Top Banner
Role of Solid State Diffusion Studies in Materials Selection and Process Design for Development of Low Enrichment U-Mo Metallic Nuclear Fuel Systems Y.H. Sohn Professor and Associate Director* Department of Materials Science and Engineering *Advanced Materials Processing and Analysis Center University of Central Florida, Orlando, FL, USA
43

Role of Solid State Diffusion Studies in Materials ... · Department of Materials Science and Engineering *Advanced Materials Processing and Analysis Center ... Diffusion barrier

May 04, 2018

Download

Documents

buidiep
Welcome message from author
This document is posted to help you gain knowledge. Please leave a comment to let me know what you think about it! Share it to your friends and learn new things together.
Transcript
Page 1: Role of Solid State Diffusion Studies in Materials ... · Department of Materials Science and Engineering *Advanced Materials Processing and Analysis Center ... Diffusion barrier

Role of Solid State Diffusion Studies in Materials Selection and Process Design for

Development of Low Enrichment U-Mo Metallic Nuclear Fuel Systems

Y.H. Sohn

Professor and Associate Director*

Department of Materials Science and Engineering

*Advanced Materials

Processing and Analysis Center

University of Central

Florida, Orlando, FL, USA

Page 2: Role of Solid State Diffusion Studies in Materials ... · Department of Materials Science and Engineering *Advanced Materials Processing and Analysis Center ... Diffusion barrier

��

U-Mo Fuel for RERTR/GTRI U-Mo Fuel: •  Developed for the program of Reduced Enrichment for Research and Test

Reactor (RERTR) – named Global Threat Reduction Initiative (GTRI) •  Dispersed or laminated in aluminum or Al alloy

RERTR/GTRI: •  Convert research and test reactor from using HEU fuels to LEU fuels •  Increase density of U isotopes in the fuel

Al

UMo

U-10wt.%Mo vs Al after irradiation**

U-Mo fuel particles Al alloy matrix Al alloy cladding

Dispersion Fuel

U-Mo fuel plate Al alloy cladding

Monolithic Fuel

Page 3: Role of Solid State Diffusion Studies in Materials ... · Department of Materials Science and Engineering *Advanced Materials Processing and Analysis Center ... Diffusion barrier

��

Fuel-Matrix and Fuel-Cladding Chemical Interaction

Fuel-Matrix and Fuel-Cladding Chemical Interaction (FMCI and FCCI)

•  Induced by interdiffusion •  Involves multiple-phases and multiple-components. •  Irradiation enhanced diffusion

Deleterious effects: •  Thins the cladding layer •  Produces phases with relative low melting point •  Cause cracks due to different thermal expansion coefficients

Engineering Solutions that Require Scientific Understanding: • Addition of alloying constituents for matrix/cladding • Placement of barrier layer (or coatings) between metallic fuel

and matrix/cladding alloys • Diffusional interaction between barrier and fuel as well as

matrix/cladding alloys

Page 4: Role of Solid State Diffusion Studies in Materials ... · Department of Materials Science and Engineering *Advanced Materials Processing and Analysis Center ... Diffusion barrier

��

Materials Research at MCEE !  RERTR/GTRI:

"  U-Mo vs. Al Matrix/Cladding Alloys "  U-Mo vs. Diffusion Barrier (e.g., Zr, Mo, Nb, Mg) "  Zr Barrier vs. Al Cladding Alloys

!  FCRD: "  U-Zr vs. Fe, Fe-Cr, Fe-Cr-Ni Alloys "  Fe, Fe-Cr, Fe-Cr-Ni Thin Films on U-Zr "  Thermotransport in U-Zr Alloys

!  ATR/NSUF "  Neutron Irradiation of

Diffusion Couples with U

!  Diffusion in Mg Alloys for Lightweight

!  Microstructural Development / Diffusion "  Ni-Mn-Ga and Ni-Mn-In Magnetocaloric Materials "  Multiscale (e.g., Nano and Mirco) Al- and Mg-Metal Matrix

Composites "  Thermal Barrier Coatings for Gas Turbines "  High Temperature Heat Transfer Fluid Corrosion

5 1/nm5 1/nm

NiMnGa M-T

Page 5: Role of Solid State Diffusion Studies in Materials ... · Department of Materials Science and Engineering *Advanced Materials Processing and Analysis Center ... Diffusion barrier

Current Research Activity at MCEE View by Periodic Chart

Major Solvent Alloying Addition Model Only

Page 6: Role of Solid State Diffusion Studies in Materials ... · Department of Materials Science and Engineering *Advanced Materials Processing and Analysis Center ... Diffusion barrier

