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Advanced Materials
Advanced Materials
Temperature Alloys
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
University Bayreuth, Advanced High Temperature Alloys 2 Uwe Glatzel, Metals and Alloys
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
University Bayreuth, Advanced High Temperature Alloys 4 Uwe Glatzel, Metals and Alloys
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
University Bayreuth, Advanced High Temperature Alloys 5 Uwe Glatzel, Metals and Alloys
Introduction
University Bayreuth, Advanced High Temperature Alloys 6 Uwe Glatzel, Metals and Alloys
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
University Bayreuth, Advanced High Temperature Alloys 7 Uwe Glatzel, Metals and Alloys
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
University Bayreuth, Advanced High Temperature Alloys 8 Uwe Glatzel, Metals and Alloys
usable strength
Overview Materials
source:
Plansee AG,
Reutte,
Tirol,
Austria
University Bayreuth, Advanced High Temperature Alloys 9 Uwe Glatzel, Metals and Alloys
usable strength
Taking Density into Account
University Bayreuth, Advanced High Temperature Alloys 10 Uwe Glatzel, Metals and Alloys
usable strength
Oxidation Resistance
University Bayreuth, Advanced High Temperature Alloys 11 Uwe Glatzel, Metals and Alloys
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.
University Bayreuth, Advanced High Temperature Alloys 12 Uwe Glatzel, Metals and Alloys
Density
Os, Ir Pt
Re
W Au
Ta
Hf
Ru, Rh, Pd
Tc Pd
Mo
Ag
Nb
Ni
University Bayreuth, Advanced High Temperature Alloys 13 Uwe Glatzel, Metals and Alloys
Abundance of Elements
in Earth's Upper Continental Crust
3 Q
u total atom 2 u kin 2 kB T 3 kB T
0 e
atom
2 R T
-4
10-20
0,75
University Bayreuth, Advanced High Temperature Alloys 19 Uwe Glatzel, Metals and Alloys
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
University Bayreuth, Advanced High Temperature Alloys 20 Uwe Glatzel, Metals and Alloys
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
600 kJ/mol
500 kJ/mol
400 kJ/mol
300
0.137 kJ/(mol·K)
≈ 17 · kB ·NATm
Tm (K)
University Bayreuth, Advanced High Temperature Alloys 22 Uwe Glatzel, Metals and Alloys
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
University Bayreuth, Advanced High Temperature Alloys 23 Uwe Glatzel, Metals and Alloys
Coefficient of Diffusion
University Bayreuth, Advanced High Temperature Alloys 24 Uwe Glatzel, Metals and Alloys
Coefficient of Diffusion with Defects
University Bayreuth, Advanced High Temperature Alloys 25 Uwe Glatzel, Metals and Alloys
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
University Bayreuth, Advanced High Temperature Alloys 26 Uwe Glatzel, Metals and Alloys
Grain Boundary Diffusion
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
University Bayreuth, Advanced High Temperature Alloys 27 Uwe Glatzel, Metals and Alloys
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
D grain boundary
D eff Dself diffusion
d grain
D gb D sd
identical creep rates if: Dsd
d grain D gb d grain
University Bayreuth, Advanced High Temperature Alloys 29 Uwe Glatzel, Metals and Alloys
Activation Energies Indicating
Mechanism Changes
100 kJ/mol
50
K temperature
0 200 400 600 °C
TmNi = 1,455°C
TmAl = 660°C
TmNiAl = 1,638°C
University Bayreuth, Advanced High Temperature Alloys 31 Uwe Glatzel, Metals and Alloys
Summary: Effects of Diffusion on
High Temperature Alloys
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:
University Bayreuth, Advanced High Temperature Alloys 33 Uwe Glatzel, Metals and Alloys
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
compare:
j D c q λ T
c T
D c a ΔT
t t
University Bayreuth, Advanced High Temperature Alloys 34 Uwe Glatzel, Metals and Alloys
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.
