GTT-Technologies' 17th Annual Users' Meeting, , July 1-3, 2015
HotVeGas database development:
Ternary systems Alk2O-MeO-P2O5
(Alk=Na,K; Me=Ca, Mg)
Mitglied der Helmholtz-Gemeinschaft
Elena Yazhenskikh1, Tatjana Jantzen2, Klaus Hack2, Michael Müller1
1
Forschungszentrum Jülich, IEK-2 (Microstructure and properties of materials), Germany
2
GTT-Technologies, Herzogenrath, Germany
Contents
Na2O
Al2O3
SiO2
CaO
MgO
P2O5
FexOy
MnxOy
K2O
Motivation and aim of the work
Solid solubilities in the ternary systems
Assessment of the systems Alk2O-MeO-P2O5:
HOTVEGAS
K2O-CaO-P2O5
K2O-MgO-P2O5
Mitglied der Helmholtz-Gemeinschaft
Na2O-CaO-P2O5
Na2O-MgO-P2O5
Conclusions and outlook
15. Dezember 2015
GTT Annual Workshop, Juli 1-3, 2015
2
Motivation and aim of work
Mitglied der Helmholtz-Gemeinschaft
SO3,S2-
State of the art:
 2-, 3- and multicomponent systems have been
thermodynamically assessed using all available
experimental data
 phase diagrams and other thermodynamic
properties can be calculated with the obtained
self-consistent datasets
Aim of our work:
development of a new data base, which is applicable for the slag relevant system containing oxides of Si,
Al, Na, K, Ca, Mg, Fe, P, S, Cr etc. and suitable for the calculations and/or predictions of the phase
equilibria and other thermodynamic properties by variation of T and composition
15. Dezember 2015
GTT Annual Workshop, Juli 1-3, 2015
3
Including P2O5
P2O5



Mitglied der Helmholtz-Gemeinschaft
MgO
Na2O
15. Dezember 2015
P2O5 is a next important slag
component to be added into the
database
P2O5 occurs in biomass ashes and
metallurgical slags
All binary systems with P2O5 have been
already evaluated and added to the
database
K2 O
CaO
Present task:
4 ternary systems Alk2O-MeO-P2O5
(Alk=Na,K; Me=Ca,Mg) are considered
including the solid solubilities regarding
complex phosphates
GTT Annual Workshop, Juli 1-3, 2015
4
The system Na2CaO
O-K
2O5
- K2O-CaO-MgO-P
O-P O
2
2
K2O - MgO - P2O5
5
K2O
0.9
0.8
0.2
0.2
0.8
0.1
0.1
0.9
K2O
K3P-K3PO4
0.7
KP-KPO3
0.5
mo
le
fra
0.6
ctio
0.6
0.5
KP
0.5
0.5
T2-K4Mg(PO4)2
0.4
0.4
cti o
n
0.6
0.6
0.3
0.7
0.3
f ra
T1-K2MgP2O7
0.7
mo
le
0.4
0.4
T3-K6MgP2O9
T2-K4CaP2O8
R-KMgPO4
0.1
0.2
0.1
0.8
CaO
- Na
- P2O5
C2P
CP2O
C2P3
C3P
0.7
0.6
0.5
0.4
0.3
0.2
P2O5
0.1
MgO
0.9
0.8
Mg(PO
Na2O
- P)2O5 - MgO