��

Outline !  Brief Experimental Details

!  Diffusion related to U-Mo and Al-alloy matrix/cladding in dispersion fuels

!  Diffusion barrier kinetics for Zr, Mo, Nb, and Mg in monolithic fuels

!  Process design for Zr diffusion barrier: •  Microstructural characterization of HIP

fuel plates •  U-Mo-Zr diffusion kinetics and phase

equilibria study with quench variation •  Zr interaction with Al-alloy cladding

!  Summary and future work

Page 7: Role of Solid State Diffusion Studies in Materials ... · Department of Materials Science and Engineering *Advanced Materials Processing and Analysis Center ... Diffusion barrier

Experimental Details

•  Solid-to-solid diffusion couple alloys were cut, polished and assembled under a controlled Ar atmosphere in a glove box.

•  Diffusion couples were encapsulated in quartz capsules in Ar atmospheres after Ar flush for heat treatment.

•  Diffusion anneal performed using a Lindberg/Blue 3-Zone horizontal tube furnace.

•  After anneal the couples were quenched in ice water to preserve the high temperature microstructures.

•  The diffusion couples were mounted in epoxy, cross-sectioned and polished for analysis.

Clamping diskAl2O3 spacer disk

Alloy disk

Page 8: Role of Solid State Diffusion Studies in Materials ... · Department of Materials Science and Engineering *Advanced Materials Processing and Analysis Center ... Diffusion barrier

Experimental Details

Page 9: Role of Solid State Diffusion Studies in Materials ... · Department of Materials Science and Engineering *Advanced Materials Processing and Analysis Center ... Diffusion barrier

��

Diffusion Couples:

U-Mo vs. Al* U-Mo vs. Al-Si**

U vs. Mo***

*"Perez,"et"al."Metall."Mater."Trans."A,"2011;"42A:"3071."

**"Perez,"et"al."Metall."Mater."Trans."A,"2013;"44A:"584."

***"K."Huang,"et"al.,"Metall."Mater."Trans."A,"2013;"44A:"738.""

Diffusion Investigations in U-Mo-Al-Si for RERTR Dispersion Fuels

Diffusion(Couples((wt.%)

Temperature((°C)

Time((hours)

U"7Mo"vs."Al"

U10Mo"vs."Al"

U12Mo"vs."Al 600 24

U"7Mo"vs."Al"

U10Mo"vs."Al"

U12Mo"vs."Al 550

1 5 20

U"7Mo"vs."AlC2Si"

U10Mo"vs."AlC2Si"

U12Mo"vs."AlC2Si 550

1 5 20

U"7Mo"vs."AlC5Si"

U10Mo"vs."AlC5Si"

U12Mo"vs."AlC5Si 550

1 5 20

Page 10: Role of Solid State Diffusion Studies in Materials ... · Department of Materials Science and Engineering *Advanced Materials Processing and Analysis Center ... Diffusion barrier

���

U-Mo vs. Al Diffusion Couples*

•  Separation of the interdiffusion zone into different phase regions takes place during anneal to produce a stratified structure.

•  Multi-phase regions composed of various intermetallic phases develop.

•  Similar microstructures are observed in diffusion couples annealed at 600˚C and 550˚C.

10µm 10µm 10µm10µm

α-U

UAl3U6Mo4Al43

UAl3UMo2Al20U6Mo4Al43UAl3

UMo2Al20U6Mo4Al43

UAl4UMo2Al20

UAl3U6Mo4Al43

UAl3 UMo2Al20 U6Mo4Al43

!-U

UAl3 U6Mo4Al43

U-10Mo vs. Al

UAl4 UMo2Al20

100 µm

(600°C, 24hrs)

•  Perez,"et"al."Metall."Mater."Trans."A"2011;42:3071."

Page 11: Role of Solid State Diffusion Studies in Materials ... · Department of Materials Science and Engineering *Advanced Materials Processing and Analysis Center ... Diffusion barrier

���

•  The interdiffusion zone developed a fine-grained microstructure with grains size less than 1µm.

•  Electron diffraction analyses were carried out for selected regions in the interdiffusion zone of the U-10Mo vs. Al diffusion couple annealed at 600˚C for 24 hours.

•  The UAl3, UAl4, U6Mo4Al43 and UMo2Al20 phases were identified in the interdiffusion zone in multi-phase layered microstructures.

