phase diagrams with factsage - university of...
TRANSCRIPT
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GTT-Technologies Annual Workshop and User‘s Meeting
Herzogenrath-Kohlscheid (Aachen, Germany)
5th July, 2013
Phase Diagrams with FACTSage Speaking different Languages for Thermochemical Properties
Michael Auinger
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Outlook
– Motivation
– Thermochemical Properties in Oxides
– Ellingham-Richardson Diagrams
– Stability Diagrams
– Thermochemistry of Oxides and Nitrides
– Nitrides in the System Iron - Chromium - Carbon
– Nitrogen and Oxygen in Iron - Silicon
– Summary
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Oxidation Processes in Steels
scale (mainly ‘FeO’)
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Grain Boundary Oxidation
Singheiser et.al., Materials & Corrosion 62 (2011) 504
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The Problem
pictures from various internet sources and FACTSage
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The Problem
pictures from various internet sources and FACTSage
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Lost in Translation?
أنا أحب الديناميكا „ “الحرارية
„Μου αρέσει
θερμοδυναμική “
„我喜歡熱力學 “
„나는 열역학을
좋아 “
„Мне нравится
термодинамики “ „আমি তাপগমতমিদ্যা পছন্দ “
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An Effective Solution
أنا أحب الديناميكا „ “الحرارية
„Μου αρέσει
θερμοδυναμική “
„我喜歡熱力學 “
„나는 열역학을
좋아 “
„Мне нравится
термодинамики “ „আমি তাপগমতমিদ্যা পছন্দ “
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An Effective Solution
„I like thermo-
dynamics“ أنا أحب الديناميكا „
“الحرارية
„Μου αρέσει
θερμοδυναμική “
„我喜歡熱力學 “
„나는 열역학을
좋아 “
„Мне нравится
термодинамики “ „আমি তাপগমতমিদ্যা পছন্দ “
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Part I
Thermochemical Properties
of Oxides
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Ellingham Diagram
Oregon State University at www.oregonstate.edu (dl 02.07.2013)
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Ellingham Diagram with FACTSage
2 Fe + O2 2 FeO
Tp
pRGGG
o
OOo
T
Feo
T
FeOo
T
22 ln22
,
)(
,
)(
,
)(
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Ellingham Diagram with FACTSage
2 Fe + O2 2 FeO
Tp
pRGGG
o
OOo
T
Feo
T
FeOo
T
22 ln22
,
)(
,
)(
,
)(
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Ellingham Diagram with FACTSage
2 Fe + O2 2 FeO
Tp
pRGGG
o
OOo
T
Feo
T
FeOo
T
22 ln22
,
)(
,
)(
,
)(
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Ellingham Diagrams for Oxide Formation
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Ellingham Diagrams for Oxide Formation
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Ellingham Diagrams for Oxide Formation
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Ellingham Diagram with FACTSage
2 Fe + O2 2 FeO
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Stability Diagrams with FACTSage
2 Fe + O2 2 FeO
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Stability Diagrams with FACTSage
2 Fe + O2 2 FeO
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Comparison
Tp
pRGGG
o
OOo
T
Feo
T
FeOo
T
22 ln22
,
)(
,
)(
,
)(
o
O
Oo
T
Feo
T
FeOo
T
p
p
RT
GGG2
2
ln22
,
)(
,
)(
,
)(
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Properties of Oxygen
Oxide Stability
0 250 500 750 1000 1250 1500 1750 20001250
1000
750
500
250
0
3/2 Fe + O2 = 1/2 Fe3
O4 2 Fe + O2 = 2 FeO
4/3 Cr + O2 = 2/3 Cr
2O3
2 Mn + O2 = 2 MnO
Si + O2 = SiO 2
Sta
ndard
fre
e e
nerg
y o
f fo
rmati
on o
f oxid
es
(-
Go =
-R
T l
n(p
O2
) /
kJ
mol-1
Temperature / °C
4/3 Al + O 2 = 2/3 Al
2O 3
0 K
O2
-25
-20
-15
-10
-5
0
Oxygen p
art
ial
pre
ssure
log(p
O2
)
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Iron – Manganese – Chromium alloy
Figure: Spatial phase distribution in an Fe, 2 wt-% Mn, 0.8 wt-% Cr alloy after
oxidation at p(O2)= 3·10-22 bar and 700 °C for 120 min and ternary phase diagram.
