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PHASE (BAINITIC) TRANSFORMATION.

GOING THROUGH SOME OF THE BASICS.

C. Garcia-Mateo
Spanish National Research Center for Metallurgy (CENIM-CSIC) Madrid, Spain

Octubre 2017
Colombia-Bogota
Crystal structure
Defects
Crystal structure
• Generals
• Ordering of atoms in solid is not random
(usually)

• To study such arrangements:


• We can assume atoms as rigid spheres
•The size of the arrangement depends on the atomic
bonds

• Such distance can be measured by XRAY


Crystal structure
• Generals
• When the arrangements of atoms is “ordered”
(crystal) :

• The structure can be represented by a unit cell

•The crystal structure is characterized by the


dimensions of the unit cell

•Such dimension is called the lattice parameter.


Crystal structure
• Generals
• Examples of 2D lattices
Crystal structure

• Generals
• To represent the crystal structure different
types of cell can be chosen

• Unit cell is that containing the smallest


number of atoms

• Unit cell is chosen so it reflects the whole


symmetry of the crystal.
Crystal structure
• Generals
• Different cells that reproduce a crystal
structure.
Crystal structure
• Most typical crystal structures.

• Simple Cubic (sc)


• Body centred cubic (bcc)
• Face centred cubic (fcc)
• Hexagonal compact (hcp)
Crystal structure
• Simple Cubic (sc)
Crystal structure
• Face centred cubic (fcc)
Crystal structure

• Single crystal
• Perfect atomic order

• There are not “interruptions” through the


whole material to such “perfection”

• There are not changes in the orientation of


the cells

• Macroscopically, it can or cannot reflect the


symmetry of the crystal structure
Crystal structure

• Single crystal

Fluorita Niquel
Crystal structure

• Polycrystalline

• Vast majority of solids are formed by “grains”


• Crystal structure within a grain is the same,
and the orientation might change from one to
the other.
The fundamental difference between…
is the length scale over which the
Single crystal
atoms are related to one another
Polycrystalline by translational symmetry
Amorphous solids ('periodicity' or 'long-range order')

single crystal  infinite periodicity


Polycrystalline  local periodicity
amorphous solids  (and liquids) have no long-range order
The fundamental difference between….
-The normal solid form of an element or compound is polycrystalline.
-Polycrystalline solid or polycrystal is made up of many crystals.
-The individual component crystallites are often referred to as grains
and the junctions between these grains are known as grain
boundaries.
Defects in crystal structures

Within a single crystal or grain, the crystal structure is not perfect. The
structure contains defects such as vacancies , where an atom is missing
altogether, and dislocations , where the perfection of the structure is
disrupted along a line.

Grain boundaries in polycrystals can be considered as two-dimensional


defects in the perfect crystal lattice..
Defects in crystal structures
Vacancies
Defects in crystal structures
Other point defects (as vacancies)
Defects in crystal structures
Dislocations
Linear defect.
Atoms around it are misaligned
Defects in crystal structures
Dislocation motion
Defects in crystal structures
Grain boundaries
2D planar defect

Computer simulation Real (Al)


INDEX

1 Intro. Sobre cristalografía y defectos

Acero. Diagramas de fase, CCT y TTT. Tipos de


2 transformaciones de fase

3 Bainita (nano y no-nano). Principios básicos

4 Caracterización de bainita nanoestructurada.


Dilatometria
Xray
TEM+HRTEM
3D Atom Probe
Phase Diagrams (Equilibrium)

CCT & TTT diagrams (No-equilibrium)


Phase Diagrams
• Introduction
• When two or more metals are mixed together,
and then solidified they form intermetallic
compounds
• Also known as alloys
• Depending on the chemical composition,
pressure and temperature those compounds
can present one or more phases.
• A phase is defined as a region where the
material is physically homogeneous
Phase Diagrams

• Solubility limit
• When the structure has a composition such
that is not stable, and atoms tend to re-order
in two phases, the solubility limit has been
reached.

