Course

October 2022

Solidification and Casting

of Low Carbon
Alloyed Steels
Nawaz Mahomed
Mechanical and Mechatronic Engineering

Photo by Stefan Els

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Low Carbon Steel Alloys

• Low carbon steels: C < 0.7 %𝑤𝑤

• Includes peritectic range: 0.09 ≤ C ≤ 0.53 %𝑤𝑤
• Special interest in hyper-peritectic steels:
0.17 ≤ C ≤ 0.53 %𝑤𝑤
• High toughness applications ……
• Effect of alloying elements on phase
transformation: Concept of Carbon Equivalent.
• Investigate effects of ferrite-forming Ni and
austenite forming Cr.
• 𝑇𝑙𝑙𝑙 = 1514 °C; 𝑇𝑝𝑝𝑝 = 1495 °C; 𝑇𝑠𝑠𝑠 = 1470 °C
• 𝐶𝑙𝑙 = 0.53 %𝑤𝑤 C
• 𝑚𝑙𝑙 = −79 °C/%𝑤𝑤 C
• 𝑘𝑙𝑙 = 0.17

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Effect of Alloying Elements

Chromium Cr = 2.0 %𝑤𝑤 – Ferrite stabiliser:

• 𝑇𝑙𝑙𝑙 = 1510 °C; 𝑇𝑝𝑝𝑝 = 1490 °C; 𝑇𝑠𝑠𝑠 = 1470 °C
• 𝐶𝑙𝑝 = 0.53 %𝑤𝑤 C
• 𝑚𝑙𝑙 = −81
• 𝑘𝑙𝑙 = 19

Nickel Ni = 1.0 %𝑤𝑤 – Austenite stabiliser:

• 𝑇𝑙𝑙𝑙 = 1509 °C; 𝑇𝑝𝑝𝑝 = 1498 °C; 𝑇𝑠𝑠𝑠 = 1467 °C
• 𝐶𝑙𝑝 = 0.44 %𝑤𝑤 C
• 𝑚𝑙𝑙 = −82
• 𝑘𝑙𝑙 = 16 Exercise 1:
(a) Compare the equilibrium freezing range 𝑇𝑙𝑙𝑙 − 𝑇𝑠𝑠𝑠 for the two alloys for
C = 0.3 %𝑤𝑤. What can be deduced?
(b) What is the effect of Ni and Cr on the solute distribution before peritectic?
(c) What is the effect of Ni on the peritectic range?
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Carbon Equivalent

Carbon equivalent (Xia et al):

(Cequivalent = [C] + 0.02[Mn] − 0.037[Si] + 0.023[Ni] − 0.0189[Mo] − 0.7[S] + 0.0414[P] +
0.003[Cu] − 0.0254[Cr] − 0.0267[Ti] + 0.7[N])

Chromium Cr = 2.0 %𝑤𝑤: Cequivalent = 0.30 − 0.0254[2.0] = 0.25 %𝑤𝑤

Nickel Ni = 1.0 %𝑤𝑤: Cequivalent = 0.30 + 0.0230[1.0] = 0.32 %𝑤𝑤

On Fe-C Phase Diagram due

to alloying elements
Exercise 2: How much nickel can be added to the FeC alloy to avoid peritectic
reaction? Check the accuracy on the phase diagram.

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Microsegregation:
Phase Distribution and Lever Rule
• Partition coefficient 𝑘0 (“0” indicates equilibrium conditions).
• Lever Rule: Assumption of complete diffusion of solute (𝐶) in (both) phases (liquid and solid).
• We use, as an example, Fe-C alloy with 𝐶 = 0.3 %𝑤𝑤.

Exercise 3:
a) Generate the phase diagram using Thermocalc.
b) Determine the liquidus temperature.
c) At 𝑇 = 1500 °𝐶, what is the C composition in the 𝛿-ferrite phase and the liquid phase? Determine
the phase distribution (using Lever Rule).
𝐶𝑙 − 𝐶0
𝑔𝛿,1500°𝐶 =
𝐶𝑙 − 𝐶𝑠
d) At the peritectic temperature, the solubility limit of C in 𝛿-ferrite increases to ….? Determine the
phase distributions WHEN THE LIQUID REACHES THE PERITECTIC TEMPERATURE?
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Microsegregation:
Phase Distribution and Lever Rule
• At this point, for the hyperperitectic (above C = 0.17 wt%) steel, the phase fractions of δ-ferrite (of
0.09 wt% C) and liquid can be calculated using the lever rule as follows:
0.53 − 0.30
𝛿−𝑓𝑓𝑓𝑓𝑓𝑓𝑓: 𝑔𝛿 = = 0.53 𝑎𝑎𝑎 𝑙𝑙𝑙𝑙𝑙𝑙: 𝑔𝑙 = 1 − 𝑔𝛿 = 0.47
0.53 − 0.09
• Now, for peritectic transition to occur, using the lever rule at C = 0.171 wt% (peritectic composition),
the fractions of δ-ferrite (of 0.09 wt% C) and liquid (of 0.53 wt% C) are given as:
0.53 − 0.17
𝛿−𝑓𝑓𝑓𝑓𝑓𝑓𝑓: 𝑔𝛿, 𝑝𝑝𝑝 = = 0.84 𝑎𝑎𝑎 𝑙𝑙𝑙𝑙𝑙𝑙: 𝑔𝑙, 𝑝𝑝𝑝 = 1 − 𝑔𝛿, 𝑝𝑝𝑝 = 0.16
0.53 − 0.10
• Hence, in our case of a hyperperitectic steel (C = 0.3%), there is a shortage of δ-ferrite to react with
the amount of liquid fraction for a full peritectic transition to austenite. The amount of liquid fraction
that is transformed with the δ-ferrite fraction of 0.53 into austenite at the peritectic temperature is
only 0.53⁄0.84 × 0.16 = 0.10 (referred to as the peritectic REACTION). The resulting fractions of
liquid and austenite just below the peritectic temperature are therefore given as:
𝑙𝑙𝑙𝑙𝑙𝑙: 𝑔𝑙,𝑝𝑝𝑝+ = 0.47 − 0.10 = 0.37 𝑎𝑎𝑎 𝛾−𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎: 𝑔𝛾,𝑝𝑝𝑝+ = 1 − 𝑔𝑙 = 0.63

