Advanced Materials

Advanced High
Temperature Alloys
Prof. Dr.-Ing. Uwe Glatzel

Metals and Alloys
University Bayreuth
SS 2015
University Bayreuth, Advanced High Temperature Alloys 1 Uwe Glatzel, Metals and Alloys
Lecturer:
Prof. Dr.-Ing. habil. Uwe Glatzel
• born Dez. 1960
• Physik-Diplom (B.Sc. and M.Sc) in Tübingen
(exchange year in Corvallis, Oregon, USA)
• PhD thesis at the Institute for Metals Research, Technical
University Berlin, Prof. Monika Feller-Kniepmeier
• post-doc (1 Jahr) 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, Jena
• 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
Literature
• R. Bürgel, 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 für 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, Düsseldorf
• P. Sarrazin, A. Galerie, J. Fouletier, Mechanisms of High Temperature Corrosion, Trans. Tech. Publ.
• N. Cumpsty, Jet Propulsion, Cambridge Univ. Press
lecture notes: http://www.metalle.uni-bayreuth.de then "Lehre" then "Vorlesungen",

you will Bayreuth,
University find the linkHigh
Advanced to this lecture
Temperature Alloysnotes 3and three review talks we
Uwewill doMetals
Glatzel, at the end.
and Alloys
What You Should Know:
• basic thermodynamics
• introduction to diffusion
• introduction to dislocations
• phase diagrams
• theory of elasticity
• ...
• basic materials science courses
Content
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
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
Tmax  Tmin
• efficiency of Carnot heat enging η
Tmax
(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 Tmax.
• melting processes (glass, metal, ... ).
• chemical process (PTFE, ... ).
• many other applications ...
• jet engines, see Single Crystal Ni-Base Superalloys
Maximum Temperatures for
Applications of Different Materials
maximum service temperature
Group deformation/damage mechanism
[°C]
Polymer up to 300 melting, decomposing (pyrolyze)
Glass up to 800 viscous flow
Fe-Basis (coated) up to 1100
Fe-ODS up to 1300
Ni- and Co-base up to 1200
creep, dislocation climb,
Metals Pt-base up to 1600
grain boundary sliding
refractory metals in inert
atmosphere above 1600
MoSi2 up to 1800
viscous flow, glass transition
Ceramics SiC up to 1600 temperature, grain boundary
sliding
Composits (SiC/C) up to 1600 complex
usable strength
Overview Materials
source:
Plansee AG,
Reutte,
Tirol,
Austria
500 temperature [°C] 1500 2000
usable strength
Taking Density into Account
usable strength
Oxidation Resistance
Refractory Metals:
wider
definition Most common definition of
of
refractory refractory metals (refractory =
metals widerspenstig, halsstarrig):
two elements of the 5. and
three elements of the 6. period
with melting points higher
Tm of platinum
than Pt. Processing in general
by powder metallurgy.
Density
Os, Ir Pt
Re
W Au
Ta
Hf
Ru, Rh, Pd
Tc Pd
Mo
Ag
Nb
Ni
Abundance of Elements
in Earth's Upper Continental Crust
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 3
u kin atom
 kB T
2
3 Q
u total atom  2  u kin  2  kB  T  3 kB  T 
   0  e
atom
2 R T
U total mol  3  R  T  0,33 eV, bzw. 32 kJ/mol bei 1000°C Arrhenius-plot

Vacancy Concentration
F = U - T·S  non-zero vacancy concentration is
in thermodynamic equilibrium
Q vac

cv  e R T Qvacnickel = 1,36 eV (energy necessary to create one vacancy)
T[°C] 20 300 450 800 1000 1200 1454
T/Tm 0.17 0.33 0.42 0.62 0.74 0.85 1.00
cv 10-23 3·10-12 10-9 10-6 10-5 7·10-5 3·10-4
equilibrium vacancy concentration for nickel

Nickel Vacancy Concentration
Qvac

k B T
100
cv  e
Tm/2
-5
10
with:
vacancy concentration
10-10 Qvacnickel = 1,36 eV

kB = 8.60210-5 eV/K
10-15
vacancy concentration [10 ]

