Advanced High Temperature Alloys

Advanced High Temperature Alloys
Prof. Dr.-Ing. g Uwe Glatzel Metals and Alloys University Bayreuth SS 2010
University Bayreuth, Advanced High Temperature Alloys 1 Uwe Glatzel, Metals and Alloys
Lecturer:
Prof Dr Prof. Dr.-Ing. Ing habil habil. Uwe Glatzel
born Dez. 1960 Physik-Diplom (B.Sc. (B Sc and M.Sc) 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 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)
phone: h +49 (0) ( ) 921 - 55-5555 e-mail: uwe.glatzel@uni-bayreuth.de
2 Uwe Glatzel, Metals and Alloys
postal address: Ludwig-Thoma-Str. d i h 36b b D-95447 Bayreuth, Germany
University Bayreuth, Advanced High Temperature Alloys
Literature
R. Brgel R Brgel, Handbuch Hochtemperatur-Werkstofftechnik Hochtemperatur Werkstofftechnik, Vieweg R.C. Reed, The Superalloys - Fundamentals and Applications, Cambridge Univ. Press H. Frost, M. Ashby, Deformation-Mechanism Maps, Pergamon Press G M G. Meetham, th M M. V Van d der V Voorde, d Materials M t i l f for Hi High h Temperature T t Engineering E i i Applications, Springer J. Betten, Creep Mechanics, Springer Askeland: Materialwissenschaften, Spektrum Lehrbuch; 1994 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 H. J. Bargel Bargel, G. G Schulze, Schulze Werkstoffkunde, VDI VDI-Verlag Verlag, Dsseldorf P. Sarrazin, A. Galerie, J. Fouletier, Mechanisms of High Temperature Corrosion, Trans Tech Publications
lecture notes: http://www.metalle.uni-bayreuth.de then "Lehre" then "Vorlesungen", you will find the link to this lecture notes 3 and three review talks we will do at the end. University Bayreuth, Advanced High Temperature Alloys Uwe Glatzel, Metals and Alloys
What You Should Know:

basic thermodynamics introduction to diffusion introduction to dislocations phase diagrams theory of elasticity ... basic materials science courses
Contents
1. Introduction 1 Introduction, Basics 2. Stability of Microstructure 3. Mechanical Properties ) Static a) b) Cyclic (Fatigue) 4 High Temperature Corrosion 4. 5. High Temperature Alloys 6. Lost Wax Investment Casting p g on Time: Lectures on 7. Depending
a) SX Ni-Base Superalloys b) LEK 94 c) Pt-Base Superalloys
Introduction
only alloys will be looked at (no ceramics, ceramics no polymers). no coatings (BUT : practically all high temperature systems are coated!), simply not enough time time.
Uwe Glatzel, Metals and Alloys
Maximum Temperatures for Applications li i of f Different iff Materials i l

Group Polymer Glass i service i temperature t t maximum [C] up to 300 up to 800 Fe-Basis (coated) up to 1100 Fe-ODS Fe ODS up to 1300 Ni-base up to 1200 Pt-base up to 1600 refractory metals in inert atmosphere h above b 1600 MoSi2 up to 1800 SiC up to 1600 (SiC/C) ( ) up p to 1600 deformation/damage mechanism melting, decomposing (pyrolyze) viscous flow
Metals
creep, dislocation climb, grain boundary sliding
Ceramics p Composits
viscous flow, glass transition temperature grain boundary temperature, sliding complex p
Overview Materials
usable strength u
source: Plansee AG, AG Reutte, Tirol, Austria
500
temperature [C]
8
1500
2000
Taking Density into Account
usable strength u
500
temperature [C]
9
1500
2000
Oxidation Resistance
usable strength u
500
temperature [C]
10
1500
2000
Refractory Metals:
wider definition of refractory metals
Tm of platinum
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.
11
Density
Re R W Ta Ru, Rh, Pd Hf Pd Nb Ag Os, Ir Pt Au
Tc Mo
12
Abundance of Elements
to find 1 atom Rh within a bunch of Siatoms is comparable to find one individual person within the word population
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: i t
oxidation corrosion
combinations:
thermo thermo-mechanical mechanical fatigue (TMF) stress corrosion cracking, stress oxidation, ...
Basics
Thermodynamics Kinetics
Boltzmann-statistics: energy of movement increases with temperature p
u kin
atom
3 kB T 2
u total atom = 2 u kin

