In-situ Scattering Study of Phase Transformation Kinetics

Xun-Li Wang Neutron Scattering Science Division Oak Ridge National Laboratory

Outline
Why are phase transformations of interest? Why kinetics? How are neutrons used to study phase transformations? Future opportunities

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The structure of a material at various length scales

Graphite

Diamond

Metallic Glass

TRIP Steel
OAK RIDGE NATIONAL LABORATORY Nanocrystalline Ni Nanoscale clusters
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Structure Affects Properties

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Structural change during curing of cement

(Chakomakous et al., Acta Cryst. 1992)

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Structure of metallic glass?

Miracle, Nature Mat.

crystalline

amorphous?

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The structure of a material at various length scales

Graphite

Diamond

Metallic Glass

TRIP Steel
OAK RIDGE NATIONAL LABORATORY Nanocrystalline Ni Nanoscale clusters
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NANOCLUSTERS IN IRON MATRIX

4nm

2nm

The nanoclusters were estimated to be 2-3 nm in diameter with a spacing of 12 nm in agreement with APT.
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14YWT 1 h at 1000C

Small Angle Neutron Scattering showed a bi-modal size distribution

0.025

Particle Size Distribution Function (N*v)

0.020

0.015

0.010

0.005

0.000 0 5 10 15

Particle Size Radius (nm)

and thermally stable up to 1400 C

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Structure Determines Properties - Microstructure

Cross-section of a friction stir weld showing distinct microstructure zones generated by heat and mechanical work

Hardness profile through the different microstructure zones reflects the changes in microstructure

Wang et al., 1999

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Microstructure of TRIP Steel

TRansformation Induced Plasticity steels Retained austenite transforms into martensite (a hard phase) during deformation Hard martensite delays the onset of necking resulting in high total elongation
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Extremely high fatigue U. S. DEPARTMENT OF ENERGY

endurance

Why Kinetics?
Because we must !
Mechanisms of nucleation Mechanisms of growth Nature of intermediate and meta-stable phase Ultimate goal is achieve structure control Effect on properties

Because we can !

In-situ time-resolved measurements

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What we are interested in are evolution of the structures at multiple length scales
Length & Time

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Examples
Kinetic study of order-disorder phase transformation in Ni3Mn (1986) Kinetic study of phase transformation in Mn (1999) Fatigue-induced phase transition (on-going) Transient behavior during welding Crystallization of bulk metallic glass

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How are neutrons used to determine structures?

small angle scattering

Ni (Al, Fe)
+ data -- refined -- error | peak position
(220) (211) (210) (111) (110) (200) (100)

Grain morphology and size distribution

Ni Fe Al

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Order-disorder phase transformation in Ni3Mn

Very difficult to study with X-ray
Mn Z=25 Ni Z=28

Ideal for neutrons

Ni b=10.3 fm Mn b=-3.8 fm

Tc=510 C

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Real-time measurements peak width

(211) reflection
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Kinetic study of phase transformation in Mn

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Kinetic study of phase transformation in Mn

Experiments done on HRPD at ISIS
100 m instrument Very high d/d resolution of ~ 4 10-4

Time resolution: 5 minutes per data set

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Multiphase Rietveld analysis to yield volume fraction

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Multiphase Rietveld analysis to yield volume fraction

Tremendous difference in growth rates

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Growth behavior follows scaling by Johnson-Mehl-Avrami theory

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Phase transformation induced by cyclic loading (fatigue)

The Case of ULTIMET 54Co-26Cr-9Ni-5Mo-3Fe-2W (wt%)

fcc

hcp
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*Source: Binary Alloy Phase Diagrams, ASM, Metals Park, OH, 1986, vol.1, p. 759.

In-situ Neutron Diffraction

Incident Neutron Beam Axial Detector Bank

ENGIN-X at the ISIS facility, UK. Pulsed neutron source. 40 minute count times, Co scatters poorly. Sampling volume: ~120 mm3.

Transverse Detector Bank

Specimen Load Frame

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In-situ Neutron Diffraction

Collimator

Specimen

Strain-controlled fatigue: R = -1, tension-compression (R is the ratio of the minimum strain to maximum strain). Total strain range, = 2.5 %. Cycling frequency, f = 0.5 Hz.

Extensometer

Cylindrical specimens of 8 mm gage diameter, 24 mm gage length, M12 threaded ends.

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Evolution of the hcp phase during fatigue test

Overlay of the axial detector bank diffraction patterns measured at point 1.
500 cycles 250 cycles 100 cycles 75 cycles 50 cycles 30 cycles 12 cycles 8 cycles 4 cycles 1 cycle 0 cycles

111 311 103 220 102 200 101

1,500

1,000

X
0 0.5 1 1.5

500

0 -1.5 -1

-0.5

-500

fcc
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hcp

-1,000

-1,500

Increase in the HCP Peak Intensity as a Function of Fatigue Cycles

Increase in intensity of the hcp (101) peak. Demonstrates the incubation period found in austenitic stainless steels during low cycle fatigue*. Demonstrates increase in volume fraction as fatigue progresses and strain accumulates. Similar trends in both the axial and transverse detector banks. Attributed to the interaction of stacking faults during low cycle fatigue.**

Axial Detector Bank

Transverse Detector Bank

* Source: ASM Handbook, Vol. 18. ASM International, 1997. **Source: L. Jiang, C. R. Brooks, P. K Liaw, J. Dunlap, C. J. OAK RIDGE NATIONAL LABORATORY Rawn, R. A. Peascoe, and D. L. U. S. DEPARTMENT OF ENERGY Klarstrom, Met Trans A (2004) 35 3 785-796.

Bulk Metallic Glass Materials Exhibit Unconventional Properties

Excellent mechanical properties Controllable magnetic properties
Nd-Fe-Co-Al

15 10

M (kAm kg )

-1 2

5 0 -5 -10 -2000 -1000 0 1000

-1

as-cast 723 K 748 K Ribbon

2000

H (kAm )

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Partially Crystallized Bulk Metallic Glass Contains High-density Nanometer Sized Crystallites

e.g., upon isothermal annealing Density 1023-1024 m-3 Crystallite size ~10-50 nm Even for temperatures close to Tg

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Simultaneous Diffraction and Small Angle Scattering in Bulk Metallic Glass Show Concurrent Structural and Chemical Ordering
amorphous crystalline

Structural changes in two length scales

Diffraction

SAXS

(s ec )

Ti m

Q (A-1)

Q (A-1)

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Wang et al., Phys. Rev. Letter., 2003 Wang et al., unpublished

Ti m

(s ec )

In-situ Neutron Diffraction Measurements Revealed for the first time Stress and Temperature Profiles during Friction Stir Welding

z y

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VULCAN Technical Data

Flight paths
Incident ~ 43.5 m Scatting ~ 2 m

Satellite building Resolution ~ 0.2% ~ 0.9-3.5 Flux on sample (n/s/cm2/)

3107 in high-reso. mode 1.2108 in high-int. mode

Wide angle detector coverage, 60-150 SANS Q-range

0.01 0.2 -1
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Summary
Next generation neutron scattering instruments, with high flux, will lead to major breakthroughs in our understanding and, ultimately, the control of structural evolution in materials.

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