1,00
-4
10-20
0,75
Nickel Vacancy Concentration Nickel Vacancy Concentration

0,50
10-25
0 200 400 600 800 1000 1200 1400 1600 0,25
temperature [°C] Tm 0,10
0 200 400 600 800 1000 1200 1400 1600

temperature [°C] Tm
Diffusion
 
j   D  c 1. Fick's law
[j] = (atoms) · m-2 · s-1
[D] = m2 · s-1
[c] = (atoms) · m-3
vacancy diffusion or
volume diffusion
Coefficient of Diffusion
Qvac energy to create a vacancy
Qmigration activation energy to migrate a vacancy
Qsd activation energy for volume diffusion
Qsd = Qvac + Qmigration
 ( Qvac  Qmigration )  Qsd
D  D0  e k T
 D0  e k T
Qsd ≈ 17 ·kB ·Tm  Qsdnickel ≈ 2.5 eV = 244 kJ/mol

(for a perfect crystal; defects will lower the activation energies)
Qsd versus Tm
600 kJ/mol
500 kJ/mol
400 kJ/mol
300
0.137 kJ/(mol·K)
≈ 17 · kB ·NATm
Tm (K)
Dependence Melting Point and
Enthalpy of Vacancy Creation
Tm 17·R·Tm Qvac crystal
element
[°C] [eV] [eV] 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.
fcc Small elements diffuse
γ-iron bcc
α-iron faster.
Diffusion in fcc crystals
slower than in bcc crystals.
Coefficient of Diffusion with Defects
surface diffusion Coefficient of diffusion of Th

in W.
grain boundary diffusion
Overall velocity for diffusion
depending on grain boundary
volume diffusion
thickness, grain size and
pipe
diffusion dislocation density.
Pipe Diffusion
Deff = Dsd + adisl. · ρ · Ddisl.
disl. adisl. area of dislocation core
volume diffusion ( ≈ 5 b2 ≈ 0.3 nm2)
dominant
ρ dislocation density
pipe diffusion
dominant Ddisl. pipe diffusion along
disl.
increasing
dislocation core
sd atom flux ~ D·area
decreasing
 atoms   atoms 
  ~ Dsd  d grain
2
  ~ D disl.  b  n
2
 time  grain  time  disl.
dashed line: diffusion in crystal by the velocity of pipe diffusion
D sd b2  
identical atom fluxes if: Dsd  d 2
grain  D disl.  b  n
2

D disl. d grain
Grain Boundary Diffusion
Deff = Dsd + π ·  / d · Dgrain bound.

gb
volume diffusion
dominant
grain boundary diffusion with:
dominant
 effective grain boundary
fine
grain thickness ( ≈ 2 b ≈ 0.5 nm)
gb
coarse
sd grain d grain size
Ddisl. pipe diffusion along dislocation
core
dashed line: diffusion in crystal by the velocity of grain boundary diffusion
D sd   
identical atom fluxes if: Dsd  d grain
2
 D gb      d grain 
D gb d grain
Diffusional Creep
• Nabarro-Hering creep (pure volume diffusion)
D self diffusion 
 NH  2
d 2
grain k T
C-c
• Coble creep (grain boundary diff.)
 D grain boundary  NH-c
 C  2
d 3grain k T
 thickness of grain boundary, Ω atomic volume

Combined NH and Coble Creep:
    Dself diffusion    D grain boundary   D eff

 diffusion creep   NH   C  2    ~  2

k T  d grain2 3
d grain  kT d grain

   D grain boundary
D eff  Dself diffusion 
d grain
for real geometry (non-cuboidal grains)
D gb     D sd   
identical creep rates if: Dsd  
d grain D gb d grain
Activation Energies Indicating
Mechanism Changes
150 kJ/mol ~ Qsd
100 kJ/mol
50
K temperature
0 200 400 600 °C
Single crystal aluminium, oriented such that <110>{111} slip is activated.
Lytton, Shepard and Dorn, Trans. AIME 212 (1958) 220

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 Tm
TmNi = 1,455°C
TmAl = 660°C
TmNiAl = 1,638°C
Summary: Effects of Diffusion on
High Temperature Alloys
• fcc preferred: lower coefficient of diffusion (Dclose to Tm ~ factor of