U total mol = 3 R T
atom
3 = 2 kB T = 3 kB T 2
0,33 eV, bzw. 32 kJ/mol bei 1000C

16
& = &0 e
Q R T
Arrhenius-plot
Vacancy Concentration
F = U - TS T S non-zero vacancy concentration t ti is i in thermodynamic equilibrium
cv = e
T[C] T/Tm cv
Q vac R T
Qvacnickel = 1,36 eV (energy necessary to create one vacancy) 20 0.17 300 0.33 450 0.42 10-9 800 0.62 10-6 1000 0.74 10-5 1200 0.85 710-5 1454 1.00 310-4
10-23 310-12
equilibrium vacancy concentration for nickel

Nickel Vacancy Concentration

100
vac cancy concentration
5 10-5
10-10
10-15
vacancy con ncentration [10 ]
1,00
-4
10-20

10-25 0 200 400 600 800 1000 1200 1400 1600
temperature [C]
Tm
0,10 0,01 0 200 400 600 800 1000 1200 1400 1600
temperature [C]
Tm
18
Diffusion
r v j = D c
1. Fick's law
2 s-1 1 [j] = (atoms) ( ) m-2
[D] = m2 s-1 [c] = (atoms) m-3

vacancy diffusion diff i or volume diffusion
19
Coefficient of Diffusion
Qvac Qmigration i ti QSD energy to create a vacancy activation energy to migrate a vacancy activation energy for volume diffusion QSD = Qvac + Qmigration
D = D0 e
QSD 17 kB Tm
( Q vac + Q migration ) k T
= D0 e
Q SD k T
QSDnickel 2.5 eV = 244 kJ/mol

(for a perfect crystal; defects will lower the activation energies)

Dependence Melting Point and Enthalpy of Vacancy Creation

element Pb Al Cu Ag Ni Pt Mo W Tm [C] 327 660 1 085 1 235 1 455 1 768 2 623 3 422
21
17RTm 0 88 0.88 1.36 1.99 2.21 2.53 2 98 2.98 4.23 5.40
Qvac [eV] 0 57 0.57 0.68 1.29 1.12 1.78 1 32 1.32 3.00 4.00
crystal t l structure fcc fcc fcc fcc fcc fcc bcc bcc
QSD versus Tm
400 kJ/mol
0 13 k 0.137 kJ/(molK) /( l ) 17 kB NA
22
Coefficient of Diffusion
Steep p slope p indicates a high activation energy. Small S ll elements l t diffuse diff faster. Diffusion in fcc crystals slower than in bcc crystals. y
23
Coefficient of Diffusion with Defects
surface diffusion
Coefficient of diffusion of Th i W. in W Overall velocity for diffusion depending on grain boundary thickness, grain size and dislocation density.
grain boundary diffusion
volume diffusion pipe diffusion
24
Pipe Diffusion
Deff = DSD + adisl. Ddisl. adisl. area of dislocation core
volume ol me diffusion diff sion dominant pipe diffusion dominant
increasing
( 5 b2 0 0.3 3 nm2) dislocation density Ddisl. pipe i diffusion diff i along l dislocation core atom t flux fl ~ Darea D
decreasing
atoms 2 ~ DSD d grain time grain
atoms 2 ~ D disl. b n i time disl. n d grain
dashed line: diffusion in crystal by the velocity of pipe diffusion
identical atom fluxes if:

DSD d grain = D disl. b 2 = D disl. b 2
25
Grain Boundary Diffusion

Deff = DSD + / d Dgrain bound.
volume diffusion dominant grain boundary diffusion dominant
fine grain coarse grain
with: d effective grain boundary thickness ( 2 b 0.5 nm) grain size
dashed line: diffusion in crystal y by y the velocity y of grain boundary diffusion

University Bayreuth, Advanced High Temperature Alloys 26
Ddisl. pipe diffusion along dislocation core
Activation Energies Indicating Mechanism Changes

