Metallic Materials Topic 2. Solidification of Metals

Universidad
Carlos III de Madrid AEROSPACE MATERIALS II

www.uc3m.es CIENCIA E INGENIERÍA DE MATERIALES
METALLIC MATERIALS
TOPIC 2. SOLIDIFICATION OF METALS
1. Solidification. Nucleation
2. Solidification. Growth
3. Cast structures
4. Defects in Castings
Dpt. Materials Sci. and Eng. and Chemical Eng. UC3M Aerospace Materials II
Metallic Materials. Topic 2: Solidification
1. Solidification
Solidification: transformation from the liquid (melt) to the solid state

During solidification:
Liquid ↔ Solid + Heat (latent heat of fusion)
Solid forms from liquid in an interface
Necessary:
• Negative free energy change (G<0)
• Heat extraction → UNDERCOOLING, ΔT
ΔT=Tm- T ( Tm: melting temp, T: T real)
Variation of free energy G with temperature

for pure liquid Gl and solid Gs. Above Tm , Gl
Solidification occurs in two stages: <Gs , liquid is in equilibrium. Below Tm solid is
stable, Gs<Gl The driving force ΔG is the
Nucleation and Growth difference between the two curves.
Nucleation: formation of stable groups of atoms (nuclei)
Homogeneous Nucleation: formation of small cluster (nucleus) surrounded by liquid.
• Thermodynamic considerations ( condition for transformation: G must be <0)
 Critical radius, rc : size of stable nuclei
 Undercooling: ΔT=Tm - T
r*
4 Gint erface = 4r 2 LS

Trasformation L to S Gvolume = r 3 Gv
3
- Creation of interface
4
- Nucleation with no preferential sites Gtotal = r 3 Gv + 4r 2 LS
- Isotropic solid → sphere 3
Nucleation:
• Homogeneous: Clusters are stable only if r≥ rcritical (i.e. if Gtotal decreases)
defined as the radius at which ΔGtotal is maximum, d(ΔGtotal)/dr=0
2· LS 2· LS ·Tm ΔH: latent heat of fusion

Critical radius: rc = = ΔT: undercooling
Gv H ·T LS: liquid-solid interfacial energy
• At higher udercooling, lower critical radius, higher nuclei number
For pure metals and homogenous nucleation : Tunder = 0.2Tm (very large)
The nº of nuclei determines the grain size of the solid metal and therefore its
properties.
Heterogeneous Nucleation:
• Existing surfaces provide low energy nucleating sites

• The initial interface is provided by a foreign particle (impurity, inclusion) and
existing surface (i.e. mold wall).
• A greater radius is achieved with very little total surface between the solid
and liquid and lower nuclei volume
• Most common nucleation process
Lower undercooling is necessary for

heterogeneous nucleation
Structure in detail
- Fine structure (Chill zone)

- Coarser structure
(Columnar zone)
- Equiaxed grains
Growth parallel and

opposite to the
direction of heat flow
Which is the direction of the heat flow?
Growth: incorporation of atoms from the liquid to the solid

• A nucleus can only grow if rrcritical (since this will cause a decrease in G)
• Latent heat of fusion must be removed → undercooling
• Heat extraction way and rate determine growth mechanism and structure
of the solidification front (planar, cellular, dendritic, equiaxed)
• Growth occurs opposite to the heat flux direction and in preferred
orientations depending on the material
Preferred orientation
o Cubic <100>
o HC <0001>
Development of a preferred texture at a cool

mold wall. Only favorably oriented grains grow
away from the surface of the mold.
2. Solidification. Growth in pure systems
Heterogeneous nucleation typically initiates at the mold walls
( I ) Positive thermal gradient ( I I ) Negative thermal gradient
Temperature
Temperature
Undercooled
zone
Tmelting T
m
grad T < 0
highest from O-M
undercooling T
1
mold liquid mold
distance O M distance
High number of grains nucleate at the Temperature increases due to
mold walls because the undercooling is latent heat of fusion from T1 to Tm
highest.
2. Solidification. Growth in pure systems
For a pure metal solidification takes place at constant temperature Tm .
+ T gradient - T gradient
If the liquid ahead of the interphase is

Any protuberance is surrounded by liquid undercooled a protuberance will grow as a
at T > Tm and it will not grow (dissolves) Dendrite → Dendritic solidification front
→ Planar solidification front (Latent heat is removed by raising the
(Latent heat is removed through the solid) temperature of the liquid to Tm. Secondary
and tertiary dendrite arms develop)
2. Solidification. Growth in pure metals
For a pure metal : – temp. gradient → dendritic solification front
planar
cellular
VIDEO
dendritic
https://www.youtube.com/watch?v=S07fPo45BvM
2. Solidification. Growth - Binary alloys
• Alloys solidify in a range of temperatures: freezing range = TL-Ts≠ 0
Constitucional supercooling:
solute distribution
coefficient, k.
𝐶𝑆
𝑘=
𝐶𝐿
Solute is partitioned into the liquid ahead of the

interface
solidification front → corresponding variation in the

liquidus temperature. There is, however, a positive
temperature gradient in the liquid, giving rise to a
supercooled zone of liquid ahead of the interface
11
2. Solidification. Growth Binary alloys
Transition of growth morphology from planar, to cellular, to dendritic, for alloys as
cositutional undercooling increases → equivalent to G/v↓).
planar Constitutional supercooling

criterion:
𝑣∆𝑇
𝐺=
𝐷
D diffusion coefficient of solute the liquid.
(For most metallic systems, D ≈10-9 m 2/s)
cellular
ΔT: frezzing range (TL-TS)
V: Interface velocity
G/v ~ 1010 -1012 : planar solidification front