10 lower than bcc (DNi = 210-13 m2 s-1, DCr = 210-12 m2 s-1).
• Grain size as large as possible (→ directionally solidified or single
crystal parts)
• intermetallic phases helpful: at least a factor 2 lower coefficient of
diffusion. At 1000°C:
Ni in Ni: 2.210-16 m2 s-1
Ni in NiAl and Ni in Ni3Al: 110-16 m2 s-1.
• low dislocation density helpful (implies lower stress levels, which
is helpful in general)
Second Fick's Law
Can be concluded directly from first Fick's law.
c
 D  c
t Similar in heat transfer systems, electrical
potential, ... .
f1 ( x )  1  x 
1
 x 
0.8 f 2 ( x )  1   
 0.5 
0.6
f1(x)  x 
0.4 f 3 ( x )  1   
f2(x)  0.05 
0.2
 x  f3(x)
solution to these
c( x , t )  c1  c1  c 0    
2 Dt 
0.5 1 1.5 2
boundary conditions:  
Thermal Conductivity
The most simple, stationary case: no heat radiation, constant
temperatures in front and back of component.
λ … coefficient of heat (or thermal)
conductivity: λ = a · cp · ρ
a … coefficient of temperature conductivity

cp … heat capacity
ρ … density
 ... coefficient of heat transfer
compare:
   
j   D  c q   λ  T
c T
 D  c  a  ΔT
t t
Temperature Distribution with
Thermal Barrrier Coating (TBC)
cooling air
hot air
TBC
Wärmedämm- bond coat
Haftvermittlerschicht substrate
Grundwerkstoff
schicht
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
heat cond. heat cap. density temp. cond.
material/property λ cp ρ a
 W   J   g   6 m 2 
 m  K   kg  K   cm 3  10 
   s 
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
Al2O3 bei RT 25 800 3.9 8.4
( Al2O3 bei 1000°C ) ( 6)
source: Bürgel
Attention: Heat conductivity strongly depends on alloy composition, see steels and pure
Ni with 91 W/(mK) in comparison to Ni-base alloys with 11 W/(mK)
Content
a) Static
b) Cyclic (Fatigue)
Microstructure is NOT stable
annealed deformed
stress-relieved recrystallized
Recrystallization
fully re-crystallized
time dependence of
recrystallization can be
approximated by
Avrami-Johnson-Mehl
function:
partly re-crystallized
n
 t 
 t0 
fr  1 e
, deformed
Grain Coarsening
• driving force: reduction of grain boundary
energy
• T > 0.7 · Tm
• no pre-deformation necessary
• self-similar system
• Ostwald ripening d ~ t1/3 (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
solution heat treatment
• in general: cooling rate as
high as possible, thereafter quenching
annealing (in the two-phase annealing
region) to let grow the furnace cooling
precipitates
Thermodynamic ↔ Kinetic
Example: Al-Cu Alloy
Guinier-Preston
solution heat treatment Zones leading to
θ-Precipitates
quenching
(Al2Cu) have
paved the way
annealing
annealing
to the success of
quenching Al-alloys
supersaturated solid solution
Other Examples of
precipitate hardening:
Al2Cu in AlCu alloy:
platinum-base superalloy nickel-base superalloy

Time Dependence of
Precipitation Hardening
nucleation, growth, coarsening
T = const.
dT precipitate size λT distance between precipitates

fT volume fraction of precipitates
Coherent - Semicoherent - Incoherent
(mit Orientierungsbezug) (ohne Orientierungsbezug)
ap  am ap  am ap  am a
misfit  :   
1
2 a p  am  am ap a
Energy Consideration for
Gtotal = Gvol + Gboundary + Gstrain + Gdefect
total change in free enthalpy
strain enthalpy (elastic energy + dislocation line energy)

reduction of enthalpy by precipitation coupled with a defect
enthalpy of phase boundary (scales with surface)
enthalpy of formation of matrix to precipitate (scales with volume)
Heterogeneous Nucleation
dislocations
subgrain grain boundaries
boundaries
surface (internal
and external)
vacancy cluster
stacking faults
incoherent
precipitates coherent
twin boundaries
TEM-Micrograph of TiC Precipitates at
Dislocations in an Austenitic Steel
Ostwald-Ripening of Precipitates
d3 - d03 ~ Dt here for T/Tm  0.74

