David C.

Van Aken
Curators’ Teaching Professor of Metallurgical Engineering
Ferrous Microstructures Seminar
Caterpillar Inc.
August 28-29, 2012
Ferrous microstructures seminar

 Robert Walter Bohl

(1925-2006)
 University of Illinois
 Lectures based on
Professor Bohl’s
notes and slides

“The physical metallurgy of steel is best

learned through the oculars of a microscope.”
The crystal structures of iron

Body centered cubic Face centered cubic or fcc

or bcc Austenite or γ-Fe
• delta ferrite (δ-Fe) ρ = 7.95 g/cm3
• alpha ferrite (α-Fe)
• ρ = 7.87 g/cm3
Atoms shaded differently for display purposes only.
Stacking of close packed planes

 {111} in fcc and (0001) in

hcp
 Central atom of “B” plane
rests in the middle of “A”
and “C” planes
 Open volume defects
for interstitials
 Symmetric distortion in
fcc for interstitial
 Planes of easy slip
 Stacking errors lead to
planar defects, e.g.
annealing twins and
stacking faults
Structure of fcc polycrystals
 Al-bronze
 Cold-worked
and annealed
 Annealing
twins
 Low stacking
fault energy
 Higher
annealing
temperatures
produce more
annealing
twins
Color tint etch and cross-polarized illumination
Austenitic steel microstructures

 Fe-14Mn-3.4Al
-1.4Si-0.2C
 Hot-worked
and
recrystallized
at 900°C
 Lower density
of annealing
twins
 Aluminum
increases the
stacking fault
energy
Photo by Meghan McGrath. Klemm’s II etch with
polarized illumination
 Deformation of fcc polycrystals
 70/30 cartridge
brass
 Processing
 surface
polished
 cold-rolled
1.65%
reduction in
thickness
 polished
surface
imaged
 Slip is planar
along {111}

Differential interference contrast

Polymorphism in metals
 80% of all metallic elements have 1 of 4
crystal structures
 bcc
 fcc with stacking of {111} ABCABC
 hcp or cph with stacking of {0001} ABABAB
 α-La hcp with stacking of {0001} ABACABAC
 At room temperature 15 elements have bcc
crystal structures
 Atomic radii depends upon coordination
number, e.g. r12Fe > r8Fe
bcc metals
 2nd nearest neighbors in bcc are closer in distance
than 2nd nearest neighbors in fcc
 Radius of atom is smaller in bcc than same atom in
fcc
 bcc have low resistance to lattice vibrations along
<110> giving rise to a greater number of vibrational
modes and thus greater entropy
 bcc tends to be the stable high temperature phase
 Li and Na are bcc at room temperature, but
transform to α-Sm (variant of α-La) at cryogenic
temperatures
 Structure of bcc polycrystals
 1010 steel
 Cold-worked
with sub-critical
anneal
 Recrystallized
ferritic
microstructure
 Fe3C located at
grain triple
points
2% nital etch
 Deformation of bcc polycrystals

 High purity iron

 Processing
 surface
polished
 cold-rolled
1.1%
reduction in
thickness
 polished
surface
imaged
 “Pencil glide”
 {110}, {112}, and
{123}
Differential interference contrast
Temperature-pressure phase equilibria

 δ and α are bcc

 γ-Fe is favored at higher
pressures because the
A4 atomic packing efficiency
is higher
 Compressive residual
stress would favor γ-Fe
A3 or retained austenite!
 ε-Fe is hexagonal close
packed
 At the triple point
 ΔV(α to ε)= -0.34 cm3/mol
 ΔV(ε to γ)= +0.13 cm3/mol
 ΔV(γ to α)= +0.21 cm3/mol
Phase stabilizing alloy additions
At 912°C (1670°F), alpha transforms to gamma upon heating

 α-Fe stabilizers: Si (dc), Cr (bcc), Mo (bcc), V (bcc), Nb

(bcc), plus B, P, S, Ti, Al (fcc): Fe3Al and Fe3Si are both DO3
 γ-Fe stabilizers: Ni (fcc), Co (hcp/fcc), Zn (hcp), Cu (fcc), Mn
(cc/fcc), N, and C
C! " !H %
= # exp $ ' ΔH = Hγ – Hα
C" # RT &
 Absolute
values of
ΔH plotted
 ΔH>0 ferrite
formers
 ΔH<0
austenite
formers
 Alloy
partitions
according to
± ΔH