022

220

242

440

[111]

UAl4Orthorhombic, Imma

100 200

110

[001]210

UAl3Cubic, Pm-3m

220

[111]

UMo2Al20Cubic, Fd-3m

422202

022

404

224[042]

200400

012

024 212

U6Mo4Al43(P63/mcm3(193))

U-Mo vs. Al Diffusion Couples*

•  Perez,"et"al."Metall."Mater."Trans."A"2011;42:3071."

Page 12: Role of Solid State Diffusion Studies in Materials ... · Department of Materials Science and Engineering *Advanced Materials Processing and Analysis Center ... Diffusion barrier

���

U-Mo vs. Al-Si Diffusion Couples*

•  Diffusion couples containing Si in the Al-alloys showed stratification of the interdiffusion zone.

•  Complex multi-phase regions developed within 1 hour anneal time. •  Initially discontinuous Al and Si-rich layers develop in the

interdiffusion zone. •  After longer diffusion anneal, the observed Si-rich regions grow and

develop into continuous layers.

U-12Mo vs. Al-2Si (550°C for 1 hour)

U-12Mo vs. Al-2Si (550°C for 5 hours)

U-12Mo vs. Al-2Si (550°C for 20 hours)

25µm 25µm 25µm

Si-rich

Al-rich

Si-rich

Al-rich

Si-rich

Al-rich

*"Perez,"et"al."Metall."Mater."Trans."A,"2013;"44A:"584."

"

Page 13: Role of Solid State Diffusion Studies in Materials ... · Department of Materials Science and Engineering *Advanced Materials Processing and Analysis Center ... Diffusion barrier

���

•  The (U,Mo)(Al,Si)3 and UMo2Al20 phases were

positively identified.

•  The (U,Mo)(Al,Si)3 appears to be distributed through the interdiffusion zone with variation in compositions. –  This phase shows promising results

during irradiation and is considered a favored phase.

•  More importantly, the UAl4 and U6Mo4Al43 phases do “not” develop. –  The U6Mo4Al43 potentially behaves poorly

with void formation during irradiation.**

(U,Mo)(Al,Si)3, Cubic, Pm3m

100

110

111

200

UMo2Al20Cubic Fd-3m

440

404 844448

404220

202422

[111]

**J.(Gan,(D.D.(Keiser,(Jr.,((JNM,(396((2010)(234.(

U-Mo vs. Al-Si Diffusion Couples*

*"Perez,"et"al."Metall."Mater."Trans."A,"2013;"44A:"584."

Page 14: Role of Solid State Diffusion Studies in Materials ... · Department of Materials Science and Engineering *Advanced Materials Processing and Analysis Center ... Diffusion barrier

���

U-Mo vs. Al-Si Diffusion Couples: Growth Constants

The growth constant for the interdiffusion zone (i.e., intermetallic phases), assuming simple parabolic growth, was calculated:

21tTK =

Diffusion(Couples(Growth(Constant,(K(

(µm/sec½)(

UCMo"vs."Al"(600˚C)" 0.9"C"1.8"

UCMo"vs."Al"(550˚C)" 0.4"C"0.7"

UCMo"vs."AlC2Si"(550˚C)" 0.1"C"0.2"

UCMo"vs."AlC5Si"(550˚C)" 0.1"–"0.2"

T(is(the(IDZ(thickness(and(t(is(the(anneal(Ome.(

•  Alloying Al with Si alters the phase constituents (no UAl4 and

U6Mo4Al43) and decreases the growth kinetics.

**"Perez,"et"al."Metall."Mater."Trans."A,"2013;"44A:"584."

Page 15: Role of Solid State Diffusion Studies in Materials ... · Department of Materials Science and Engineering *Advanced Materials Processing and Analysis Center ... Diffusion barrier

���

Diffusion Database

BSE micrograph and concentration profile from the U vs. Mo couple annealed at 1273K for 24 hours.

U XK MoXI

150$µm

00.10.20.30.40.50.60.70.80.9

1

-800 -700 -600 -500 -400 -300 -200 -100 0 100

FittedMeasurement 1 EPMAMeasurement 2 EPMA

XK = -70

Distance to Matano Plane, x (µm)

Con

cent

ratio

n of

Mo

(at.

frac

.)

X0

0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4

Inte

rdiff

usio

n C

oeff

icie

nt (m

2 /s) 1273K this study

1173K this study1073K this study973K this study923K this study1323K Adda.1273K Adda.1223K Adda.1123K Adda.

