Atomization and Powder Processing of
High Temperature Ferritic Stainless Steel
Iver E. Anderson1, Joel R. Rieken2, David J. Byrd1, and M.J. Kramer1
1Division
of Materials Sciences and Engineering, Ames Laboratory (USDOE), Ames, IA
2Materials Science and Engineering Department, Iowa State University, Ames, IA
25th Annual Conference on Fossil Energy Materials
Portland, Oregon
April 26, 2011
Support from U.S. Department of Energy-Office of Fossil Energy is gratefully
acknowledged through Ames Laboratory contract no. DE-AC02-07CH11358
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Advanced Materials for Future Generation Power Plants
*
**
*R. Viswanathana, et al., J. Press. Ves. and
Pip., 2006. 83: p. 778-783.
***
**U.S. DOE Nuclear Energy Research Advisory Committee,
and Generation IV International Forum GIF, GIF-002-00
OECD Nuc. E. Agency, 2002: p. 1-90.
***ITER, The ITER Device. [Link]
index_nav_4.htm, 2009.
Material
Cost/kg (USD)
Notes
Ferritic Stainless Steel
~$2-5
446 Plate form
Austenitic Stainless Steel
~$3-7
316L Plate form
F/M Fe-9Cr steels
<$5.50
Plate form
Ni-based
~$30-35
Inconel 718 Sheet (Special Metals), Inconel 617 (Special Metals)
Fe-based ODS
~$165, ~$345
MA956 Sheet (Special Metals), PM 2000 (Plansee)
V-4Cr-4Ti
~$200
SiCf/SiCm composites
~$1000, ~$200
Plate form (Average between 1994 and 1996 US fusion program large heats)
Chemical vapor infiltration, and Chemical vapor reaction
J.T. Busby, J. Nuc. Mat., 2009. 392: p. 304
K. Savolainen, J. Mononen, R. Ilola, and H. Hnninen, 2005, Helsinki University of
Technology, Laboratory of Engineering Materials Publications.
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ODS
Processing
Cost!
S.J. Zinkle and N.M Ghoniem, Fusion Engineering and Design 2000. 51(52): p. 55-71.
Special Metals Price Quote
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Fe-Based ODS Processing Comparison
* Mechanical Alloying
Long milling times
Batch commercial process (~2000 kg)
Powder contamination (C, O, N, Ar)
Anisotropic microstructure
** Gas Atomization (GARS + RSP)
Higher processing rates (10-30 kg/min)
Continuous processing capacity
Minimized contamination
Isotropic microstructure capability
* R.L. Terpstra, et al., Advances in Powder Metallurgy and Particulate Materials, 2006.
*C. Suryanarayana, ASM Handbook, Vo. 7, ASM International, Materials Park, OH, 1998, pp. 80-90.
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**R.M. German, Powder Metallurgy and Particulate Materials Processing, 2005, MPIF, Princeton, [Link] Science and Technology
Gas Atomization Reaction Synthesis (GARS)
Fe-Cr-Y-Hf-O
Element
Basic Alloy
Design
Approx. Conc.
(at.%)
Cr
Surface reactant
15.0-16.0
Y
Hf
O2
Nano-metric oxide
dispersoid former
Dispersoid stabilizer
Surface oxidant and
dispersoid former
0.1-0.2
0.1-0.3
0.35-0.70
10nm
~0.1s
real time
Particle Matrix
Oxide Shell
Gold Layer
O
Cr
Fe
Y
Hf
Au
Particle Matrix
Oxide Shell
20nm
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Protective Gold Layer
*The electron microscopy was performed at the Electron Microscopy Center
for Materials Research at Argonne National Laboratory
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of Science and Technology
Dispersoid Formation Mechanism
Solid-State Microstructure Evolution
(Internal Oxygen Exchange Reaction)
Nucleation / growth of Y-enriched intermetallic
particles (solidification or low temperature HIP)
Dissociation of
metastable Cr-enriched
boundary oxide
Diffusion of
oxygen
Dissociation of metastable prior particle boundary
Cr-enriched oxide
Nucleation / growth of
Y-enriched
intermetallic particles
Oxygen diffusion away from PPBs
Nano-metric Y-enriched oxide formation
Dispersoid formation
(conversion of intermetallic
particles)
Full dissociation of PPB oxide will be necessary for
ideal mechanical properties
Cr2O3
Metastable Cr-Enriched Oxide
Increasing Stability
Y-enriched intermetallic particles
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TiO2
Ti3O5
Ti2O3
TiO
HfO2
Y2O3
Sauert F., et al., Thermochemical Data of Pure Substances, 2nd
Edition 1992.
