Advanced High Temperature Alloys

University Bayreuth, Advanced High Temperature Alloys Uwe Glatzel, Metals and Alloys 1
Prof. Dr.-Ing. Uwe Glatzel

Metals and Alloys
University Bayreuth
SS 2014
Advanced High
Temperature Alloys
Lecturer:
Prof. Dr.-Ing. habil. Uwe Glatzel
born Dez. 1960
Physik-Diplom (B.Sc. and M.Sc) in Tbingen
(exchange year in Corvallis, Oregon, USA)
PhD thesis at the Institute for Metals Research, Technical
University Berlin, Prof. Monika Feller-Kniepmeier
post-doc (1 J ahr) at Stanford University
Habilitation TU-Berlin
Gerhard-Hess award of the German Science Foundation
(DFG) for young scientist (400.000 )
1996-2003 full professor for Metals and Alloys, J ena
since April 2003 Bayreuth (Chair for Metals and Alloys)
postal address:
Ludwig-Thoma-Str. 36b phone: +49 (0) 921 - 55-5555
D-95447 Bayreuth, Germany e-mail: uwe.glatzel@uni-bayreuth.de
R. Brgel, Handbuch Hochtemperatur-Werkstofftechnik, Vieweg
R.C. Reed, The Superalloys - Fundamentals and Applications, Cambridge Univ. Press
M.J . Donachie, S.J . Donachie, Superalloys - A Technical Guide, ASM International
H. Frost, M.F. Ashby, Deformation-Mechanism Maps, Pergamon Press
M.F. Ashby, Materials Selection in Mechanical Design, Elsevier
G. Meetham, M. Van der Voorde, Materials for High Temperature Engineering Applications, Springer
J . Betten, Creep Mechanics, Springer
R.E. Reed-Hill, Physical Metallurgy Principles, PWS-KENT Publishing
D.R. Askeland: Materialwissenschaften, Spektrum Lehrbuch; 1994
W.D. Callister: Materials Science and Engineering - An Introduction, Wiley, New York, 1999
H. Schumann, Metallographie, Deutscher Verlag fr Grundstoffindustrie, Leipzig
F. Vollertsen, S. Vogler, Werkstoffeigenschaften und Mikrostruktur, Hauser Verlag
P. Haasen, Physikalische Metallkunde, Springer-Verlag, Berlin
H.-J . Bargel, G. Schulze, Werkstoffkunde, VDI-Verlag, Dsseldorf
P. Sarrazin, A. Galerie, J . Fouletier, Mechanisms of High Temperature Corrosion, Trans. Tech. Publ.
N. Cumpsty, Jet Propulsion, Cambridge Univ. Press
Literature
lecture notes: http://www.metalle.uni-bayreuth.de then "Lehre" then "Vorlesungen",
you will find the link to this lecture notes and three review talks we will do at the end.
What You Should Know:
basic thermodynamics
introduction to diffusion
introduction to dislocations
phase diagrams
theory of elasticity
...
basic materials science courses
1. Introduction, Basics
2. Stability of Microstructure
3. Mechanical Properties
a) Static
b) Cyclic (Fatigue)
4. High Temperature Corrosion
5. High Temperature Alloys
6. Lost Wax Investment Casting
7. Depending on Time: Lectures on
a) SX Ni-Base Superalloys b) LEK 94 c) Pt-Base Superalloys
Content
Introduction
only alloys will be looked at (no ceramics, no
polymers).
no coatings (BUT : practically all high
temperature systems are coated!), simply not
enough time.
Motivation for High
Temperature Alloys
efficiency of Carnot heat enging
(with hot and cold temperatures). Several research
projects related to jet engines, stationary gas turbines
and waste-to-energy plant are carried out within my
group with the goal to increase T
h
.
melting processes (glass, metal, ... ).
chemical process (PTFE, ... ).
many other applications ...
jet engines, see Single Crystal Ni-Base Superalloys
max
min max
T
T T
=
Maximum Temperatures for
Applications of Different Materials
Group
maximum service temperature
[C]
deformation/damage mechanism
Polymer up to 300 melting, decomposing (pyrolyze)
Glass up to 800 viscous flow
Metals
Fe-Basis (coated) up to 1100
Fe-ODS up to 1300
Ni- and Co-base up to 1200
Pt-base up to 1600
refractory metals in inert
atmosphere above 1600
MoSi
2
up to 1800
creep, dislocation climb,
grain boundary sliding
Ceramics SiC up to 1600
viscous flow, glass transition
temperature, grain boundary
sliding
Composits (SiC/C) up to 1600 complex
Overview Materials
temperature [C]
500 1500 2000
u
s
a
b
l
e

s
t
r
e
n
g
t
h

source:
Plansee AG,
Reutte,
Tirol,
Austria
Taking Density into Account
500 1500 2000
temperature [C]
u
s
a
b
l
e