NMo (atomic fraction)

10-11

10-12

10-13

10-14

10-15

10-16

10-17

1050 1100 1150 1200 1250 1300 1350

Trac

er d

iffus

ivity

of U

(m2 /s

)

Temperature (K)

Exp. Pure U by AddaExp. Nmo=0.1 by AddaIdeal/CALPHAD/Subreg. Sol.Reg. Sol.Vamberskii

NMo=0NMo=0.08

NMo=0.07

NMo=0.1

NMo=0.06

10-11

10-12

10-13

10-14

Interdiffusion Coefficient Tracer Diffusion Coefficients

K."Huang,"et"al.,"Metall."Mater."Trans."A,"2013;"44A:"738.""

Page 16: Role of Solid State Diffusion Studies in Materials ... · Department of Materials Science and Engineering *Advanced Materials Processing and Analysis Center ... Diffusion barrier

���

Diffusion Couples:

U-10Mo vs. Zr* U-10Mo vs. Mo** U-10Mo vs. Nb*** U-10Mo vs. Mg***

Diffusion Investigations in U-Mo for RERTR Monolithic Fuels

*(Huang(et(al.,(JPED,(2012;(33:(443.(**(Huang,(et(al.,(JPED,(2013;(34:(307.((***(Huang,(et(al.,(JPED,(2014;(35:(146.(****(Huang(et(al.,(DDF,(2013;(333:(199.(

(

Diffusion(Couples Temperature((°C)

Time((hours)

U10Mo"vs."Mo

1000 96 900 240 800 480 700 720 600 960

UC10Mo"vs."Zr

1000 96 900 240 800 480 700 720 600 960

UC10Mo"vs."Nb

1000 96 900 240 800 480 700 720 600 960

UC7Mo"vs."Mg 550 96

Page 17: Role of Solid State Diffusion Studies in Materials ... · Department of Materials Science and Engineering *Advanced Materials Processing and Analysis Center ... Diffusion barrier

��

Barrier Materials Candidates Refractory element Zr, Mo and Nb*: ! Diffusion of U is slow. ! High melting points and thermal conductivity ! Corrosion resistant is good. Mo: ! Maintain the system to be simple binary. ! One intermetallic phase forms between U-Mo and Mo. ! Largest variation in the composition of U-10wt.%Mo fuel can be less than

15 at.% Mo. Zr: ! Neutrons adsorption rate is one of the lowest among natural metal [4]. ! Compatible with current hot rolling process

adopted by Idaho National Lab (INL)**. Nb: ! Forms complete solid solution with U ! Forms less number of intermetallic phases with Al compared to Zr and Mo.

*Davis Jr, et al. ASM Handbook 1992. **Perez, et al. J Nucl Mater 2010;402:8

U Mo

Tem

pera

ture

( ℃)

U-10wt.%Mo

Page 18: Role of Solid State Diffusion Studies in Materials ... · Department of Materials Science and Engineering *Advanced Materials Processing and Analysis Center ... Diffusion barrier

��

0

10

20

30

40

50

60

70

80

90

100

UMoZr

U-Mo α-Zr

Zr rich phase

Mo2Zr β-Zr

150$µm

800⁰C 480 hours

Diffusion path: 800 °C(Phase diagram: 750 °C)

MeasuredEstimated

Diffusion Microstructure and Diffusion Paths: U-Mo vs. Zr

! Boned well at 1000 -600⁰C. ! γ-U, Mo2Zr, Zr rich, two phases

region, pure Zr were observed. ! Mo2Zr gets denser when anneal

temperature decreased according to the phase diagrams.

! Uphill diffusion of U. ! The estimated diffusion paths

agree well with the ternary phase diagram.

! Mo plays a significant role on the diffusion path especially at 700°C.

! About 104-102 times slower than those between U-10wt.%Mo vs. Al and Al-Si, respectively.

Page 19: Role of Solid State Diffusion Studies in Materials ... · Department of Materials Science and Engineering *Advanced Materials Processing and Analysis Center ... Diffusion barrier

���

U-Mo MoXI

50#µm900°C for 240 hrs

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1

-300 -250 -200 -150 -100 -50 0 50

Con

cent

rati

on o

f M

o (a

t. f

rac.

)

Distance to Matano plane (µm)

EPMA 1EPMA 2Smoothed

X0 XI =8.5

IZ=144

900°C"for"240"hrs""

Diffusion Microstructure and Diffusion Paths: U-Mo vs. Mo

0 0.1 0.2 0.3 0.4 0.5

Inte

rdiff

usio

n co

effic

ient

(m2 /s

)

NMo (at. frac.)

