Thermodynamics of Mechanical Alloying Thermodynamics of Mechanical Alloying

A. Badmos and H. K. D. H. Bhadeshia, Metall. & Mater. Trans. A, 18A (1997) 2189. H. K. D. H. Bhadeshia, Proceedings of the Royal Microscopical Society, 35 (2000) 95. Materials Science and Technology, 16 (2000) 1404. H. K. D. H. Bhadeshia & H. Harada, Applied Surface Science, 67 (1993) 328.

Evolution of Solutions Evolution of Solutions

Mechanically Alloyed Oxide Dispersion Strengthened Metals

Normal Grain Size

Sub Micron Grain Size Grain junctions powerful pinning points for small grains, which are no longer topologically independent

Fe-20Cr-5Al0.5Ti-0.3 yttria wt% 90% reduction

Capdevila & Bhadeshia, 2000

Helical grains

Capdevila & Bhadeshia, 2000

Capdevila & Bhadeshia, 2000

Atom probe image of MA957

MA956
100

Atomic Percent

80 60 40 20 0 0 20 40

Fe Cr

60

80

100

Cluster Number (50 Ion Clusters)

Chou & Bhadeshia, 1994

20

Frequency / %

Atom-Probe Binomial

15 10 5

Total Ions : 12006 Fe ions : 8229

MA956

20

Frequency / %

15 10 5

20

Frequency / %

15 10 5 0

2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48

52 54 56 58 60 62 64 66 68 70 72 74 76 78 80 82 84 86 88 90 92 94 96 98

Iron / at%
Atom-Probe Binomial Total Ions : 12006 Cr ions : 2434

Chromium / at%
Total Ions : 12006 Al ions : 1231 Atom-Probe Binomial

Chou & Bhadeshia, 1994

2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48

Aluminium / at%

Gibbs free energy per mole

Mechanical Mixture
A B

free energy of mechanical mixture

G* o A

1-x B

(1-x)

Concentration x of B

Solution
Gibbs free energy per mole
free energy of mechanical mixture

G* o A G M

G{x}
free energy of solution

atomic solution

Composition

Entropy
P

P/2

For a random mixture, number of configurations given by:

Boltzmann

Classical theory for entropy of mixing

Solution-like behaviour when particles about 1000 atoms in size

10 10 10 10 10 10
4

mol / MJ -G

-1

-1

Free energy of mixing due to configurational entropy alone

10

10

10

10

10

Atoms per particle

Enthalpy

Surface per unit volume

Sv
Particle size

Solution formation impossible!

coherent coherent incoherent

100 - 100 J mol T = 1000 K 50

-1
x = 0.02 x = 0.14 x = 0.50

100

50

Single barrier to solution formation when components attract

-50 (b)

-50

-100 -100 1e+00 1e+02 1e+04 1e+06 1e+08 1e+10 Atoms per particle
Badmos and Bhadeshia, 1997

100 = 100 J mol T = 1000 K 50

-1

x = 0.02 x = 0.14 x = 0.5

100

50

Double barrier to solution formation when components immiscible

-50

-50

-100 -100 1e+00 1e+02 1e+04 1e+06 1e+08 1e+10 Atoms per particle
Badmos and Bhadeshia, 1997

Barrier to solution formation

50 = - 100 J mol - 1 T = 1000 K 50 0 0

-50

-50

10 9 atoms per particle 10 7

-100 (b) -150 0.00 0.25 0.50 x 0.75

-100

10 2
-150 1.00

Badmos and Bhadeshia, 1997

10 atoms per particle 10

9 7

40

= 100 J mol - 1

40 T = 1000 K

10

20

20

Barrier to solution formation, especially in rich solutions

(a) -20 0.00 0.25 0.50 x 0.75 -20 1.00

Badmos and Bhadeshia, 1997

 Gibbs free energy per mole

o A

A Concentration x of B

Paradox at concentration extremities vanishes in the discrete model of concentration

Molar Gibbs free energy

ferrite
o Fe

cementite

Fe

Concentration of carbon

Ae3

Austenite + Ferrite

Temperature

Ae1

Ferrite + Martensite Martensite

Time

Atom probe image of Scifer, 5.5 GPa steel wire

Bhadeshia and Harada, 1993

Scifer, 5.5 GPa with ductility!

Kobe Steel

Molar Gibbs free energy of ferrite

Mechanical Mechanical tempering tempering

o Fe

Fe

Concentration of carbon

Amorphous phase formation during mechanical alloying of Cu and Cd powders

.contribution from Cu/ interfaces, and accompanying increase in free energy, provide additional driving force for amorphisation.
Zhang & Massalski Metall. & Mater. Trans. 29A (1998) 2425