1 year
' particle size in IN 738 LC at

T = 920°C.
particle coarsening constant of

50 nm · h-1/3
+0,5 µm after 1.000 h
+1 µm after 8.000 h
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 · Tm the properties (deformation) will be time
temperature and rate dependent, creep experiment.
solid solution precipitate

deformation hardening fine grain hardening
strengthening hardening
cold deformation (RT) strong medium medium to strong medium to strong
temporary hardening, reduced strength with
reduced creep rupture fine grain material
creep (HT) medium medium to strong
strength, may lead to  coarse grain,
recrystallization better single crystal
Elastic (E-)Modulus and
Poisson's Ratio
Ni-base superalloys 120 115 110 105 0,39 - 0,41

85 @ 1000°C
E
shear modulus G G
2  (1  )
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 t1%
design by YS or UTS
High Temperature Deformation
• dislocation glide (Peierls stress, in fcc and hcp very small and for T >
0.15 Tm negligible)
• cross slip of screw dislocations and dislocation interactions (for a low
stacking fault energy  larger dislocation spacing  thermal
activation necessary, T > 0.2 Tm, influence on deformation rate)
• climb of edge dislocations to overcome obstacles:
diffusion at complete
dislocation line
 T > 0.4 Tm
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:
 int .    G  b  
Gb 1 1
dislocation =  and 
2 r r
G shear modulus, α constant 0.3 - 1, b magnitude of Burgers vector
Creep Experiment
behavior of pure metals:
primary secondary tertiary:
Creep Experimental Setup
up to 1400°C
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
single crystal (SX) nickel base superalloy (habilitation thesis Glatzel)
7 8x10-6
6 [001] orientation, 1123K, 650MPa
5 6x10-6 [001] orientation, 1123K, 650MPa
strain rate [1/s]

strain [%]
4
3 4x10-6
2
2x10-6
1
0 0
0 10 20 30 40 50 60 70 0 10 20 30 40 50 60 70
time [h] time [h]
10-5
1123K, 650 MPa

logarithm of strain rate versus strain
strain rate [1/s]
10-6
(most valuable information for
10-7
materials scientist)
0 1 2 3 4 5 6
University Bayreuth, Advanced High
strainTemperature
[%] Alloys 64 Uwe Glatzel, Metals and Alloys
Different Creep Stages
• primary creep: strain rate dε/dt decreases 
material hardens
• secondary creep stage: strain rate constant 
hardening and softening are in equilibrium 
dislocation multiplication and annihilation in
equilibrium  disl. density ρ = const.
• tertiary creep: necking (creep pores) develop
 local stress and strain rate increases
drastically.
World Record
Japan, Germany
NIMS: 14.853 days on 24. Feb. 2012,

probably still running (started in 06/1969!)
Siemens: 14,852 days terminated in 2000
http://www.nims.go.jp/eng/news/press/2011/02/p201102240.html
Modelling of Primary and
Secondary Creep Stage
density   velocity
    b  v  and:
Preußner et al.
Int. J. Plasticity 25 (2008) 973
Problem with Low Creep Rates
Life time of stationary gas turbines > 20 years and
max. = 3%
steady state ≈ 5·10-11 s-1

Reliable data in lab down to 1·10-9 s-1:
Δl = 1 μm with l0 = 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!
Engineering Creep Curves
raw data creep curves:
time to failure:  time – strain

(e.g. 1%)
isochrone time to failure:  isochrone strain
Natural Creep Law
 steady state    b  v
2
  external 
 
 Gb 
v~ 1
external
 3
  ~ external
natural creep law
G b 2
Norton Creep Law (Empirical)
 Qcreep
with Norton creep exponent "n"
ε steady state  A  σ n
external e R T
and Qcreep ≈ Qself diffusion
power law break

down (plb) stress dependence
of the stationary
T = const. creep rate of the
austenitic steel 800
dislocation
H at 900°C and
climb
1000°C:
diffusional creep
Temperature Dependence of
Stationary Creep Rate
fcc alloys:
 = 28 MPA = const.
QsdNi ≈ 244 kJ/mol

QsdFe ≈ 290 kJ/mol
n  Qc
3, 5   
 s  A   SF     e RT
E
this equation used in:

Austenitischer Stahl 800H Fleischmann et al., Acta Mat. 87 (2015) 350
Activation Energy for Creep
slope = 1
Constant Load ↔ Constant Stress
n n
 F  F  (1  ) 
   0     0      0  
n
   0   0n  1   n
A  A0 
failure
in case the gauge length
deforms uniform with
constant volume
This method is applicable to

determine the stress exponent "n"
only, if the secondary creep state
lasts to at least 10%
ln  = ln  0 + n · ln 0 + n · ln (1+ε) = const. + n · ln (1+ε)