s
t
r
e
n
g
t
h

Oxidation Resistance
500 1500 2000
temperature [C]
u
s
a
b
l
e

s
t
r
e
n
g
t
h

University Bayreuth, Advanced High Temperature Alloys Uwe Glatzel, Metals and Alloys
T
m
of platinum
Refractory Metals:
12
Most common definition of
refractory metals (refractory =
widerspenstig, halsstarrig):
two elements of the 5. and
three elements of the 6. period
with melting points higher
than Pt. Processing in general
by powder metallurgy.
wider
definition
of
refractory
metals
Density
13
Ru, Rh, Pd
Re
W
Ta
Hf
Pt
Au
Tc
Mo
Nb
Pd
Ag
Os, Ir
Ni
Abundance of Elements
14
to find 1 Rh atom
within a bunch of
Si-atoms is
comparable to
find one
individual person
within the word
population
U.S. Geological Survey Fact Sheet 087-02 (2002)
Material Choice
temperature
environment
moving/non-moving part
design complexity (how to manufacture)
price constrictions (depending on application
of system). Reduction of 1 kg in weight:
car ~ 0 - 5
plane ~ 100 500
aerospace ~ 100.000 - 500.000
Influence of ... on ...
temperature:
phase transitions, volume fractions, ...
diffusion ( recrystallization, dislocation climb, diffusional creep, ... )
thermal fatigue (TF)
mechanical:
creep
fatigue (low cycle, LCF, high cycle fatigue, HCF)
environment:
oxidation
corrosion
combinations:
thermo-mechanical fatigue (TMF)
stress corrosion cracking, stress oxidation, ...
Basics
Thermodynamics Kinetics
Boltzmann-statistics: energy of
movement increases with temperature
T k
2
3
u
B
atom
kin
=
T R
Q
0
e

=

T k 3 T k
2
3
2 u 2 u
B B
atom
kin
atom
total
= = =
Arrhenius-plot T R 3 U
mol
total
=
0,33 eV, bzw. 32 kJ /mol bei 1000C
Vacancy Concentration
F =U - TS non-zero vacancy concentration is
in thermodynamic equilibrium
T[C] 20 300 450 800 1000 1200 1454
T/T
m
0.17 0.33 0.42 0.62 0.74 0.85 1.00
c
v
10
-23
310
-12
10
-9
10
-6
10
-5
710
-5
310
-4
T R
Q
v
vac
e c

=
Q
vac
nickel
=1,36 eV (energy necessary to create one vacancy)
equilibrium vacancy concentration for nickel
Nickel Vacancy Concentration
temperature [C]
0 200 400 600 800 1000 1200 1400 1600
v
a
c
a
n
c
y

c
o
n
c
e
n
t
r
a
t
i
o
n
10
0
10
-5
10
-10
10
-15
10
-20
10
-25
T
m
temperature [C]
0 200 400 600 800 1000 1200 1400 1600
v
a
c
a
n
c
y

c
o
n
c
e
n
t
r
a
t
i
o
n

[
1
0
-
4
]
1,00
0,75
0,50
0,25
0,10
T
m
T k
Q
v
B
vac
e c

=
with:
Q
vac
nickel
=1,36 eV
k
B
=8.60210
-5
eV/K
T
m
/2
Diffusion
c D j =

1. Fick's law
[j] =(atoms) m
-2
s
-1

[D] =m
2
s
-1

[c] =(atoms) m
-3
vacancy diffusion or
volume diffusion
Coefficient of Diffusion
Q
vac
energy to create a vacancy
Q
migration
activation energy to migrate a vacancy
Q
sd
activation energy for volume diffusion

Q
sd
= Q
vac
+ Q
migration

T k
Q
T k
Q Q
sd
migration vac
e D e D D

+
= =
0
) (
0
Q
sd
17 k
B
T
m
Q
sd
nickel
2.5 eV =244 kJ /mol
(for a perfect crystal; defects will lower the activation energies)
Q
sd
versus T
m
400 kJ /mol
0.137 kJ /(molK)
17 k
B
N
A
Dependence Melting Point and
Enthalpy of Vacancy Creation
element
T
m

[C]
17RT
m
Q
vac

[eV]
crystal
structure
Pb 327 0.88 0.57 fcc
Al 660 1.36 0.68 fcc
Cu 1 085 1.99 1.29 fcc
Ag 1 235 2.21 1.12 fcc
Ni 1 455 2.53 1.78 fcc
Pt 1 768 2.98 1.32 fcc
Mo 2 623 4.23 3.00 bcc
W 3 422 5.40 4.00 bcc
Coefficient of Diffusion
Steep slope indicates a
high activation energy.
Small elements diffuse
faster.
Diffusion in fcc crystals
slower than in bcc crystals.
fcc
-iron
bcc
-iron
Coefficient of Diffusion with Defects
Coefficient of diffusion of Th
in W.
Overall velocity for diffusion
depending on grain boundary
thickness, grain size and
dislocation density.
surface diffusion
grain boundary diffusion
volume diffusion
pipe
diffusion
Pipe Diffusion
D
eff
=D
sd
+a
disl.
D
disl.