published in Mater. Sci. Forum 969 (2011) p.76
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Part II
Gaseous Nitriding in the system
Fe – Cr – C
Nitriding of Fe, 1 wt-% Cr, 0.10 wt-% C and
Conditions: 48 h at 500 °C
p(NH3) : p(H2) = 100 (KN = 1 000)
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Gaseous Nitriding Process
g´-Phase (Fe4N)
e-Phase (Fe2N)
Diffusion Zone
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Theoretical Principles
Figure: Lehrer-Diagram of iron nitrides according to literature (left) and calculated
with the programme FactSage (right).
450 500 550 600 650 7000.01
0.1
1
10
-4
-3
-2
-1
0
1
2
g-Iron (fcc)
-Iron (bcc)
g'-Phase (Fe4N)
KN
= p
NH
3
/p1.
5
H2
temperature / °C
e-Phase (Fe2N)
log
10(p
2 NH
3
/p3 H
2
)
http://www.ipsenusa.com (dl 12.10.2010)
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Iron – Chromium – Carbon alloy
published in HTM J. Heat Treatm. Mat. 66 (2011) p.100
Figure: Spatial phase distribution in an Fe, 1 wt-% Cr, 0.1 wt-% C alloy after gas
nitriding at KN= 2.4 and 500 °C for 48 h and phase stability diagram.
-10
-5
0
5
0.00 0.25 0.50 0.75 1.0010
-9
10-7
10-5
10-3
10-1
101
CrN
Cr2N
Cr 3
C2
Cr 7
C3
K
N =
p0
.5
o p
NH
3
/p1
.5
H2
xCr
/ (xCr
+xC)
Cr 2
3C
6
Fe + C + Cr3C
2
Fe + Cr
+Cr23
C6
Fe + C + CrN
Fe4N + CrN + C
Fe2N + CrN + C
log
10(p
N2
) /
bar
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Binary Phase Diagrams
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Binary Phase Diagrams
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The System Iron – Nitrogen
Figure: Nitrogen Solubility in Iron at 1 bar (left) and binary Iron-Nitrogen phase
diagram, calculated with FACTSage (right).
H. Zitter, L. Habel Arch. Eisenhüttenwes. 44 (1973) 181.
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The System Iron – Nitrogen
Figure: Nitrogen Solubility in Iron at 1 bar (left) and binary Iron-Nitrogen phase
diagram, calculated with FACTSage (right).
H. Zitter, L. Habel Arch. Eisenhüttenwes. 44 (1973) 181.
p1
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The System Iron – Nitrogen
Figure: Nitrogen Solubility in Iron at 1 bar (left) and binary Iron-Nitrogen phase
diagram, calculated with FACTSage (right).
H. Zitter, L. Habel Arch. Eisenhüttenwes. 44 (1973) 181.
p1 p2
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Part III
Gaseous Nitriding and Oxidation in the system Fe – Si
Nitriding of Fe, 1 wt-% Si
Conditions: 20 h at 550 °C (KN = 1 000)
4 h at 550 °C (KO ≈ 0.01)
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Stability Diagram of Iron – Silicon
Figure: Stability diagram of an Fe, 1 wt-% Si alloy at 550 °C with respect to the
partial pressures of nitrogen and oxygen (SGTE Pure Substance Database).