This study 1000 °CThis study 900 °CThis study 800 °CPrevious study 1000 °CPrevious study 900 °CPrevious study 800 °C

10-12

10-13

10-14

10-15

10-16

! Boned well at 1000 -600⁰C. ! No intermetallics formation. ! Atomic mobility and vacancy wind

parameters determined for U-Mo solid solution.

! More than 105 times slower than those between U-10wt.%Mo vs. Al and Al-Si, respectively.

Page 20: Role of Solid State Diffusion Studies in Materials ... · Department of Materials Science and Engineering *Advanced Materials Processing and Analysis Center ... Diffusion barrier

���

800⁰C"480"hours""

U10Mo

U-Mo-Nb S.S

Pure U

Nb

Thermal crack

30#µm

IZ

Diffusion Microstructure and Diffusion Paths: U-Mo vs. Nb

!  Intermetallic formation and growth. ! Significant quench cracks after all

temperatures of anneal. ! More than 106 times slower than

those between U-10wt.%Mo vs. Al and Al-Si, respectively.

10-12

10-13

10-14

10-15

10-16

10-17

10-18

10-190.6 0.8 1 1.2 1.4 1.6 1.8

Gro

wth

rat

e (m

2 /s)

1000/T(K)

U"Mo%vs.%Zr%(measured)U"Mo%vs.%Zr%(predicted)U"Mo%vs.%Mo%(measured)U"Mo%vs.%Mo%(predicted)U"Mo%vs.%Nb%(measured)U"Mo%vs.%Nb%(predicted)

10-11

The growth rate of interdiffusion zone between U-10Mo with Zr, Mo, Nb is about 104, 105 and 106 times slower than those in diffusion couples of U-10Mo vs. Al or Al-Si, respectively.

Page 21: Role of Solid State Diffusion Studies in Materials ... · Department of Materials Science and Engineering *Advanced Materials Processing and Analysis Center ... Diffusion barrier

���

Mg: ! There is no reactions between Mg with U or Mo based on binary phase

diagram. ! Reaction between Mg and Al alloy is insignificant during improved hot

rolling process at 275°C reported*. ! The neutron absorption rate of Mg is one of the lowest among natural

metal**. ! Thermal conductivity is high, 156 W·m−1·K−1 .

*Wiencek TC, et al. 1998 International Meeting on RERTR. São Paulo, Brazil, 1998. **Davis Jr, et al. ASM Handbook 1992.

Barrier Materials Candidates

Page 22: Role of Solid State Diffusion Studies in Materials ... · Department of Materials Science and Engineering *Advanced Materials Processing and Analysis Center ... Diffusion barrier

���

Diffusion Microstructure and Diffusion Paths: U-Mo vs. Mg

U7Mo

150$µm

MgXI

560⁰C(96(hours((

Mg

U-7Mo

Mg

U-7Mo

0

10

20

30

40

50

60

70

80

90

100

0 50 100 150 200 250 300 350 400

Conc

entra

tion (

at.%

)

Distance (nm)

U"

Mo"

Mg"

O"

Page 23: Role of Solid State Diffusion Studies in Materials ... · Department of Materials Science and Engineering *Advanced Materials Processing and Analysis Center ... Diffusion barrier

���

Zr Diffusion Barrier

Rolled, HIP’ed and Annealed Fuel Assembly*

U-Mo-Zr Diffusion Kinetics and

Phase Equilibria**

Zr vs. Al-Alloy Cladding*** *Y.(Park(et(al.,(Journal(of(Nuclear(Materials,(2014;(447:(215.(**Y.(Park(et(al.,(and(N.(Eriksson(et(al.,(Unpublished.(***J.(Dickson(et(al.,(Intermetallics,(2014;(49:(154.((***A.(Paz(y(Puente,(et(al.,((J.(Ref.(Met.(Hard(Mater.,(2014;(43:(317.((

Page 24: Role of Solid State Diffusion Studies in Materials ... · Department of Materials Science and Engineering *Advanced Materials Processing and Analysis Center ... Diffusion barrier

���

!  U-Mo alloy by arc-melting. !  Acid cleaned and laminated, in a carbon steel can, using pure Zr

(99.9% pure) foil with a starting thickness of 250 µm. !  The Zr-laminated U-Mo coupon: pre-heated at 650°C for 30 minutes in

a furnace, and co-rolled 15 times. A post-rolling annealing treatment was performed at 650°C for 45 minutes.