a
disl.
area of dislocation core
( 5 b
2

0.3 nm
2
)
dislocation density
D
disl.
pipe diffusion along
dislocation core
atom flux ~Darea
dashed line: diffusion in crystal by the velocity of pipe diffusion
2
~
grain sd
grain
d D
time
atoms
|
.
|
\
|
n b D d D
2
. disl
2
grain sd
=
identical atom fluxes if:
n b D ~
time
atoms
2
. disl
. disl

|
.
|
\
|
volume diffusion
dominant
pipe diffusion
dominant
increasing
decreasing
disl.
disl.
sd
grain
2
. disl
sd
d
b
D
D
=
Grain Boundary Diffusion
D
eff
=D
sd
+ / d D
grain bound.

with:
effective grain boundary
thickness ( 2 b 0.5 nm)
d grain size
D
disl.
pipe diffusion along dislocation
core
dashed line: diffusion in crystal by the velocity of grain boundary diffusion
volume diffusion
dominant
grain boundary diffusion
dominant
fine
grain
coarse
grain
gb
sd
gb
grain gb
2
grain sd
d D d D =
identical atom fluxes if:
grain gb
sd
d D
D
=
Diffusional Creep
Nabarro-Hering creep (pure volume diffusion)

Coble creep (grain boundary diff.)
T k d
D
2
2
grain
diffusion self
NH
T k d
D
2
3
grain
boundary grain
C
thickness of grain boundary, atomic volume

NH-c
C-c
Combined NH and Coble Creep:
2
grain
eff
3
grain
boundary grain
2
grain
diffusion self
C NH creep diffusion
d
D
T k
~
d
D
d
D
T k
2

|
|
.
|
\
|

+

= + =

for real geometry (non-cuboidal grains)
grain
boundary grain
diffusion self eff
d
D
D D

+ =
grain
gb
sd
d
D
D

=
identical creep rates if:
grain gb
sd
d D
D
=
Activation Energies Indicating
Mechanism Changes
Single crystal aluminium, oriented such that <110>{111} slip is activated.
Lytton, Shepard and Dorn, Trans. AIME 212 (1958) 220
~Q
sd
Diffusion in Ordered Structures
(Intermetallic Phases)
High binding energies high activation energies
low coefficient of diffusion
Example NiAl: very high enthalpy of ordered B2
structure high enthalpy outweighs low entropy
ordered up to T
m

T
m
Ni
= 1,455C
T
m
Al
= 660C
T
m
NiAl
= 1,638C
Second Fick's Law
c D
t
c
=
Can be concluded directly from first Fick's law.

Similar in heat transfer systems, electrical
potential, ... .
0. 5 1 1. 5 2
0. 2
0. 4
0. 6
0. 8
1
f
1
(x)
f
2
(x)
f
3
(x)
( ) x 1 ) x ( f
1
=
|
.
|
\
|
=
5 . 0
x
1 ) x ( f
2
|
.
|
\
|
=
05 . 0
x
1 ) x ( f
3
( )
|
|
.
|
\
|
=
t D 2
x
c c c ) t , x ( c
0 1 1
solution to these
boundary conditions:
Thermal Conductivity
The most simple, stationary case: no heat radiation, constant
temperatures in front and back of component.
coefficient of heat (or thermal)
conductivity: = a c
p

a coefficient of temperature conductivity
c
p
heat capacity
density
... coefficient of heat transfer
c D j =

T q =

c D
t
c
=
T a
t
T
=
compare:
Temperature Distribution with
Thermal Barrrier Coating (TBC)
Wrmedmm-
schicht
Haftvermittlerschicht Grundwerkstoff
hot air
cooling air
TBC bond coat substrate
In case of transients, the temperature should reach a stable distribution as fast as possible in
order to reduce thermal stresses ( temperature conductrivity as high as possible).
In case of stationary circumstances, heat conductivity leads to heat flow into the solid.
Material Parameters at RT
(
K m
W
(
K kg
J
(
3
cm
g
(

s
m
10
2
6
material/property
heat cond.

heat cap.
c
p

density

temp. cond.
a
ferritic steel 45 460 7.8 13.0
austenite steel 15 500 8.0 3.8
Ni-base alloys 11 450 8.2 3.0
Mo 145 240 10.2 59.0
Ti alloys (-rich) 7 530 4.5 2.9
Al 210 890 2.7 87.0
Al
2
O
3
bei RT
( Al
2
O
3
bei 1000C )
25
( 6)
800