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Microsegregation:
Solid Fraction and Lever Rule
Exercise 4:

a) Plot the solid fraction versus temperature curve for the peritectic Fe-C alloy with 𝐶 = 0.3 %𝑤𝑤. We
will later compare our result with the solid fraction versus temperature curve generated using
ThermoCalc.

b) Derive the lever rule in terms of temperature (assume equilibrium temperature conditions):
1 𝑇 − 𝑇𝑙𝑙𝑙
𝑔𝛿 =
1 − 𝑘𝛿 𝑇 − 𝑇𝛿

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Microsegregation:
Gulliver-Scheil
• Segregation at the microstructural scale (microsegregation) will affect the solidification profile of
alloy.
• Different coefficients of diffusion for the solute in the liquid phase 𝐷𝑙 and the solid phase 𝐷𝛿 .
• Extreme case: No diffusion in the solid phase; complete mixing in the liquid phase.

𝐶 Gulliver-Scheil Equation

𝐶𝑒𝑒𝑒
𝐶𝑠 = 𝑘𝛿 𝐶0 (1 − 𝑔𝛿 )𝑘𝛿−1 Exercise 5: Show that the Gulliver-Scheil
equation: 𝐶𝑠 = 𝑘𝛿 𝐶0 (1 − 𝑔𝛿 )𝑘𝛿−1 can be
written in terms of temperature as:
1
𝑇 − 𝑇𝛿 𝑘𝛿 −1
𝐶𝑙 𝑡 = 𝑡𝑖 𝑔𝛿 = 1 −
𝑇𝑙𝑙𝑙 − 𝑇𝛿
𝐶0 𝑡=0
𝑘𝛿 𝐶𝑙
𝑘𝐶0 𝑡 = 0 + ∆𝑡 Why is this more useful (temperature versus
solid fraction)?
𝑔𝑠
0 𝑔𝑠,𝑒𝑒𝑒 1

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Microsegregation:
Scheil versus Lever Rule
• We will generate the Fe-C phase diagram in
ThermoCalc, and run the Scheil Simulation for
𝐶 = 0.3 %𝑤𝑤.
• Note: Terminate on 𝑇𝑒𝑒𝑒 (fraction of liquid phase =
0.01). Start at liquidus. Classic Scheil. Mass percent.
Mole fraction of solid phase.

Exercise 6
• Compare the values of solid fraction at the critical
points: 𝑇𝑝𝑝𝑝 , 𝑇𝑝𝑝𝑝+ , 𝑇𝑠𝑠𝑠 (for Lever Rule only) and
𝑇𝑒𝑒𝑒 (for Scheil only).
• For Scheil comparison, we use the Table Renderer
in ThermoCalc.

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Microsegregation:
Carbon as a fast diffuser
• We can compare the Classic Scheil and Lever Rule with a case in which carbon is considered a fast diffuser
in the 𝛿-ferrite and 𝛿-austenite phases.

• Note that there are 2 solid phases of different

crystallographic structure: BCC 𝛿-ferrite and FCC 𝛾-
austenite. In which phase will carbon diffuse faster?
• We will investigate this next.

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Solidification: Peritectic Reaction

• During peritectic reaction, a layer of FCC 𝛿-

austenite forms along the BCC 𝛿-ferrite.
• This in known to be a rapid reaction (formation
of reaction layer).

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Solidification: Peritectic Reaction

• In steels, experimental
evidence suggests that the 𝛿-
austenite nucleates INTO the 𝛿-
ferrite. (In FeNi alloys,
evidence suggests that the 𝛾-
austenite nucleates INTO the
liquid).

• In any case, for the BCC 𝛿-

ferrite to transform into FCC 𝛾-
austenite, C needs to diffuse
through the 𝛾-austenite layer.