~ QSD
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 lli Phases) h ) High binding energies high activation energies low coefficient of diffusion For example NiAl: very low enthalpy of ordered B2 structure low enthalpy outweighs entropy ordered up to melting t temperature t TmNi = 1454C TmAl = 660C TmNiAl = 1638C
Second Fick Fick's s Law

c = D c t
C be Can b concluded l d d directly di tl from f first fi t Fick's Fi k' law. l Similar in heat transfer systems, systems electrical potential, ... .
f1 ( x ) = 1 (x )
1 0.8 0.6 0.4
x f 2 ( x ) = 1 0.5
f1(x) f2(x)
0.2
x f 3 ( x ) = 1 0.05
1 1.5 2
solution to these boundary conditions:
x c( x , t ) = c1 (c1 c 0 ) 2 Dt
29
f3(x)
0.5
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 cp a coefficient of temperature conductivity cp heat capacity density
compare:
r r j = D c
c = D c t
r r & = T q
T = a T t
Temperature Distribution with Thermal h l Barrrier i Coating i (TBC) ( )
cooling air
hot air
Wrmedmmschicht
TBC
Haftvermittlerschicht
bond coat
Grundwerkstoff
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). I case of In f stationary t ti circumstances, i t heat h t conductivity d ti it leads l d to t heat h t flow fl into i t the th solid. lid
Material Parameters at RT
material/property ferritic steel austenite steel Ni-base alloys Mo Ti alloys (-rich) Al Al2O3 bei RT ( Al2O3 bei 1000C ) heat cond. cond
W m K
heat cap. cap cp

J kg gK
density
g cm 3
temp. cond. temp cond a

6 m 2 10 s
45 15 11 145 7 210 25 ( 6)
460 500 450 240 530 890 800
7.8 8.0 8.2 10.2 4.5 2.7 3.9
13.0 3.8 3.0 59.0 2.9 87.0 8.4

source: Brgel
Attention: Heat conductivity strongly depends on alloy composition, composition see steels and pure Ni with 91 W/(mK) in comparison to Ni-base alloys with 11 W/(mK)
Contents
1. Introduction 1 Introduction, Basics 2. Stability of Microstructure 3. Mechanical Properties a) Static b) Cyclic (Fatigue) 4 High Temperature Corrosion 4. 5. High Temperature Alloys 6. Lost Wax Investment Casting 7. Depending on Time: Lectures on
Microstructure is NOT stable

annealed deformed
stress-relieved
recrystallized
Recrystallization
time dependence of recrystallization can be approximated by Avrami Johnson Mehl Avrami-Johnson-Mehl function:
fr = 1 e
tt 0
35
Grain Coarsening
driving force: reduction of grain boundary gy energy T > 0.7 Tm no pre-deformation d f i necessary se self-similar s sys system e Ostwald ripening d ~ t1/3 (big grains eat up small ll grains) i ) new g grains have low dislocation density y
Grain Coarsening
monomodal
bimodal (some grain boundaries are pinned, e.g. by precipitates)
37
Precipitate Hardening
Requirements: solid solution at higher t temperatures t (ability ( bilit to t homogenization heat treatment) during cooling a two-phase region g should be reached in general: cooling rate as g as possible, p thereafter high annealing (in the two-phase region) to let grow the precipitates i i
Thermodynamic Kinetic
39
Example: Al-Cu Al Cu Alloy

Guinier-Preston G i i P t Zones leading to -Precipitates (Al2Cu) have paved the way to the success of Al-alloys
40
Other Examples of precipitate i i hardening: h d i

Al2Cu in AlCu alloy:
platinum-base superalloy
nickel-base superalloy
Time Dependence of Precipitation Hardening

nucleation growth, nucleation, growth coarsening
T = const.
dT precipitate size
T distance between precipitates

fT volume fraction of precipitates
Coherent - Semicoherent - Incoherent
(mit Orientierungsbezug)
(ohne Orientierungsbezug)
aT aM a T a M a T a M a misfit := 1 (a + a ) aM aT a 2 T M
Energy Consideration
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 py of p phase boundary y( (scales with surface) ) enthalpy of formation of matrix to precipitate (scales with volume)
44
Heterogeneous Nucleation
45
TEM-Micrograph of TiC Precipitates at Di l Dislocations i in i an Austenitic A i i Steel S l
46
Ostwald-Ripening Ostwald Ripening of Precipitates