• Example : water + sugar is homogeneous as


far as we dont ad too much sugar
(precipitation as solid phase)
Phase Diagrams

• Phase diagram

• Maps that according to certain system


conditions provides with information about

• Thermodynamically stable phases

• Chemical composition of such phases

• Amount of each phase


Phase Diagrams

• Water phase diagram


Phase Diagrams
• Phase diagram Fe-C
Steel :
alloy of Fe with C and (usually)
other elements
(B, N, O, Al, Si, P, S, Ti, V, Cr, Mn, Co, Ni, Co, Zn, Mb, Mo, W, Zr,
Cu, Ta…..)
Steel (essentially Fe + C) Equilibrium

fcc

bcc

orthorhombic
Steel (essentially Fe + C) Equilibrium

fcc

bcc

orthorhombic
Steel
Fe + C+ other elements

Closed g field
Open g field
Si, Al, P, Ti, V, Mo, Cr
Ni & Mn
g stabilisers

a stabilisers

Expanded g field Contracted g field


C, N, Cu B,Nb
a stabilisers
g stabilisers
CCT Diagrams
Continuous Cooling Transformation
• Stability of phases during continuous cooling of
austenite
TgºC, tg s

HRºC/s
100-05ºC/s
CCT Diagrams
Continuous Cooling Transformation

• Stability of phases during continuous cooling of


austenite
TTT Diagrams
Temperature Time Transformation
• Stability of phases during isothermal decomposition of
austenite
TgºC, tg s

CR > CCR ºC/s

T iso, t iso
HR ºC/s
CR ºC/s
4
TTT Diagrams
Temperature Time Transformation
• Stability of phases during isothermal decomposition of austenite
• Kinetics of the transformations

TgºC, tg s

CR > CCR ºC/s

T iso, t iso
HR ºC/s
CR ºC/s
4
TTT Diagrams
Temperature Time Transformation

• Stability of phases during


isothermal decomposition of
austenite

• Kinetics of the
transformations
Type of Transformations
Atomic Mechanisms of Transformation

https://www.phase-trans.msm.cam.ac.uk/2008/Steel_Microstructure/SM.html
Major transformation products according to the atomic mechanisms of transformation
Atomic Mechanisms of Transformation

https://www.phase-trans.msm.cam.ac.uk/2008/Steel_Microstructure/SM.html
Atomic Mechanisms of Transformation
Atomic Mechanisms of Transformation
Atomic Mechanisms of Transformation
Diffusional

Displacive

Diffusionless
&Displacive
INDEX

1 Intro. Sobre cristalografía y defectos

Acero. Diagramas de fase, CCT y TTT. Tipos de


2 transformaciones de fase

3 Bainita (nano y no-nano). Principios básicos

4 Caracterización de bainita nanoestructurada.


Dilatometria
Xray
TEM+HRTEM
3D Atom Probe
BAINITE

Diffusional

Displacive

Diffusionless
&Displacive

H.K.D.H Bhadeshia. Bainite in Steels. The Institute of Materials (2001) London. 3d Edition
Some remarks
How the transformation takes place

g  ab
Nucleation (thermodynamically speaking)
Under paraequilibrium* condition (only C diffuses)

g (g a ) p
G  GN
*The concentration ratios of all elements but C should be equal in the bulk
material as in the retained austenite (g) and bainitic ferrite (a)
(xFe/xj)bulk = (xFe/xj)g

j denotes any substitutional element in the alloy


xFe and xj are the concentrations of Fe and of the substitutional elements

Bhadeshia, H. K. D. H. (2001). Bainite in Steels. Transformations, Microstructure and Properties.


Garcia-Mateo, C. and H. K. D. H. Bhadeshia (2004). Mater. Sci. Eng. A
g (g a ) p
G  GN
defines the minimum free energy change necessary in any steel, in order to
nucleate bainite
It is a universal nucleation function :

1
GN  3.5463T ( K )  3499.4 J mol

C. Garcia-Mateo, H. Bhadeshia. Nucleation theory for high-carbon bainite, Mater. Sci. Eng. A 378 (2004) 289-292.
Growth (thermodynamically speaking)

Diffusionless growth
No change of chemical composition from the
parent phase to the product phase

Bhadeshia, H. K. D. H. and A. R. Waugh (1982). Acta Metall.