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 Tm at moderate and higher stress levels. At low
temperatures (< 0.4Tm) dislocation glide has the lower boundary in the range of the elastic stress limit
(typically 10-3E).
Dislocation Climb: At higher temperatures (> 0.4Tm) 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 - Tm). Relevance only at very
low stress levels and T close to Tm: 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 i    G  b    solid solution

and impurity (low temp.)
b) stationary dislocation
pinned by impurities
(Cottrell clouds)
c) pulled off Cortrell clouds
(Lüders 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
i    G  b    solid solution  precipitate
threshold stress concept (with n ≈ 3 - 4 and Qcreep = Qself diffusion):

n  Qc
  0 
 ss  A     e R T
 E 
coherent and semi-
in-coherent phase
mechanism temperature coherent phase
boundaries
boundaries
cutting 0 K up to Ts yes no
bypass by Orowan 0 K up to Ts yes yes
climb over obstacles > 0.4Ts yes no
Orowan Stress
Line tension leads to a back stress,

the Orowan stress, due to obstacles
(in most cases precipitates) with an L
average distance L between these 2r

precipitates.  Tsin
T T
r

Gb
σ Orowan 
L
Hardening Mechanisms as
Function of Precipitate Size
dT0 initial precipitate size
1 and 2 arbitrary external stress levels

= cutting
passing by:  ~ d T
1
climbing:  ~
d T2
Cutting is relevant only for coherent
precipitates
 Dependence of stationary creep rate on

initial precipitate size for two different
external stress levels
Pinning of Dislocations by
Carbides in Austenitic Steel
T = 1000°C, σ = 25 MPa, carbides of the type TiC und M23C6

Very High Volume Fractions
Volume fractions of 70% are only achievable with non-spherical precipitates.
Spacing between precipitates is getting smaller  Orowan stress
Orowan ≈ G·b/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:
G  b  3 f γ'
Orowan ≈
d part.
Dispersion Hardening
(oxide dispersion strengthened alloys (ODS-alloys))
yield
precipitate strengthened
stress
dispersion strengthened
temperature Tm
temperature regime for

dissolution of precipitates back-side pinning of dislocation by
ODS-particle (Rössler + Arzt)
Summary:
Hardening Mechanisms
Internal back stress in steady state regime: i   G b 
Orowan stress in case of precipitates or particles: Orowan ≈ G·b/L
Δr
Solid solution strengthening: σsolid solution  const. 
r
Δa
In case of coherent precipitates: σ coherency  E  ε misfit  E
a
Size effects, see paper E. Arzt (Acta mat. 46 (1998), 5611-5626)

Creep Damage
creation of a creep pore in poly-
crystalline material due to disloction glide:
a) cracks at grain boundaries b) cavities (micropores) at grain boundaries

Creep Damage
fracture
nucleation, not detectable with OM
micropore, difficult to detect

micro cracks
pear necklace like chain of

micropores (easy detectable)
Extrapolation of Time-to-Fracture Data
(Larson-Miller plot, Larson-Miller parameter)
Monkmann-Grant relation with constant K and exponent m ≈ 1:
K
tf  m ↔ ln(t f )  K  m  ln ss 
 ss
Q creep Q creep 1
ε ss  A 0  σ  e
n

R T
 Be

R T ↔ ln( ss )  B1  B2 
T
1 1
ln(t f )  K  m  B1  m  B 2    C  P 
T T ~ 1952 @ GE
with material dependent constants C and P.

→ Larsson-Miller plot: P = T[C + ln(tf)]10-3 , with CNi-base = 20, T in K, tf in h
Example: tf =100 h, T = 1273 K → P = 31.3 (relation tf with T at σ = const.)
Larson-Miller-Plot
stationary gas turbine, about 20 years of service ~ 130.000 h
Comparison of CMSX-6,
LEK 94 and CMSX-4,
patent Wöllmer, Glatzel,
Mack, Wortmann P = T[20 + ln(tf)]10-3 (T in K, tf in h)
Comparison LEK 94 with
CMSX-4 and CMSX-6
CMSX-6 [Wortmann 88] 8.0 g/cm3
500 CMSX-4 [Erickson 94] 8.7 g/cm3
CMSX-4 [Frasier 90] 8.7 g/cm3
3
LEK-2 8.5 g/cm
3
 K LEK-4 8.2 g/cm
LEK-5 8.2 g/cm3
stress [MPa]
LEK-3 8.1 g/cm3