d3 - d03 ~ Dt here for T/Tm 0.74
' particle ti l size i in i IN 738 LC at t T = 920C. particle coarsening constant of (50 nm)3/h
47
Contents
Room Temperature (RT) versus Hi h Temperature High T (HT) Deformation D f i most alloy properties at room temperature are time and rate independent (elastic constants, tension stress, ... ), tension stress experiment. properties p (deformation) ( ) will be time For T > 0.4 Tm the p and rate dependent, creep experiment.
deformation hardening cold deformation (RT) creep (HT) strong temporary hardening, reduced creep rupture strength, may lead to recrystallization fine grain hardening medium reduced strength with fine grain material coarse grain, ideally single crystal solid solution strengthening medium to strong medium precipitate hardening medium to strong medium to strong
49
Change in Materials Properties with Temperature
Material properties of steel and Ni alloys at elevated Ni-alloys temperatures. Comparison b t between short-term h tt and d longl term parameters.
50
Tension Creep Experiment
51
Elastic (E-)Modulus and Poisson's i Ratio i
shear modulus G
E G= 2 (1 + )
Anisotropy and Temperature Dependence of El i Constants Elastic C in i Ni-base Ni b Superalloys S ll
D. Siebrger, H. Knake, U. Glatzel, Mat. Sci. Eng. A298 (2001)
Orientation dependence of Youngs modulus E of matrix phase Distance from the center to phase. the surface indicates the magnitude of the Youngs modulus i this in thi direction. di ti
High Temperature Deformation

dislocation glide (Peierls stress, in fcc and hcp very small and for T > 0.15 Tm negligible) cross slip li of f screw dislocations di l ti and d dislocation di l ti interactions i t ti (for (f a low l stacking fault energy larger dislocation spacing thermal activation necessary, necessary T > 0.2 0 2 Tm, influence on deformation rate) climb of edge dislocations to overcome obstacles: diffusion at complete p dislocation line T > 0.4 Tm
54
Dislocation Climb
climb of edge dislocations to annihilate each other. arrangement in low energy configurations (sub-grain boundaries), climbing around b l (leaving (l i the h glide lid abstacles plane) movement of screw dislocations with ith kink
56
Internal Back Stress

Dislocations il i climb li b allows ll annihilation ihil i of f dislocations di l i and to establish a constant dislocation density, resulting in an internal back stress of:
int . = G b
Gb 1 dislocation = 2 r
and
1 = r
G shear modulus, constant 0.3 - 1, b magnitude of Burgers vector
57
Creep Experiment
behavior of pure metals:
primary
secondary
58
tertiary:
Creep Experimental Setup up to 1400C
Constant temperature and a d stress st ess o or load
59
Creep Experimental Setup for Electrical Conductivity y Material up to Melting Temperature
Pyrometer from left, optical strain measurement from right, g , both contact-free.
Interrupted creep tests

single crystal (SX) nickel base superalloy (habilitation thesis Glatzel)
7 6 strain [%] s 5 4 3 2 1 0 0
10-5 strain rate [1/s] ]
8x10-6
[001] orientation, orientation 1123K, 1123K 650MPa

strai in rate [1/s] 6x10-6 4x10-6 2x10-6 0
[001] orientation, 1123K, 650MPa
10
20
30
40
50
60
70
10
20
30
40
50
60
70
time [h]
1123K, , 650 MPa
10-6
time [h]
10-7 0 1 2 3 4 5 6
logarithm of strain rate versus strain (most valuable information for materials i l scientist) i i )
University Bayreuth, Advanced High Alloys strainTemperature [%]
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 drastically.
Modelling of Primary and Secondary d Creep Stage
density
velocity l i
& = bv
63
Problem with Low Creep Rates

Life time of stationary gas turbines > 20 years. years Assuming a maximum deformation of 3%, this leads to an assumed steady d state strain i rate (neglecting ( l i primary i and d tertiary i &steady state = 510-11 s-1. Reliable data in labs creep) of about can only be obtained down to 110-9 s-1 (1 m change with l0 = 25 mm after 10 h one creep experiment with 3.5% strain per year!). Therefore Th f within ithi university i it l labs b we are t two and d more orders of magnitude too fast than real life in a stationary gas turbine!
Engineering Creep Curves
raw data creep curves:
time to failure:
time - strain
isochrone time to failure:
isochrone strain
65
Natural Creep Law

& steady state = b v
external Gb v~
1 external 2
&~ G b
3 external 2
natural creep law
66
Norton Creep Law (Empirical)

& = A
n external
Q creep R T
with the Norton creep exponent "n" and Qcreep Qself diffusion
power law l break b k 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:
Diffusional Creep
Nabarro-Hering creep (pure volume diffusion)
& NH = 2 D self h
diffusion 2
k T
Coble creep (grain boundary diff.)