!  Each laminated foil was polished and stacked with AA6061 cladding. !  HIP’ed at various temperatures (520, 540, 560 and 580°C) and

durations (45, 60, 90 180 and 345 minutes) !  The HIP heated to the target temperature with a ramp-up and cool-

down rate of 280°C per hour with constant pressure at 103 MPa (~15 ksi) using argon pressurizing medium.

Rolled, HIP’ed and Annealed Fuel Assembly"

250 µm!

25 µm!

330 µm!Zr U-Mo Alloy

AA6061

AA6061

HIP Pressure 103 MPa (15 ksi)

HIP Pressure 103 MPa (15 ksi)

Page 25: Role of Solid State Diffusion Studies in Materials ... · Department of Materials Science and Engineering *Advanced Materials Processing and Analysis Center ... Diffusion barrier

���

Rolled, HIP’ed and Annealed Fuel Assembly"

250 µm!

25 µm!

330 µm!Zr U-Mo Alloy

AA6061

AA6061

HIP Pressure 103 MPa (15 ksi)

HIP Pressure 103 MPa (15 ksi)

Can we employ higher HIP temperature and longer HIP duration?

Improved adhesion strength, but want

to avoid excessive diffusional interactions.

Page 26: Role of Solid State Diffusion Studies in Materials ... · Department of Materials Science and Engineering *Advanced Materials Processing and Analysis Center ... Diffusion barrier

���

Diffusion Barrier: Zr Rolled, HIP’ed and Annealed Fuel Assembly

HIP(Run� Sample� Temperature((˚C)� Hold(Time(((minute)� Pressure((ksi)�

81a� 81d4� 560� 90� 15�

82� 82d5� 580� 90� 15�

83� 83d5� 540� 90� 15�

84� 84d4� 520� 90� 15�

85� 85d5� 560� 180� 15�

86� 86d5� 560� 45� 15�

87� 87d5� 560� 345� 15�

88� 88d5,(88d2b� 560� 60� 15�

N/A� Alloy(402d2� 650� 90� (�

UdMo/Zr/6061(foils(codrolled(at(650˚C(for(90(minutes.

Page 27: Role of Solid State Diffusion Studies in Materials ... · Department of Materials Science and Engineering *Advanced Materials Processing and Analysis Center ... Diffusion barrier

��

AA6061 Zr

U10Mo

AA6061

Zr

U10Mo

100 µm

2 µm

Diffusion Barrier: Zr Rolled, HIP’ed and Annealed Fuel Assembly

U10Mo

UZr2

Mo2Zr

Zr

AA6061

Al3Zr

α-U

Zr

2 µm

2 µm

Page 28: Role of Solid State Diffusion Studies in Materials ... · Department of Materials Science and Engineering *Advanced Materials Processing and Analysis Center ... Diffusion barrier

��

U-Mo vs. Zr Interface"

(Al,Si)3Zr (tI16)

(Al,Si)2Zr (hP12)

6061 vs. Zr Interface"

UZr2

Zr

Mo2Zr

α-U

γ-U(Mo)

UZr2 (hP3)

Mo2Zr (cF24)

U(α-U) (oC4)

Diffusion Barrier: Zr Rolled, HIP’ed and Annealed Fuel Assembly

Page 29: Role of Solid State Diffusion Studies in Materials ... · Department of Materials Science and Engineering *Advanced Materials Processing and Analysis Center ... Diffusion barrier

���

Hold(Ome(=(90(min.

Hold(Ome(=(90(min.

Hold(Ome(=(90(min.

Hold(Ome(=(90(min.

Diffusion Barrier: Zr Rolled, HIP’ed and Annealed Fuel Assembly

Page 30: Role of Solid State Diffusion Studies in Materials ... · Department of Materials Science and Engineering *Advanced Materials Processing and Analysis Center ... Diffusion barrier

���

Thold(=(560˚C"

Thold(=(560˚C"

Thold(=(560˚C"

Thold(=(560˚C"

Diffusion Barrier: Zr Rolled, HIP’ed and Annealed Fuel Assembly

Page 31: Role of Solid State Diffusion Studies in Materials ... · Department of Materials Science and Engineering *Advanced Materials Processing and Analysis Center ... Diffusion barrier

���

!  Negligible diffusional interaction for U-Mo / Zr interface during HIP – most interactions occur during rolling process (650°C).