3.9

8.4

source: Brgel
Attention: Heat conductivity strongly depends on alloy composition, see steels and pure
Ni with 91 W/(mK) in comparison to Ni-base alloys with 11 W/(mK)
Content
a) Static
b) Cyclic (Fatigue)
Microstructure is NOT stable
annealed deformed
stress-relieved recrystallized
Recrystallization
time dependence of
recrystallization can be
approximated by
Avrami-J ohnson-Mehl
function:
n
0
t
t
r
e 1 f
|
.
|
\
|
=
, deformed
partly re-crystallized
fully re-crystallized
Grain Coarsening
driving force: reduction of grain boundary
energy
T > 0.7 T
m

no pre-deformation necessary
self-similar system
Ostwald ripening d ~t
1/3
(big grains eat up
small grains)
new grains have low dislocation density

Grain Coarsening
monomodal

bimodal (some grain
boundaries are pinned,
e.g. by precipitates)
Precipitate Hardening
Requirements:
solid solution at higher
temperatures (ability to
homogenization heat
treatment)
during cooling a two-phase
region should be reached
in general: cooling rate as
high as possible, thereafter
annealing (in the two-phase
region) to let grow the
precipitates
solution heat treatment
quenching
annealing
furnace cooling
Thermodynamic Kinetic
Example: Al-Cu Alloy
Guinier-Preston
Zones leading to
-Precipitates
(Al
2
Cu) have
paved the way
to the success of
Al-alloys
solution heat treatment
quenching
annealing
quenching
annealing
supersaturated solid solution
Other Examples of
precipitate hardening:
nickel-base superalloy
Al
2
Cu in AlCu alloy:
platinum-base superalloy
Time Dependence of
Precipitation Hardening
d
T
precipitate size
T
distance between precipitates
f
T
volume fraction of precipitates
nucleation, growth, coarsening
T =const.
Coherent - Semicoherent - Incoherent
misfit
( ) a
a
a
a a
a
a a
a a
a a
:
p
m p
m
m p
m p
2
1
m p

=
(mit Orientierungsbezug) (ohne Orientierungsbezug)
Energy Consideration for
G
total
=G
vol
+G
boundary
+G
strain
+G
defect

total change in free enthalpy
enthalpy of formation of matrix to precipitate (scales with volume)
enthalpy of phase boundary (scales with surface)
strain enthalpy (elastic energy +dislocation line energy)
reduction of enthalpy by precipitation coupled with a defect
Heterogeneous Nucleation
dislocations
subgrain
boundaries
stacking faults
coherent
twin boundaries
incoherent
vacancy cluster
surface (internal
and external)
grain boundaries
precipitates
TEM-Micrograph of TiC Precipitates at
Dislocations in an Austenitic Steel
Ostwald-Ripening of Precipitates
d
3
- d
0
3
~Dt here for T/T
m
0.74
' particle size in IN 738 LC at
T =920C.

particle coarsening constant of
50 nm h
-1/3

+0,5 m after 1.000 h
+1 m after 8.000 h

1 year
Content
a) Static
b) Cyclic (Fatigue)
Room Temperature (RT) versus
High Temperature (HT) Deformation
most alloy properties at room temperature are time and
rate independent (elastic constants, tension stress, ... ),
tension stress experiment.
For T >0.4 T
m
the properties (deformation) will be time
temperature and rate dependent, creep experiment.
deformation hardening fine grain hardening
solid solution
strengthening
precipitate
hardening
cold deformation (RT) strong medium medium to strong medium to strong
creep (HT)
temporary hardening,
reduced creep rupture
strength, may lead to
recrystallization
reduced strength with
fine grain material
coarse grain,
better single crystal
medium medium to strong
Elastic (E-)Modulus and
Poisson's Ratio
) 1 ( 2
E
G
+
=
shear modulus G
Ni-base superalloys 120 115 110 105 0,39 - 0,41
85 @ 1000C
Change in Materials Properties
with Temperature
Material properties of steel and
Ni-alloys at elevated
temperatures. Comparison
between short-term and long-
term parameters.
Tension Creep Experiment
(UTS)
(YS)
design by YS or UTS
design by t
1%

High Temperature Deformation
dislocation glide (Peierls stress, in fcc and hcp very small and for T >
0.15 T
m
negligible)
cross slip of screw dislocations and dislocation interactions (for a low
stacking fault energy larger dislocation spacing thermal
activation necessary, T >0.2 T
m
, influence on deformation rate)
climb of edge dislocations to overcome obstacles:
diffusion at complete
dislocation line
T >0.4 T
m

Dislocation Climb
climb of edge dislocations to
annihilate each other.

