SULPHIDATION OF METALS AND ALLOYShome.agh.edu.pl/~grzesik/FHTC/09_Sulphidation of metals and...
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SULPHIDATION OF
METALS AND ALLOYS
Z. Grzesik and K. Przybylski, „Sulfidation of metallic materials” w „Developments in
high temperature corrosion and protection of materials”, Eds. Wei Gao and Zhengwei
Li, Woodhead Publishing Limited, Cambridge England, 2008, str. 599-638.
R. Cottis, M. Graham, R. Lindsay, S. Lyon, J. Richardson, J. Scantlebury, F. Stott,
„Basic Concepts, High Temperature Corrosion, tom I” w „Shreir’s Corrosion”, Elsevier,
Amsterdam, 2010.
Properties of select metal oxides and sulfides
Sulfide ∆G K1273
0
[kJ/mol S]
pS2
[Pa] Oxide
∆G K12730
[kJ/mol O]
pO2
[Pa]
Al2S3 -191 2.4⋅10-11 Al2O3 -424 1.8⋅10-30
CoS -43.8 26 CoO -145 1.2⋅10-7
Cu2S -95.7 1.4⋅10-3 Cu2O -77.7 4.3⋅10-2
CuS 63.6 1.6⋅1010 CuO -11.6 1.1⋅104
FeS -78.9 2.9⋅10-2 FeO -179 2.3⋅10-10
MnS -196.9 7.3⋅10-12 MnO -292 1.2⋅10-19
MoS2 -78.3 3.8⋅10-2 MoO2 -182 1.3⋅10-10
NiS -50.4 7.5 NiO -127 3.8⋅10-6
TiS -228 2.1⋅10-14 TiO -420 3.9⋅10-30
Properties of select metal oxides and sulfides
Sulfide Melting point
[K]
Oxide Melting point
[K]
Al2S3 1373 Al2O3 2288
CoS 1389 CoO 2068
Co3S4 ? Co3O4 1223
Cr2S3 1623 Cr2O3 2539
Cu2S 1373 Cu2O 1508
CuS 376 CuO 1599
FeS 1472 FeO 1642
MnS 1598 MnO 2058
MoS2 1458 MoO2 2200
NiS 1083 NiO 2230
TiS 2373 TiO 2023
TiS2 ? TiO2 2123
La2S3 2423 La2O3 2490
Ce2S3 2373 Ce2O3 1965
ThS2 2198 ThO2 3593
Sulfide Melting point
[K]
Oxide Melting point
[K]
Al S 1373 Al O 2288US2 1373 UO2 3151
Y2S3 1873 Y2O3 2683
InS 965 InO 1325
In2S3 1323 In2O3 2273
Properties of select metal oxides and sulfidesMetal Sulfides Oxides
Co Co4S3 CoO
Co9S8 Co3O4
CoS
Co3S4
CoS2
Cr CrS Cr2O3
Cr7S8
Cr5S6
Cr3S4
Cr2S3
Ni Ni3S2 NiO
Ni7S6
NiS
Ni3S4
NiS2
Maximum deviation from stoichiometry in select metal oxides and sulfides
Sulfide y Oxide y
Co1-yS 0.16 Co1-yO 0.009
Cr2+yS3 0.18 Cr2-yO3 0.00009
Cu2-yS 0.17 Cu2-yO 0.004
Fe1-yS 0.24 Fe1-yO 0.12
Mn1-yS 0.002 Mn1-yO 0.016
Ni1-yS 0.17 Ni1-yO 0.0006
Deviation from stoichiometry in select metal oxides and sulfides
6 7 8 9 10 11 12
10-4
10-3
10-2
10-110-5 Pa 10-7 Pa
10-9 Pa
Fe1-yO
0.1 Pa0.01 Pa
Mn1-yO
Cu2-yO
Co1-yO
Ni1-yO
MoS2+y
Mn1-yS
Fe1-yS
Co1-yS
Cr2+yS3 Ni1-yS
Cu2-yS
OxidesSulfides
T / K
.
y
T -1 104 / K-1
1473 1273 1073 873
Chemical diffusionin select metal oxides and sulfides
6 8 10 1210-8
10-7
10-6
10-5
10-4
OxidesSulfides
MoS2
.
~
MnOCoO
Fe3O4
Nb2O5 NiONi3S2
FeO
CoS
Cr2S3
FeS
NiSMnS
D
/ cm
2 s-1
T -1 10 4 / K-1
1673 1273 873
T / K
Chemical diffusionin select metal oxides and sulfides
6 8 10 1210-10
10-9
10-8
10-7
10-6
10-5
10-4
SulfidesOxides
.