Swallow, E. and H. K. D. H. Bhadeshia (1996). Mater. Sci. Technol.
Growth
Its growth is displacive:

Since the pattern of atoms changes during transformation, a disciplined motion of


atoms (individual atom movements are less than one inter-atomic spacing)
necessarily leads to a change in the shape of the transformed region, and like any
deformation, such changes cause strains in the surrounding material.

Displacive Transformation
Austenite
Austenite

Atomic correspondence FCC


IPS shape change with a significant
shear component
Interface
Interface
Diffusionless
Austenite
Austenite

BCC/BCT

Ferrite

FCC Ferrite
Austenite
Shape change:
Deformation with large shear component (S) +
Reconstructive Transformation small
Interface
dilatation normal to the plane (d)
No atomic correspondence
Growth
Displacive Theory:

•Bainite forms at a relatively high temperature when compared with martensite.


•The parent austenite is weaker at high temperatures and cannot accommodate
the large shape deformation elastically.
• It therefore relaxes by plastic deformation in the region adjacent to the bainite.

Peet, M. J. and H. K. D. H. Bhadeshia (2011). Metall. Mater.


Trans. A
Displacive (Dislocations, Nano- twins)
Relaxation of the strains
dislocations and accommodation twins

Structure r x 1015 m-2


Nanobain 2.2
Nanobain 4.5
Nanobain 6.4
Martensite 3.0-4.1
Conventional Bainite 0.2-0.4
Polygonal Ferrite 0.04-0.05

Taiwan Nat. Univ. and ORNL collab.

Garcia-Mateo et al. Scripta 61(2009)


F.G. Cabllero et al. Acta Mater. (2011)
Displacive (Dislocations, Nano- twins)
Relaxation of the strains
dislocations and accommodation twins

Crystal twinning occurs when two separate


crystals share some of the same crystal
lattice points in a symmetrical manner
Growth (thermodynamically speaking)

stored energy of the ferrite due to the displacive mechanism of transformation


400 J/mol

Bhadeshia, H. K. D. H. and A. R. Waugh (1982). Acta Metall.


Swallow, E. and H. K. D. H. Bhadeshia (1996). Mater. Sci. Technol.
Transformation Temperature (Bs)
(thermodynamically speaking)

g (g a ) p
G  GN
Temperature
MS BS g  g a
G
Free energy/ J mol-1
G SB
g a
G

GNa
GN

G aN represents the critical value of the free energy change G g a M s 


needed before the athermal, diffusionless nucleation and growth of
martensite becomes possible
G g a M s   G aN
At transformation temperature
C diffuses into austenite
Grain boundary C supersaturated ferrite plate

a a
g
g0 g0 g0
g0 g0 g
0

a
g

Faces of bainitic plates provide new potential nucleation sites for autocatalytic
nucleation
Incomplete reaction phenomena
The shown process continues by successive nucleation of subunits until the C
concentration of the residual austenite reaches the value of the To curve.
This trend is known as the incomplete reaction phenomenon because the
transformation ends before the C concentration of austenite reaches the equilibrium
value.

To = the locus of points, on a temperature versus C concentration plot, where austenite


and ferrite of the same chemical composition have the same free energy
Incomplete reaction phenomena
Due to the negative slope of a temperature vs austenite C concentration plot of the To curve, the
lower the transformation temperature, the further the transformation can proceed, because a
higher amount of C in solution is allowed in austenite; in other words, higher fractions of
bainitic ferrite are obtained.

Vb a d
Vb T
At transformation temperature
Cementite can then precipitate from the enriched austenite between the ferrite plates
and within the bainitic ferrite plates (both upper and lower bainite); the difference comes
from the competition between the rate at which cementite can precipitate from ferrite and
the speed with which C is partitioned from supersaturated ferrite into austenite.