arrangement in low energy
configurations (sub-grain
boundaries), climbing around
abstacles (leaving the glide
plane)

movement of screw
dislocations with kink
Internal Back Stress
Dislocations climb allows annihilation of dislocations
and to establish a constant dislocation density,
resulting in an internal back stress of:

dislocation
= and

G shear modulus, constant 0.3 - 1, b magnitude of Burgers vector
= b G
. int
r
1
2
b G
r
1
=
Creep Experiment
behavior of pure metals:
primary secondary tertiary:
Creep Experimental Setup
up to 1400C
Constant
temperature
and stress or
load
Creep Experimental Setup for
Electrical Conductivity Material
up to Melting Temperature
Pyrometer from left, optical strain
measurement from right, both contact-free.
Interrupted creep tests
[001] orientation, 1123K, 650MPa
time [h]
0 10 20 30 40 50 60 70
s
t
r
a
i
n

[
%
]
0
1
2
3
4
5
6
7
single crystal (SX) nickel base superalloy (habilitation thesis Glatzel)
[001] orientation, 1123K, 650MPa
time [h]
0 10 20 30 40 50 60 70
s
t
r
a
i
n

r
a
t
e

[
1
/
s
]
0
2x10
-6
4x10
-6
6x10
-6
8x10
-6
1123K, 650 MPa
strain [%]
0 1 2 3 4 5 6
s
t
r
a
i
n

r
a
t
e

[
1
/
s
]
10
-7
10
-6
10
-5
logarithm of strain rate versus strain
(most valuable information for
materials scientist)
Different Creep Stages
primary creep: strain rate d/dt decreases
material hardens
secondary creep stage: strain rate constant
hardening and softening are in equilibrium
dislocation multiplication and annihilation in
equilibrium disl. density = const.
tertiary creep: necking (creep pores) develop
local stress and strain rate increases
drastically.
World Record
J apan, Germany
65
http://www.nims.go.jp/eng/news/press/2011/02/p201102240.html
NIMS: 14.853 days on 24. Feb. 2012,
probably still running (started in 06/1969!)

Siemens: 14,852 days terminated in 2000
Modelling of Primary and
Secondary Creep Stage
66
density velocity
v b =
Problem with Low Creep Rates
Life time of stationary gas turbines >20 years and
max.
=3%
510
-11
s
-1

Reliable data in lab down to 110
-9
s
-1
:
l =1 m with l
0
=25 mm after 10 h
3.5% strain per year!
Within university labs we are two orders of magnitude too
fast compared to real life of a stationary gas turbine!

state steady
Engineering Creep Curves
raw data creep curves:

time to failure:

isochrone time to failure:
time strain
(e.g. 1%)

isochrone strain
Natural Creep Law
v b
state steady
=
2
external
b G
|
.
|
\
|

1
external
~ v
natural creep law
b G
~
2
3
external
Norton Creep Law (Empirical)
T R
Q
n
external state steady
creep
e A

with Norton creep exponent "n"

and Q
creep
Q
self diffusion

power law break
down (plb)
T =const.
dislocation
climb
diffusional creep
stress dependence
of the stationary
creep rate of the
austenitic steel 800
H at 900C and
1000C:
Temperature Dependence of
Stationary Creep Rate
=28 MPA =const.
fcc alloys:
T R
Qc
n
5 , 3
SF s
e
E
A

|
.
|
\
|

=
Austenitischer Stahl 800H

Q
sd
Ni
244 kJ/mol
Q
sd
Fe
290 kJ /mol
Activation Energy for Creep
slope =1
Constant Load Constant Stress
failure
in case the gauge length
deforms uniform with
constant volume
( )
n
n
0 0
n
0
0
n
0
n
0
1
A
) 1 ( F
A
F
+ =
|
|
.
|
\
|
+
=
|
.
|
\
|
= =

ln =ln +n ln
0
+n ln (1+) =const. +n ln (1+)
This method is applicable to

determine the stress exponent "n"
only, if the secondary creep state
lasts to at least 10%
Ashby Deformation
Mechanism Maps
n =3
Ashby Deformation
Mechanism Maps
Versetzungsklettern !
dislocation climb !
Deformation Mechanisms:
Elastic Deformation: Spontaneous and reversible deformation. In the elastic region: =E (rule of
thumb:
e, max
10
-3
, but definitely <<1%). Plastic or non-reversible deformation achieves way higher
strains. Coble-creep (grain boundary diffusion) is in theory possible even at 0 K.
Dislocation Glide: without significant time dependent recovery (climb). Is dominant in the complete
temperature regime from 0 K up to the melting point T
m
at moderate and higher stress levels. At low
temperatures (<0.4T
m
) dislocation glide has the lower boundary in the range of the elastic stress limit
(typically 10
-3
E).
Dislocation Climb: At higher temperatures (>0.4T
m
) and lower stress levels dislocation climb plays the
major role =>time dependent constant strain rate (d/dt)
ss
~
n
, with a Norton stress exponent in-between
3 und 8.
Diffusional Creep: In principle over the complete temperature regime (0 K - T
m
). Relevance only at very
low stress levels and T close to T
m
: Coble-creep (grain boundary diffusion). For geological times a time
dependent deformation can be determined. Transition to Nabarro-Herring creep (volume diffusion) is
dependent on grain size and grain boundary thickness. The transition temperature from coble to Nabarro-
Herring creep can be explained by the different activation energies of volume and grain boundary diffusion.
Creep of Alloys
(assuming solid solution, no precipitates)
a) interaction dislocation
and impurity (low temp.)
b) stationary dislocation
pinned by impurities
(Cottrell clouds)
c) pulled off Cortrell clouds
(Lders bands)
d) gliding dislocation trails
impurities behind (viscous glide)
e) impurities faster than dislocation (very high temp., no hardening)
f) annihilation due to dislocation climb
solution solid i
b G + =
e precipitat solution solid i
b G + + =
threshold stress concept (with n 3 - 4 and Q
creep
=Q
self diffusion
):
T R
Qc
n
0
ss
e
E
A

