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Physical Metallurgy Division, PMD Indira Gandhi Centre for Atomic Research

Kalpakkam – 603 102, India





Characterisation of Microstructure in model

ODS Alloys



Arup Dasgupta



Physical Metallurgy Division

Indira Gandhi Centre for Atomic Research

Kalpakkam – 603102, INDIA





A collaborative work between IGCAR, Kalpakkam and

International Advanced Research Centre for Powder

Metallurgy and New Materials, Hyderabad

22 July 2008 1

WS&FT-08

Physical Metallurgy Division, PMD Indira Gandhi Centre for Atomic Research

Kalpakkam – 603 102, India



SCHEME



• The Issue

– What kind of alloy is under development

– Processing Scheme

– Importance of microstructure and microchemistry

investigations in alloy development



• This Talk

– Types of samples studies so far

– Results and Discussion

– Summary



22 July 2008 2

WS&FT-08

Physical Metallurgy Division, PMD Indira Gandhi Centre for Atomic Research

Kalpakkam – 603 102, India



The Alloy under development

9Cr-0.12C-2W-0.2Ti-0.35Y2O3 Ferritic/Martensitic steel chosen

because of advantages over austenitic stainless steels:



• Higher thermal conductivity

• Lower thermal expansion

• Lower void swelling during irradiation

• Excellent high temperature creep resistance

• W  Mo replacement for solid solution strengthening;

reduced activation

• Ti  Helps to get finer dispersoids





Mandate: Clad Tubes (6.6mm OD, 0.45mm thick, 2.65 m long)