0.7
Mg3(PO4)2
Mg2P2O7
0.6
0.5
0.3
0.8
0.9
0.2
0.8
0.1
0.2
N3P
0.6
0.5
0.5
NP
T2-Na4CaP2O8
0.4
B3-Na4CaP6O18
0.2
0.1
0.2
0.1
C2P
15 December 2015
0.5
CP
0.4
B1=NaMg(PO3)3
0.9
0.9
C3P
0.6
B2=Na2Mg(PO3)4
J=NaMg4(PO4)3
C2P3
0.7
D1=Na3Mg2P5O16
0.8
0.8
0.8
F1=Na8Mg6(P2O7)5
R=NaMgPO4
R-NaCaPO4
C4P
B3=Na4Mg(PO3)6
0.3
mo
le
T1-Na2CaP2O7
0.7
0.7
0.3
f ra
0.6
0.6
0.4
NP
T2=Na4Mg(PO4)2
cti o
n
f ra
N5P3
0.5
cti o
n
T3=Na6MgP2O9
0.4
0.5
mo
le
N2P
N5P3
0.4
0.6
N2P
T3-Na6CaP2O9
0.3
0.7
0.3
0.7
N3P
Mitglied der Helmholtz-Gemeinschaft
P2O5
0.1
Na2O
sections, Podhajska [1998-2005]
CaO
0.2
0.1
0.9
0.4
3 2
Na2O
0.9
0.9
0.9
B1-KMgP3O9
J-KMg4(PO4)3
CP2
C4P
0.9
B2-K2MgP4O12
W-K4Mg4P6O21
0.8
0.8
R-KCaPO4
0.2
T1-K2CaP2O7
B1-KCaP3O9
CaO
K2P-K4P2O7
K5P3O10
n
K2P
T3-K6CaP2O9
0.3
0.3
0.7
K3P
CP20.3
0.2
0.1
P2O5
MgO
0.9
GTT Annual Workshop, Juli 1-3, 2015
0.8
0.7
M3P
M2P
0.6
0.5
MP
0.4
0.3
0.2
0.1
P2O5
5
The system Na2O-K2O-CaO-MgO-P2O5
CaO - K2O - P2O5
Solid solutions
K2O
0.8
0.7
0.8
n
0.6
ctio
f ra
0.5
mo
le
0.5
KP-KPO3
0.4
T2-K4MgP2O8
R-KMgPO4
0.7
0.3
0.7
0.3
f ra
T1-K2MgP2O7
0.1
Na2O - P2O5 - MgO
Mg (PO )
MgO
(Alk2PO)
2O52(P2O5)2(Alk2O,MeO,Alk2MeO2)
0.9
0.9
C3P
0.8
0.7
C2P
0.5
CP
0.6
0.4
C2P3
0.3
0.2
0.1
0.7
Mg2P2O7
4 2
0.5
Mg(PO3)2
N3P
0.7
0.6
0.5
NP
f ra
mo
le
B3=Na4Mg(PO3)6
0.7
0.7
0.3
N5P3
T2-Na4MgP2O8
0.4
0.4
cti o
n
f ra
N2P
9
0.6
0.6
B3-Na4CaP6O18
F1=Na8Mg6(P2O7)5
R=NaMgPO4
0.2
B2=Na2Mg(PO3)4
0.8
D1=Na3Mg2P5O16
0.8
R-NaCaPO4
0.9
0.1
0.9
B1=NaMg(PO3)3
0.1
0.2
2
T2=Na4Mg(PO4)2
0.3
0.6
0.5
cti o
n
NP
T2-Na4CaP2O8
T1-Na2CaP2O7
6
0.5
0.5
mo
le
N5P3
P2O5
0.1
N3P
0.4
T3-Na6MgP
O9O
T3=Na2MgP
N2P
9
0.4
2
0.2
0.3
0.3
0.7
N3P
6
0.3
0.2
0.8
N3P
T3-Na6CaP
T3-Na CaP
O9
2O
0.4
0.1
0.2
0.8
0.6
Na2O
Alk3PO4-Alk4Me(PO4)2-Alk6MeP
O9 [1998-2005]
sections,2Podhajska
0.1
0.9
Na2O
0.8
3
0.9
0.2
0.1
CaO - Na2O - PCP2
2O5
B1-KMgP3O9
J-KMg4(PO4)3
0.9
Alk3P-T2-T3 solid solutions
for HT,(MT),LT modifications
0.9
B1-KCaP3O9
B2-K2MgP4O12
W-K4Mg4P6O21
0.8
R-KCaPO4
0.8
0.2
T1-K2CaP2O7
C4P
Mitglied der Helmholtz-Gemeinschaft
0.6
T2-K4CaP2O8
0.4
9
T2-K4Mg(PO4)2
0.6
cti o
n
2
0.5
0.5
mo
le
6
0.4
0.4
KP
T2-K4CaP2O8
CaO
K2P-K4P2O7
K5P3O10
T3-K6MgP
O9O
T3-K2
MgP
K2P
9
0.6
2
0.3
6
K3P
K3P-K3PO4
0.3
0.7
K3P
K3P
0.2
0.2
T3-K O
T3-K6CaP
2CaP9O
0.1
0.1
0.9
K2O
0.9
K2O - MgO - P2O5
J=NaMg4(PO4)3
C2P3
C4P
CaO