10-9
10-7
10-5
10-3
10-1
101
10-10
10-5
100
105
1010
-10 -5 0 5
-45
-40
-35
-30
-25
-20
-15
-10
Fe
2N
Fe3O
4 + SiO
2
Fe3O
4 + Fe
2SiO
4
K
O =
pH
2O
/pH
2
KN = p
NH3
/p1.5
H2
Fe + Si
SiO2
Fe2SiO
4
Fe2O
3 + SiO
2
Si3N
4
Si2ON 2
Fe
4N
log
10(p
O2
) / b
ar
log10
(pN
2
) / bar
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Simulation Results with ASTRID
Figure: Spatial phase distribution in Fe, 1 wt-% Si after gaseous nitriding for 20 h at
KN = 1 000 and oxidation for 4 h and KO ≈ 0.01 (ptot= 1 atm, 550 °C) .
Appl. Simul. of Thermodyn. Reactions and Interphase Diffusion
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Ternary Phase Diagrams
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Ternary Phase Diagrams
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Ternary Phase Diagrams
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Conclusions - The Problem
pictures from various internet sources and FACTSage
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Conclusions – An Effective Solution
pictures from various internet sources and FACTSage
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Conclusions – An Effective Solution
pictures from various internet sources and FACTSage
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Conclusions – An Effective Solution
pictures from various internet sources and FACTSage
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Acknowledgements
Dirk and Alexandra Vogel,
Else-Marie Müller-Lorenz,
Monika Nellessen
Prof. H. Danninger
Vera G. Praig, Markus Holzweber,
Kurt Piplits
Dr. D. Paesold
Bernhard Linder, Klaus Rendl,
Andreas Muhr
Funding
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www.oberoesterreich.at (dl 03.07.2013)
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Backup Slides
Additional Slides for the Presentation
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Where we work…
Max-Planck-Institut
für Eisenforschung GmbH
Head: Prof. Dierk Raabe
Founded in 1917 from the “Kaiser Wilhelm Institute”
by Fritz Wüst.
3 Departments:
Computational Materials Design
Interface Chemistry and Surface Engineering
Microstructure Physics and Alloy Design
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From where I am
Austria
Area: 83 879 km²
Inhabitants: ~ 8 405 000
Language: German
Capital: Vienna
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Fisher’s Model of Diffusion
3
5
56
log3292.0
z
c
t
DDs GB
Whipple – Le Claire equation
3
5
56
log4704.0
z
c
t
DDs GB
Levine – MacCallum equation
I. Kaur “Fundamentals of … Boundary Diffusion” WILEY (1995)
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Some Published Works on HT-Corrosion
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Programme Algorithm
0.00 0.25 0.50 0.75 1.00-40
-35
-30
-25
-20
-15
-10
Fe2O
3 (hematite) + Al
2O
3
Fe3O
4 + FeAl
2O
4
oxyg
en p
ress
ure
log(
p(O
2)
/ po)
mole fraction aluminium xAl
Fe + Al
Fe + Al2O
3
'FeO' + FeAl2O
4
Fe + FeAl2O
4
Fe3O
4 + Al
2O
3
Al2O
3 + FeAl
2O
4
700 °C
element migration chemical reaction
tx,iTx,i
tx,ic.D=
dt
dcdiv
ASTRID, published in Oxid. Met. 76 (2011) 247
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Data Handling
Al - total
Al
Al-Oxide
Figure: Spatial phase distributions of Fe, 2 wt-% Al (4.05 mol-% Al) after oxidation
at p(O2) = 10-22 bar for 60 min at 700 °C.
Al
Al2O3
FeAl2O4
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Detail of a Grain Boundary
Figure: Spatial distribution of chromium oxides Cr2O3 and FeCr2O4 along a grain
boundary in Fe, 3 wt-% Cr after finished cooling from 650 °C.