22 July 2008 3

WS&FT-08

Physical Metallurgy Division, PMD Indira Gandhi Centre for Atomic Research

Kalpakkam – 603 102, India



Processing Scheme









Machining Mult. Pass CW

Extr. Rods Mother Tubes Int. Heat Trtmt. Clad Tubes



Courtesy: IGCAR ODS Task force, ARCI - Hyderabad

22 July 2008 4

WS&FT-08

Physical Metallurgy Division, PMD Indira Gandhi Centre for Atomic Research

Kalpakkam – 603 102, India



Importance of Microstructural & Microchemical

Investigations MA systems

• Grain morphology

• Phase stability

• Microstructural Uniformity

• Mechanical Interdiffusion

(Microchemical Uniformity) Milling process

Dispersoid  Large strain fields +

• Shape Subsequent Annealing Steps

• Size

• Distribution

• Interface with matrix

• Dislocations, other defects

Impurities  Microstr.  Mech. Prop. Purity of feed powders, containers,

• Microstructure / Microchemistry milling conditions



22 July 2008 5

WS&FT-08

Physical Metallurgy Division, PMD Indira Gandhi Centre for Atomic Research

Kalpakkam – 603 102, India



Samples Studied

#ODS 0: 48h Milled Fe-0.2Ti-0.35Y2O3 Powder

#ODS 1: Fe-0.35Y2O3

Fe (150µm) and Y2O3 (1.33µm) ball milled / 30h, annealed at 973K /

vacuum , double compacted, double sintered at 1323K / H2

#ODS 2: Fe-0.2Ti-0.35Y2O3

Fe (150µm), Ti (105µm) and Y2O3 (1.33µm) ball milled / 30h, annealed at

973K / vac., double compacted, double sintered at 1323K / H2

#ODS 3: Fe-0.2Ti-0.35Y2O3 - Forged

Fe (150µm), Ti (105µm) and Y2O3 (10-20nm) attritor milled / 20h, degassed

at 723K & sealed. Can hipped/ forged at 1323K/ 1000MPa

#ODS 4: Fe-0.12C-9Cr-2W-0.2Ti – Pre-alloyed Powder – SEM Only

#ODS 5: Yttria Powder

#ODS 6: Fe-9Cr-2W-0.2Ti-0.35Y2O3-0.12C – Milled Powder

#ODS 7: Fe-9Cr-2W-0.2Ti-0.35Y2O3-0.12C – Extruded at 1050oC

B1-ODS-S150-Z04-C46-D04-E1050-ER09

22 July 2008 6

WS&FT-08

Physical Metallurgy Division, PMD Indira Gandhi Centre for Atomic Research

Kalpakkam – 603 102, India



Samples Studied

#ODS 0: 48h Milled Fe-0.2Ti-0.35Y2O3 Powder

#ODS 1: Fe-0.35Y2O3

Fe (150µm) and Y2O3 (1.33µm) ball milled / 30h, annealed at 973K /

vacuum , double compacted, double sintered at 1323K / H2

#ODS 2: Fe-0.2Ti-0.35Y2O3

Fe (150µm), Ti (105µm) and Y2O3 (1.33µm) ball milled / 30h, annealed at

973K / vac., double compacted, double sintered at 1323K / H2

#ODS 3: Fe-0.2Ti-0.35Y2O3 - Forged

Fe (150µm), Ti (105µm) and Y2O3 (10-20nm) attritor milled / 20h, degassed

at 723K & sealed. Can hipped/ forged at 1323K/ 1000MPa

#ODS 4: Fe-0.12C-9Cr-2W-0.2Ti – Pre-alloyed Powder – SEM Only

#ODS 5: Yttria Powder

#ODS 6: Fe-9Cr-2W-0.2Ti-0.35Y2O3-0.12C – Milled Powder

#ODS 7: Fe-9Cr-2W-0.2Ti-0.35Y2O3-0.12C – Extruded at 1050oC

B1-ODS-S150-Z04-C46-D04-E1050-ER09

22 July 2008 7

WS&FT-08

Physical Metallurgy Division, PMD Indira Gandhi Centre for Atomic Research

Kalpakkam – 603 102, India









22 July 2008 8

WS&FT-08

Physical Metallurgy Division, PMD Indira Gandhi Centre for Atomic Research

Kalpakkam – 603 102, India

3 size ranges:

(a) large, facetted

(Fe-Co)

(b) 50 – 75 nm

(Fe-Ti)

(c) sub-10 nm (Fe)









Co

Fe



Courtesy:

Institute Nano-

science Initiative

IISc, Bangalore

- Tecnai F-30

22 July 2008 9

WS&FT-08

Physical Metallurgy Division, PMD Indira Gandhi Centre for Atomic Research

Kalpakkam – 603 102, India



Samples Studied

#ODS 0: 48h Milled Fe-0.2Ti-0.35Y2O3 Powder

#ODS 1: Fe-0.35Y2O3

Fe (150µm) and Y2O3 (1.33µm) ball milled / 30h, annealed at 973K /

vacuum , double compacted, double sintered at 1323K / H2

#ODS 2: Fe-0.2Ti-0.35Y2O3

Fe (150µm), Ti (105µm) and Y2O3 (1.33µm) ball milled / 30h, annealed at

973K / vac., double compacted, double sintered at 1323K / H2

#ODS 3: Fe-0.2Ti-0.35Y2O3 - Forged

Fe (150µm), Ti (105µm) and Y2O3 (10-20nm) attritor milled / 20h, degassed

at 723K & sealed. Can hipped/ forged at 1323K/ 1000MPa

#ODS 4: Fe-0.12C-9Cr-2W-0.2Ti – Pre-alloyed Powder – SEM Only

#ODS 5: Yttria Powder

#ODS 6: Fe-9Cr-2W-0.2Ti-0.35Y2O3-0.12C – Milled Powder

#ODS 7: Fe-9Cr-2W-0.2Ti-0.35Y2O3-0.12C – Extruded at 1050oC

B1-ODS-S150-Z04-C46-D04-E1050-ER09

22 July 2008 10

WS&FT-08

Physical Metallurgy Division, PMD Indira Gandhi Centre for Atomic Research

Kalpakkam – 603 102, India









Counts (arb.un.) FeEsc Cr k









Fe k



Fe k

Cr k



Ni k









1 2 3 4 5 6 7 8

Energy (keV)