0.9
0.8
C3P
0.7
C2P
0.6
0.5
CP
15 December 2015
0.4
CP20.3
0.2
0.1
MgO
P2O5
GTT Annual Workshop, Juli 1-3, 2015
0.9
0.8
0.7
M3P
M2P
0.6
0.5
MP
0.4
0.3
0.2
0.1
P2O5
6
The system Na2O-K2O-CaO-MgO-P2O5
Description of the solid solutions
Phase
Used data
Description
N3P-Na3PO4(s1)- FZJ
N3P-LT
(Na2O)2(P2O5)(Na2O, Na2CaO2, MgO, K2MgO2)
N3P-HT
(Na2O)2(P2O5)(Na2O, Na2CaO2, MgO, K2MgO2)
K3P-LT
(K2O)2(P2O5)(K2O, CaO, K2CaO2 , MgO, K2MgO2)
T2-Na4MgP2O8(s1)-FZJ
T3-Na6CaP2O9(s1)-GTT T3-Na6MgP2O9(s1)-FZJ
N3P-Na3PO4(s2)- FZJ
T2-Na4MgP2O8(s1)-FZJ
T3-Na6CaP2O9(s2)-GTT T3-Na6MgP2O9(s1)-FZJ
K3P-K3PO4(s1)- FZJ
T2-K4CaP2O8(s1)-GTT
T3-K6CaP2O9(s1)-GTT
K3P-K3PO4(s2)-FZJ
K3P-MT
(K2O)2(P2O5)(K2O, CaO, K2CaO2 , MgO, K2MgO2)
Mitglied der Helmholtz-Gemeinschaft
T2-K4MgP2O8(s1)-FZJ
T3-K6MgP2O9(s1)-FZJ
T2-K4CaP2O8(s2)-GTT
T3-K6CaP2O9(s2)-GTT
T2-K4MgP2O8(s2)-FZJ
T3-K6MgP2O9(s2)-FZJ
Htr (s1→s2) is proposed to be equal to K3PO4 or Na3PO4
K3P-K3PO4(s3)-FZJ
K3P-HT
(K2O)2(P2O5)(K2O, CaO, K2CaO2 , MgO, K2MgO2)
T2-K4CaP2O8(s3)-GTT T2-K4MgP2O8(s3)-FZJ
T3-K6CaP2O9(s3)-GTT T3-K6MgP2O9(s3)-FZJ
Htr (s2→s3) is proposed to be equal to K3PO4 or Na3PO4
15 December 2015
GTT Annual Workshop, Juli 1-3, 2015
7
The system K2O-CaO-P2O5
Description of the system
The species with compositions R and B1 in the non-ideal associate solution were added in order to
describe the liquid phase
Liquid
species
Description
KCaPO4∙2/3
stoichiometric
Melting, °C
Name
Composition
R
KCaPO4
1580, congruent
T1
K2CaP2O7
1143, congruent
stoichiometric
T2
K4Ca(PO4)2
1645, congruent
K3P-T2-T3 solution
T3
K6CaP2O9
1750, incongruent
K3P-T2-T3 solution
B1
KCa(PO3)3
845, congruent
KCa(PO3)3∙2/5
(modelled by GTT)
stoichiometric
Mitglied der Helmholtz-Gemeinschaft
K3P-T2-T3 solid solutions for HT, MT, LT modifications
(K2O)2(P2O5)2(K2O, CaO, K2CaO2)
K3PO4-K4Ca(PO4)2-K6CaP2O9
15 December 2015
GTT Annual Workshop, Juli 1-3, 2015
8
The system K2O-CaO-P2O5
Mitglied der Helmholtz-Gemeinschaft
T. Znamierowska, Pol. J.
Chem., 52 [6] 1127-1134
(1978).
15 December 2015
T1-K2CaP2O7
Quasi-binary section Ca2P2O7-K4P2O7
T. Znamierowska, Pol. J.
Chem., 52 [10] 1889-1895
(1978).
GTT Annual Workshop, Juli 1-3, 2015
9
The system K2O-CaO-P2O5
Quasi-binary section KPO3 - CaP2O6
KPO3 - CaP2O6
T. Znamierowska-Kubicka, Rocz.
Chem., 51 [11] 2089-2098 (1977).