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Diffusion between different Phases
http://adsjapan.blogspot.com and http://www.gettyimages.com
Figures: Shibuya (渋谷) crossing in Tokyo with green and red pedestrian lights.
single phase
cDJ A LJ A
g
g
RTLc
c
RTL oc
cLLJ A
D
general description
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Modelling Segregation
[1] Blavette et al. Microsc. Microanal. 13 (2007) 464
Figure: Numerical simulation of segregation (left) and 3D atom probe tomography
of segregated boron atoms along the grain boundary in a NiAl superalloy [1] (right).
t = 0
t
concentration
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Calculation of the Oxidation Depth
0 25 50 75
0.000
0.025
0.050
0.075
0.100
Rel
ativ
e ab
un
dan
ce
Oxidation depth in Sample x / µm
µ, s
0 25 50 75 100
0.00
0.25
0.50
0.75
1.00
Data: Data1_C
Model: SLogistic1
Equation:
y = a/(1 + exp(-k*(x-xc)))
Weighting:
y No weighting
Chi^2/DoF = 0.00721
R^2 = 0.99588
a 3.20455 ±0.00818
xc 29.5835 ±0.10386
k 0.22165 ±0.00442
Fra
ctio
n o
f m
etal
lic
Ch
rom
ium
Depth into Steel Sample x / µm
Cr- oxides metallic Cr
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Multikomponentensysteme
Abbildung: Phasenverteilung einer industrienahen Legierungszusammensetzung
nach erfolgter Oxidation bei p(O2) = 10-22 bar und einer technischen Abkühlkurve.
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Temperature Dependence
Diffusion equation
tx,icT,x,tx,iTx,i
tx,if+c.D=
dt
dcdiv
RT
Q
eD=D o
iTi
1200 1100 1000 900 800 7001E-19
1E-18
1E-17
1E-16
1E-15
1E-14
1E-13
volume diffusion
grain boundary diffusion
Dif
fusi
on c
oef
fici
ent
D /
m²
s-1
Temperatue T / K
Figure: Temperature dependence of phosphorous diffusion in iron.
I. Stloukal, C. Herzig, Z. Metallkd. 93 (2002) 88
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Thermodynamic Principles
Figure: State diagram of water [2] (left) and schematic temperature evolution with constant heating (right).
[2] University of Bristol at www.enm.bris.ac.uk (dl 15.10.2010)
melting
boiling
Ice
temperatu
re T
time t
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Efficiency of the Calculation
Figure: Distribution of Cr2O3 in Fe, 0.67 wt-% Cr at 700 °C after 90 min. Simulation
with InCorr (left) and with self-written programme (right).
300 FEM-points
Calculation time: 90 min
63 000 FEM-points
Calculation time: 120 min
25 µm
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Berechnungsaufwand
Abbildung: Abhängigkeit der Rechenzeit zur Simulation des Oxidationsverhaltens
von Fe, 3 wt-% Cr bei verwendetem Kühlprogramm ab 650 °C (B).
bisher Elementarzelle Kanten Algorithmus gekreuzter0
25
50
75
100
Rec
henz
eit
t rel /
%
Algorithmus
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Fine grained
C’ – regime B’ – regime A’ – regime
Coarse grained
C – regime B – regime A – regime
Grain Boundary Diffusion Regimes
Figure: Illustration of different diffusion regimes, depending on total diffusion time and ratio of DGB/D.
I. Kaur “Fundamentals of … Boundary Diffusion” WILEY (1995)
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Experimental Set-up
N2
Ar
H2
Ar
H2
Dew-Point Sensor
H2O-Dosage
Gas Mixing Chamber
Reaction Chamber Gas Analysis
(H2O, O2-Content)
in Rev. Sci. Instr. (2013), accepted
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Selective Decarburisation at 800 °C
Figure: Experimental parameters during selective decarburisation of Fe, 0.8 wt-% C
at 800°C in Ar / 2.5 vol-% H2 / H2O.
M. Auinger, V.G. Praig, et.al., Corros. Sci., submitted
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Selective Decarburisation at 800 °C
Figure: Mass change during selective decarburisation of Fe, 0.8 wt-% C at 800°C
in Ar / 2.5 vol-% H2 / H2O.