Oxygen
Y-enriched oxide dispersoids
Dissociation of
Initial
metastable
PPB oxide
Y-enriched
Y-enriched
dispersoid
microstructure
intermetallic
Completed
oxygen
formation
with
continuous
formation
exchange
Oxygen
diffusion
PPBreaction
oxide
(proper balance of Y and O)
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Reactive Atomization Process Control
Empirically developed GARS oxidation model
Rapid oxidation kinetics
Primarily dependent on the mass flow
rate of oxygen (local pO2within
primary atomization zone)
Sensitive to atomization parameters
(i.e., gas nozzle and pour tube design)
CR-156Y-Hf
Predicted Value
J. Ting and I.E. Anderson, Mat. Sci.
Eng., A379 (2004), 264-276.
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CR-Alloy Composition and Experimental Parameters
Alloy
Fe (at.
%)
Cr (at.
%)
Hf (at.
%)
Y (at.
%)
O (at.
%)
Rxn Gas (vol.%)
Rxn Gas Inlet
CR-156YHf
Nominal
Bal.
16.0
0.12
Ar-0.12O2
HPGA Nozzle
CR-156YHf
20-53m
Bal.
15.84
0.11
Ar-0.12O2
HPGA Nozzle
CR-156YHf
5-20m
Bal.
15.84
0.11
Ar-0.12O2
HPGA Nozzle
CR-156YHf
-5m
Bal.
15.84
0.11
Ar-0.12O2
HPGA Nozzle
Size classified Powders: <5, 5-20, 20-53m)
(Solidification microstructure)
oxygen
Low temperature consolidation (700C-200MPa-4hr)
(Fe-Y intermetallic particle formation/distribution)
Elevated temperature heat treatment (1200C-2.5hr-Vac)
*Predicted from internal oxidation experiments
(Mixed nano-metric oxide dispersoid formation)
Diffusionless
Internal
Oxidation
As-Atomized
Powder
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*F. Gesmundo, and B. Gleeson, Oxidation of Metals, 1995. 44: p. 211-237
*R. A. Rapp, Corrosion, 1965. 21: p. 382-389.
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As-Atomized Surface Chemistry
~33nm thick
CR-156Y-Hf: Fe-15.84Cr-0.11Hf-0.18Y at.%
~25nm thick
~9nm thick
15-20m
-5m
40 m
32-38m
Auger depth profiles show enrichment of O and Cr at powder surface
Oxide shell thickness decreases with powder size (cooling rate sensitive)
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As-Atomized Microstructure (SEM)
CR-156Y-Hf: Fe-15.84Cr-0.11Hf-0.18Y at.%
Mote Isolation
Dia. ~20m
Dia.~40m
~40m
5
m
5
m
~15m
~5m
I.E. Anderson, et al., Undercooled Alloy Phases,
TMS-AIME, 1986, p. 269-285
Dia.
~5m
Dia. ~10m
2
m
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Solute Trapping!!
2m
R.M. German, Powder Metallurgy and
Particulate Materials Processing, 2005, MPIF,
Princeton, NJ.
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of Science and Technology
As-Atomized Microstructure (EPMA)*
CR-156Y-Hf: Fe-15.84Cr-0.11Hf-0.18Y at.%
32-38m
10-15m
Hf enrichment
Hf enrichment
Hf enrichment?
Y enrichment
Y enrichment
Y enrichment?
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-5m
*EPMA results were performed in collaboration with U.C.
Santa Barbara by Erin Haney (Odette Group)
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of Science and Technology
CR-156Y-Hf: Fe-15.84Cr-0.11Hf-0.18Y at.%
As-Atomized Microstructure: Atom Probe Tomography*
~15m Particle
~5m Particle
Matrix
Fe-(Y,Hf) Precipitate / Cluster
2-6x 1022 m-3
2-5nm
10nm
20nm
Fe-(Y,Hf) Precipitate
Fe
Cr
Hf
Nominal
Bal.