1200
[T. Znamierowska,1978]
[A. Packter, W.O.S. Doherty,1989]
[R. Andrieu, R. Diament,1964]
1100
1000
Slag
900
Slag + Ca(PO3)2(s)
800
T(C)
Slag + KCaP3O9(s)
Slag + KPO3(s4)
700
KCaP3O9(s) + Ca(PO3)2(s)
KPO3(s4) + KCaP3O9(s)
600
KPO3(s3) + KCaP3O9(s)
KCaP3O9(s) + Ca(PO3)2(s)
400
KPO3(s2) + KCaP3O9(s)
300
200
KPO3(s) + KCaP3O9(s)
100
B1-KP3CaO9
Mitglied der Helmholtz-Gemeinschaft
500
KP3CaO9(s) + Ca(PO3)2(s)
0.6
0.8
KCaP3O9(s) + Ca(PO3)2(s)
0
0
0.2
0.4
1
CaP2O6/(CaP2O6+KPO3) (g/g)
15 December 2015
GTT Annual Workshop, Juli 1-3, 2015
R. Andrieu and R. Diament, C. R. Hebd.
Seances Acad. Sci., 259 [25] 4708-4711 (1964).
10
The system K2O-CaO-P2O5
Isothermal section at 500°C
T3
CaO - K2O - P2O5
T2
o
500 C, 1 atm
T1
R
B1
30
70
20
80
10
90
K2O
K2P
50
50
T3
K3P_LT
40
60
K3P
T. Znamierowska, Zesz. Nauk. Politech.
Slask., Chem., 709 [100] , p.23-32 (1982).
60
40
T2
KP
20
90
10
80
Mitglied der Helmholtz-Gemeinschaft
70
30
T1-K2CaP2O7
R-KCaPO4
B1-KCaP3O9
Slag
CaO
90
80
15 December 2015
70
C4P 60 C3P
50
C2P
40
percent by weight
CP
C2P320 CP2
30
10
P2O5
GTT Annual Workshop, Juli 1-3, 2015
11
The system K2O-CaO-P2O5
Liquidus surface
Mitglied der Helmholtz-Gemeinschaft
T. Znamierowska, Zesz. Nauk. Politech.
Slask., Chem., 709 [100] , p.23-32 (1982).
15 December 2015
GTT Annual Workshop, Juli 1-3, 2015
12
The system K2O-MgO-P2O5
K2O - MgO - P2O5
K2O
0.6
K6MgP2O9
K3PO4
0.4
rac
tio
n
0.3
0.7
0.2
0.8
0.1
0.9
Experimental data
0.5
0.6
0.4
ma
0.5
ss
f
K 4 P 2 O7
K4Mg(PO4)2
KMgPO4
K2MgP4O12
KMgP3O9
KMg4(PO4)3
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
Mg3(PO4)2 Mg2P2O7 Mg(PO3)2
0.9
0.1
0.2
K4Mg4P6O21
0.8
MgO
KPO3
0.7
0.3
K2MgP2O7
P2O5
Mitglied der Helmholtz-Gemeinschaft
8 ternary compounds including the
solid solubility are found in the
system, the quasi-binary sections
are studies by thermal, microscopic,
dilatometric and X-ray analysis
Partial liquidus projection with invariant points labeled
Solid state compatibility observed at room temperature
J. Berak and T. Podhajska-Kazmierczak, Pol. J. Chem., 65 [7-8] 1137-1149, 1151-1163, 1165-1172, 1173-1184 (1991)
15 December 2015
GTT Annual Workshop, Juli 1-3, 2015
13
The system K2O-MgO-P2O5
Description of the system
The species with compositions R and B1 in the non-ideal associate solution were added in order to
describe the liquid phase
Liquid
species
Description
KMgPO4∙2/3
stoichiometric
Melting, °C
Composition
R
KMgPO4
J
KMg4(PO4)3
1175, incongruent
stoichiometric
W
K4Mg4P6O21
792, incongruent
stoichiometric
T1
K2MgP2O7
736, incongruent
stoichiometric
T2