!  Arrhenius temperature dependence for 6061 / Zr Interface - Rolling: 473.30 kJ/mol and Transverse: 473.83 kJ/mol.

Diffusion Barrier: Zr Rolled, HIP’ed and Annealed Fuel Assembly

Page 32: Role of Solid State Diffusion Studies in Materials ... · Department of Materials Science and Engineering *Advanced Materials Processing and Analysis Center ... Diffusion barrier

���

Diffusion Barrier: Zr Time Dependent Interaction at 650°C

"  Consistent(observaOon(of(phase(consOtuents(and(microstructure.(

"  Nondparabolic(growth(rate(or(incubaOon(period((?).(

Page 33: Role of Solid State Diffusion Studies in Materials ... · Department of Materials Science and Engineering *Advanced Materials Processing and Analysis Center ... Diffusion barrier

���

Diffusion Barrier: Zr Negligible Interaction at 600°C (960 hrs)

1EC18"

1EC17"

1EC16"

1EC15"

1EC14"

1EC13"

1EC12"

1EC11"

0.7" 0.8" 0.9" 1" 1.1" 1.2"Grow

th(Con

stan

t((m2/s)(

1000/T((1/K)(

!  On-going study on U-Mo-Zr diffusional interactions at lower temperature (650°C to 520°C) as a function of time.

Page 34: Role of Solid State Diffusion Studies in Materials ... · Department of Materials Science and Engineering *Advanced Materials Processing and Analysis Center ... Diffusion barrier

���

Diffusion Barrier: Zr Phase Equilibria of U-Mo-Zr

900°C for 168 hr Water Quenched

650°C for 3 hrs Water Quenched

Water Quenched

560°C for 1.5 hrs

Furnace Cooled

Air Cooled

Alloys

U-10Mo U-10Mo-0.5Zr U-10Mo-1Zr U-10Mo-2Zr U-10Mo-5Zr

U-10Mo-10Zr U-10Mo-20Zr

Quantitative Analyses

XRD, SEM-Image

Analysis

Page 35: Role of Solid State Diffusion Studies in Materials ... · Department of Materials Science and Engineering *Advanced Materials Processing and Analysis Center ... Diffusion barrier

���

Diffusion Barrier: Zr Phase Equilibria of U-Mo-Zr

1 U10Mo2 U10Mo.5Zr3 U10Mo1Zr4 U10Mo2Zr5 U10Mo5Zr6 U10Mo10Zr7 U10Mo20Zr

0"

200"

400"

600"

800"

30" 40" 50" 60" 70" 80"

U10Mo5Zr)

Page 36: Role of Solid State Diffusion Studies in Materials ... · Department of Materials Science and Engineering *Advanced Materials Processing and Analysis Center ... Diffusion barrier

Diffusion Barrier: Zr Phase Equilibria of U-Mo-Zr and Cooling Rate

!  Generally in good agreement with equilibrium phase diagrams at respective high temperature.

Page 37: Role of Solid State Diffusion Studies in Materials ... · Department of Materials Science and Engineering *Advanced Materials Processing and Analysis Center ... Diffusion barrier

��

The(binary(phase(diagram(indicates(the(formaOon(of(many(possible(intermetallics(in(the(temperature(range(of(interest.(

Low(TE(=(660°C((

Diffusion Barrier: Zr Zr vs. Al Alloys Diffusion Couples

Familiar System but Unusual Observations

Page 38: Role of Solid State Diffusion Studies in Materials ... · Department of Materials Science and Engineering *Advanced Materials Processing and Analysis Center ... Diffusion barrier

��

Excellent(agreement(with(previously(reported((e.g.,(Kidson,(1964;(Laik,(2004)(kineOcs(at(temperature(above(525°C.(

*J.(Dickson(et(al.,(Intermetallics,(2014;(49:(154.((

Diffusion Barrier: Zr Zr vs. Al Alloys Diffusion Couples

Page 39: Role of Solid State Diffusion Studies in Materials ... · Department of Materials Science and Engineering *Advanced Materials Processing and Analysis Center ... Diffusion barrier

���

Diffusion Barrier: Zr Zr vs. Al Alloys Diffusion Couples

Al2Si(

Zr(τ1((Al5SiZr2)((

2 1/nm2 1/nm

0"2"0"

1"1"0"[0"0"1]"

(Si,Al)2Zr+–+oC12+

5 1/nm5 1/nm

1"1"4"

1"1̅"4"[4"0"1̅]"