15.84
0.18
0.11
0.38
Matrix
Bal.
15.72
0.02
0.01
0.01
Precipitate
Bal.
11.58
4.86
2.93
0.00
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Fe
Cr
Hf
Nominal
Bal.
15.84
0.18
0.11
0.38
0.02
Matrix
Bal.
16.81
0.01
0.01
0.02
0.01
2.00
Precipitate
Bal.
11.78
6.25
5.18
0.01
5.18
*APT results were performed in collaboration with U.C.
Santa Barbara by Dr. Erich Stergar (Odette Group)
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Microstructure Evolution (SEM)
20-53m
-5m
5-20m
Y-Hf Segregation
Residual Porosity
Heat Treated 1200C
As-HIPped 700C
Y-Hf Segregation
CR-156Y-Hf: Fe-15.84Cr-0.11Hf-0.18Y at.%
Increasing Total Oxygen Content
Decreasing Residual Intermetallic Precipitates
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Microstructure Evolution (TEM)
CR-156Y-Hf (5-20um)
CR-156Y-Hf (-5um)
As-HIPped 700C
CR-156YHf (20-53m)
CR-156Y-Hf: Fe-15.84Cr-0.11Hf-0.18Yat.%
Fe-Y intermetallic precipitates
CR-156Y-Hf (5-20um)
Fe-Y intermetallic precipitates
CR-156Y-Hf (-5um)
Heat Treated 1200C
CR-156YHf (20-53m)
Fe-Y intermetallic precipitates
Y-enriched oxide particles
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Y-enriched oxide particles
Y-enriched oxide particles
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CR-156Y-Hf: Fe-15.84Cr-0.11Hf-0.18Yat.%
Microstructure Evolution (TEM)
CR-156Y-Hf (5-20um)
CR-156Y-Hf (-5um)
As-HIPped 700C
CR-156YHf (20-53m)
2 8 nm
3 E 22 m-3
22 52 nm
3E 21 m-3
4 19 nm
8E 21 m-3
2 6 nm
5 E 22 m-3
3 12 nm
3 E 22 m-3
Heat Treated 1200C
3 60 nm
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XRD Characterization of Dispersoid Formation
CR-156Y-Hf: (20-53m)
CR-156Y-Hf: Fe-15.84Cr-0.11Hf-0.18Y at.%
Y2O3
Y2Hf2O7
CR-156Y-Hf: (5-20m)
HfO2
20-53m
-5m
5-20m
CR-156Y-Hf: (-5m)
Heat Treated 1200C
Dispersoid phase formation
seems related to precursor
intermetallic composition
As-HIPped 700C
To be confirmed using
HE-XRD
As-Atomized
Y2O3
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Y2Hf2O7
HfO2
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Dislocation Substructure Development
TMT Procedure
~20%
20-53m
5-20m
~20%
~40%
~40%
~60%
~60%
~80%
~80%
As-heat treated 1200C - 2.5hr
(~0.45 vol.% oxide dispersoid phase)
Cold Rolled to 80% RA
(~10% RA per pass)
Annealed at 500 or 600C for 1hr
(dislocation recovery)
Recrystallized
Recovered
MA-956
M.F. Hupalo, et al., ISIJ Inter., 2004. 44(11)
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B.A. Wilcox, et al., in Strength of Metals and Alloys. 1967.
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Dislocation Substructure Development
CR-156YHf (20-53m)
CR-156Y-Hf: Fe-15.84Cr-0.11Hf-0.18Y at.%
CR-156Y-Hf (5-20um)
As-Reacted
ODS Microstructure
(Heat Treated 1200C)
Avg. Substructure ~450nm
Avg. Substructure ~250nm
Cold Rolled 80% RA
Annealed 500C-1hr
(Dislocation Recovery)
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Vickers Microhardness Results
CR-156Y-Hf: Fe-15.84Cr-0.11Hf-0.18Y at.%
MA957
As-Cold Rolled
Recrystallized (600C)
PM2000
MA956
Recovered (500C)
-5m
5-20m
20-53m
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CR-Alloy Microstructure Summary
A new simplified processing* technique involving gas atomization and in situ
oxidation has been developed to produce precursor ferritic stainless steel powder that
can be consolidated into an oxide dispersion strengthened alloy with an equiaxed
microstructure.