&C = 2 D grain h
boundary 3
k T
h grain size,
thickness of grain boundary

Combined NH and Coble Creep:
& diffusion diff i creep
Dself diffusion D grain boundary D eff & NH + &C = 2 = + ~ 2 2 3 k T h h kT h

D eff = Dself diffusion + D grain boundary h
real geometry (non-cuboidal grains)
69
Temperature Dependence of Stationary i Creep Rate
= 28 MPA = const.
fcc alloys:
3, 5 & s = A SF e R T E n Qc
Austenitischer Stahl 800H

Activation Energy for Creep
slope = 1
71
Constant Load Constant Stress

F (1 + ) F n n n &= &0 = &0 = &0 & ( ) = 1 + 0 0 A A 0
failure
n n
in case the gauge length deforms uniform with constant volume

This method is applicable to determine the stress exponent "n" only, y, if the secondary y creep p state lasts to at least 10%
ln & 0 + n ln 0 + n ln (1+) = const. + n ln (1+) & = ln

Ashby Deformation Mechanism Maps
n=3
73
Ashby Deformation Mechanism Maps

Versetzungsklettern ! dislocation climb !
74
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 p (g (grain boundary y diffusion) ) is in theory y possible p 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 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 In-between between 0 K und 0.8Tm and very low stress levels: Coble Coble-creep creep (grain boundary diffusion). Below 0.4Tm not measurable. 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 thickness. The transition temperature from coble to Nabarro-Herring Nabarro Herring creep can be explained by the different activation energies of volume and grain boundary diffusion.
Creep of Alloys
a) interaction dislocation and impurity (low temp.) b) stationary dislocation pinned by impurities (C (Cottrell ll clouds) l d) c) pulled off Cortrell clouds (Ld bands) (Lders b d) d) gliding dislocation trails i impurities iti behind b hi d (viscous ( i glide) lid ) e) impurities faster than dislocation (very high temp., no hardening) f) annihilation due to dislocation climb
i = G b + solid solution
Precipitation Hardening
i = G b + solid solution + precipitate
threshold stress concept (with n 3 - 4 and Qcreep = Qself diffusion):
0 & ss = A e R T E
mechanism cutting bypass by Orowan climb li b over obstacles b l temperature 0 K up to Ts 0 K up to Ts > 0.4 0 4Ts
77
Qc
coherent and semicoherent phase boundaries yes yes yes
in-coherent phase boundaries no yes no

Hardening Mechanisms as Function of Precipitate Size

dT0 initial precipitate size 1 and 2 arbitrary external stress levels
= cutting
& ~ dT passing by:

&~ climbing: li bi 1 2 dT
Cutting is relevant only for coherent precipitates
Dependence of stationary creep rate on initial p precipitate p size for two different external stress levels
Pinning of Dislocations by Carbides bid in i Austenitic i i Steel l
T = 1000C, 1000C = 25 MPa, MP carbides bid of f th the t type TiC und d M23C6
Very High Volume Fractions

Volume fractions of 70% are only achievable with non-spherical non spherical precipitates. precipitates Spacing between precipitates is getting smaller Orowan stress Orowan G Gb/L b/L necessary. For small strains precipitates are not cut by O dislocations. With G = 90 GPa, b = 0.25 nm, L 75 nm => Orowan 300 MPa
nickel base superalloys
ODS alloys: ll
G b f vol. Orowan d part.
Dispersion Hardening
(oxide dispersion strengthened alloys (ODS-alloys))
yield stress
precipitate strengthened
dispersion strengthened
temperature
back-side p pinning g of dislocation by y ODS-particle (Rssler + Arzt)