University Bayreuth, Advanced High Temperature Alloys 35 Uwe Glatzel, Metals and Alloys
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
stress-relieved recrystallized
University Bayreuth, Advanced High Temperature Alloys 38 Uwe Glatzel, Metals and Alloys
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
University Bayreuth, Advanced High Temperature Alloys 39 Uwe Glatzel, Metals and Alloys
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
University Bayreuth, Advanced High Temperature Alloys 40 Uwe Glatzel, Metals and Alloys
Grain Coarsening
monomodal
University Bayreuth, Advanced High Temperature Alloys 41 Uwe Glatzel, Metals and Alloys
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
University Bayreuth, Advanced High Temperature Alloys 42 Uwe Glatzel, Metals and Alloys
Thermodynamic ↔ Kinetic
University Bayreuth, Advanced High Temperature Alloys 43 Uwe Glatzel, Metals and Alloys
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
University Bayreuth, Advanced High Temperature Alloys 44 Uwe Glatzel, Metals and Alloys
Other Examples of
precipitate hardening:
Al2Cu in AlCu alloy:
T = const.
ap am ap am ap am a
misfit :
1
2 a p am am ap a
University Bayreuth, Advanced High Temperature Alloys 47 Uwe Glatzel, Metals and Alloys
Energy Consideration for
Precipitate Hardening
University Bayreuth, Advanced High Temperature Alloys 48 Uwe Glatzel, Metals and Alloys
Heterogeneous Nucleation
dislocations
subgrain grain boundaries
boundaries
surface (internal
and external)
vacancy cluster
stacking faults
incoherent
precipitates coherent
twin boundaries
University Bayreuth, Advanced High Temperature Alloys 49 Uwe Glatzel, Metals and Alloys
TEM-Micrograph of TiC Precipitates at
Dislocations in an Austenitic Steel
University Bayreuth, Advanced High Temperature Alloys 50 Uwe Glatzel, Metals and Alloys
Ostwald-Ripening of Precipitates
University Bayreuth, Advanced High Temperature Alloys 51 Uwe Glatzel, Metals and Alloys
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
University Bayreuth, Advanced High Temperature Alloys 52 Uwe Glatzel, Metals and Alloys
Room Temperature (RT) versus
High Temperature (HT) Deformation
University Bayreuth, Advanced High Temperature Alloys 53 Uwe Glatzel, Metals and Alloys
Elastic (E-)Modulus and
Poisson's Ratio
E
shear modulus G G
2 (1 )
University Bayreuth, Advanced High Temperature Alloys 54 Uwe Glatzel, Metals and Alloys
Change in Materials Properties
with Temperature
University Bayreuth, Advanced High Temperature Alloys 55 Uwe Glatzel, Metals and Alloys
Tension ↔ Creep Experiment
(UTS)
design by YS or UTS
University Bayreuth, Advanced High Temperature Alloys 56 Uwe Glatzel, Metals and Alloys
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
University Bayreuth, Advanced High Temperature Alloys 57 Uwe Glatzel, Metals and Alloys
Dislocation Climb
climb of edge dislocations to
annihilate each other.
movement of screw
dislocations with kink
University Bayreuth, Advanced High Temperature Alloys 58 Uwe Glatzel, Metals and Alloys
University Bayreuth, Advanced High Temperature Alloys 59 Uwe Glatzel, Metals and Alloys
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
Gb 1 1
dislocation = and
2 r r
G shear modulus, α constant 0.3 - 1, b magnitude of Burgers vector
University Bayreuth, Advanced High Temperature Alloys 60 Uwe Glatzel, Metals and Alloys
Creep Experiment
behavior of pure metals:
University Bayreuth, Advanced High Temperature Alloys 61 Uwe Glatzel, Metals and Alloys
Creep Experimental Setup
up to 1400°C
Constant
temperature
and stress or
load
University Bayreuth, Advanced High Temperature Alloys 62 Uwe Glatzel, Metals and Alloys
Creep Experimental Setup for
Electrical Conductivity Material
up to Melting Temperature
University Bayreuth, Advanced High Temperature Alloys 63 Uwe Glatzel, Metals and Alloys
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
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
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.
University Bayreuth, Advanced High Temperature Alloys 65 Uwe Glatzel, Metals and Alloys
World Record
Japan, Germany
http://www.nims.go.jp/eng/news/press/2011/02/p201102240.html
University Bayreuth, Advanced High Temperature Alloys 66 Uwe Glatzel, Metals and Alloys
Modelling of Primary and
Secondary Creep Stage
density velocity
b v and:
Preußner et al.