LEK-6 8.3 g/cm3
3
230 LEK-1C 8.4 g/cm
3
LEK-1B 8.3 g/cm
3
LEK-1A 8.2 g/cm
T = 10 K
 K
120
10 K
Not corrected
25 26 27 28 29 30 31 32
regarding density!
Larsen-Miller-parameter
-3
P = T (20+log tf) 10
Content
a) Static
b) Cyclic (Fatigue)
Time Dependent Variation of Stress
and/or Temperature and/or ...
Wöhler diagram for T < 0.4·Tm. Z time fatigue limit, D endurance

fatigue limit
a) type I metal (bcc) b) type II metal (fcc) endurance limit at 2·107
Change in Wöhler 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 :
εthermal = αthermal · ΔT, or: σthermal = E · εthermal
 thermal = E · αthermal · ΔT
Lower E-Modulus is Helpful:
<111>
<001>
 orientation of single crystals in <100> direction reduces thermal stresses

Siebörger et al., Mat. Sci. Eng. A298 (2001) 26–33
Anisotropy and Temperature Dependence of
Elastic Constants in Ni-base Superalloys
D. Siebörger, H. Knake, U. Glatzel, Mat. Sci. Eng. A298 (2001)
Orientation dependence of
Young’s modulus E of matrix
phase. Distance from the center to
the surface indicates the
magnitude of the Young’s modulus
in this direction.
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
air right hand and lower axes

 O2 partial pressure at T = 0.
As an example pO2 of
10-15 Pa = 10-20 bar = 10-17 mbar
HV is shown as a dashed line.
UHV
only the oxides below this line

are thermodynamic stable.
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 (Δm/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)
Oxide TiO MgO Al2O3 MgO2 Ti2O3 ZrO2 Ti3O5 NiO FeO TiO2 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 Cr2O3 FeCr2O4 Fe3O4 Fe2O3 SiO2 Ta2O5 Nb2O5 W

PB 2.05 2.10 2.11 2.15 2.15 2.50 2.68 3.40
ideal is 1.1 to 1.3

Of course thermal expansion coefficients also play a major role for the stability of oxide scales.
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
1000°C
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 NiAl2O4 , NiTa2O6, Cr2O3 thick and porous layer consisting of two fractions
3 third oxide layer Al2O3 dense and thin monophase layer

4 γ’-free layer see Tab. 1 Al-content of 2.2 wt. %
5 γ’ reduced layer composition in-between layer number 4 and 6 reduced Al content, γ’ morphology change
6 two-phase centre region nominal composition of René N5 (Tab. 1) regular γ’/ γ structure, see Fig. 6 f)
Content
a) Static
b) Cyclic (Fatigue)
High Temperature Alloys
T > 500°C, Application in:
• energy generation
• engines (cars, trains, airplanes, ships, ... )
• chemical industry
• metallurgy
• mechanical engineering
Overview Metals
ele struc- Ttrans.Tm  max. O-solubility advantages/disadvantages
m. ture [°C] [g/cm3] [at.%]
Ti  hdp 882 4.5 31.9 + low density