|
.
|
\
|

=
mechanism temperature
coherent and semi-
coherent phase
boundaries
in-coherent phase
boundaries
cutting 0 K up to T
s
yes no
bypass by Orowan 0 K up to T
s
yes yes
climb over obstacles >0.4T
s
yes no
Orowan Stress
79
L
b G
Orowan

r
2r

T
T
L
Tsin
Line tension leads to a back stress,
the Orowan stress, due to obstacles
(in most cases precipitates) with an
average distance L between these
precipitates.
Hardening Mechanisms as
Function of Precipitate Size
d
T0
initial precipitate size
1
and
2
arbitrary external stress levels
passing by:
climbing:
Cutting is relevant only for coherent
precipitates

Dependence of stationary creep rate on
initial precipitate size for two different
external stress levels
T
d ~
2
T
d
1
~
=cutting
Pinning of Dislocations by
Carbides in Austenitic Steel
T =1000C, =25 MPa, carbides of the type TiC und M
23
C
6

Very High Volume Fractions
Volume fractions of 70% are only achievable with non-spherical precipitates.
Spacing between precipitates is getting smaller Orowan stress
Orowan
Gb/L necessary. For small strains precipitates are not cut by
dislocations. With G = 90 GPa, b = 0.25 nm, L 75 nm =>
Orowan
300 MPa
nickel base superalloys
ODS alloys:
Orowan

part.
3
'
d
f b G
Dispersion Hardening
(oxide dispersion strengthened alloys (ODS-alloys))
back-side pinning of dislocation by
ODS-particle (Rssler +Arzt)
precipitate strengthened
dispersion strengthened
yield
stress
temperature
T
m

temperature regime for
dissolution of precipitates
Summary:
Hardening Mechanisms
84
Internal back stress in steady state regime:

Orowan stress in case of precipitates or particles:
Orowan
Gb/L

Solid solution strengthening:

In case of coherent precipitates:
= b G
i
r
r
const.
solution solid

E E
a
a
misfit coherency
=
Creep Damage
a) cracks at grain boundaries b) cavities (micropores) at grain boundaries
creation of a creep pore in poly-
crystalline material due to disloction glide:
Creep Damage
nucleation, not detectable with OM
micropore, difficult to detect
pear necklace like chain of
micropores (easy detectable)
micro cracks
fracture
Extrapolation of Time-to-Fracture Data
(Larson-Miller plot, Larson-Miller parameter)
m
ss
f
K
t
Monkmann-Grant relation with constant K and exponent m 1:

( )
ss f
ln m K ) t ln( =

T R
Q
T R
Q
n
0 ss
creep creep
e B e A

= =
T
1
B B ) ln(
2 1 ss
=
T
P C
T
m m K t
f
1 1
) ln(
2 1
+ = + = B B
with material dependent constants C and P.
Larsson-Miller plot: P =T[C +ln(t
f
)]10
-3
, with C
Ni-base
=20, T in K, t
f
in h
Example: t
f
=100 h, T =1273 K P = 31.3 (relation t
f
with T at =const.)

~ 1952 @ GE
Larson-Miller-Plot
P =T[20 +ln(t
f
)]10
-3
(T in K, t
f
in h)

Comparison of CMSX-6,
LEK 94 and CMSX-4,
patent Wllmer, Glatzel,
Mack, Wortmann
stationary gas turbine, about 20 years of service ~130.000 h
Comparison LEK 94 with
CMSX-4 and CMSX-6
Larsen-Miller-parameter
P =T (20+log t
f
) 10
-3
25 26 27 28 29 30 31 32
s
t
r
e
s
s

