SULPHIDATION OF METALS AND ALLOYShome.agh.edu.pl/~grzesik/FHTC/09_Sulphidation of metals and alloys_RG.pdf · „Basic Concepts, High Temperature Corrosion, tom I” w „Shreir’s

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