ods alloy development...ods alloy development ian wright , bruce pint, claudette mckamey oak ridge...
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OAK RIDGE NATIONAL LABORATORYU. S. DEPARTMENT OF ENERGY
ODS Alloy Development
Ian Wright , Bruce Pint, Claudette McKameyOak Ridge National Laboratory
17th Annual Fossil Energy Materials ConferenceBaltimore, Maryland, April 22-24, 2003
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OAK RIDGE NATIONAL LABORATORYU. S. DEPARTMENT OF ENERGY
Barriers:• Joining• Highly-directional properties: for tubes, transverse strength << axial• Unusual mechanical behavior; strain-rate sensitivity/mode of failure• Cost
Options:• Unconventional joining approaches• Innovative processing to obtain the desired microstructure• Improved quantification of alloy properties and characteristics so that there are no surprises
Scientific approach:• Understand and quantify all available routes for joining• Develop mechanistic understanding for understanding how to control the alloy microstructure; and of the oxidation behavior
Goal: Facilitate the Exploitation of ODS Alloys
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OAK RIDGE NATIONAL LABORATORYU. S. DEPARTMENT OF ENERGY
• Creep strength to temperatures > conventional high-temperature alloys• Potential for use to temperatures where typically ceramics are considered • Excellent oxidation resistance• Resistance to sulfidation; steam oxidation• Current Focus: ODS-FeCrAl alloys
Related work:• Special Metals Inc: ODS tubing• European COST programs• SBIR at MER Corp.• ARM programs:
–Foster Wheeler–UCSD–U. Liverpool
• ORNL: ‘nano-clusters’
Why ODS Alloys?
1
10
100
1000
600 700 800 900 1000 1100 1200
Ave
rage
100
kh S
tress
Rup
ture
Stre
ngth
, MP
a
Metal Temperature,°C
CurrentAverage
TheoreticalMaximum
ODS-FeCrAls(longitudinal)
USC
HT-HX
Afte
r Sta
rr &
Shi
bli,
2002
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OAK RIDGE NATIONAL LABORATORYU. S. DEPARTMENT OF ENERGY
Alloys of Interest
ORNL developmentY2O3-Al2O3Ti,Si15.92.2BalODS-Fe3Al
oxidation comparator‘ZrO2-Al2O3’Ti,Si5.520BalKanthal APM
Dour MetalY2O3-Al2O3Ti4.516.5BalODM751
PlanseeY2O3-Al2O3Ti5.520BalPM2000
956 modificationY2O3-Al2O3Ti,Si5.721.6BalMA956H
Special Metals Inc.Y2O3-Al2O3Ti4.520BalMA956
REotherAlCrFeRemarksComposition, weight percentAlloy
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OAK RIDGE NATIONAL LABORATORYU. S. DEPARTMENT OF ENERGY
Presentation Content
• Joining
• Temperature limits– fireside/steam-side compatibility
• Mechanical properties– transverse (hoop) strength
• ODS-specific issues– strain-sensitivity/mode of failure
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OAK RIDGE NATIONAL LABORATORYU. S. DEPARTMENT OF ENERGY
Joining of ODS Alloys•Joining must avoid
– redistributing the Y2O3 dispersed phase– changing the grain structure size/shape/orientation
•Challenges:– fusion processes: probably a last resort
brazing in COST-522 program– friction/inertia welding: distortion of microstructure– diffusion bonding
TLP: successfully demonstrated on other ODSplasma-assisted diffusion bonding: MER Corp
– others:explosive bonding: successfully demonstrated (COST-501) pulsed magnetic weldingmechanical--threading + brazing
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OAK RIDGE NATIONAL LABORATORYU. S. DEPARTMENT OF ENERGY
Tested Configurations for ODS Joints
Bayonet tubes (COST-522)
ODS tube
Ceramic tube
Joints
HeaderAIR INAIR OUT
ODS tube
Header
‘Safe’ end
Explosive bond
British Gas ‘Harp’ Joint
Conventional weld