Summary: Hardening d i Mechanisms h i

Internal back stress in steady state regime: Orowan stress in case of precipitates or particles: Solid solution strengthening: In case of coherent precipitates:
i = G b
Orowan Gb/L
solid solution const. a coherency E a
82
Creep Damage
creation of a creep pore in polycrystalline 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)
84
Extrapolation of Time-to-Fracture Data (L (Larson-Miller Mill plot, l Larson-Miller L Mill parameter) ) M k Monkmann-Grant G t relation l ti with ith constant t t K and d exponent t m 1: 1
K tf = m & ss
Q creep R T
or:
& ss ) ln(t f ) = K m ln(
& ss = B e
or:
1 & ss ) = B1 B2 ln( ( T
1 1 ln(t f ) = K m B1 m B2 = C + P T T
with material dependent constants C and P
Larson Miller Plot Larson-Miller-Plot

stationary t ti gas turbine, t bi about b t 20 years of f service i ~ 130.000 130 000 h
Comparison of CMSX-6, LEK 94 and d CMSX-4, CMSX 4 patent Wllmer, Glatzel, Mack, Wortmann
P = T[20 + ln(tf)]10-3 (T in K, tf in h)
Comparison LEK 94 with CMSX-4 and d CMSX-6

500
24 K
230
T = 10 K
CMSX-6 [Wortmann 88] 8.0 g/cm3 CMSX-4 [Erickson 94] 8.7 g/cm3 CMSX-4 [Frasier 90] 8.7 g/cm3 3 LEK-2 8.5 g g/cm 3 LEK-4 8.2 g/cm LEK-5 8.2 g/cm3 LEK-3 8.1 g/cm3 LEK-6 LEK 6 8 8.3 3 g/cm3 3 LEK-1C 8.4 g/cm 3 LEK-1B 8.3 g/cm 3 LEK-1A 8.2 g/cm
29 K
stress [M MPa]
120
10 K
25
26
27
28
29
30
31
32
Not corrected regarding density!
Larsen Miller parameter Larsen-Miller-parameter -3 P = T (20+log tB) 10

Contents
Time Dependent Variation of Stress and/or d/ Temperature T and/or d/ ...
Whler di Whl diagram for f T < 0.4T 0 4 Tm. Z time ti fatigue f ti limit, li it D endurance d fatigue limit a) type I metal (bcc) b) type II metal (fcc) endurance limit at 2107
89 Uwe Glatzel, Metals and Alloys University Bayreuth, Advanced High Temperature Alloys
Change in Whler Diagram with Temperature and d Holding ldi Time i
90
Thermal Fatigue
Thermal breathing of turbine blade:

a) c) heating phase: edges reach high temperatures faster than interior repeated thermal cycles lead to thermal fatigue cracks at edges
b) cooling phase: edges cool faster than interior
Thermal Strains and Stresses :

thermal = thermal T, or: thermal = E thermal thermal = E thermal T
92
Lower E-Modulus E Modulus is Helpful:
orientation of single crystals in <100> direction reduces thermal stresses

TMF and many other Time Dependent Test Techniques
Can not be covered in this lecture!
94
Contents
High Temperature Corrosion

oxidation: external and internal, passivation carburization (internal carbides) nitration: internal, seldom nitrite passivation sulfurization: external (sometimes passivation), p ss v o ), se seldom do internal e
Worldwide 1 ton iron per minute corrodes to rust (low temperature aqueous corrosion). corrosion)
Ellingham Richardson Diagram Ellingham-Richardson-Diagram

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 is shown as a dashed line. only the oxides below this line are thermodynamic stable.
97
Time Dependent Oxidation
98
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 g (m/A) )2 ~ t. Diffusion through g p oxidation layer (either oxygen or metal). Most favorable oxidation behavior. 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, Mo, W Cr, Cr Pt). Pt) You can see it inside a broken light bulb. bulb
Pilling-Bedworth Pilling Bedworth Ratio

