A U.S. Department of EnergyOffice of Science LaboratoryOperated by The University of Chicago

Argonne National Laboratory

Office of ScienceU.S. Department of Energy

Characterization of Actinide Alloys as Nuclear

Transmutation Fuels

Characterization of Actinide Alloys as Nuclear

Transmutation Fuels

J. Rory Kennedy

OECD/NEA Eighth Information Exchange Meeting On Partitioning and Transmutation (IEMPT-8)November 10, 2004

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AcknowledgementsAcknowledgements

Alloy Fabrication: Mr. Jim Stuart, Mr. Gavin Knighton, Ms. Kaylyne Weatherstone, Mr. Brian Forsmann, Mr. James SommersSample Preparation: Mr. Tom DiSanto, Ms. Maryanne Noy, Mr. Brian ForsmannPhase (XRD) measurements: Dr. Steven Frank Microstructure (SEM): Dr. Dennis Keiser Thermal Analysis: Ms. Jennifer Sloppy, Ms. Jacklyn Gates, Ms. Allison BourkeThermal Diffusivity: Mr. Andrew Maddison, Mr. Samuel Bays, Dr. Marsha Lambregts Chemical Analysis: Dr. Jeffrey Giglio, Mr. Dan Cummings, Mr. Jeffrey Berg, Ms. Pam Crane, Mr. Michael Mitchlik, Material transfer: Mr. Scott Wilde, Mr. Ron Briggs, Mr. Bevin Brush,Health Physics personnel, MC&A personnel, FMF personnel

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OutlineOutline• ANL-W Characterization Capabilities

• Fuel Fabrication

• Am Retention

• As-cast Phase Identification

• As-cast Microstructure

• Thermal Analysis - Differential Scanning Calorimetry (DSC, temps, Cp)- Thermal Mechanical Analysis (TMA, density))- Thermal Diffusivity (Laser Flash Method, LFD)- Thermal Conductivity

• Fuel-Cladding-Chemical-Interaction (FCCI)

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ANL-W Fabrication CapabilitiesANL-W Fabrication Capabilities

• Radioactive isotopes or non-radioactive isotopes

• Alloys

• Ceramics (oxides, nitrides, carbides, composites, etc.)

• Compounds and molecular species

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ANL-W Characterization CapabilitiesANL-W Characterization Capabilities• Phase Identification

- XRD and elevated variable temperature XRD

• Microstructure

- SEM, EDS, WDS and TEM

• Chemical Analysis

- ICP-MS, ICP-AES, gamma spec, LECO, etc

• Density

- immersion

• Thermal Analysis

- DSC, TMA, TGA, LFD

• Fuel-Cladding-Chemical-Interaction

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AFCI Metal Alloy Fuels Under StudyAFCI Metal Alloy Fuels Under Study

• AFC1-B,D Non-fertile (4.0mm diameter; ~83% 239Pu)- 40Pu-60Zr- 60Pu-40Zr- 50Pu-10Np-40Zr- 48Pu-12Am-40Zr- 40Pu-10Am-10Np-40Zr

• AFC1-F Low fertile (4.0mm diameter)- 35U-35Pu-30Zr (DU: base composition) - 35U-29Pu-4Am-2Np-30Zr (78% 235U)- 30U-25Pu-3Am-2Np-40Zr (93% 235U)- 40U-34Pu-4Am-2Np-20Zr (33% 235U)- 35U-28Pu-7Am-30Zr (93% 235U)

• FUTURIX-FTA (4.9mm diameter)• 35U-29Pu-4Am-2Np-30Zr (78% 235U)• 48Pu-12Am-40Zr

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Americium Retention Americium Retention Element Vapor PressuresElement Vapor Pressures

1E-301E-291E-281E-271E-261E-251E-241E-231E-221E-211E-201E-191E-181E-171E-161E-151E-141E-131E-121E-111E-101E-091E-081E-071E-061E-05

0.00010.001

0.010.1

110

1001000

500 600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700

Temperature (C)

Vap

or P

ress

ure

(to

rr)

Americium (solid and liquid) Plutonium (solid) Plutonium (liquid)

Neptunium (solid) Neptunium (liquid) Zirconium (solid)

Am vapor pressure 4-6 orders of magnitude

higher than Pu

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Powder Metallurgical ApproachPowder Metallurgical Approach

inte

nsit y

30 40 50 60 70 80 90two-theta

*

*

*

**

**

delta Pu-Zr (*) + alpha-Zr (no mark)

Pu-rich -(Pu-Zr)