C and Mn are important alloy additions to stabilize the

austenite. From Andrews, JISI 184, p.414 (1956).
Solute strengthening of austenite

Irvine, Llewellyn and Pickering, JISI vol. 199, p.153 (1961)

Solute strengthening of ferrite

Strengthening from
interstitials is much
greater in bcc metals, but
solubility is low
Fe-Fe3C equilibria and terminology
 Both δ and α
are referred to
as ferrite
 γ is called
austenite
 θ is called
cementite and
has the Fe3C
composition at
6.67wt.%C
 Combinations
of α and θ
produce
 pearlite
 bainite
 spheroidite
 tempered
martensite
Polymorphic transformation: α-Fe → γ-Fe

727°C 912°C
 Thermal expansion
for
 a is Fe
 b is Fe-0.77wt.%C
 c is Fe-0.40wt.%C
 Volume change
upon heating: α→ γ
 -0.8% for Fe
 at 912°C (1670°F)
rbcc=1.258 Å and
rfcc= 1.292 Å
Fe-C solid solutions
 (a) fcc
 octahedral r = 0.52 Å
 tetrahedral r = 0.28 Å
 (b) bcc
 octahedral r = 0.19 Å
 tetrahedral r = 0.36 Å
 Interstitial radii
 nitrogen r = 0.7 Å
 carbon r = 0.8 Å
 Paired defects: Mn-C

 Location of carbon
based upon elastic
calculations
 Mn radius is 1.28 Å
 Fe radius is 1.24 Å
 Octahedral site size
 smaller, i.e. least
favored
 larger, i.e. most
favored

W.C. Leslie, The Physical Metallurgy of Steels, p. 137

 Julia Medvedeva: Density Functional Theory
Solving Schrödinger equation which describes interactions between all
electrons and atomic cores in a periodic unit cell:

#! 1 " 2 +V ( r ) + µ ( r )% ' k ( r ) = ! k ' k ( r )

$ 2 xc & i i i

• Total energy • La*ce parameters

• Heat of forma0on Energy Structure • Elas0c constants
• Phase stability • Impuri0es, defects
2
ρ( r ) = ∑ Ψik ( r )

Electronic Magne0c Op0cal

• Charge density
• Magne0c moment •Absorp0on spectra
• Fermi surface
 Scope of DFT calculations
 Capabilities: structural, energetic, electronic,
optical and magnetic properties
 Generality: any element in the periodic table
any bonding situation
bulk, surface, interface, molecules
 Accuracy: inter-atomic distances ±0.02 Å
bond angles ± 2-10º
binding energies ±10 kJ/mol
band gaps ±0.2 eV
 System size: 102 -103 atoms/unit cell
Atomistic modeling of fracture and deformation
To model brittle vs. ductile behavior, we compare the energetics of two
competing processes:
(i) opening of a crack
(ii) dislocation emission from a crack tip

(i) Fracture (ii) Slip system

γs, σmax d γus, σshear

Unstable stacking fault energy γus -

Ideal cleavage energy γs -
energy required to shift half of the
energy required to cleave
crystal along some direction in the slip
crystal
plane
Fracture rather than slip for 0.3 γs/γus<1
 Carbon and manganese in bcc Fe

Carbon occupies octahedral interstitial sites in both α-Fe and γ-Fe phases
Manganese prefers to substitute for the apical Fe site closest to C
(other Mn positions result in higher total energy by ~50-230 meV)
Fe Mn Mn
1.87 Å 1.79 Å 1.79 Å

Fe Fe Mn

• Mn and apical Fe atoms move toward C, forming strong bonds

• Planar Fe-C distances (1.97 Å) are not affected by Mn presence
 Manganese and carbon distribution in
ferrite Fe-Mn-C

Mn
Mn

Fe C Fe

Fe
Fe

• Calculations demonstrate the reorientation of Mn magnetic moment as dependent on

the carbon distribution.
• Charge density distribution plot for (110) bcc plane reveals that Mn-C-Fe atoms form
180° defect complex
• The binding energy of Mn-C pair ~ 0.1-0.2 eV: segregation of carbon near
manganese and the formation of Mn-C clusters are predicted to affect dislocation
movement and retard the phase transformations in Fe-Mn-C steel.
Distribution of carbon and manganese
in austenitic matrix