22 July 2008 11

WS&FT-08

Physical Metallurgy Division, PMD Indira Gandhi Centre for Atomic Research

Kalpakkam – 603 102, India



Samples Studied

#ODS 0: 48h Milled Fe-0.2Ti-0.35Y2O3 Powder

#ODS 1: Fe-0.35Y2O3

Fe (150µm) and Y2O3 (1.33µm) ball milled / 30h, annealed at 973K /

vacuum , double compacted, double sintered at 1323K / H2

#ODS 2: Fe-0.2Ti-0.35Y2O3

Fe (150µm), Ti (105µm) and Y2O3 (1.33µm) ball milled / 30h, annealed at

973K / vac., double compacted, double sintered at 1323K / H2

#ODS 3: Fe-0.2Ti-0.35Y2O3 - Forged

Fe (150µm), Ti (105µm) and Y2O3 (10-20nm) attritor milled / 20h, degassed

at 723K & sealed. Can hipped/ forged at 1323K/ 1000MPa

#ODS 4: Fe-0.12C-9Cr-2W-0.2Ti – Pre-alloyed Powder – SEM Only

#ODS 5: Yttria Powder

#ODS 6: Fe-9Cr-2W-0.2Ti-0.35Y2O3-0.12C – Milled Powder

#ODS 7: Fe-9Cr-2W-0.2Ti-0.35Y2O3-0.12C – Extruded at 1050oC

B1-ODS-S150-Z04-C46-D04-E1050-ER09

22 July 2008 12

WS&FT-08

Physical Metallurgy Division, PMD Indira Gandhi Centre for Atomic Research

Kalpakkam – 603 102, India









Ti k

FeEsc Cr k









Counts (arb.un.)





Cr k

Al k

Ni k









Fe k



Fe k

1 2 3 4 5 6 7 8

Energy (keV)

22 July 2008 13

WS&FT-08

Physical Metallurgy Division, PMD Indira Gandhi Centre for Atomic Research

Kalpakkam – 603 102, India



Samples Studied

#ODS 0: 48h Milled Fe-0.2Ti-0.35Y2O3 Powder

#ODS 1: Fe-0.35Y2O3

Fe (150µm) and Y2O3 (1.33µm) ball milled / 30h, annealed at 973K /

vacuum , double compacted, double sintered at 1323K / H2

#ODS 2: Fe-0.2Ti-0.35Y2O3

Fe (150µm), Ti (105µm) and Y2O3 (1.33µm) ball milled / 30h, annealed at

973K / vac., double compacted, double sintered at 1323K / H2

#ODS 3: Fe-0.2Ti-0.35Y2O3 - Forged

Fe (150µm), Ti (105µm) and Y2O3 (10-20nm) attritor milled / 20h, degassed

at 723K & sealed. Can hipped/ forged at 1323K/ 1000MPa

#ODS 4: Fe-0.12C-9Cr-2W-0.2Ti – Pre-alloyed Powder – SEM Only

#ODS 5: Yttria Powder

#ODS 6: Fe-9Cr-2W-0.2Ti-0.35Y2O3-0.12C – Milled Powder

#ODS 7: Fe-9Cr-2W-0.2Ti-0.35Y2O3-0.12C – Extruded at 1050oC

B1-ODS-S150-Z04-C46-D04-E1050-ER09

22 July 2008 14

WS&FT-08

Physical Metallurgy Division, PMD Indira Gandhi Centre for Atomic Research

Kalpakkam – 603 102, India









140

Pore Size Distribution

120

Frequency









100

80

60 Porosity ~ 1%

40

20

0

2 4 8 More

Pore dia. (mm)

22 July 2008 15

WS&FT-08

Physical Metallurgy Division, PMD Indira Gandhi Centre for Atomic Research

Kalpakkam – 603 102, India



SADP

SADP Intensity Profile (arb.un.) Fe (211) Y2O3 (400)bcc/(200)fcc









Y2O3 (222)bcc/(111)fcc

Fe (200)





Fe (110)

Fe (310)









Y2O3 (622)bcc/(311)fcc



Selection Rule

Y2O3 (440)bcc/(220)fcc



FCC : (h k l) all

Fe (220)









-Fe - JCPDS # 06-0696

(a=2.866Å) odd / even

bcc - Y2O3 - JCPDS # 41-1105 BCC : h + k + l

(a=10.60) even

Fe (222)









fcc - Y2O3 - JCPDS # 43-0661

(a=5.140)

Y2O3 (211)bcc







1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0

d (Å)

22 July 2008 16

WS&FT-08

Physical Metallurgy Division, PMD Indira Gandhi Centre for Atomic Research

Kalpakkam – 603 102, India



DF









Fek 40



35



30

Counts (arb.un.)









Frequency 25



20



15



Tik 10

Fek

Yl

5

Tik Yk

0

2 4 6 8 10 12 14 16 20 30 40 50 60 70 80

Energy (keV) Size (nm)