MoS2
~
NbS2
MnO
CoO
Fe3O4
Nb2O5 NiONi3S2
FeO
CoSFeS
Cr2S3
FeSNiSMnS
D
/ cm
2 s-1
T-1 104 / K-1
T / K87312731673
Temperature dependence of self-diffusion coefficientsfor several metal sulfides and oxides
5 10 1510-16
10-14
10-12
10-10
10-8
10-6Fe1-yO
Cu2-yOMn1-yO
Co1-yO
Cr2+yO3
Ni1-yO
Oxides
Nb1+yS2
MoS2+y
Mn1-yS
Cr2+yS3
Ni1-yS
Co1-yS
Fe1-yS
Sulfides
DM
e /
cm
2 s-1
T -1 104 / K-1
1873 1473 1073 673
.
T / K
Comparison between metal sulphidation and oxidation rates
6 8 10 12 1410-12
10-10
10-8
10-6
10-4
0.1 kPa
100 kPa
10 kPa
1 kPa
10 kPa
1 kPa
21 kPa 1 kPa
100 kPa
67 kPa
OxidationSulfidation
Ni
Nb
Cr
Mo
Co
CrFe Co
Ni
Fe
.
k p /
g2 cm
-4s-1
T -1 104 / K-1
1473 1273 1073 873T / K
Cr influence on the sulphidation and oxidation rate of several metals
0 20 40 60 80 10010-8
10-7
10-6
10-5
10-4
T = 1073 KpS2 = 100 kPa
Co-Cr Fe-Cr Ni-Cr
Cr content, % at.
k p , g2 cm
-4s-1
Cr influence on the sulphidation and oxidation rate of several metals
4 20 40 60 80 100
-5
-4
-310
10
single phase scale(Cr2+yS 3 doped with Me)heterogenous double
layer scale
Me(Co, Ni, Fe) Cr
singlephasescale
(Me1-ySdoped
with Cr)
k p , g2 cm
-4s-1
Cr , at. %
10
range I range IIIrange II
FORMATION OF A THREE-LAYER SULFIDE SCALEACCORDING TO THE DISSOCIATION MECHANISM
Chromium influence on the iron sulphidation and oxidation rate
0 20 40 60 80 10010-13
10-11
10-9
10-7
10-5
at. % Cr
k p , g2 cm
-4s-1 Sulfidation
Fe-CrT = 1173K
Oxidation
Aluminum influence on the iron sulphidation and oxidation rate
Aluminum and chromium influence on the iron sulphidation and oxidation rate
10-7 10-4 10-1 102 10510-13
10-11
10-9
10-7
10-5
Fe/FeS Fe
Fe-25Cr-10Al
Smeltzer et al. (1982) Smeltzer et al. (1979) Mrowec et al. (1980) Meussner and Birchenall (1957) Narita and Nishida (1973)
T = 1073 K
pS2 , Pa
k p , g2 cm
-4s-1
Comparison between sulphidation and oxidation rates of several alloys
6 8 10 12 1410-15
10-13
10-11
10-9
10-7
10-5 SulfidationOxidation
104 / T , K-1
k p , g2 cm
-4s-1
1573 1373 1173 973 773
Co-40Cr
Co-10Cr
Ni-30Cr
Fe-20Cr
Co-35Cr
β-NiAl
Ni-10Cr-5Al
Fe-5Cr-4Al
Ni-4CrNi-12Cr
Co-20CrFe-18Cr
Fe-19Cr-2Al
Co-25Cr-3AlCo-25Cr-12Al
Fe-18Cr-20Al
β-NiAl
T , K
Mo and Nb influence on the nickel oxidation rate
0 10 20 30 40 5010-11
10-9
10-7
10-5
Mo
Nb
Ni - MoNi - Nb
T = 873K
k p, g2 cm
-4s-1
wt.% Mo or Nb
Al and Mo influence on the nickel oxidation rate
0 5 10 1510-14
10-12
10-10
10-8
10-6
pureMowt.% Al
k p , g2 cm
-4s-1
Ni-30Mo-xAl
1073 K
973 K
873 K
Comparison between sulphidation rates of several Ni alloys with Mo and Al
6 8 10 1210-13
10-11
10-9
10-7
10-5
104 / T , K-1
k p , g2 cm
-4s-1
1473 1273 1073 873
Ni
Ni-30MoNi-30Mo-3.8Al
Ni-30Mo-7.5Al
Ni-30Mo-15Al
Mo
T , K
Al and Mo influence on the iron oxidation rate
0 2 4 6 8 1010-13
10-11
10-9
10-7
pureMowt.% Al
k p , g2 cm
-4s-1
Fe-30Mo-xAl
1173 K1073 K973 K
Comparison between sulphidation rates of several Fe alloys with Mo and Al
7 8 9 10 1110-13
10-11
10-9
10-7
10-5
104/T , K-1
k p , g2 cm
-4s-1
1373 1273 1173 1073 973
Fe
Fe-30Mo