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Solidification: Peritectic Reaction
Diffusion in 𝜹 vs 𝜸

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Solidification: Peritectic Reaction
Diffusion in 𝜹 vs 𝜸
Exercise 7
• Compare the diffusion through the
FCC 𝛾-austenite layer to that through
the BCC 𝛿-ferrite layer across a 500
µm layer in 10 seconds. The initial
solute gradient is from 0.1 %𝑤𝑤 C to
0.3 %𝑤𝑤 C.
• The 𝛾-austenite layer acts as a
diffusion barrier for 𝛿 → 𝛾
transformation.
• Since this transformation can be
Austenite Ferrite
delayed, the density variations will
lead to volumetric shrinkage in the
casting, since FCC (𝛾-austenite) has a
lower molar volume in the region of
2.5 - 3.0%.
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Solidification:
Moving Solid/Liquid Interface
• We will now study the movement of a solid interface through a liquid, as occurs in casting. In this
example, there is no driving force due to undercooling.
• We will only visualise the diffusion behaviour and moving boundary, from a state of non-equilibrium
concentration towards one of equilibrium concentration.
• We will use the following parameters:
• Starting temperature: 𝑇𝑙𝑙𝑙 = 1514 °C;
• Final temperature: 𝑇𝑝𝑝𝑝 = 1495 after 10 seconds.

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Solidification: The Microscale Mushy Zone

• What is the point of the previous analysis? If we

know the temperature versus solid fraction, then we

Liquid
Solid
can understand how the steel solidifies from it’s
liquidus temperature down to its final solidification
temperature, and so we can predict the extent of
the Mushy Zone. We can then determine other

Solid Fraction 𝑔𝑠
𝑔𝑙 + 𝑔𝑠 = 1 𝒗𝑙
characteristics of the steel, such as permeability.
• This, in turn, allows us to estimate the feeding 𝐺 𝑇𝑙𝑙𝑙𝑙𝑙𝑙𝑙𝑙

Temperature 𝑇
efficiency of the casting, as well as to predict the 𝑇(𝑔𝑙 (𝒙))

shrinkage microporosity. . Mushy zone

𝑇𝑠𝑠𝑠𝑠𝑠𝑠𝑠

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Solidification of Binary (2-phase) System:
Planar, Directional, Dendritic and Equiaxed
• We now look at how the entire mushy zone
advances through the solidifying liquid melt.
• The length and morphology of the MZ depends
highly on the temperature gradient at the S-L
interface!
• Planar front (single crystal) solid phase growing
into liquid phase.
• We can define the Local Solidification Time.

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Solidification of Binary (2-phase) System:
Planar, Directional, Dendritic and Equiaxed
• Planar Interface is on solidus isotherm corresponding to 𝐶0 .
𝐶0
• Concentration at the S-L interface: 𝐶𝑙∗ =
𝑘0

• Liquidus line: 𝑇𝑙𝑙𝑙 = 𝑇𝑓 + 𝑚𝑙 𝐶𝑙∗

𝐶0
• → 𝑇 ∗ = 𝑇𝑙𝑙𝑙 = 𝑇𝑓 + 𝑚𝑙
𝑘0
𝐶0
• What is solute profile in solid? 𝐶𝑠∗ = 𝑘0 𝐶𝑙∗ = 𝑘0 = 𝐶0 = 𝑐𝑐𝑐𝑐𝑐.
𝑘0

• → 𝐶𝑠 = 𝐶0
• Solution: 1 − 𝑘0 𝜈∗
𝐶𝑙 = 𝐶0 + 𝐶0 𝑒𝑒𝑒 − 𝑥
𝑘0 𝐷𝑙

1 − 𝑘0 𝜈∗
𝑇𝑙𝑙𝑙 = 𝑇𝑓 + 𝑚𝑙 𝐶0 + 𝐶0 𝑒𝑒𝑒 − 𝑥
𝑘0 𝐷𝑙
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Planar Solidification: Bridgman Process

• Single crystal castings are produced using techniques of

selecting a single, properly orientated grain. The spiral
selector (helix) technique is used, which is based on the
selection of one crystal from a set of columnar grains
with low-modulus [001] texture orientation to the
solidification direction.
• Characterised by high temperature gradient.

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Solidification of Binary (2-phase) System:
Planar, Directional, Dendritic and Equiaxed
• Directionally solidified structures
provide improved strength in the
solidification direction (anisotropic
properties).
• Not conventional sandcasting.
Vacuum investment casting – single
crystal, columnar morphology.

• For sufficiently low G or high v⃰ , a constitutionally undercooled region develops in the

liquid ahead of the interface; this is an unstable situation, where a small perturbation
will start to grow, and eventually form into a columnar-arranged dendrite.

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Solidification of Binary (2-phase) System:
Planar, Directional, Dendritic and Equiaxed
• For even lower G or higher v⃰ , nucleation will occur ahead
of the columnar dendrites, leading to equiaxed dendrites.
• Multiple nucleation sites lead to the formation of equiaxed
microstructures (granular structure).
• In such cases of non-equilibrium solidification, it is possible
to have the formation of intergranular eutectic.

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Thank you
Enkosi
Dankie

Photo by Stefan Els

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