[
M
P
a
]
120
230
500
CMSX-6 [Wortmann 88] 8.0 g/cm
3
CMSX-4 [Erickson 94] 8.7 g/cm
3
CMSX-4 [Frasier 90] 8.7 g/cm
3
LEK-2 8.5 g/cm
3
LEK-4 8.2 g/cm
3
LEK-5 8.2 g/cm
3
LEK-3 8.1 g/cm
3
LEK-6 8.3 g/cm
3
LEK-1C 8.4 g/cm
3
LEK-1B 8.3 g/cm
3
LEK-1A 8.2 g/cm
3
T =10 K
24 K
10 K
29 K
Not corrected
regarding density!
Content
a) Static
b) Cyclic (Fatigue)
Time Dependent Variation of Stress
and/or Temperature and/or ...
Whler diagram for T <0.4T
m
. Z time fatigue limit, D endurance
fatigue limit
a) type I metal (bcc) b) type II metal (fcc) endurance limit at 210
7
Change in Whler Diagram with
Temperature and Holding Time
10 CrMo9-10
Thermal Fatigue
Thermal breathing of turbine blade:
a) heating phase: edges reach high temperatures faster than interior
b) cooling phase: edges cool faster than interior
c) repeated thermal cycles lead to thermal fatigue cracks at edges
Thermal Strains and Stresses :
thermal
=
thermal
T, or:
thermal
=E
thermal

thermal
=E
thermal
T
Lower E-Modulus is Helpful:
orientation of single crystals in <100>direction reduces thermal stresses
<001>
<111>
Anisotropy and Temperature Dependence of
Elastic Constants in Ni-base Superalloys
96
Orientation dependence of
Youngs modulus E of matrix
phase. Distance from the center to
the surface indicates the
magnitude of the Youngs modulus
in this direction.
D. Siebrger, H. Knake, U. Glatzel, Mat. Sci. Eng. A298 (2001)
TMF and many other Time
Dependent Test Techniques
Can not be covered in this lecture!
Content
a) Static
b) Cyclic (Fatigue)
High Temperature Corrosion
oxidation: external and internal, passivation
carburization (internal carbides)
nitration: internal, seldom nitrite passivation
sulfurization: external (sometimes
passivation), seldom internal
Worldwide 1 ton iron per minute corrodes to rust (low
temperature aqueous corrosion).
Ellingham-Richardson-Diagram
right hand and lower axes
O
2
partial pressure at T =0.

As an example p
O
2

of
10
-15
Pa =10
-20
bar =10
-17
mbar
is shown as a dashed line.

only the oxides below this line
are thermodynamic stable.
UHV
HV
air
Time Dependent Oxidation
Oxidation Mechanisms
logarithmic (not shown) low temperature oxidation which
eventually comes to a stop or no measurable increase in oxide scale
thickness (e.g. Al, Cr, Mg).
parabolic mass change (m/A)
2
~t. Diffusion through oxidation layer
either oxygen or metal. Most favorable oxidation behavior (Al
passivation at high temperatures).
linear mass change: oxide layer with cracks continuous contact
with metal (e.g. Ta, Nb).
mass loss: volatile oxides catastrophic oxidation (e.g. V, Mo, W,
Cr, Pt). You can see it inside a broken light bulb.
Pilling-Bedworth Ratio
PB =(volume of oxide of one metal atom)/(volume of metal atom)
ideal is 1.1 to 1.3
Of course thermal expansion coefficients also play a major role for the stability of oxide scales.
Oxide TiO MgO Al
2
O
3
MgO
2
Ti
2
O
3
ZrO
2
Ti
3
O
5
NiO FeO TiO
2
CoO
PB 0.70 0.81 1.28 1.34 1.50 1.56 1.65 1.65 1.70 1.73 1.86
Oxide Cr
2
O
3
FeCr
2
O
4
Fe
3
O
4
Fe
2
O
3
SiO
2
Ta
2
O
5
Nb
2
O
5
W
PB 2.05 2.10 2.11 2.15 2.15 2.50 2.68 3.40
Alloying Effects:
different elements have
different oxygen affinity

concentration changes

diffusion rates are different

oxide layer contains other
metals
Example Ni-Cr-Al
Ni Cr 10 Al 5
oxide layer and
internal
oxidation occurs
1000C
Observations for the
Superalloy Rene N5
Bensch et al., Acta Mat. 2010
and Acta Mat. 2012
layer number layer composition properties
1 cover oxide layer NiO, CoO thick and porous monophase layer
2 interlayer of oxides NiAl
2
O
4
, NiTa
2
O
6
, Cr
2
O
3
thick and porous layer consisting of two fractions
3 third oxide layer Al
2
O
3
dense and thin monophase layer
4 -free layer see Tab. 1 Al-content of 2.2 wt. %
5 reduced layer composition in-between layer number 4 and 6 reduced Al content, morphology change
6 two-phase centre region nominal composition of Ren N5 (Tab. 1) regular / structure, see Fig. 6 f)
Content
a) Static
b) Cyclic (Fatigue)
High Temperature Alloys
T > 500C, Application in:
energy generation
engines (cars, trains, airplanes, ships, ... )
chemical industry
metallurgy
mechanical engineering
Overview Metals
ele
m.
struc-
ture
T
trans.
T
m