Fe-30Mo-1Al
Fe-30Mo-3Al
Fe-30Mo-5Al
Mo
T , K
Sulphidation rates of several Ni and Fe alloys with Mo and Al
6 8 10 12 1410-15
10-13
10-11
10-9
10-7
10-5 SulfidationOxidation
104 / T , K-1
k p , g2 cm
-4s-1
1573 1373 1173 973 773
Fe-30Mo-5AlCo-40Cr
Co-10Cr
Ni-30Cr
Fe-20Cr
Co-35Crβ-NiAl
Ni-10Cr-5Al Fe-5Cr-4Al
Ni-4CrNi-12Cr
Co-20CrFe-18Cr
Fe-19Cr-2Al
Co-25Cr-3AlCo-25Cr-12Al
Fe-18Cr-20Al
β-NiAl
Ni-40Mo
Ni-30Mo-7AlMo
T , K
Suphidation rates of high-melting metal alloys with aluminum
7 8 9 10 1110-14
10-13
10-12
10-11
10-10
10-9
Al-80Ta
Al-50Nb
Al-(34-46)Mo
pS2 = 103 Pak p ,
g2 cm-4s-1
104 / T , K-1
1373 1273 1173 1073 973
T , K
Sulphidation rates of molybdenum alloys with aluminum
7 8 9 10 1110-14
10-13
10-12
10-11
10-10
10-9
Al-34Mo Al-39Mo Al-46Mo
10-1 Pa(H2/H2S) Fe-30Mo-9Al
E = 168 kJ/mol
MoE = 166 kJ/mol
Al-MoE = 226 kJ/mol
Sulfidation
k p , g2 cm
-4s-1
104 / T, K-1
1373 1273 1173 1073 973
T, K
Sulphidation rates of molybdenum alloys with aluminum
100 101 102 103 104 10510-13
10-12
10-11
10-10
10-9
kp ~ pS2
1/4
kp ~ pS2
1/2
Mo
Al-34Mo
SulfidationT = 1173 K
k p , g2 cm
-4s-1
pS2 , Pa
Temperature dependence of the Mo-Cr alloy sulphidation rate on the background of the same dependence obtained for Mo
8 9
10-11
10-10SiarkowaniepS2
= 103 Pa
MoMo-25%CrMo-35%CrMo-53%Cr
.
k p /
g2 cm-4
s-1
T-1 104 / K-1
1273 1173 1073T / K
Pressure dependence of the parabolic rate constant for Mosulphidation in pure and Li2S-containing sulfur vapours
10-2 10-1 100 101 102 103 10410-1310-1210-1110-1010-910-810-710-610-510-410-3
1273 K1173 K1073 K
S2 - Li2S S2
Siarkowanie Mo
1/n = 1/2
k p /
g2 cm-4
s-1
pS2 / Pa
Temperature dependence of the parabolic rate constant for sulphidation of Mn-5%Cr alloy
8 9 10
10-9
10-8
10-7
104 / T , K-1
pS2 = 4 Pa
Mn-5%CrEa = 85 kJ/mol
MnEa = 127 kJ/mol
k p , g2 cm
-4s-1
1273 1173 1073 973
T , K
Pressure dependence of the parabolic rate constant for sulphidation of Mn-5%Cr alloy
10-1 100 101 102 103 10410-9
10-8
10-7
T = 1073 K
T = 1273 K
Mn-5%Cr
Mn-5%Cr
Mn
Mn
k p , g2 cm
-4s-1
pS2 , Pa
Pressure dependence of kp for pure and Li-doped Mn
100 101 102 103 10410-11
10-10
10-9
10-8
10-7
Mn - Li
1/2kp ~ pS2
1/6kp ~ pS2
Mn
T = 1173 K
k p , g2 cm
-4s-1
pS2 , Pa
Temperature dependence of kp for pure and Li-doped Mn
7,5 8,0 8,5 9,0 9,510-12
10-11
10-10
10-9
10-8
10-7
Sulfidation pS2 = 1 Pa
Mn - LiE'A = 205 kJ/mol
MnEA = 127 kJ/mol
k p , g2 cm
-4s-1
104 / T , K-1
1000 900 800T , oC
Temperature dependence of kp for pure and Li-doped Mn
6 8 10 12 1410-14
10-12
10-10
10-8
10-6
10-4
Mn, Mn-Li Grzesik, 2003
1 PaMn-Li
1 PaMn
Mo
Cr
Nb
Cr
NiCo
CoNi
Fe
Fe
Lillerud, Kofstad, 1980Mrowec, Grzesik, 2003Mrowec, Grzesik, 2004Footner et al., 1967
Przybylski, Potoczek, 1993Danielewski, 1988
Mrowec et al., 1987Mrowec et al., 1998Mrowec et al., 1962
Mrowec et al., 1980
0.1 kPa
100 kPa
10 kPa
1 kPa
10 kPa
1 kPa21 kPa
1 kPa
100 kPa
67 kPa
Oxidation
Sulfidation
Ni
Nb
Cr
Mo
Co
CrFe
Co
Ni
Fe
k p , g2 cm
-4s-1
104/ T , K-1
1200 1000 800 600
T , oC
THE END