 C-C interaction is repulsive, second carbon atom prefers to

occupy the most remote location 5
 Alloying with manganese leads to the formation of Mn-C
pairs: Mn is located in position 1 and the Mn-C interaction is
attractive.
 Second Mn atom prefers to occupy the position 1 forming a
180° Mn-C-Mn complex.
 Dynamic strain aging (DSA) in high Mn
Steels
 DSA produces
rapid work
hardening rates
 Leslie1,2 first
postulated Mn-C
defect couple to
explain DSA

1. W.C. Leslie: Metallurgical effects at High Strain Rates, p. 571, Plenum Press, NY
(1973)
2. Y.N. Dastur and W.C. Leslie, “Mechanisms of Work Hardening in Hadfield
Manganese Steels,” Met. Trans A , 12, p. 749, (1981).
 Defect formation in austenitic Fe-Mn-Al-C steel

Mn 9

C 2

1 3

Site 3 is lowest energy

Site 9 is higher by 2.3 meV
Sites 1,2, 4-8, 10, 11 higher by 5-10 meV
Strong preference for Al to order austenite into κ-carbide
 Addition of aluminum to Hadfields Steel
1.1  Al addition slows the
1 diffusion of carbon
Vol loss alloy/Vol loss 1020

0.9 and restricts DSA to

0.8 higher temperatures1
0.7  Al decreases the
0.6 abrasive wear
0.5
10 Al resistance but
0.4 7 Al
improves the high
stress wear
3 Al
0.3
1 2 3 4 5 6 7 8 9 10 11 12
Al/C ratio resistance1
Missouri S&T ASTM G65 wear tests of  Al additions delay
Fe-30Mn -1.4Si-0.5Mo steel with verying TWIP to higher
Al and C contents. stress/strain levels2

1. B.K. Zuidema, D.K. Subramanyam, and W.C. Leslie, Met. Trans. 18A, p.1629 (1987).
2. D. Canadinc et al., Acta Materialia 53, p. 1831 (2005).
 Stacking fault energy in Austenitic Matrix
Deformation mechanisms associated with the enhanced plasticity and high strength in high
manganese austenitic alloys is controlled by stacking fault energy (SFE):
low SFE – martensite formation, intermediate SFE – twinning, high SFE –
glide.

Impurities strongly affect SFE and deformation mechanism –

how to predict SFE?

From thermodynamic model SFE = 2ρΔGγ-ε + 2 σ γ/ε, where ΔGγ-ε is a

difference in the Gibbs free energies of γ-austenite and ε phases, which are
estimated from the regular solution model for multicomponent systems:

However, this model does not adequately take into account the
changes in structure and chemical bonding caused by alloying,
3
as well as the impurity distribution 0
Generalized stacking fault energy in γ-Fe

(a) d=0, (b) d=0.5 (USFE), (c ) d=1.0(SFE) (d) d=2

(MAX), Kibey et al, 2006
 SFE is nega0ve – fcc structure is unstable rela0ve hcp.
 Alloy addi0ons that decrease SFE would stabilize the hcp phase
and favor the γ → ε transforma0on, while those that increase SFE
will suppress the forma0on of ε‐martensite.
31
 Carbon effect on the generalized stacking
fault energies in γ-Fe

The SF energies (mJ/m2) for single impurity in the n-layer

below SF and two impurity atoms in k- and l- layers (n = k,l).

n=0 n=1 n=2 n=3 n = 0,0

Mn gUS 423 430 433 435 409 Carbon sharply increases

gISF -372 -354 -349 -347 -392 SFE – strong austenite
C gUS 547 541 493 449 601
stabilizer.
gISF 49 -51 -145 -320 203 Carbon prefers to be far
from stacking fault.
Al gUS 319 432 429 435 232

gISF -284 -295 -343 -347 -192

Only those impurities which are distributed within two layers

near the stacking fault plane affect SFE
32
 Manganese effect
on the generalized stacking fault energies

fcc Fe

These calculations predict SFE < -150 mJ/

m2 for all Mn concentrations.