K4Mg(PO4)2
1374, congruent
K3P-T2-T3 solution
T3
K6MgP2O9
1570, incongruent
K3P-T2-T3 solution
B1
KMg(PO3)3
906, congruent
B2
K2Mg(PO3)4
730, incongruent
Mitglied der Helmholtz-Gemeinschaft
Name
1520, congruent
KMg(PO3)3∙2/5
(modelled by FZJ)
stoichiometric
stoichiometric
K3P-T2-T3 solid solutions for HT, MT, LT modifications
(K2O)2(P2O5)2(K2O, MgO, K2MgO2)
K3PO4-K4Mg(PO4)2-K6MgP2O9
15 December 2015
GTT Annual Workshop, Juli 1-3, 2015
14
The system K2O-MgO-P2O5
Sections MgO-K3PO4 and K3PO4-KMgPO4
K2O - MgO - P2O5
0.6
K6MgP2O9
K3PO4
0.4
rac
tio
n
0.3
0.7
0.2
0.8
0.1
0.9
K2O
0.5
ma
0.6
0.4
0.5
ss
f
K4P2O7
K4Mg(PO4)2
KMgPO4
K2MgP4O12
KMgP3O9
KMg4(PO4)3
0.9
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.9
0.1
0.2
K4Mg4P6O21
0.8
MgO
KPO3
0.7
0.3
K2MgP2O7
0.1
Mg3(PO4)2 Mg2P2O7 Mg(PO3)2
P2O5
K3PO4 - MgO
K3PO4 - KMgPO4
1 atm
1 atm
3000
1800
1600
Slag
2500
Slag
1200
K3P_HT
1000
K3P_HT
MgO
1000
T3=K6MgP2O9
K3P_HT + MgO(s)
K3P_MT + MgO(s)
500
K3P_LT + MgO(s)
800
R=KMgPO4
T(C)
1500
600
K3P_MT
400
KMgPO4(s) + K3P_LT
K3P_LT
200
0
0
0
0.2
0.4
0.6
0.8
1
0
K 3PO4/(K 3PO4+MgO) (g/g)
15 December 2015
GTT Annual Workshop, Juli 1-3, 2015
K3P_MT
KMgPO4(s) + K4MgP2O8(s2)
0.2
0.4
K3PO4
Slag + K3P_HT + KMgPO4(s)
T2=K4MgP2O8
K3PO4
Slag + MgO(s)
T(C)
Mitglied der Helmholtz-Gemeinschaft
2000
1400
K3P_LT
0.6
0.8
1
K 3PO4/(K 3PO4+KMgPO4) (g/g)
15
The system K2O-MgO-P2O5
Preliminary isothermal section at 25°C
K2O - P2O5 - MgO
o
25 C, 1 atm
J. Berak and T. Podhajska-Kazmierczak, Pol. J.
Chem., 65 [7-8] 1137-1149 (1991).
0. 3
0. 7
0. 2
0. 8
0. 1
0. 9
K2O
K3P
0. 6
0. 4
T3
K2P
0. 5
0. 3
R
W
0. 8
0. 1
J
0.9
0.8
0.7
GTT Annual Workshop, Juli 1-3, 2015
0.6
M 3P
0.5
mass fraction
B1
0.4
M 2P
0.3
MP
0.2
0. 9
MgO
15 December 2015
B2
0. 2
The solid solubilities based on K3PO4K4Mg(PO4)2-K6MgP2O9 are included into
the database.
KP
T1
0. 7
Mitglied der Helmholtz-Gemeinschaft
0. 6
0. 4
0. 5
T2
0.1
P2O5
16
The system K2O-MgO-P2O5
Sections K4P2O7-KMgPO4 and K4P2O7-K4MgP2O8
K2O - MgO - P2O5
0.6
K6MgP2O9
K3PO4
0.4
rac
tio
n
0.3
0.7
0.2
0.8
0.1
0.9
K2O
0.5
ma
0.6
0.4
0.5
ss
f
K4P2O7
K4Mg(PO4)2
KMgPO4
KMgP3O9
KMg4(PO4)3
0.9
0.8
0.7
0.6
0.5
K2MgP4O12
0.4
0.3
0.2
0.1
Mg3(PO4)2 Mg2P2O7 Mg(PO3)2
0.9
0.1
0.2
K4Mg4P6O21
0.8
MgO
KPO3
0.7
0.3
K2MgP2O7
P2O5
K4P2O7 - K4MgP2O8
K4P2O7 - KMgPO4
1 atm
1600
1800
1400
1600
Slag
1400
1200
1200
Slag + KMgPO4(s)
400
K4MgP2O8(s) + K4P2O7(s)
800
600
400
200
KMgPO4(s) + K4P2O7(s3)
200
0
0
0.2
0.4
0.6
0.8
1
K2P=K4P2O7
600
K2P=K4P2O7
K4MgP2O8(s2) + K4P2O7(s3)
R=KMgPO4
T(C)
1000
800
T2=K4MgP2O8
T(C)
1000