ODS Corner block
ODS tubes
TLP bond
TLP joint: HiPPS program
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OAK RIDGE NATIONAL LABORATORYU. S. DEPARTMENT OF ENERGY
Other Possible Configurations for ODS Joints
Reinforced joints
Threaded & brazed Overlapped and brazed Inertial welded
tube-to-flange joint
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OAK RIDGE NATIONAL LABORATORYU. S. DEPARTMENT OF ENERGY
Inertia welding of MA-956 tubes
• 63.5 mm diam. x 7 mm wall thickness, unrecrystallized MA-956 tube
• mechanically robust joints have be produced in using inertia welding
• process window was determined based on the integrity of the joint in bend tests in coupons cut from joined tubes
• reproducibility of joining parameters is excellent
B. Kad/Interface Welding
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OAK RIDGE NATIONAL LABORATORYU. S. DEPARTMENT OF ENERGY
Very sharp demarcation of deformed microstructure after inertia welding
JOINT
Tube outer surface
B. K
ad, 2
003
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OAK RIDGE NATIONAL LABORATORYU. S. DEPARTMENT OF ENERGY
Plasma-Assisted Diffusion Bonding
MA956
• MER Corp-SBIR-II
• ‘clean’ joint
• thin joined zone
• apparent grain continuity
Bond line
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OAK RIDGE NATIONAL LABORATORYU. S. DEPARTMENT OF ENERGY
Bond line
AlTi
Y
O
BSE
SE
• EPMA suggests an accumulation of Ti, Al, Y, and O along the bond line
• predominantly Ti• alloy contains approx. 0.5 %Ti
Bond-line exhibits Ti-rich precipitates
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TEM indicates discrete particles
Grain/Side 1
Imag
e K
arre
n M
ore
(853
)
BoundaryParticles alongboundary
0.5 µm
Grain/Side 2
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Particles are TiC and Al2O3
Al2O3 particles at boundary
TiC particles at boundary
Al O
Ti C
0.25 µmImage Karren More (858 + maps 859…)
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OAK RIDGE NATIONAL LABORATORYU. S. DEPARTMENT OF ENERGY
TLP Joining: Collaborative Effort
J. Hurley/N.A. Bornstein, 2003
MA956
•EERC-N.A. Bornstein-ORNL
•TLP approach based on concepts demonstrated for HiPPS joints
•special considerations for application to an alumina scale-forming alloy
•proof-of-concept TLP alloy
Bond line
Extent of interdiffusion
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OAK RIDGE NATIONAL LABORATORYU. S. DEPARTMENT OF ENERGY
Temperature LimitsThe basis for modeling the oxidation-limited lifetimes of these alloys is
relatively straightforward, since:
• they form essentially Al2O3 scales that are uniform in thickness
• there is negligible internal attack (life can’t be equated to section thinning)
• the Al concentration gradient in the alloy is flat until very near the end of life
As a result, it is possible simply to equate the oxidation lifetime to the rate of consumption of the available Al to form the alumina scale:
Life = Al available for oxidation/oxidation rate
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OAK RIDGE NATIONAL LABORATORYU. S. DEPARTMENT OF ENERGY
The oxidation kinetics of these alloys have a characteristic form
P1 P2
0
5
10
15
20
0 200 400 600 800 1000 1200 1400 160
MA956H1300°C
Tota
l Mas
s Cha
nge,
mg/
cm2
Time (hr, in 100 hr cycles)
'Breakaway'(end of life)
Parabolic oxidation 'stage 2'
Linear oxidation'stage 3'
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OAK RIDGE NATIONAL LABORATORYU. S. DEPARTMENT OF ENERGY
Current ModelThe current expression of the model is:
tb = {[S*10-4*ρA*Aτ*e-Qτ/(1.987*T)]2/(3600*A2*e-Q2/(1.987*T))} + {[1/(3600*M)*(V/A)*(ρM/(A3*e-Q3/(1.987*T)))*[(CBo-CBb) – M*S*10-4*(A/V)*(ρA/ρM)*Aτ*e-Qτ/(1.987*T)]} hours
Input required is:1. Alloy data: ρM; CBo; CBb (need to measure CBb)2. Oxide data: ρA; M; S; (constants based on oxide/alloy stoichiometry)3. Alloy oxidation descriptors: Arrhenius data A2, Q2; A3, Q3, and Aτ, Qτ
4. The metal temperature (T), and the component size (V/A)
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OAK RIDGE NATIONAL LABORATORYU. S. DEPARTMENT OF ENERGY
Summary of Oxidation Kinetics
P1 P2
-13.5
-13
-12.5
-12
-11.5
-11
-10.5
-10
0.6 0.65 0.7 0.75 0.8
log
k 2
1000/T°K
ODS-Fe3Al
MA956
MA956: k2 = 53 x e -86,600/RT
ODS-Fe3Al: k
2 = 28 x e -85,554/RT
13001250 1200 1100 1000Temperature, °C
Parabolic oxidation ‘stage 2’
-10.5
-10
-9.5
-9
-8.5
-8
0.6 0.65 0.7 0.75 0.8
log
k 3
1000/T°K
ODS-Fe3Al
MA956H
MA956H: k3 = 0.2 x e -56,900/RT
ODS-Fe3Al: k
3 = 3 x e -62,436/RT
13001250 1200 1100 1000Temperature, °C
Linear oxidation ‘stage 3’
Some alloys haven’t run long enough to establish the Stage 3 oxidation rate
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OAK RIDGE NATIONAL LABORATORYU. S. DEPARTMENT OF ENERGY
Calculated Lifetimes
P1 P2
100
1000
104
105
0.2 0.4 0.6 0.8 1
V/A, mm
1200°C
1300°C
1100°C
1000°C
1250°C
Oxi
datio
n Li
fetim
e, h
Dashed Lines: predicted lives for MA956H using 2-stage model
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OAK RIDGE NATIONAL LABORATORYU. S. DEPARTMENT OF ENERGY
Calculated vs Observed Lifetimes
P1 P2
100
1000
104
105
0.2 0.4 0.6 0.8 1
V/A, mm
Dashed Lines: predicted lives (2-stage model )
1200°C
1300°C
Data Points: observed lifetimes
1100°C1000°C
1250°C
Data for MA956H
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OAK RIDGE NATIONAL LABORATORYU. S. DEPARTMENT OF ENERGY
Calculated vs Observed Lifetimes
P1 P2 Reasonable predictions for 1100-1300°C
100
1000
104
105
0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Oxi
datio
n-Li
mite
d Li
fetim
e, h
r
V/A, mm
Dashed Lines: predicted lives (2-stage model)
1200°C
1300°C
Data Points: Observed Lifetimes
1100°C
1000°C
1250°C
Data for MA956
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OAK RIDGE NATIONAL LABORATORYU. S. DEPARTMENT OF ENERGY
Calculated Lifetimes at 1100°C
P1 P2TUBE 1in OD x 0.1in (25.4 x 2.54 mm), V/A = 0.64 mm
6000
8000
104
3 104
5 104
0.2 0.4 0.6 0.8 1
V/A, mm
ODM751
MA956MA956H
ODS-Fe3Al
Data for 1100°C/2012°F
PM2000
KanthalAPM
Based on CBb values:
FeCrAls--0.001
Fe3Al--0.056
• CBb is difficult to measure
• don’t know if it is T-dependent
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Cross section of scale on MA956H
Karren More (875 + 876)
Al2O3 scale
1 µm
Alloy substrate
voids in Al2O3 scale(not many)
100h, 1200°C, air
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Alloy-oxide interface on MA956H
Ti-enriched at interface
Ti
Y-containing particles in alloyThere is also Y-enrichment at Al2O3
grain boundaries (not shown)
Y
0.25 µm
Karren More (879 + maps 880…)
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Scale cross section on MA956
thicker Al2O3 scale than on 956H
Karren More (881 + 882)
1 µm
voids in Al2O3 scale(many more )
TiC particleat interface
elongated Y-Ti-Si-C grain(no oxygen!) ~4 mm longbetween Al2O3 grains (red bars show ends of grain)
Alloy substrate
100h, 1200°C, air
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OAK RIDGE NATIONAL LABORATORYU. S. DEPARTMENT OF ENERGY
Current approach under-predicts oxidation lifetime
• Predictions should be conservative!