Y2O3

Fe

Carbon

Zr rich -(Pu-Zr)

-Zr

Developed as low temperature fabrication route to prevent Am loss. Hot pressing.Inhomogeneous microstructure after

processing at ~ 800°C High impurity content

Complex process - impractical remote process scale-up

•Powder handling•Material loss• Time

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Americium RetentionAmericium Retention

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AFC1 Metal Alloy Fuels AFC1 Metal Alloy Fuels As-Cast Room Temp Phase Results (XRD)As-Cast Room Temp Phase Results (XRD)

40Pu-60Zr -Zr (hcp)

60Pu-40Zr -Pu (fcc)

48Pu-12Am-40Zr -Pu (fcc)

50Pu-10Np-40Zr -Pu (fcc) + -MZr2 (-UZr2 hex)

40Pu-10Am-10Np-40Zr -Pu (fcc) + -MZr2 (-UZr2 hex)

30U-25Pu-3Am-2Np-40Zr -MZr2 (-UZr2 hex)

35U-29Pu-4Am-2Np-30Zr -MZr2 (-UZr2 hex) + ζ-U (? minor)

35U-28Pu-7Am-30Zr -MZr2 (-UZr2 hex) + ζ-U (? minor)

40U-34Pu-4Am-2Np-20Zr -MZr2 (-UZr2 hex) + ζ-U (?)

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AFC1 Metal Alloy Fuels AFC1 Metal Alloy Fuels As-Cast Room Temp Phase Results (XRD)As-Cast Room Temp Phase Results (XRD)

Pu-40Zr

Pu-12Am-40Zr

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AFC1 Metal Alloy Fuels AFC1 Metal Alloy Fuels As-Cast Microstructure Results (SEM)As-Cast Microstructure Results (SEM)

Pu-40Zr Pu-12Am-40Zr

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AFC1 Metal Alloy Fuels AFC1 Metal Alloy Fuels As-Cast Results (DSC, TMA)As-Cast Results (DSC, TMA) Pu-40Zr Pu-12Am-40Zr

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AFC1 Metal Alloy Fuels AFC1 Metal Alloy Fuels As-Cast Room Temp Phase Results (XRD)As-Cast Room Temp Phase Results (XRD)

Pu-10Np-40Zr

Pu-10Np-10Am-40Zr

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AFC1 Metal Alloy Fuels AFC1 Metal Alloy Fuels As-Cast Microstructure Results (SEM)As-Cast Microstructure Results (SEM)

Pu-10Np-40Zr Pu-10Np-10Am-40Zr

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DSC/DTA and TMA Heating Curves DSC/DTA and TMA Heating Curves Pu-10Np-40Zr As-CastPu-10Np-40Zr As-Cast

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AFC-1F Metal Alloy Fuels XRD StudyAFC-1F Metal Alloy Fuels XRD Study

0

500

1000

1500

2000

2500

30 40 50 60 70 80 90

2-Theta (degrees)

Inte

ns

ity

MH036 30U-25Pu-3Am-2Np-40ZrMG034 40U-34Pu-4Am-2Np-20ZrMF032 35U-28Pu-7Am-30ZrMI037 35U-29Pu-4Am-2Np-30ZrUZr2 calculatedhexagonal orderedUZr2 calculated bccorderedalpha-Zr calculated

A U.S. Department of EnergyOffice of Science LaboratoryOperated by The University of Chicago

Argonne National Laboratory

Office of ScienceU.S. Department of Energy

U-25Pu-3Am-2Np-40Zr (MH036)

“30U-30Pu-40Zr”

U-28Pu-7Am-30Zr (MF032)

“35U-35Pu-30Zr”

U-29Pu-4Am-2Np-30Zr(MI037) *

“36U-34Pu-30Zr”

U-34Pu-3Am-2Np-20Zr(MG034)

“41U-39Pu-20Zr”

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SEM Micrographs of As-Cast SEM Micrographs of As-Cast 30U-25Pu-3Am-2Np-40Zr Alloys (MH036)30U-25Pu-3Am-2Np-40Zr Alloys (MH036)

• Even elemental distribution overall.• Some globule formation (oxide enriched).• Few pores.

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SEM Micrographs of As-Cast SEM Micrographs of As-Cast 40U-34Pu-4Am-2Np-20Zr Alloys (MG040)40U-34Pu-4Am-2Np-20Zr Alloys (MG040)

• Multiphase• Globule formation (Zr enriched).