Mitglied der Helmholtz-Gemeinschaft
Slag
Slag + K3P_HT
KMgPO4(s) + K4P2O7(s)
0
0
K 4P2O7/(K 4P2O7+K 4MgP2O8) (g/g)
15 December 2015
GTT Annual Workshop, Juli 1-3, 2015
0.2
0.4
0.6
K 4P2O7/(K 4P2O7+KMgPO4) (g/g)
0.8
17
1
The system K2O-MgO-P2O5
Pseudo-binary section MgP2O6-KPO3
K2O - MgO - P2O5
0.6
K6MgP2O9
K3PO4
0.4
rac
tio
n
0.3
0.7
0.2
0.8
0.1
0.9
K2O
0.5
0.6
0.4
0.5
ma
ss
f
K4P2O7
K4Mg(PO4)2
KMgPO4
KMg4(PO4)3
0.9
0.8
0.7
0.6
0.5
K2MgP4O12
KMgP3O9
0.4
0.3
0.2
0.9
0.1
0.2
K4Mg4P6O21
0.8
MgO
KPO3
0.7
0.3
K2MgP2O7
0.1
Mg3(PO4)2 Mg2P2O7 Mg(PO3)2
P2O5
KPO3 - MgP2O6
1 atm
FactSage
1400
1200
1000
Slag
800
400
200
P2MgO6(s) + KMgP3O9(s)
K2MgP4O12(s) + KPO3(s3)
K2MgP4O12(s) + KPO3(s2)
KP=KPO3
MP=MgP2O6
600
B2=K2MgP4O12
B1=KMgP3O9
Mitglied der Helmholtz-Gemeinschaft
T(C)
Slag + P2MgO6(s)
K2MgP4O12(s) + KPO3(s)
0
0
15 December 2015
0.2
0.4
0.6
KPO3/(KPO3+MgP2O6) (g/g)
GTT Annual Workshop, Juli 1-3, 2015
0.8
1
18
The system K2O-MgO-P2O5
Mitglied der Helmholtz-Gemeinschaft
Liquidus surface
J. Berak and T. Podhajska-Kazmierczak,
Pol. J. Chem., 65 [7-8] 1137-1149, 11511163, 1165-1172, 1173-1184 (1991)
15 December 2015
GTT Annual Workshop, Juli 1-3, 2015
19
The system Na2O-CaO-P2O5
Description of the system
The species with compositions R and T2 in the non-ideal associate solution were added in order to
describe the liquid phase
Melting, °C
Description
Name
Composition
Liquid species
R
NaCaPO4
1830, congruent
T1
Na2CaP2O7
814, incongruent
T2
Na4Ca(PO4)2
1750, congruent
T3
Na6CaP2O9
1800, congruent
N3P-T3 solution
B3
Na4Ca(PO3)6
733, congruent
stoichiometric
NaCaPO4∙2/3
(modelled by GTT)
Stoichiometric
Stoichiometric
Na4Mg(PO4)2∙2/7
Stoichiometric
Mitglied der Helmholtz-Gemeinschaft
N3P-T3 solid solutions for HT, LT modifications
(Na2O)2(P2O5)2(Na2O, Na2CaO2)
Na3PO4-Na6CaP2O9
15 December 2015
GTT Annual Workshop, Juli 1-3, 2015
20
The system Na2O-CaO-P2O5
Solubility between Na3PO4 and Na6CaP2O9
Na3PO4 - CaO
3000
2500
Slag
Slag + CaO(s)
T(C)
2000
Mitglied der Helmholtz-Gemeinschaft
1500
1000
N3P_HT
CaO(s) + N3P_HT
500
N3P_LT
CaO(s) + N3P_LT
0
0
0.2
0.4
0.6
0.8
1
Na3PO4/(Na3PO4+CaO) (g/g)
15 December 2015
GTT Annual Workshop, Juli 1-3, 2015
J. Berak and T. Znamierowska, Rocz.
Chem., 46 [10] 1697-1708 (1972).
21
The system Na2O-CaO-P2O5
Section NaCaPO4-Na4CaP2O8
NaCaPO4 - Na4CaP2O8
2000
1800
Slag
Slag + NaCaPO4(s)
1600 Slag + Na4CaP2O8(s)
1400
T2-Na4CaP2O8
1000
800
Mitglied der Helmholtz-Gemeinschaft
600
400
R- NaCaPO4
T(C)
1200
Na4CaP2O8(s) + NaCaPO4(s)
200
J. Berak and T. Znamierowska, Rocz.
Chem., 46 [11] 1921-1929 (1972).