PB = (volume of oxide of one metal atom)/(volume of metal atom)
Oxide PB TiO 0.70 Oxide PB MgO 0.81 Cr2O3 2.05 Al2O3 1.28 FeCr2O4 2.10 MgO2 1.34 Fe3O4 2.11 Ti2O3 1.50 Fe2O3 2.15 ZrO2 1.56 Ti3O5 1.65 SiO2 2.15 NiO 1.65 Ta2O5 2.50 FeO 1.70 Nb2O5 2.68 TiO2 1.73 W 3.40 CoO 1.86
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 y contains other metals
101
Example Ni Ni-Cr-Al Cr Al
Ni Cr 10 Al 5
oxide layer y and internal oxidation occurs
102
[MB1]noch
andere Eigenschaften reinschreiben?
Observations for the Superalloy Rene N5
Diploma thesis Bensch, 2009 and submitted paper

layer number 1 2 3 4 5 6 layer cover oxide layer interlayer of oxides third oxide layer -free layer reduced layer two-phase centre region composition NiO, CoO NiAl2O4 , NiTa2O6, Cr2O3 Al2O3 see Tab. 1 composition in-between in between layer number 4 and 6 nominal composition of Ren N5 (Tab. 1) properties thick and porous monophase layer thick and porous layer consisting of two fractions dense and thin monophase layer Al-content of 2.2 wt. % reduced Al content, content morphology change regular / structure, see Fig. 6 f)
103
Contents
High Temperature Alloys

T > 500C, Application in: energy generation engines (cars, trains, airplanes, ships, ... ) chemical industry metallurgy mechanical engineering
105
Overview Metals
ele m. Ti strucstruc ture
hdp krz k
Ttrans.Tm [C] 882 1855
[g/cm3]
max O-solubility max. O solubility [at.%] 31.9 8
advantages/disadvantages + low density + high melting point + abundant b d t available il bl + low th. (~ 10-5 K-1) now alloy known with adequate strength for temperatures > 600C high oxygen and nitrogen solubility > 700C, increased brittleness linear oxidation > 800C low thermal conductivity ignition hazard
catastrophic oxidation; Tm(V2O5) = 658C very brittle at RT; conventionally not processable
4.5 4.5
V Cr Mo
krz krz krz
1910 1863 2623
6.1 7.2 10.2
17 0.0053 0.03
+ very high creep strength + lowth, high thermal conductivity, good thermal fatigue strength very brittle at RT catastrophic p oxidation; Tm( (MoO5) = 795C no long lasting coating available + 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 > 1000C durch hohe WO3-Abdampfrate no long lasting coating available 106 very high density Uwe Glatzel, Metals and Alloys
krz
3422
19.3
Overview Metals
elem. structure Ttrans. Tm [C] 912 1395 1538
[g/cm3]
max. Osolubility [at.%] 0.0008 0.0098 0.029
advantages/disadvantages
Fe
krz kfz krz
7.9 7.7 7.4
+ very yg good corrosion resistance by y alloying y g 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 + very good corrosion resistance by alloying with Cr or (Cr + Al) + Co-alloys castable in air good weldability only moderate hardening available Ni-additions necessary to stabilize fcc structure, reduces strength + broad b d possibilities ibili i for f alloying, ll i high hi h strength h increase i possible ibl + very good corrosion resistance by alloying with Cr or (Cr + Al) + processable relatively low melting point th. g , low thermal conductivity y th high, + high corrosion and oxidation resistance + high melting point very high density very expensive (~ 33 /g)
Co
hdp kfz
422 1495
8.8 8.7
0 0.048
Ni i
kf kfz
14 1455
89 8.9
00 0.05
Pt
kfz
1772
21.5
107
Evolution of materials used in aero-engines

The earlier approach of technology technolog transfer from military militar to civil ci il is tending to switch direction.
www.azom.com
10 000 h Life Time 10.000
109
Example of Intermetallic Phases (Ni-Al-System)
110
Ni-Al Ni Al Intermetallic Phases

phase structure Ttrans. Tm [C] 1383
[g/cm3]
advantages/disdavantages
Ni3Al
L12
7.5
+ anomalous temperature dependence of strength + same structure base b than h Ni matrix i (fcc) (f ) + stable for larger Al variations > 1 wt.% Al + ductile as single crystal high density brittle b ittl as polycrystal l t l (can ( be b hindered hi d d by b boron b doping d i (grain ( i boundary strengthener) Al-content not sufficient to build stable Al2O3-layer reduced high temperature oxidation resistance + very good oxidation resistance, since 30 wt.% Al + high melting point + low density p to melting g point p + ordered structure up + 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
L10
1638
5.85
NiAl, B2 Ordered Intermetallic Phase