[C]

[g/cm
3
]
max. O-solubility
[at.%]
advantages/disadvantages
Ti hdp
krz
882
1855
4.5
4.5
31.9
8
+low density
+high melting point
+abundant available
+low
th.
(~10
-5
K
-1
)
no alloy known with adequate strength for temperatures >600C
high oxygen and nitrogen solubility >700C, increased brittleness
linear oxidation >800C
low thermal conductivity
ignition hazard
V krz 1910 6.1 17 catastrophic oxidation; T
m
(V
2
O
5
) =658C
Cr krz 1863 7.2 0.0053 very brittle at RT; conventionally not processable
Mo krz 2623 10.2 0.03 +very high creep strength
+low
th
, high thermal conductivity, good thermal fatigue strength
very brittle at RT
catastrophic oxidation; T
m
(MoO
5
) =795C
no long lasting coating available
W krz 3422 19.3 0 +highest melting point of metals (only C with even higher T
m
)
+very high creep strength
+low
th
, high thermal conductivity, good thermal fatigue strength
very brittle at RT
catastrophic oxidation >1000C durch hohe WO
3
-Abdampfrate
no long lasting coating available
very high density
Overview Metals
elem. structure T
trans.

T
m

[C]

[g/cm
3
]
max. O-
solubility
[at.%]

Fe
krz
kfz
krz
912
1395
1538
7.9
7.7
7.4
0.0008
0.0098
0.029
+very good corrosion resistance by alloying with Cr or (Cr +Al)
+-structure can be stabilized down to RT (by Ni)
+very good processable and weldable
+low cost (~1 /kg)
strength at high temperatures (>700C) limited
Co hdp
kfz
422
1495
8.8
8.7
0
0.048
+Co-alloys castable in air good weldability
only moderate hardening available
Ni-additions necessary to stabilize fcc structure, reduces strength
Ni kfz 1455 8.9 0.05 +broad possibilities for alloying, high strength increase possible by
alloying with Al, leading to '-phase (Ni
3
Al)
+processable
relatively low melting point
th.
high, low thermal conductivity
Pt kfz 1772 21.5 0 +high corrosion and oxidation resistance
+high melting point
very high density
very expensive (~33 /g)
Evolution of materials
used in aero-engines
111
The earlier approach of technology transfer from military to civil is
tending to switch direction.
www.azom.com
Example of Intermetallic
Phases (Ni-Al-System)
Ni-Al Intermetallic Phases
phase structure T
trans.

T
m

[C]

[g/cm
3
]
Ni
3
Al L1
2
1383 7.5 +anomalous temperature dependence of strength
+same structure base than Ni matrix (fcc)
+stable for larger Al variations >1 wt.% Al
+ductile as single crystal
high density
brittle as polycrystal (can be hindered by boron doping (grain
boundary strengthener)
Al-content not sufficient to build stable Al
2
O
3
-layer reduced high
temperature oxidation resistance
NiAl B2 1638 5.85 +very good oxidation resistance, since 30 wt.% Al
+high melting point
+low density
+ordered structure up to melting point
+high thermal conductivity
+low coefficient of thermal expansion
extremely brittle at temperatures below 500C (von Mises criterion
not fulfilled)
low strength at high temperatures
NiAl, B2 Ordered
Intermetallic Phase
At a first sight very interesting (see
advantages) but despite many efforts and many
100 Mio. US$ research money spent, up today
no bulk usage of NiAl has been achieved.

BUT: aluminum coatings leading to NiAl
layers is heavily used.
Content
a) Static
b) Cyclic (Fatigue)
MTS-Factory in Bayreuth
ground-breaking ceremony: 20.02.2008, topping-out ceremony: 06.06.2008
start of production: ~12/2008
MTS-Factory, J une 2008
Processing of a Turbine
Blade
FPI
X-Ray
Feinguss, Wachsausschmelzverfahren, lost wax investment casting, ...
Turbine Casting
Additionally: hollow geometries possible (core insertion)!
Archaeological Evidence
(Bibracte) ~50 B.C.
cloth clip
ceramic mould filled with wax
Turbine Casting
Single Crystal Casting
Metals and Alloys, Bayreuth
<20 s
0,8...400
mm/min
Content
a) Static
b) Cyclic (Fatigue)

Advanced High Temperature Alloys

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Advanced High Temperature Alloys

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University Bayreuth, Advanced High Temperature Alloys Uwe Glatzel, Metals and Alloys 1

Prof. Dr.-Ing. Uwe Glatzel

thickness of grain boundary, atomic volume

Can be concluded directly from first Fick's law.

with Norton creep exponent "n"

Austenitischer Stahl 800H

This method is applicable to

Monkmann-Grant relation with constant K and exponent m 1:

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