No Si/Al Si/Al rich steels

a
g
gabq gab

q
At room temperature Bainitic ferrite +2nd phases g
a’
Attending to the phases present
q within and/or between ferrite plates
“Traditional”
0.4%C bainitic steels
a

q a
Lower bainite 0.11%C
a

Upper bainite

a plates + cementite q Martensite

50 mm
Attending to the phases present
(1 to 6)
0.54 mm

Carbide free bainitic steels


g between sub-units  thin films
between sheaves of bainite  blocks

a' between sheaves of bainite  blocks

0.3%C 1%C
Nanostructured bainite Carbide free bainitic
Low Temperature bainite steels

NANOBAIN, SuperBainite.....
Isothermal T = 200ºC

g a

a g

a
Attending to Different Morphologies

Granular carbide free bainite

Martensite or M/A
Bainitic ferrite

High Temperature
Continuous cooling
Low Carbon steels
0.1% C
Attending to Different Morphologies
Lath/plate like bainite
1%C 0.3%C

Sheaves of bainite = sub-units sharing common crystallographic orientations


Giving its displacive nature :
The large strain associated with the transformation implies that the transformation
product is constrained to be in the form of a thin plate/lath, a shape which minimizes
the strain energy when the plate is elastically accommodated.

3D reconstruction of bainitic ferrite lath & plate


by means of FIB-Focused Ion Beam.
K. Liu, T.Q. et al Mater. Charact. 62 (2011) 340-
345.
lath

a a a

plate g g
g
0.1 mm
About kinetics
 is the time
T is the transformation temperature (Kelvin)
p, z ,Q´ and C4 are constants

Lee, J. L. and H. K. D. H. Bhadeshia (1993). Mater. Sci. Eng. A


Bhadeshia, H. K. D. H. (1982). Met. Sci.
About kinetics
Content (wt.%)
0 0.5 1 1.5 2 2.5 3
-200
1C-1.5Si-X
G ga at 200 ºC (Jmol-1)

-600

-1000 Mn
Cr
Mo

-1400

Calculated driving force for diffusionless transformation in different alloys systems


About kinetics
C content (wt.%)
0 0.5 1 1.5
-200
XC-1.5Si-1.5Mn
G ga at 200 ºC (Jmol-1)

XC-1.5Si-1.5Mn-2.25Cr

-600

-1000

-1400

Calculated driving force for diffusionless transformation in different alloys systems


About kinetics
About kinetics
700
1% Mn
0% Mn 3% Mn
600

500
1%C-1.5%Si-1%Cr-XMn
Temperature ( ºC)

1.5ºC/s
400

300

200

100

0
1.E-03 1.E+00 1.E+03 1.E+06 1.E+09 1.E+12 1.E+15
Time (h)
Example of the TTT diagrams calculations as a function of the chemical composition.
About kinetics
Far more complex models exists on the literature describing the transformation
kinetics during isothermal treatment.
For carbide free bainites
Bhadeshia, Rees & Bhadeshia, Sigh & Bhadeshia, Opdenacker & Bhadeshia, Santofimia et all.

Nucleation rate

Autocatalytic nucleation

Grain boundary nucleation

Santofimia, et al. (2006)


Note:
Displacive vs. Reconstructive. 70 Years of Controversy
Austenite
Austenite
Displacive Theory: bainitic ferrite
Displacive Transformation
Atomic correspondence
forms by shear and the individual atom
IPS shape change with a significant
movements are less than shear
onecomponent
inter- Interface
Interface
atomic spacing Diffusionless
Austenite
Austenite

Ferrite
Ferrite

Austenite
Austenite

Reconstructive Transformation
Interface
Interface
No atomic correspondence
Reconstructive Theory: bainitic
No shape change with shear
ferrite forms by thermallycomponent
activated
atom movements and grows Possibleby the change
composition
migration of growth ledges on the
broad faces of the interface.
Ferrite
Ferrite
Note:
Displacive vs. Reconstructive. 70 Years of Controversy
Today it is accepted that bainite grows with a displacive mechanism i.e. as
plate-shaped (or lath-shaped) transformation product exhibiting an invariant plane
strain surface relief effect. But there is still much discussion on the diffusion
or diffusionless nature of bainite.

When it is stated that ferrite grows with a displacive mechanism, it does not imply
that it is also diffusionless. For instance, Widmanstätten ferrite forms with a
displacive but diffusional growth mechanism.

