous Applications 30
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
0.10.20.30.40.50.60.70.80.9
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
CA2S2CgNeC3APWC2AS2b-A
Gummer (1943)CaAl2Si2O8
CaSiO3 NaAlSiO4mass fraction
CaAl2Si2O8
CaSiO3 NaAlSiO4mass fraction
T(min) = 1163.86 oC, T(max) = 1555
oC
Feldspar
CaSiO3(s2)
Melilite
Carnegieite
10/25/2008
D:\Work\CRCT\2007_MoldFlux_POSCO\Na2O-CaO-SiO2-Al2O3\quaternary_parameter\PD_CaSiO3-CaAl2Si2O8-NaAlSiO4.emfCaO
Al2O3
Na2O
SiO2
15
00
Important phases and phase diagrams: Na2O-Al2O3-SiO2-CaO system
Database Selection for Ferrous Applications 31
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
0.10.20.30.40.50.60.70.80.9
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1:2:32:1:3CgNePWNSW
Spivak (#1342)NaAlSiO4
CaSiO3 Na2SiO3mass fraction
NaAlSiO4
CaSiO3 Na2SiO3mass fraction
NaAlSiO4
CaSiO3 Na2SiO3mass fraction
NaAlSiO4
CaSiO3 Na2SiO3mass fraction
T(min) = 919.18 oC, T(max) = 1540.17
oC
Carnegieite
Nepheline
1:2:3
CaSiO3(s2)
2:1:3
Na2SiO3(s)
10/25/2008
D:\Work\CRCT\2007_MoldFlux_POSCO\Na2O-CaO-SiO2-Al2O3\quaternary_parameter\PD_NaAlSiO4-CaSiO3-Na2SiO3.emf
CaO
Al2O3
Na2O
SiO2
Important phases and phase diagrams: Na2O-Al2O3-SiO2-CaO system
Database Selection for Ferrous Applications 32
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
0.10.20.30.40.50.60.70.80.9
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
SiO2
Na2O CaOmass fractions /(SiO2+CaO+Na2O)
T(min) = 812.79 oC, T(max) = 2394.5
oC
CaO(s)
1:1:2 Ca2SiO4(s3)
Ca2SiO4(s2)Melilite
Ca3Si2O7(s)
1:2:3CaSiO3(s2)
Nepheline
Feldspar
Al6Si2O13(s)
Na2Ca3Si6O16(s)
Feldspar
NaAlO2-NaAlSiO41
NaAlO2-NaAlSiO4
NaAlO2-NaAlSiO41
SiO2 - CaO - Na2O - Al2O3
15wt% Al2O
3 section
SiO2
CaO
Al2O3
Na2O
1400
1300
1200
1100
Important phases and phase diagrams: Na2O-Al2O3-SiO2-CaO system
Database Selection for Ferrous Applications 33
Modified Quasichemical Model
Bond fraction (Silicate network structure)
Activation energy of bond breaking reaction: Binary
parameters + Association energy for M+Al3+ replacing Si4+ in
silicate network
Prediction of multicomponent systems (oxide and oxy-
fluoride)
Heterogeneous (solid + liquid): Einstein-Rosco equation
Database for molten slag
CaO-MgO-SiO2-Al2O3-FeO-Fe2O3-MnO-TiO-TiO2-Na2O-K2O-
B2O3-F (-PbO-NiO)
Database for glass (supercooled melt)
CaO-MgO-SiO2-Al2O3-Na2O-K2O-B2O3-PbO-…
Slag Viscosity: Structural Viscosity Model
Database Selection for Ferrous Applications 34
The Na2O-Al2O3-SiO2 system
1200 1400 1600°C
below liquidus
Toplis et al. 1997mole fraction SiO2 = 0.5
Riebling, 1966
1600°C
1400°C
1200°C
molar ratio Al2O3 / (Al2O3+Na2O)
ln(v
isc)
[PaS
]
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
-5
0
5
10
15
20
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
0.10.20.30.40.50.60.70.80.9
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
SiO2
Na2O Al2O3mole fraction
T = 1400°C
10
0-1-2-3
2
3
4
5
6
7
1
Riebling, 1966
Toplis et al., 1997
Fig. 16
Fig. 17
Fig. 18
Fig. 19
Fig. 20
Database Selection for Ferrous Applications 35
The Na2O-Al2O3-SiO2 system
1200 1400 1600°C
below liquidus
Toplis et al. 1997
Stein and Spera, 1993
mole fraction SiO2 = 0.67
Riebling, 1966
Kim and Lee, 1997
1200°C1400°C
1600°C
molar ratio Al2O3 / (Al2O3+Na2O)
ln(v
isc)
[PaS
]
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
0
5
10
15
20
25
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
0.10.20.30.40.50.60.70.80.9
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
SiO2
Na2O Al2O3mole fraction
T = 1400°C
10
0-1-2-3
2
3
4
5
6
7
1
Riebling, 1966
Toplis et al., 1997
Fig. 16
Fig. 17
Fig. 18
Fig. 19
Fig. 20
Database Selection for Ferrous Applications 36
Viscosity of CaO-Al2O3-SiO2-R2O (R=K, Na, Li)
0.0 0.1 0.2 0.3-5
-4
-3
-2
-1
0
1
2006, Sukenaga et al.
Addition of K2O Na
2O Li
2O Initial Composition (wt.%)
32CaO-48SiO2-20Al
2O
3
40CaO-40SiO2-20Al
2O
3
44CaO-36SiO2-20Al
2O
3
Addition of K2O
Addition of Na2O
Addition of Li2O
ln
(P
a·s)
Mole fraction of alkali oxide R2O
T = 1600 oC
Database Selection for Ferrous Applications 37
Viscosities of various systems
-6 -4 -2 0 2 4 6 8 10 12-6
-4
-2
0
2
4
6
8
10
12
Al2O
3-SiO
2
CaO-Al2O
3
CaO-SiO2
MgO-SiO2
K2O-SiO
2
Na2O-SiO
2
ln[P
a·s],
Exp
eri
me
nta
l
ln[Pa·s], Calculated
-6 -4 -2 0 2 4 6 8 10 12 14 16 18-6
-4
-2
0
2
4
6
8
10
12
14
16
18
ln[P
a·s],
Exp
eri
me
nta
l
ln[Pa·s], Calculated
CaO-MgO-SiO2
CaO-Na2O-SiO
2
Na2O-Al
2O
3-SiO
2
CaO-Al2O
3-SiO
2
MgO-Al2O
3-SiO
2
-4 -3 -2 -1 0 1 2 3 4 5 6 7 8-4
-3
-2
-1
0
1
2
3
4
5
6
7
8
ln[P
a·s],
Expe
rim
en
tal
ln[Pa·s], Calculated
CaO-Al2O
3-MgO-SiO
2
CaO-Al2O
3-Na
2O-MgO-SiO
2