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Differential Scanning Calorimetry of As-Cast Differential Scanning Calorimetry of As-Cast 30U-25Pu-3Am-2Np-40Zr Alloy30U-25Pu-3Am-2Np-40Zr Alloy

• Transition from -UZr2 to bcc over 565ºC - 600ºC range

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Differential Scanning Calorimetry of As-Cast 40U-34Pu-4Am-2Np-20Zr Alloy

• Transition from -UZr2 at 541ºC.• Transition to bcc at 592ºC.

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Zr – 50U50Pu Vertical Section through U-Pu-Zr Zr – 50U50Pu Vertical Section through U-Pu-Zr Phase DiagramPhase Diagram

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Laser Flash Diffusivity Laser Flash Diffusivity MeasurementsMeasurementsAnter Laser Flash Diffusivity System

Modified for glove-box operationZero power and finite pulse width corrected

Radiative Heat Loss

Front Face

Back FaceTemperature Rise

Instantaneous Laser Pulse

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Thermal Conductivity Thermal Conductivity (Clark & Taylor Correction)(Clark & Taylor Correction)

0

0.05

0.1

0.15

0.2

0.25

0.3

0 200 400 600 800 1000 1200

Temperature (ºC)

Th

erm

al C

on

du

ctiv

ity,

λ

(W c

m-1

K-1

)

U-29Pu-4Am-2Np-30Zr

Pu-12Am-40Zr

U-34Zr

U-50Zr

U-Zr values taken from Takahashi, Yamawaki, Yamamoto J. Nucl. Mater. 1988, 154, 141.

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Thermal Diffusivity of Pu-12Am-40ZrThermal Diffusivity of Pu-12Am-40Zr

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Thermal Diffusivity of U-29Pu-4Am-2Np-Thermal Diffusivity of U-29Pu-4Am-2Np-30Zr30Zr

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Fuel-Cladding Chemical Interaction (fcci)Fuel-Cladding Chemical Interaction (fcci)

steelsteel

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FUTURIX-FTA Metal Alloy Fuels FCCI 650FUTURIX-FTA Metal Alloy Fuels FCCI 650ººC 7hrsC 7hrsU-29Pu-4Am-2Np-30Zr – AIM1 SS Diffusion CoupleU-29Pu-4Am-2Np-30Zr – AIM1 SS Diffusion Couple

BSE SE Fe

Ni Cr Zr

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FUTURIX-FTA Metal Alloy Fuels FCCI 650FUTURIX-FTA Metal Alloy Fuels FCCI 650ººC 7hrsC 7hrsU-29Pu-4Am-2Np-30Zr – AIM1 SS Diffusion CoupleU-29Pu-4Am-2Np-30Zr – AIM1 SS Diffusion Couple

BSE U Np

Am Pu O

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FUTURIX-FTA Metal Alloy Fuels FCCI 650FUTURIX-FTA Metal Alloy Fuels FCCI 650ººC 7hrsC 7hrsPu-12Am-40Zr – AIM1 SS Diffusion CouplePu-12Am-40Zr – AIM1 SS Diffusion Couple

BSE

SE

Pu

Am

O

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FUTURIX-FTA Metal Alloy Fuels FCCI 650FUTURIX-FTA Metal Alloy Fuels FCCI 650ººC 7hrsC 7hrsPu-12Am-40Zr – AIM1 SS Diffusion CouplePu-12Am-40Zr – AIM1 SS Diffusion Couple

BSE SE Fe

Ni Cr Zr

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FUTURIX-FTA Metal Alloy Fuels FCCI 650FUTURIX-FTA Metal Alloy Fuels FCCI 650ººC 7hrsC 7hrsPu-12Am-40Zr – AIM1 SS Diffusion CouplePu-12Am-40Zr – AIM1 SS Diffusion Couple

BSE – Fe 120 m BSE – Fe 600 m BSE – Fe 1000 m

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AFCI Metal Alloy Fuels FCCI 650AFCI Metal Alloy Fuels FCCI 650ººC 200hrsC 200hrsPu-10Am-10Np-40Zr – 422 SS Diffusion CouplePu-10Am-10Np-40Zr – 422 SS Diffusion Couple

1100 m

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SummarySummary• Successfully Arc-Cast Series of Non-fertile and Low-

fertile Alloys Composed of Varying Amounts of U, Pu, Np, Am, Zr

• Good Retention of Am from Fabrication Process

• Continuing the Quantitative Characterization of the Fuels for Phase (XRD), Microstructure (SEM), Thermal Analysis (DSC, TMA, LFD), Thermal Conductivity, and FCCI

• Initial PIE looks good