Our results correlate with the experimental phase diagram of Fe-

Mn:
• ε –martensite is not formed above 30% Mn
• Correct parabolic dependence of SFE on x, when manganese is at SF
• No effect for Mn located more than one interlayer distance away SF (blue line)
• SFE linearly increases for x>20 at.%Mn and becomes positive for x>50 at.%Mn
• Formation of Mn-C couples restrain the increase of SFE
33
Thermodynamics of TRIP

Composition
used from ΔGγ→ε, J/mol ΔGγ→α, J/mol ΔGε→α, J/mol
Reference:
Present TRIP -84 -862 -778
Last Region to
Solidify Predicted -77 -90 -13
with Scheil Model
Frommeyer et al.
[24] 8 -925 -933
Yang et al. [2] -338 -263 75
Cai et al. [25] -88 -2036 -1948
Effect of Al on Generalized stacking fault
energy

!
 Single Al increases SFE
 Single Al decreases USFE-energy barrier to reach SF
 Short range Al-ordering restrains the SFE growth.
 Short range order strongly decreases USFE (from 450 to
83 mJ/m2) making the formation of stacking fault much
easier (low barrier for stacking fault dislocations), but does
not affect SFE. This can explain softening.
 Lightweight FeMnAlC TRIP steels

 Reduce C and Al Alloy 3

 Reduced Carbon 0.07
Manganese
stacking fault Silcon
15.3
2.85
energy Aluminum 2.4
Phosphorus 0.011
 No δ-ferrite Sulfur 0.019
stringers Copper < 0.05
Nickel 0.07
 27% retained Calculated
15.9
austenite; 13% γSFE, mJ/m2
α-martensite; Calculated
-65
Ms, °C
60% ε- Measured 7.664 ±
martensite Density, g/cm 3
0.032
TRIP behavior of Alloy 3 with straining

Vf γ Vf α Vf ε
Before Testing 0.268 0.134 0.598
2% Strain 0.228 0.160 0.612
4% Strain 0.199 0.150 0.651
10% Strain 0.103 0.447 0.450
14% Strain 0.097 0.456 0.447
18% Strain 0.065 0.604 0.331
23% Strain 0.056 0.752 0.191
After Testing 0 1 0
Strain hardening behavior

 Stage I: saturation of ε-martensite

 Stage II: Trip of ε-martensite to α-martensite
 Post stage II are segregation effects where stage I and stage II occur at higher
strains
TRIP in chemically banded structure

10% strain 20% strain

 MnS inclusions are “markers” for last region to solidifiy
 10% strain shows stage I TRIP to ε-martensite has occurred
in bands containing MnS; Stage II TRIP to α-martensite
elsewhere
 Stage II TRIP to α-martensite near MnS at 20% strain
 Aluminum encourages planar slip and
formation of high density dislocation walls
60%

50%
Percent Elongation

40%

30%

20%
0 2 4 6 8 10 12
Al/C Ratio

 S&T cast material

 Solution treated condition (austenitic)
 Fe-28Mn-0.9Si-0.6Mo with varying C and Al
Cementite: θ-Fe3C

Orthorhombic
 a = 4.5235 Å
 b = 5.0888 Å
 c = 6.7431 Å
 12 Fe, 4 C
 ρ = 7.69 g/cm3

Mn, Cr, Mo, W and V can substitute for Fe

 Structure of Fe11MC4
 M = 3d or 4d transition
metal in Feg or Fes
 Feg bonding (8)
 11 Fe-Fe
 3 Fe-C

 Fes bonding (4)

 12 Fe-Fe
 2 Fe-C
Medvedeva, et al., Phys. Status  Feg-C distance is larger
Solidi B 246, No. 9 p. 2167(2009)
than Fes-C
Formation Energy (eV/f.u.) for Cementite with 2p and 3p Impurities
Fe3C Fe3C0.75B0.25 Fe3C0.75N0.25 Fe3C0.75P0.25 Fe3C0.75S0.25 Fe3C0.75O0.25 Fe2.75Al0.25C Fe2.75Si0.25C
ΔH 0.22 -0.06 0.18 0.21 0.29 0.33 0.65 1.29
Calculated physical properties

Model predictions:
 Strong ferromagnetic
coupling for Mn, Co, Ni,
Ru, Rh, & Pd
 Strong volume change
with 4d transition
metals
 Sc, Ti, V, Cr, Zr and Nb
stabilize Fe3C
 Ni, Cu, Pd and Ag
destabilize Fe3C
Other carbides, nitrides, and borides

 Mn does not form

carbides in steel, but
substitutes for Fe in
M3 C
 Mn will promote M7C3
 From Schick,
Thermodynamics of
Certain Refractory
Compounds, Academic
Press (1966)
Relative hardness of
carbides, nitrides,
borides and other
ceramics
Summary

 Iron has very simple crystal structures

 Alloy can modify phase stability
 Moderate strengthening can occur by
substitutional alloying
 Substantial strengthening from
interstitials in bcc
 First principles calculations are helping
to explain the empirical metallurgical
knowledge