0 20 40 60 80 100 120 140-2.0
-1.5
-1.0
-0.5
0.0
mass c
hange
m / m
g c
m-2
time t / min
measurement from 27.04.2012
measurement from 26.04.2012
measurement from 04.08.2012
Fe, 0.8 wt-%C, 800 °C, Ar/2.5% H2, DP+13°C
M. Auinger, V.G. Praig, et.al., Corros. Sci., submitted
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Selective Decarburisation at 800 °C
Figure: Cross section of Fe, 0.8 wt-% C after oxidation at 800 °C in Ar / 2.5 % H2 /
H2O for 60 min. The cross section was etched with 1 % HNO3 / Ethanol for 15 s.
M. Auinger, V.G. Praig, et.al., Corros. Sci., submitted
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Selective Decarburisation at 800 °C
Figure: Evolution of the decarburised zone depth in Fe, 0.8 wt-% C after oxidation
at 800 °C in Ar / 2.5 % H2 / H2O. The solid lines represent theoretical results.
M. Auinger, V.G. Praig, et.al., Corros. Sci., submitted
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Selective Decarburisation at 800 °C
Figure: Evolution of the mass change in Fe, 0.8 wt-% C during oxidation at 800 °C
in Ar / 2.5 % H2 / H2O. The solid lines represent the theoretical results.
M. Auinger, V.G. Praig, et.al., Corros. Sci., submitted
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Ellingham – Formulas + FACTSage Pic
Text here
2 Fe + O2 2 FeO
Formation
)(TG
o
OOo
TFe
Feo
TFeO
FeOo
T
p
pRTGaRTGaRTG 22 lnln22ln220
,
)(
,
)(
,
)(
0!
Tp
pRGGG
o
OOo
T
Feo
T
FeOo
T
22 ln22
,
)(
,
)(
,
)(
d
2
)()()(22
O
T
Fe
T
FeO
T
y
FeFeO
o
OOo
T
Feo
T
FeOo
TaRTaRT
p
pRTGGG lnln2ln22 22
,
)(
,
)(
,
)(
ormationo
TG F,
)(
0
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Properties of Nitrogen
figures from Landoldt-Börnstein (right) and FACTSage (left)
Nitride Stability
0 250 500 750 1000 1250 1500 1750 2000750
500
250
0
-250
2 Cr2N + N2
= 4 CrN
8 Fe + N2 = 2 Fe4
N
4 Cr + N2 = 2 Cr2
N
8 Mn + N2 = 2 Mn4
N
3/2 Si + N 2 = 1/2 Si 3
N 4
Sta
ndar
d fr
ee e
nerg
y of
for
mat
ion
of n
itri
des
(-
Go =
-R
T ln
(pN
2
) / k
J m
ol-1
Temperature / °C
2 Al + N 2 = 2 AlN
0 K
N2
-15
-10
-5
0
5
Nit
roge
n pa
rtia
l pre
ssur
e lo
g(p
N2
)
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Theoretical Principles
0 250 500 750 1000
1E-5
1E-4
1E-3
0.01
0.1
1
10
100
1000
N2 + 3H
2 2 NH
3
Kp =
pN
H3
/ (p
3/2
H2
p1/
2
N2
) p
0
Temperatur / °C
N2 + 3H
2 2 NH
3
3
,
222
1
2
3NHNH Tp
05.1
!
2
3 pp
pK
H
NH
N
0
)(
2 p
KpK
Tp
NN
05.05.1)(
22
3 ppp
pK
NH
NH
Tp
02
1
2
3 !
)()()(223
N
T
H
T
NH
T GGG RT
GGG
Tp
oTN
oTH
oTNH
eK
)(,2)(,2)(,3 2
1
2
3
)(
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Theoretical Principles
450 500 550 600 650 7002
3
4
5
6
7
102
103
104
105
106
107
g-Eisen (fcc)
-Eisen (bcc)
g'-Phase (Fe4N)
e-Phase (Fe2N)
log
10(p
N2
/p0)
Temperatur / °C
pN
2
/p
0
http://www.ipsenusa.com (dl 12.10.2010)
Figure: Lehrer-Diagram of iron nitrides according to literature (left) and stability
diagram calculated with the programme FactSage (right).