Na5P3O10(s) + CaO(s) + NaCaPO4(s)
Na5P3O10+ CaO+ Na4CaP2O8
Na5P3O10(s) + CaO(s) + Ca4(PO4)2O(s)
0
0
0.2
0.4
0.6
0.8
1
NaCaPO4/(NaCaPO4+Na4CaP2O8) (g/g)
15 December 2015
GTT Annual Workshop, Juli 1-3, 2015
22
The system Na2O-CaO-P2O5
Liquidus surface
Mitglied der Helmholtz-Gemeinschaft
J. Berak, T. Znamierowska, Rocz.
Chem. Ann. Soc. Chim. Polonorum,
46(1972), 1697-1708.
15 December 2015
GTT Annual Workshop, Juli 1-3, 2015
23
The system Na2O-MgO-P2O5
Description of the system
The species with compositions F1 and T2 in the non-ideal associate solution were added in order to
describe the liquid phase
Melting, °C
Description
Composition
R
NaMgPO4
960, incongruent
T2
Na4Mg(PO4)2
1655, congruent
T3
Na6MgP2O9
1665, congruent
N3P-T2-T3 solution
B1
NaMg(PO3)3
942, incongruent
stoichiometric
B2
Na2Mg(PO3)4
916, congruent
stoichiometric
B3
Na4Mg(PO3)6
784, incongruent
stoichiometric
F1
Na8Mg6(P2O7)5
D1
Na3Mg2P5O16
Mitglied der Helmholtz-Gemeinschaft
Name
808, congruent
Liquid species
(modelled by FZJ)
stoichiometric
Na4Mg(PO4)2∙2/7
N3P-T2-T3 solution
Na8Mg6(P2O7)5∙1/12 stoichiometric
675, incongruent
stoichiometric
N3P-T2-T3 solid solutions for HT, LT modifications
(Na2O)2(P2O5)2(Na2O, MgO, Na2MgO2)
Na3PO4-Na4Mg(PO4)2-Na6MgP2O9
15 December 2015
GTT Annual Workshop, Juli 1-3, 2015
24
The system Na2O-MgO-P2O5
Sections Na3PO4-Mg3P2O8 and Na3PO4-MgO
Na2O - P2O5 - MgO
Na2O
sections, Podhajska [1998-2005]
0.2
0.8
2000
0.1
0.9
Na3PO4 - Mg3P2O8
N3P
1800
0.3
0.7
Slag
Slag
N2P
1600
0.6
T3=Na6MgP2O9
0.4
Slag
N5P3
Slag + N3P_HT
NP
0.4
cti o
n
T2=Na4Mg(PO4)2
200
N3P_HT + NaMgPO4(s)
D1=Na3Mg2P5O16
0.3
mo
le
0.2
T2=Na4MgP 2O8
400
N3P_HT
B2=Na2Mg(PO3)4
B1=NaMg(PO3)3
0.1
R=NaMgPO4
600
B3=Na4Mg(PO3)6
F1=Na8Mg6(P2O7)5
R=NaMgPO4
0.9
M3P=Mg3P2O8
800
J=NaMg 4Mg(PO4)3
Slag + NaMg4P3O12(s)
0.8
KP-K3PO4
1000
0.7
T(C)
f ra
Slag + N3P_HT
0.6
1200
0.5
0.5
1400
J=NaMg4(PO4)3
MgO
0.9
0.8
0.7
M3P
M2P
0.6
0.5
0.4
0.3
0.2
P2O5
0.1
MP
N3P_LT
NaMg4P3O12(s) + NaMgPO4(s)
0
0
0.2
0.4
0.6
0.8
1
Na3PO4/(Na3PO4+Mg3P2O8) (g/g)
T.Podhajska-Kazmierczak, T.Znamierowska, Pol. J. Chem., 73 [2] 279-286
(1999).
Na3PO4 - MgO
3000
2700
2400
Slag
2100
Slag + MgO(s)
T(C)
1800
1500
T3=Na6MgP 2O9
Mitglied der Helmholtz-Gemeinschaft
MgO(s) + N3P_HT
900
600
Na3PO4
N3P_HT
1200
300
MgO(s) + N3P_LT
N3P_LT
0
0
0.2
0.4
0.6
0.8
Na3PO4/(Na3PO4+MgO) (g/g)
