2019. 05. 27.

Phase transformation processes

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István Mészáros

Budapest University of Technology and Economics

Department of Materials Science and Engineering
2019.

Phase transformations
T, P, C change Þ new equilibrium state
New phase(s): stable or metastable
Phase transformation: A process. During phase
transformation new phase(s) with different structure (lattice,
microstructure) originates from the old phase(s).

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Examples for phase transformations

Crystallisation, melting (solid - liquid)

Phase transformations in solid phase
allotropy, recrystallisation, segregation,
precipitation…

Types of phase transformations

diffusion controlled: movement of individual atoms

diffusionless (martensitic): collective atomic movement
without diffusion process

Thermodynamical driving force of phase

transformations

Example: crystallisation of a
pure metall
F = U – TS
Equilibrium condition of one
component systems.
Driving force: DF
Melting/freezing point DF=0
Þ DT (undercooling)

F=C-P+1=1-2+1=0 (nonvariant)
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Kinetics of diffusion controlled phase transformations

Phase transformation (crystallisation):

1. Nucleation (homogenous, inhomogeneous)
2. Crystal growth (material transport: diffusion)

Homogenous nucleation
Nucleus: spherical (r)
DFV: decrease of free energy (in a unit volume)
g: free energy of the surface area of the phase boundary (in a
unit surface)
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4p 3
dF = - r DFV + 4pr 2g
3
dF
= -4pr 2 DFV + 8prg
dr
2g
r* = Crytical radius of
DFV
nuclei
Stable, instable

2gTE
r* =
LDT
2
16pg 3 æ TE ö
dF = *
ç ÷ Activation energy
3L2 è DT ø
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T = TE
Fa = Ua - TE Sa = U b - TE S b = Fb
Ua - U b L
Sa - S b = =
TE TE
L = Ua - U b

T ¹ TE
DF V = Fa - Fb = Ua - U b - T (Sa - S b )
DF V = L - T (Sa - S b )
TL æ T ö æT -T ö DT
DF V = L - = Lçç1 - ÷÷ = Lçç E ÷÷ = L
TE è TE ø è TE ø TE

2gTE
r* =
LDT
2
16pg 3 æ TE ö
dF =
*
ç ÷
3L2 è DT ø
DT ® 0 Þ r * ® ¥
DT ® 0 Þ dF * ® ¥

Undercooling is a
thermodynamical necessity.
Cooling curve (10-15%)

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Rate of diffusion controlled phase transformations

Nucleation rate

number _ of _ cores é 1 ù
N= ê mm 3 s ú
time × volume ë û

Growth rate
DD é mm ù
G=
Dt êë s úû
Grain size (N, G)
N small N big
G small Fine
grains
G big Rough
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grains

Transformed phase ratio: sigmoid curve

y = 1 - exp( -kt n )
Avrami’s equation

Rate of phase transformation:

1
r=
t0,5
Q
r = A × exp( - )
kT
Incubation time

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Isothermal transformation diagrams

Time - Temperature - Transformation (TTT)
Rate of diffusion controlled phase transformations

Thermodynamically controlled
region

Diffusion controlled region

Fast cooling, keeping at a constant temperature: beginning

and end of phase transformation 11

Typical TTT diagram of an eutectoidal steel 12

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Heterogeneous nucleation
Probability of nucleation is not equal in all parts of the
volume.
Foreign nuclei. Additive effect. Artificial increase of
nucleation.
Undercooling is smaller.

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Effect of grain size on the mechanical properties

Yield stress 1
-
Hall-Petch equation Re = R0 + kd 2

Re: polycrystalline yield stress

R0: single crystalline yield stress
d: grain size

Fatigue properties
Inhomogeneous plastic deformation

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Typical crystallisation forms

Poligonal
crystallisation

Dendritic crystallisation
Dendron 15

Radial crystallisation
Shape anisiotropy

Sperolitic crystallisation
sphero - litos
Globular cast iron

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Allotropy, polimorfism
Equilibrium lattice (T, P)
Allotropic transformation, allotropic form
Solid – solid phase transformation

Sn (tin disease)
a Sn (diamond lattice) Û b Sn (bc tetragonal) 13,2 C°

SiO2 (quartz glass)

Al2O3

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Allotropic transformations of iron

ferrite - austenite
bcc Þ fcc (911°C, 1,04 %)

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Martensitic phase transformation

Bain-model
z direction: ­¯
x, y directions: «

Fast cooling (quench) of austenite (Ms » 220 °C)

Diffusionless
Single phase martensite (tetragonal), C content is the same
than in the initial martensite
about 4% spec. Volume increase Þ stress
In between MS , MF (rest austenite)
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Habit plan, homogenious shearing deformation + rotation.

Brittle, hard phase Þ annealing (austempering)

Martensite and
rest austenite

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Kurdjumov-Sachs orientation relation:

(111)g II (011)martenzit
[1 01]g II [1 1 1]martenzit
Structure of martensite:
lath, block, paket

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4 packets, eatch contain 3-3 blocks and 2-2 sub-blocks.

Therefore, 4*6=24 martensite variants.

Tipical sizes:

Block: 1-10 µm
Latch thikness: 100-200 nm

Az ausztenites, lean-duplex korrózióálló acélok ausztenit

szemcséiben alakítás hatására alakítási martenzit (ε-
martenzit és α'-martenzit) jöhet létre.
γ→ε, γ→ε→α' vagy γ→α' kinetika szerint történhet.

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Recrystallization
Cold working + heat treatment (Th > 0,5)
Driving force: energy of point defects and dislocations
Nucleation, diffusion, grain
1. Recovery growth
Poligonisation
Thermal activated
2. Recrystallization
3. Grain growth Q
r = A × exp(- )
4. Secondary recrystallization kT
Incubation time.
Recrystallization diagram
No undercooling.
Alloying slow down (Cottrell). No C-curve.
Dislocations increase the rate. 27

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