22 July 2008 17

WS&FT-08

Physical Metallurgy Division, PMD Indira Gandhi Centre for Atomic Research

Kalpakkam – 603 102, India



IMPURITY









22 July 2008 18

WS&FT-08

Physical Metallurgy Division, PMD Indira Gandhi Centre for Atomic Research

Kalpakkam – 603 102, India



Samples Studied

#ODS 0: 48h Milled Fe-0.2Ti-0.35Y2O3 Powder

#ODS 1: Fe-0.35Y2O3

Fe (150µm) and Y2O3 (1.33µm) ball milled / 30h, annealed at 973K /

vacuum , double compacted, double sintered at 1323K / H2

#ODS 2: Fe-0.2Ti-0.35Y2O3

Fe (150µm), Ti (105µm) and Y2O3 (1.33µm) ball milled / 30h, annealed at

973K / vac., double compacted, double sintered at 1323K / H2

#ODS 3: Fe-0.2Ti-0.35Y2O3 - Forged

Fe (150µm), Ti (105µm) and Y2O3 (10-20nm) attritor milled / 20h, degassed

at 723K & sealed. Can hipped/ forged at 1323K/ 1000MPa

#ODS 4: Fe-0.12C-9Cr-2W-0.2Ti – Pre-alloyed Powder – SEM Only

#ODS 5: Yttria Powder

#ODS 6: Fe-9Cr-2W-0.2Ti-0.35Y2O3-0.12C – Milled Powder

#ODS 7: Fe-9Cr-2W-0.2Ti-0.35Y2O3-0.12C – Extruded at 1050oC

B1-ODS-S150-Z04-C46-D04-E1050-ER09

22 July 2008 19

WS&FT-08

Physical Metallurgy Division, PMD Indira Gandhi Centre for Atomic Research

Kalpakkam – 603 102, India





FeK



CrK









Counts

CrK FeK







TiK





W L









3 4 5 6 7 8 9 10

Energy (keV)



Element Wt. %

Ti 0.57

Cr 9.78

Fe 87.18

W 2.46

22 July 2008 20

WS&FT-08

Physical Metallurgy Division, PMD Indira Gandhi Centre for Atomic Research

Kalpakkam – 603 102, India



Samples Studied

#ODS 0: 48h Milled Fe-0.2Ti-0.35Y2O3 Powder

#ODS 1: Fe-0.35Y2O3

Fe (150µm) and Y2O3 (1.33µm) ball milled / 30h, annealed at 973K /

vacuum , double compacted, double sintered at 1323K / H2

#ODS 2: Fe-0.2Ti-0.35Y2O3

Fe (150µm), Ti (105µm) and Y2O3 (1.33µm) ball milled / 30h, annealed at

973K / vac., double compacted, double sintered at 1323K / H2

#ODS 3: Fe-0.2Ti-0.35Y2O3 - Forged

Fe (150µm), Ti (105µm) and Y2O3 (10-20nm) attritor milled / 20h, degassed

at 723K & sealed. Can hipped/ forged at 1323K/ 1000MPa

#ODS 4: Fe-9Cr-2W-0.2Ti – Pre-alloyed Powder – SEM Only

#ODS 5: Yttria Powder

#ODS 6: Fe-9Cr-2W-0.2Ti-0.35Y2O3-0.16C – Milled Powder

#ODS 7: Fe-9Cr-2W-0.2Ti-0.35Y2O3-0.16C – Extruded at 1050oC

B1-ODS-S150-Z04-C46-D04-E1050-ER09

22 July 2008 21

WS&FT-08

Physical Metallurgy Division, PMD Indira Gandhi Centre for Atomic Research

Kalpakkam – 603 102, India



YL EDS: Yttria Powder, as received









Counts (arb.un.)

OK







YK







YK



1 2 3 14 15 16 17 18 19 20

Energy (keV)