Int. J. Plasticity 25 (2008) 973
University Bayreuth, Advanced High Temperature Alloys 67 Uwe Glatzel, Metals and Alloys
Problem with Low Creep Rates
Life time of stationary gas turbines > 20 years and
max. = 3%
University Bayreuth, Advanced High Temperature Alloys 68 Uwe Glatzel, Metals and Alloys
Engineering Creep Curves
University Bayreuth, Advanced High Temperature Alloys 69 Uwe Glatzel, Metals and Alloys
Natural Creep Law
steady state b v
2
external
Gb
v~ 1
external
3
~ external
natural creep law
G b 2
University Bayreuth, Advanced High Temperature Alloys 70 Uwe Glatzel, Metals and Alloys
Norton Creep Law (Empirical)
Qcreep
with Norton creep exponent "n"
ε steady state A σ n
external e R T
and Qcreep ≈ Qself diffusion
diffusional creep
University Bayreuth, Advanced High Temperature Alloys 71 Uwe Glatzel, Metals and Alloys
Temperature Dependence of
Stationary Creep Rate
fcc alloys:
= 28 MPA = const.
n Qc
3, 5
s A SF e RT
E
University Bayreuth, Advanced High Temperature Alloys 72 Uwe Glatzel, Metals and Alloys
Activation Energy for Creep
slope = 1
University Bayreuth, Advanced High Temperature Alloys 73 Uwe Glatzel, Metals and Alloys
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
n=3
University Bayreuth, Advanced High Temperature Alloys 75 Uwe Glatzel, Metals and Alloys
Ashby Deformation
Mechanism Maps
Versetzungsklettern !
dislocation climb !
University Bayreuth, Advanced High Temperature Alloys 76 Uwe Glatzel, Metals and Alloys
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 (< 0.4Tm) dislocation glide has the lower boundary in the range of the elastic stress limit
(typically 10-3E).
Dislocation Climb: At higher temperatures (> 0.4Tm) 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.
University Bayreuth, Advanced High Temperature Alloys 77 Uwe Glatzel, Metals and Alloys
Creep of Alloys
(assuming solid solution, no precipitates)
University Bayreuth, Advanced High Temperature Alloys 78 Uwe Glatzel, Metals and Alloys
Precipitate Hardening
University Bayreuth, Advanced High Temperature Alloys 79 Uwe Glatzel, Metals and Alloys
Orowan Stress
r
Gb
σ Orowan
L
University Bayreuth, Advanced High Temperature Alloys 80 Uwe Glatzel, Metals and Alloys
Hardening Mechanisms as
Function of Precipitate Size
dT0 initial precipitate size
ODS alloys:
G b 3 f γ'
Orowan ≈
d part.
University Bayreuth, Advanced High Temperature Alloys 83 Uwe Glatzel, Metals and Alloys
Dispersion Hardening
(oxide dispersion strengthened alloys (ODS-alloys))
yield
precipitate strengthened
stress
dispersion strengthened
temperature Tm
Δr
Solid solution strengthening: σsolid solution const.
r
Δa
In case of coherent precipitates: σ coherency E ε misfit E
a
University Bayreuth, Advanced High Temperature Alloys 87 Uwe Glatzel, Metals and Alloys
Extrapolation of Time-to-Fracture Data
(Larson-Miller plot, Larson-Miller parameter)
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
Be
R T ↔ ln( ss ) B1 B2
T
1 1
ln(t f ) K m B1 m B 2 C P
T T ~ 1952 @ GE
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)
University Bayreuth, Advanced High Temperature Alloys 89 Uwe Glatzel, Metals and Alloys
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]
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
University Bayreuth, Advanced High Temperature Alloys 90 Uwe Glatzel, Metals and Alloys
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
University Bayreuth, Advanced High Temperature Alloys 91 Uwe Glatzel, Metals and Alloys
Time Dependent Variation of Stress
and/or Temperature and/or ...
10 CrMo9-10
University Bayreuth, Advanced High Temperature Alloys 93 Uwe Glatzel, Metals and Alloys
Thermal Fatigue
thermal = E · αthermal · ΔT
University Bayreuth, Advanced High Temperature Alloys 95 Uwe Glatzel, Metals and Alloys
Lower E-Modulus is Helpful:
<111>
<001>
University Bayreuth, Advanced High Temperature Alloys 96 Uwe Glatzel, Metals and Alloys
Anisotropy and Temperature Dependence of
Elastic Constants in Ni-base Superalloys
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.