Al2Si+

(Si,Al)2Zr+

τ1+(Al5SiZr2)+2+tI16+++

τ1+(Al5SiZr2)++

1"μm"

Zr (Al,Si)3Zr Al3SiZr2 Al2Zr

5 1/nm5 1/nm

1"1"4"1"1̅"4"

[4"0"1̅]"

(Al,Si)3Zr+–+tI16+

5 1/nm5 1/nm

2"1̅"0"1"1"2"

[2"4"3̅]"

Al3SiZr2+–+hP12++

"  FormaOon(and(growth(of(τ1((Al5SiZr2)(ternary(intermetallic(phase.(

"  Similar(for(Al5Si(Alloy.(

*J.(Dickson(et(al.,(Intermetallics,(2014;(49:(154.((

Page 40: Role of Solid State Diffusion Studies in Materials ... · Department of Materials Science and Engineering *Advanced Materials Processing and Analysis Center ... Diffusion barrier

���

Diffusion Barrier: Zr Zr vs. Al Alloys Diffusion Couples

0"

10"

20"

30"

40"

50"

60"

70"

80"

90"

100"

0" 50" 100" 150" 200"

Concen

tra)

on*(a

t.%)*

Distance*(μm)*

(Al,Si)3Zr*τ1**

Al*

Zr*

Si* (Al,Si)2Zr*

Zr#Al# Al3Zr# Al2Zr#

Zr#Al(Si#Alloy#

τ1#(Al5SiZr2)#

(Al,Si)3Zr#

Zr#AA6061# (Al,Si)3Zr#

(Si,Al)2Zr#Al2Zr#

τ1#(Al5SiZr2)# (Al,Si)2Zr#

Al3SiZr2#

"  FormaOon(and(growth(of(both(τ1((Al5SiZr2)(ternary(intermetallic(and(binary((Al,Si)3Zr(phases.(

"  DisOnguished(by(Si(content.(

*J.(Dickson(et(al.,(Intermetallics,(2014;(49:(154.((

Page 41: Role of Solid State Diffusion Studies in Materials ... · Department of Materials Science and Engineering *Advanced Materials Processing and Analysis Center ... Diffusion barrier

���

Unusual(behavior(at(lower(temperature.(

625°C&

560°C&

525°C&

425°C& 450°C& 425°C&

1E-17

1E-16

1E-15

1E-14

1E-13

1E-12

1.10 1.15 1.20 1.25 1.30 1.35 1.40 1.45

k (

m2/s)

1000/T(K)

High Temperature

Low Temperature

Dickson(et(al.,(Unpublished(Research.(

Diffusion Barrier: Zr Zr vs. Al Alloys Diffusion Couples

Page 42: Role of Solid State Diffusion Studies in Materials ... · Department of Materials Science and Engineering *Advanced Materials Processing and Analysis Center ... Diffusion barrier

���

1.  For U-Mo vs. Al diffusion couples, the interdiffusion zones in diffusion couples U-Mo vs. pure Al annealed at 550˚ and 600˚C consisted of finely distributed UAl3, UAl4, U6Mo4Al43 and UMo2Al20 phases in stratified microstructures.

2.  For U-Mo vs. Al-Si diffusion couples, fast diffusing Si and Al result in the development of the (U,Mo)(Al,Si)3 and UMo2Al20 phases. The UAl4 and U6Mo4Al43 (potentially with poor irradiation behavior) phases do “not” develop in the interdiffusion zone. Addition of Si decreases the growth rate of interaction zone.

3.  Zr, Mo, Nb and Mg barriers were examined for interaction kinetics with U-Mo alloy; all exhibited significant reduction in the rate of interaction by few to several orders of magnitude.

RERTR: Summary

Page 43: Role of Solid State Diffusion Studies in Materials ... · Department of Materials Science and Engineering *Advanced Materials Processing and Analysis Center ... Diffusion barrier

���

RERTR: Summary 4.  Rolled, HIP’ed and annealed fuel plate samples are being

examined for phase constituents and interdiffusion/reaction kinetics as functions of temperature and time.

5.  U-Mo-Zr phase equilibria as a function of temperature and

quench is being investigated – preliminary results indicate that phase constituents generally agree with respective high temperature.

6.  Detailed interdiffusion and reaction mechanisms, including

those at lower temperature, are being investigated for interaction between Zr and Al alloys.

Authors sincerely appreciate financial support and technical assistance of Dr. Dennis Keiser, Jr., at Idaho National Laboratory.

Acknowledgements