• Are lab results overly affected by specimen shape?
• V/A is a ‘shape factor,’ but doesn’t discriminate among parallelepipeds
• Other shapes:
0.80
0.64
1.13
0.67
V/A mm
452400523Cylinder
46068612.5231.6Standard parallelepiped
28043512.5141.6Parallelepiped-2
283
Volume mm3
353
Surface area mm2
151.6Disc
Width mm
Length mm
Thickness mm
Shape
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OAK RIDGE NATIONAL LABORATORYU. S. DEPARTMENT OF ENERGY
Effect of Specimen Shape
P1 P2
0
5
10
15
20
25
30
35
0 500 1000 1500 2000 2500 3000
MA956, 1250°C
Tota
l Mas
s Gai
n, m
g/cm
2
Time, h
Large p'ped
P'piped(square)
Disc
Cylinder
PLAN
CROSS SECTION
some shapes make less efficient use of the Al reservoir?
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OAK RIDGE NATIONAL LABORATORYU. S. DEPARTMENT OF ENERGY
Possible Shape Factors
Shortest diffusion path from center of specimen thickness to outer surface (dmin) is given by locus of surface of a sphere of radius = d/2
dDe = diffusion length to an edge
dDc = diffusion length into a corner
Longest diffusion path is from the center of mass (= dDcm)
ddDc
dDcmdDe
center of mass
l
w
dmin = d/2d/2
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OAK RIDGE NATIONAL LABORATORYU. S. DEPARTMENT OF ENERGY
Shape Factors: Diffusion Lengths
0.707 x d
—
0.707 x d
EdgedDe
0.5 x sqrt(d2 + diam2)0.707 x dDisc
0.5 x sqrt(l2 + diam2)0.707 x diamCylinder0.866 x d
CornerdDc
0.5 x sqrt(l2 + w2 + d2)
Center of MassdDcm
P’piped
Shape
d = specimen thickness I = specimen lengthw = specimen width
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OAK RIDGE NATIONAL LABORATORYU. S. DEPARTMENT OF ENERGY
Summary
• Joining–3 routes are being evaluated
– inertia welding--controlled microstructural distortion– plasma-assisted diffusion--clean joints (?); examining reinforced design– TLP bonding--questions about amount of residual elements and their effects
–significant effort on other techniques in the Vision 21-SM project–Temperature limits
–generating data for all available ODS-FeCrAls–have an initial working model for life prediction
– continuing long-term exposures to validate and improve the model– issues of over-prediction, and the influence of shape
– lifetimes of 30-70kh at 1100°C in air for typical tube sizes–continuing to generate data in steam, other environments
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OAK RIDGE NATIONAL LABORATORYU. S. DEPARTMENT OF ENERGY
Sensitivity to CBb
P1 P2Don’t know if CBb is T-dependent
104
105
0.2 0.4 0.6 0.8 1
V/A, mm
Data for ODS-Fe3Al, 1100°C/2012°F
PM2000
KanthalAPM
CBb
1%2%3%4%5%
Tube2.5 mm (0.1 in)wall thickness
PM2000, APM: CBb
= 0.1%