Av. Particle Size (XRD) : 42 nm





22 July 2008 22

WS&FT-08

Physical Metallurgy Division, PMD Indira Gandhi Centre for Atomic Research

Kalpakkam – 603 102, India



Samples Studied

#ODS 0: 48h Milled Fe-0.2Ti-0.35Y2O3 Powder

#ODS 1: Fe-0.35Y2O3

Fe (150µm) and Y2O3 (1.33µm) ball milled / 30h, annealed at 973K /

vacuum , double compacted, double sintered at 1323K / H2

#ODS 2: Fe-0.2Ti-0.35Y2O3

Fe (150µm), Ti (105µm) and Y2O3 (1.33µm) ball milled / 30h, annealed at

973K / vac., double compacted, double sintered at 1323K / H2

#ODS 3: Fe-0.2Ti-0.35Y2O3 - Forged

Fe (150µm), Ti (105µm) and Y2O3 (10-20nm) attritor milled / 20h, degassed

at 723K & sealed. Can hipped/ forged at 1323K/ 1000MPa

#ODS 4: Fe-0.12C-9Cr-2W-0.2Ti – Pre-alloyed Powder – SEM Only

#ODS 5: Yttria Powder

#ODS 6: Fe-9Cr-2W-0.2Ti-0.35Y2O3-0.12C – Milled Powder

#ODS 7: Fe-9Cr-2W-0.2Ti-0.35Y2O3-0.12C – Extruded at 1050oC

B1-ODS-S150-Z04-C46-D04-E1050-ER09

22 July 2008 23

WS&FT-08

Physical Metallurgy Division, PMD Indira Gandhi Centre for Atomic Research

Kalpakkam – 603 102, India









22 July 2008 24

WS&FT-08

Physical Metallurgy Division, PMD Indira Gandhi Centre for Atomic Research

Kalpakkam – 603 102, India



Samples Studied

#ODS 0: 48h Milled Fe-0.2Ti-0.35Y2O3 Powder

#ODS 1: Fe-0.35Y2O3

Fe (150µm) and Y2O3 (1.33µm) ball milled / 30h, annealed at 973K /

vacuum , double compacted, double sintered at 1323K / H2

#ODS 2: Fe-0.2Ti-0.35Y2O3

Fe (150µm), Ti (105µm) and Y2O3 (1.33µm) ball milled / 30h, annealed at

973K / vac., double compacted, double sintered at 1323K / H2

#ODS 3: Fe-0.2Ti-0.35Y2O3 - Forged

Fe (150µm), Ti (105µm) and Y2O3 (10-20nm) attritor milled / 20h, degassed

at 723K & sealed. Can hipped/ forged at 1323K/ 1000MPa

#ODS 4: Fe-0.12C-9Cr-2W-0.2Ti – Pre-alloyed Powder – SEM Only

#ODS 5: Yttria Powder

#ODS 6: Fe-9Cr-2W-0.2Ti-0.35Y2O3-0.12C – Milled Powder

#ODS 7: Fe-9Cr-2W-0.2Ti-0.35Y2O3-0.12C – Extruded at 1050oC

B1-ODS-S150-Z04-C46-D04-E1050-ER09

22 July 2008 25

WS&FT-08

Physical Metallurgy Division, PMD Indira Gandhi Centre for Atomic Research

Kalpakkam – 603 102, India





Pore Density ~0.3% aligned

along Extrusion direction  Tears









22 July 2008 26

WS&FT-08

Physical Metallurgy Division, PMD Indira Gandhi Centre for Atomic Research

Kalpakkam – 603 102, India









FeK-

CrK-

Y L : 0.63 %









FeK-

Ti K : 0.36 %

Cr K : 8.95 %

Intensity (au.)



Fe K : 87.6 %

W L : 2.44 %









CrK-

WM-









NiK-

YL- TiK-

WL-





2 4 6 8 10

Energy (keV)

22 July 2008 27

WS&FT-08

Physical Metallurgy Division, PMD Indira Gandhi Centre for Atomic Research

Kalpakkam – 603 102, India









Fe (110)

SADP Intensity Profile (arb.un.)



Fe (211)



Fe (200)









Y2O3 (400)bcc

Fe (310)









Y2O3 (222)bcc

Fe (220)









0









1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0

d (Å)

22 July 2008 28

WS&FT-08

Physical Metallurgy Division, PMD Indira Gandhi Centre for Atomic Research

Kalpakkam – 603 102, India



Summary

Seven sets of model materials studied (powders, milled, compacted products)



Higher Milling Duration  Agglomeration



The sintered products were porous, 14-20% but forged material had a

porosity ~1%. Extruded material had porosity ~0.3% only!



Yttria  bcc with a=10.6 Å



Forged sample  fine bcc yttria particles with an av. size ~ 10-20 nm; some

were ~ 5-7 nm and some were agglomerated; there appeared to be an

orientation between the Yttria and the rextallised ferrite grains



Prealloyed powder & yttria powder  desired sizes + quite pure



The extruded ODS steel  desired composition, fine martensite laths (~100

nm wide) within the elongated grains, very fine (~ 3nm) yttria.

22 July 2008 29

WS&FT-08

Physical Metallurgy Division, PMD Indira Gandhi Centre for Atomic Research

Kalpakkam – 603 102, India



Contributors

IGCAR, Kalpakkam ARCI, Hyderabad



Arup Dasgupta*, R Vijay, S

R Divakar, S Saroja, Sudhakara Sarma, A

E Mohandas, Venugopala Reddy

M Vijayalakshmi,

PV Sivaprasad,

KBS Rao &

Baldev Raj

22 July 2008 30

WS&FT-08


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