University Bayreuth, Advanced High Temperature Alloys 97 Uwe Glatzel, Metals and Alloys
TMF and many other Time
Dependent Test Techniques
University Bayreuth, Advanced High Temperature Alloys 98 Uwe Glatzel, Metals and Alloys
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
University Bayreuth, Advanced High Temperature Alloys 99 Uwe Glatzel, Metals and Alloys
High Temperature Corrosion
As an example pO2 of
10-15 Pa = 10-20 bar = 10-17 mbar
HV is shown as a dashed line.
UHV
University Bayreuth, Advanced High Temperature Alloys 101 Uwe Glatzel, Metals and Alloys
Time Dependent Oxidation
University Bayreuth, Advanced High Temperature Alloys 102 Uwe Glatzel, Metals and Alloys
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.
University Bayreuth, Advanced High Temperature Alloys 103 Uwe Glatzel, Metals and Alloys
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
University Bayreuth, Advanced High Temperature Alloys 104 Uwe Glatzel, Metals and Alloys
Alloying Effects:
concentration changes
University Bayreuth, Advanced High Temperature Alloys 105 Uwe Glatzel, Metals and Alloys
Example Ni-Cr-Al
Ni Cr 10 Al 5
oxide layer and
internal
oxidation occurs
1000°C
University Bayreuth, Advanced High Temperature Alloys 106 Uwe Glatzel, Metals and Alloys
Observations for the
Superalloy Rene N5
2 interlayer of oxides NiAl2O4 , NiTa2O6, Cr2O3 thick and porous layer consisting of two fractions
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)
University Bayreuth, Advanced High Temperature Alloys 107 Uwe Glatzel, Metals and Alloys
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
University Bayreuth, Advanced High Temperature Alloys 108 Uwe Glatzel, Metals and Alloys
High Temperature Alloys
T > 500°C, Application in:
• energy generation
• engines (cars, trains, airplanes, ships, ... )
• chemical industry
• metallurgy
• mechanical engineering
University Bayreuth, Advanced High Temperature Alloys 109 Uwe Glatzel, Metals and Alloys
Overview Metals
ele struc- Ttrans.Tm max. O-solubility advantages/disadvantages
m. ture [°C] [g/cm3] [at.%]
University Bayreuth, Advanced High Temperature Alloys 111 Uwe Glatzel, Metals and Alloys
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
University Bayreuth, Advanced High Temperature Alloys 112 Uwe Glatzel, Metals and Alloys
Example of Intermetallic
Phases (Ni-Al-System)
University Bayreuth, Advanced High Temperature Alloys 113 Uwe Glatzel, Metals and Alloys
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
University Bayreuth, Advanced High Temperature Alloys 114 Uwe Glatzel, Metals and Alloys
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.
University Bayreuth, Advanced High Temperature Alloys 115 Uwe Glatzel, Metals and Alloys
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
University Bayreuth, Advanced High Temperature Alloys 116 Uwe Glatzel, Metals and Alloys
MTS-Factory in Bayreuth
University Bayreuth, Advanced High Temperature Alloys 118 Uwe Glatzel, Metals and Alloys
MTS-Factory, June 2008
University Bayreuth, Advanced High Temperature Alloys 119 Uwe Glatzel, Metals and Alloys
MTS-Factory, June 2008
University Bayreuth, Advanced High Temperature Alloys 120 Uwe Glatzel, Metals and Alloys
Processing of a Turbine
Blade
FPI
X-Ray
Turbine Casting
Feinguss, Wachsausschmelzverfahren, lost wax investment casting, ...
Additionally: hollow geometries possible (core insertion)!
University Bayreuth, Advanced High Temperature Alloys 121 Uwe Glatzel, Metals and Alloys
Archaeological Evidence
(Bibracte) ~ 50 B.C.
Turbine Casting
ceramic mould filled with wax
cloth clip
University Bayreuth, Advanced High Temperature Alloys 122 Uwe Glatzel, Metals and Alloys
Single Crystal Casting
Metals and Alloys, Bayreuth
< 20 s
0,8...400
mm/min
University Bayreuth, Advanced High Temperature Alloys 123 Uwe Glatzel, Metals and Alloys
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
University Bayreuth, Advanced High Temperature Alloys 124 Uwe Glatzel, Metals and Alloys