At a first sight very interesting (see g ) but despite p many y efforts and many y advantages) 100 Mio. US$ research money spent, up today no bulk usage of NiAl has been achieved. achieved BUT: aluminum coatings leading to NiAl layers is heavily used.
112
Contents
MTS-Factory MTS Factory in Bayreuth
ground-breaking g g ceremony: y 20.02.2008, , topping-out pp g ceremony: y 06.06.2008 start of production: ~ 12/2008

MTS-Factory MTS Factory, June 2008
115
116
117
Processing of a Turbine Blade l d
FPI X-Ray y
F i Feinguss, Wachsausschmelzverfahren, W h h l f h lost l wax investment i casting, i ...

Archaeological Evidence (Bibracte) ~ 50 B.C.

ceramic mould filled with wax
cloth clip
Singly Crystal Castin in Bayreuth at the h Chair h i for f Metals l And d Alloys ll
120
Contents

Advanced High Temperature Alloys

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Advanced High Temperature Alloys

postal address: Ludwig-Thoma-Str. d i h 36b b D-95447 Bayreuth, Germany

University Bayreuth, Advanced High Temperature Alloys

What You Should Know:

University Bayreuth, Advanced High Temperature Alloys

University Bayreuth, Advanced High Temperature Alloys

Uwe Glatzel, Metals and Alloys

Maximum Temperatures for Applications li i of f Different iff Materials i l

creep, dislocation climb, grain boundary sliding

University Bayreuth, Advanced High Temperature Alloys

Uwe Glatzel, Metals and Alloys

source: Plansee AG, AG Reutte, Tirol, Austria

University Bayreuth, Advanced High Temperature Alloys

Taking Density into Account

University Bayreuth, Advanced High Temperature Alloys

University Bayreuth, Advanced High Temperature Alloys

University Bayreuth, Advanced High Temperature Alloys

Uwe Glatzel, Metals and Alloys

University Bayreuth, Advanced High Temperature Alloys

Uwe Glatzel, Metals and Alloys

Influence of ... on ...

u total atom = 2 u kin

0,33 eV, bzw. 32 kJ/mol bei 1000C

University Bayreuth, Advanced High Temperature Alloys

Uwe Glatzel, Metals and Alloys

equilibrium vacancy concentration for nickel

Nickel Vacancy Concentration

vac cancy concentration

Nickel Vacancy Concentration

Nickel Vacancy Concentration

University Bayreuth, Advanced High Temperature Alloys

Uwe Glatzel, Metals and Alloys

[D] = m2 s-1 [c] = (atoms) m-3

University Bayreuth, Advanced High Temperature Alloys

Uwe Glatzel, Metals and Alloys

QSDnickel 2.5 eV = 244 kJ/mol

(for a perfect crystal; defects will lower the activation energies)

Dependence Melting Point and Enthalpy of Vacancy Creation

17RTm 0 88 0.88 1.36 1.99 2.21 2.53 2 98 2.98 4.23 5.40

University Bayreuth, Advanced High Temperature Alloys

University Bayreuth, Advanced High Temperature Alloys

Uwe Glatzel, Metals and Alloys

University Bayreuth, Advanced High Temperature Alloys

Uwe Glatzel, Metals and Alloys

Coefficient of Diffusion with Defects

grain boundary diffusion

volume diffusion pipe diffusion

University Bayreuth, Advanced High Temperature Alloys

Uwe Glatzel, Metals and Alloys

atoms 2 ~ DSD d grain time grain

atoms 2 ~ D disl. b n i time disl. n d grain

dashed line: diffusion in crystal by the velocity of pipe diffusion

identical atom fluxes if:

University Bayreuth, Advanced High Temperature Alloys

Uwe Glatzel, Metals and Alloys

Grain Boundary Diffusion

with: d effective grain boundary thickness ( 2 b 0.5 nm) grain size

dashed line: diffusion in crystal y by y the velocity y of grain boundary diffusion

Ddisl. pipe diffusion along dislocation core

Uwe Glatzel, Metals and Alloys

Activation Energies Indicating Mechanism Changes

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

Second Fick Fick's s Law

1 0.8 0.6 0.4