 krz 1855 4.5 8 + high melting point
+ abundant available
+ low th. (~ 10-5 K-1)
 no alloy known with adequate strength for temperatures > 600°C
 high oxygen and nitrogen solubility > 700°C, increased brittleness
 linear oxidation > 800°C
 low thermal conductivity
 ignition hazard
V krz 1910 6.1 17  catastrophic oxidation; Tm(V2O5) = 658°C
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; Tm(MoO5) = 795°C
 no long lasting coating available
W krz 3422 19.3 0 + highest melting point of metals (only C with even higher Tm)
+ very high creep strength
+ low th, high thermal conductivity, good thermal fatigue strength
 very brittle at RT
 catastrophic oxidation > 1000°C durch hohe WO3-Abdampfrate
 no long lasting coating available
University Bayreuth, Advanced High Temperature Alloys 110 very high density Uwe Glatzel, Metals and Alloys
Overview Metals
elem. structure Ttrans.  max. O- advantages/disadvantages
Tm [g/cm3] solubility
[°C] [at.%]
 krz 912 7.9 0.0008 + very good corrosion resistance by alloying with Cr or (Cr + Al)
 kfz 1395 7.7 0.0098 + -structure can be stabilized down to RT (by Ni)
Fe  krz 1538 7.4 0.029 + very good processable and weldable
+ low cost (~ 1 €/kg)
 strength at high temperatures (> 700°C) limited
Co  hdp 422 8.8 0 + very good corrosion resistance by alloying with Cr or (Cr + Al)
 kfz 1495 8.7 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 (Ni3Al)
+ very good corrosion resistance by alloying with Cr or (Cr + 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
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 Ttrans.  advantages/disadvantages
Tm [g/cm3]
[°C]
Ni3Al L12 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 Al2O3-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 500°C (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, June 2008
Processing of a Turbine
Blade
FPI
X-Ray
Turbine Casting
Feinguss, Wachsausschmelzverfahren, lost wax investment casting, ...
Additionally: hollow geometries possible (core insertion)!
Archaeological Evidence
(Bibracte) ~ 50 B.C.
Turbine Casting
ceramic mould filled with wax
cloth clip
Single Crystal Casting
Metals and Alloys, Bayreuth
< 20 s
0,8...400
mm/min
Content
a) Static
b) Cyclic (Fatigue)

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Advanced High

Prof. Dr.-Ing. Uwe Glatzel

lecture notes: http://www.metalle.uni-bayreuth.de then "Lehre" then "Vorlesungen",

• only alloys will be looked at (no ceramics, no

Composits (SiC/C) up to 1600 complex

500 temperature [°C] 1500 2000

500 temperature [°C] 1500 2000

500 temperature [°C] 1500 2000

to find 1 Rh atom within a

© U.S. Geological Survey Fact Sheet 087-02 (2002)

U total mol  3  R  T  0,33 eV, bzw. 32 kJ/mol bei 1000°C Arrhenius-plot

T[°C] 20 300 450 800 1000 1200 1454

T/Tm 0.17 0.33 0.42 0.62 0.74 0.85 1.00

cv 10-23 3·10-12 10-9 10-6 10-5 7·10-5 3·10-4

equilibrium vacancy concentration for nickel

10-10 Qvacnickel = 1,36 eV

vacancy concentration [10 ]

Nickel Vacancy Concentration Nickel Vacancy Concentration

temperature [°C] Tm 0,10

0 200 400 600 800 1000 1200 1400 1600

Qsd ≈ 17 ·kB ·Tm  Qsdnickel ≈ 2.5 eV = 244 kJ/mol

Steep slope indicates a

surface diffusion Coefficient of diffusion of Th

Deff = Dsd + π ·  / d · Dgrain bound.

 thickness of grain boundary, Ω atomic volume

    Dself diffusion    D grain boundary   D eff

for real geometry (non-cuboidal grains)

150 kJ/mol ~ Qsd

Single crystal aluminium, oriented such that <110>{111} slip is activated.

Lytton, Shepard and Dorn, Trans. AIME 212 (1958) 220

• fcc preferred: lower coefficient of diffusion (Dclose to Tm ~ factor of

a … coefficient of temperature conductivity

ferritic steel 45 460 7.8 13.0

bimodal (some grain

platinum-base superalloy nickel-base superalloy

dT precipitate size λT distance between precipitates

(mit Orientierungsbezug) (ohne Orientierungsbezug)

Gtotal = Gvol + Gboundary + Gstrain + Gdefect

total change in free enthalpy

strain enthalpy (elastic energy + dislocation line energy)

enthalpy of phase boundary (scales with surface)

enthalpy of formation of matrix to precipitate (scales with volume)

d3 - d03 ~ Dt here for T/Tm  0.74

' particle size in IN 738 LC at

particle coarsening constant of

• most alloy properties at room temperature are time and

solid solution precipitate

Ni-base superalloys 120 115 110 105 0,39 - 0,41

Material properties of steel and

(YS) design by t1%

arrangement in low energy

primary secondary tertiary:

Pyrometer from left, optical strain

strain rate [1/s]

1123K, 650 MPa

NIMS: 14.853 days on 24. Feb. 2012,

Siemens: 14,852 days terminated in 2000

steady state ≈ 5·10-11 s-1

≈ 3.5% strain per year!

Within university labs we are two orders of magnitude too fast

raw data creep curves:

time to failure:  time – strain

isochrone time to failure:  isochrone strain