T. Podhajska-Kazmierczak, Pol. J. Chem., 77 [3] 295-301 (2003).
15 December 2015
GTT Annual Workshop, Juli 1-3, 2015
25
1
The system Na2O-MgO-P2O5
Sections NaPO3-Na8Mg6P10O35 and NaPO3-MgP2O6
Na2O - P2O5 - MgO
Na2O
0.2
0.8
sections, Podhajska [1998-2005]
0.1
1000
0.9
NaPO3 - Na8Mg6P10O35
N3P
0.3
0.7
800
Slag
N2P
0.4
T3=Na6MgP2O9
0.6
Slag + Na8Mg6P10O35(s2)
N5P3
600
0.5
0.5
Slag + Na8Mg6P10O35(s)
0.4
cti o
n
0.3
B3=Na4Mg(PO3)6
F1=Na8Mg6(P2O7)5
R=NaMgPO4
0.2
D1=Na3Mg2P5O16
B2=Na2Mg(PO3)4
0.8
NaPO3
mo
le
f ra
F1=Na8Mg 6P10O35
0.9
B1=NaMg(PO3)3
0.1
Na8Mg6P10O35(s) + NaPO3(s)
0.7
400
NP
T2=Na4Mg(PO4)2
0.6
T(C)
Slag + NaPO3(s2)
Na8Mg6P10O35(s) + NaPO3(s2)
J=NaMg4(PO4)3
200
NaPO3(s) + Na5P3O10(s) + Na3Mg2P5O16(s)
MgO
Na5P3O10(s) + Na3Mg2P5O16(s) + Na8Mg6P10O35(s)
0.9
0.8
0.7
M3P
0.6
M2P
0.5
0.4
0.3
0.2
0.1
MP
P2O5
0
0
0.2
0.4
0.6
0.8
1
NaPO3/(NaPO3+Na8Mg6P10O35) (g/g)
T. Podhajska-Kazmierczak and T. Znamierowska, J. Therm. Anal., 45 [6]
1541-1546 (1995)
MgP2O6 - NaPO3
1400
Slag
1200
T(C)
1000
800
Mg(PO3)2
B1=NaMg(PO3)3
200
NaPO3
400
B2=Na2Mg(PO3)4
B3=Na4Mg(PO3)6
Mitglied der Helmholtz-Gemeinschaft
600
0
0
0.2
0.4
0.6
0.8
MgP2O6/(MgP2O6+NaPO3) (g/g)
T. Podhajska-Kazmierczak and T. Znamierowska, Pol. J. Chem., 65 [7-8]
1121-1125 (1991).
15 December 2015
GTT Annual Workshop, Juli 1-3, 2015
26
1
The system Na2O-MgO-P2O5
Isothermal section and liqiudus surface
Na2O - P2O5 - MgO
o
300 C
0. 4
0. 6
0. 3
0. 7
0. 2
0. 8
0. 1
0. 9
Na2O
N3P
0. 5
0. 5
T3
n
N3P_LT
N2P
N5P3
NP
0. 7
0. 3
we
i gh
t fr
0. 6
0. 4
ac
tio
T2
B3
D1
F1
0. 8
0. 2
R=NaMgPO4
0.9
0.8
0.7
0.6
0.5
M3P
B1
0.4
M2P
0.3
MP
0.2
0.1
P2O5
Mitglied der Helmholtz-Gemeinschaft
MgO
0. 9
0. 1
B2
J
15 December 2015
GTT Annual Workshop, Juli 1-3, 2015
27
Conclusions
 All ternary compounds in the ternary systems Alk2O-MeO-P2O5 (Alk=Na, K;
Me=Ca, Mg) have been included into the oxide database. The preliminary
thermodynamic dataset including solubilities between Alk3PO4-Alk4Me(PO4)2Alk6MeP2O9 allows the description the phase equilibria in the different
sections
 The corresponding ternary species have been included into the slag of the
system Na2O-K2O-CaO-MgO-P2O5. The liquid phase in all subsystems was
evaluated using non-ideal associate species model (two cations per species).
 All systems were assessed using experimental phase diagram information.
Mitglied der Helmholtz-Gemeinschaft
 The quasi-binary sections and liquidus surfaces in the systems Alk2O-MeOP2O5 have been calculated using the corresponding data
Outlook
 Thermodynamic assessment of further P2O5-containing systems
 Extension of the database by addition of further oxides
15 December 2015
GTT Annual Workshop, Juli 1-3, 2015
28
Mitglied der Helmholtz-Gemeinschaft
On behalf of all co-authors:
Thank you for your attention!
Vielen Dank für Ihre Aufmerksamkeit!
Благодарю за внимание!
15 December 2015
GTT Annual Workshop, Juli 1-3, 2015
29