Resulting oxygen content was successfully predicted using an empirically developed
linear processing model, depending inversely on particle size.
Phase analysis confirmed that nano-metric Y-enriched oxide dispersoids formed by
oxygen release/transport/reaction with intermetallic particles or dissolved solute
during elevated temperature heat treatment.
Resulting ODS microstructures were shown to be cellular/dendritic with cell spacing
inversely dependent on powder particle size (i.e., rapid solidification rate).
Particles with maximum amount of solute trapping (<5m) resulted in smaller and
more evenly distributed nano-metric oxide dispersoids.
Selection of powder particle size range (solidification morphology) was shown to be a
viable method to control the final ODS microstructure.
Thermal-mechanical processing was used to develop a fine scale dislocation
substructure, which resulted in significant increases (~2X) in alloy microhardness, as a
preliminary test of ultimate mechanical properties.
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*I.E. Anderson, and (estate of) R.L. Terpstra, Dispersoid Reinforced Alloy
Powder and Method of Making, USPatent No. 7,699,905 B1, April 20, 2010.
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Analysis of Atomization Melt Flow Control by Orifice Design
High Speed Video: Atomization of Fe-Based ODS Alloys
GA-1-162: Straight
GA-1-164: Trumpet + 4 Slots
GA-1-166: Trumpet
2000fps
4000fps
8000fps
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Effect on Oxidation Reaction
Alloy
Fe (at.
%)
Cr (at.
%)
Hf (at.
%)
Y (at.
%)
O (at.
%)
Rxn Gas (vol.%)
Rxn Gas Inlet
CR-164HfY
-20m
Bal.
15.55
0.12
Ar-0.19O2
HPGA Nozzle
CR-166TiY
-20m
Bal.
15.91
0.12
Ar-0.19O2
HPGA Nozzle
Trumpet bell profile for melt orifice: gas
melt follows interior wall (pre-filming)
melt
gas
Rapid oxidation kinetics in atomization
spray
Primarily dependent on the mass flow
rate of oxygen (local pO2within primary
atomization zone)
Sensitive to atomization parameters (gas
nozzle and pour tube design)
Longer residence time within pre-filming
regime at high pO2within trumpet bell
pour tube increases oxygen content
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J. Ting and I.E. Anderson, Mat. Sci.
Eng., A379 (2004), 264-276.
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of Science and Technology
Powder Yield Results
Cut -106m
Riffled (statistical sampling)
Microtrac analysis
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Example:
Alloy
Powder Size (um)
Yield (%)
CR-164HfY
40
67
CR-166TiY
40
57
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Recent Consolidation and Dispersoid Formation
Diffusionless
Internal
Oxidation
HIPped 700C 300MPa 4hrs (full consolidation, intermetallic precipitation, and
restricted oxygen exchange reaction)
Heat treated at 1200C 2.5hrs Vac. (dispersoid formation through internal
oxidation of precursor intermetallic precipitates), predicted using internal
oxidation model (Rapp) and experimental results (Rhines packs)
Samples intended for mechanical testing at elevated temperature (key milestone)
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Coarsening Experiment In-Progress
Coarsening schedule for both CR-164HfY and CR-166TiY
Temperature (C)
Time (hr)
1200
50
1200
100
1200
500
1200
1000*
* Analysis in progress
Determine dispersoid thermal stability
(Y-Hf-O vs. Y-Ti-O)
XRD analysis (Scherrer analysis)
TEM analysis (line intercept)
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(peak broadening)
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Acknowledgments
Support from the Department of Energy-Office of
Fossil Energy is gratefully acknowledged through
Ames Laboratory contract no. DE-AC02-07CH11358.
Jim Anderegg1, Elliot Fair2, and Alex Spicher2
Dr. Robert Odette3, Dr. Erich Stergar3, and Erin Haney3
Jon Hiller4and Dr. Russ Cook4
1Division of Materials Sciences and Engineering, Ames Laboratory (USDOE)
2Iowa State University, Material Science and Engineering (Undergraduate Students)
3University California Santa Barbara, Mechanical and Environmental Engineering
4Electron Microscopy Center for Materials Research, Argonne National Laboratory (USDOE)
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