Diffusionless Theory: bainitic ferrite grows without any diffusion of carbon, and
carbon supersaturation is subsequently relieved by partitioning to austenite, or
through carbide precipitation.

Diffusional Theory: bainitic ferrite growth is controlled by carbon diffusion, and


not distinctly different in character from Widmanstätten ferrite with carbide
precipitation at the austenite/ferrite boundaries.
ACICULAR MICROSTRUCTURES
Exactly as bainite but nucleation takes place on specific
precipitates/oxides

Advantage : more chaotic arrangement of the bainitic ferrite plates,


better for toughness.

Yang, J. R. and H. K. D. H. Bhadeshia (1987). Conference: Advances in Welding Science and Technology, AsM, Metals Park Ohio,
Rees, G. I. and H. K. D. H. Bhadeshaa (1994). Mater. Sci. Technol.
The role of inclusions on AF nucleation.
(a) Inclusion surface acts as an inert surface for nucleation and therefore large
inclusions are potent sites.

Babu, S. S. (2004). Curr. Opin. Solid State Mat. Sci.


B. Ralph. Mater. Sci. Technol. Vol 6, 1990
The role of inclusions on AF nucleation.
(b) Matching between ferrite and inclusion lattice will decrease the interfacial
energy between inclusion and ferrite in comparison to inclusion–austenite interface.

Babu, S. S. (2004). Curr. Opin. Solid State Mat. Sci.


D. Brooksbank and K.W. Andrews. J. Iron Steel Inst. Vol. 210, 1972, p. 246
The role of inclusions on AF nucleation.
(c) Local depletion of hardening elements such as carbon and/or manganese which
might lead to an increase in driving force for nucleation of ferrite from austenite.

Babu, S. S. (2004). Curr. Opin. Solid State Mat. Sci.


D. S. Sarma, A.V. Karasev and P.G. Jönsson. ISIJ Int. Vol. 49, 2009,
The role of inclusions on AF nucleation.
(d) Strain energy near the inclusion may increase due to differences in thermal
expansion between austenite and inclusion, which might reduce the activation energy
for nucleation.

Babu, S. S. (2004). Curr. Opin. Solid State Mat. Sci.


A.R. Mills, G. Thewlis and J.A. Whitemen. Mater. Sci. Technol. Vol. 3, 1987,
E. Pagounis, V.K. Lindroos. Scr. Mater. Vol. 37, 1997
How to favour AF instead of Bainite?

1. Presence of effective
Inclusions/precipitates within g.

2. Bigger AGS, decrease of


Bainite nucleation sites

Side effect

Higher density of precipitates


trapped within g.

3. Dishabilitate bainite nucleation


sites by allotriomorphic ferrite
formation on grain boundaries.
How to favour AF instead of Bainite?

1. Presence of effective
Inclusions/precipitates within g.

2. Bigger AGS, decrease of


Bainite nucleation sites

Side effect

Higher density of precipitates


trapped within g.

3. Dishabilitate bainite nucleation


sites by allotriomorphic ferrite
formation on grain boundaries.
How to favour AF instead of Bainite?

1. Presence of effective
Inclusions/precipitates within g.

2. Bigger AGS, decrease of


Bainite nucleation sites

Side effect

Higher density of precipitates


trapped within g.

3. Dishabilitate bainite nucleation


sites by allotriomorphic ferrite
formation on grain boundaries.

Babu, S. S. and H. K. D. H. Bhadeshia (1990). Mater. Sci. Technol.


Thank you !!

Garcia De Andres, C., C. Capdevila, I. Madariaga and I. Gutierrez (2001). Scr. Mater.
Diaz-Fuentes, M., A. Iza-Mendia and I. Gutierrez (2003). Metall. Mater. Trans. B
Acknowledgements
I am deeply grateful to
Prof. Francisca G. Caballero
Prof. C. Garcia de Andres
Prof. Mauricio Sierra
Prof. Carlos Bohorquez Avila
Prof. Ismael Marquez

Universidad Libre de Colombia

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