G/v ~ 105-107 : dentrite solidification front
dendritic
G: thermal gradient (102-103 K/m)

v: velocity (rate) at which the liquid/solid interface moves (~10-3-10-4 m/sec)
D diffusion coefficient of solute the liquid. (For most metallic

systems, D ≈10-9 m2/s) 𝑣∆𝑇
𝐺?
Interface got to move with:
𝐷
- Transfer of atoms across the boundary
- Solute diffusion: The composition of the solid is not the same
as the composition of the liquid
ΔT: frezzing range (TL-TS) → GRADIENT

OF THE LIQUIDUS PROFILE AT THE
INTERFACE. ΔT ≈ 5K
G: thermal gradient (102-103 K/m) → ACTUAL

TEMPERATURE GRADIENT IN THE LIQUID
G=104 K/m
v: velocity (rate) at which the liquid/solid interface

moves (~10-3-10-4 m/sec)
Vcr = ? 2x10^(-6) m/sec
How must be the velocity of the interface with respect to the critical velocity to
avoid constitutional supercooling?
𝑣∆𝑇
𝐺>
planar 𝐷
𝑣 ≤ 𝑣𝑐𝑟
𝑣∆𝑇
cellular 𝐺<
𝐷
𝑣 > 𝑣𝑐𝑟
𝑣∆𝑇
𝐺≪
𝐷
dendritic
𝑣 ≫ 𝑣𝑐𝑟
▪Secondary Dendrite Arm Spacing

(SDAS) depends on solidification
time and defines strength of alloy.
▪Rapid solidification procedures fine
dendritic structure: higher strength
SDAS = k (ts)m
K,m →cst
ts →solidification time
Effect of solidification time on secondary dendrite spacing

and on mechanical properties of a cast aluminium alloy
a b
Solidification time c
The effect of solidification time on the microstructure of an
Al7.4Si3.3Cu alloy.
a Average solidification time 0.7 min (average SDAS 23 μm).
b Average solidification time 16 min (average SDAS 70 μm).
c Average solidification time 43 min (average SDAS 100 μm)
2. Solidification. Growth in alloys
• Most common form of growth in engineering alloys is in the form of
dendrites : tree-like form structures (from the greek word δεντρο which
means tree)
Ice dendrite formation on a snowflake
cobalt-samarium-copper alloy
showing primary cobalt
dendrites when the Co17 Sm 2
matrix is etched away
Al-Si alloy (A356)

Dendirtes in Al alloy
3. Cast structures
• Structures of castings are controlled by :
– Composition: solidification of pure metals or alloys. Cooling curve
– Heat flow conditions : Solidification regarding the heat flow of the mold
IN GENERAL, as-cast metal exhibits three distinct zones of grain structures:
➢ A chill zone of very small crystals produced by rapid cooling at mold walls
➢ A zone of long, thin columnar crystals lying along the direction of heat flow
➢ A region of roughly spherical equiaxed crystals at the center of the casting

All three zones may not be present in a particular case. Relative sizes of zones
depend on many factors, among them temperature of the melt, cooling rate, thickness
of casting
3. Cast structures: pure metals
Cooling curve for solidification of pure metals:

• Solidification takes place at constant temperature Ts-TL=0
Pouring temperature
∆T
= cooling rate
∆t
Superheat
Chill zone (equiaxed)

tr
Columnar
tt zone
t r= real(local) solidification
time
t t= total solidification time
3. Cast structures: cooling curves
Cooling curve for solidification of alloys:
• Alloys solidify in a range of temperatures : freezing range = T L-Ts≠ 0
Columnar
Temperature
Pouring zone
temperature
(1455 o C) liquid
liquidus Cooling of liquid
Tliquidus
Chill zone (equiaxed)

Temperature
l+s Tsolidus Equiaxed

tr
solidus Cooling zone
(1083 o C) tt of solid
liquid
Solid solution +
liquid solid
solid
Ni 50% Cu time
%Cu
t r= real(local) solidification time Solidification range (approx.):

t t= total solidification time Iron alloys: 50ºC,
Mg Al alloys: 110ºC
3. Cast structures
Theories on origin of central equiaxed nuclei:
▪ Dendrite detachment: nuclei for the equiaxed zone come from the detached
dendrite arms that are carried to the centre of the mold by convection currents.
▪ Big Bang: equiaxed grains result from the pre-dendritic nuclei formed during
metal pouring due to the initial chilling action of the mold. The grains are then
carried into the bulk by fluid flow and survive (for low superheats)
▪ Constitutional supercooling: as liquid solidifies, remaining liquid has a
higher solute concentration and hence lower liquidus temperature. Therefore,
liquid at the center of the cast is undercooled and heterogeneous nucleation can
occur.
No costitutional supercooling in Costitutional supercooling in

the middle of the casting the middle of the casting 22
3. Cast structures
Eutectic alloys:
▪ For eutectic compositions: solidification takes place at constant temperature
Teutectic ( L → α + β)
▪ For hypo-eutectic or hyper eutectic: a final amount of liquid solidifies at the eutectic
temperature (and has the eutectic composition and structure)
Microstructures of hypo- and hyper

eutectic alloys showing primary and
eutectic constituents
Formation of cells with intercellular eutectic in the

directionally solidified Sn-20Pb alloy. G = 31 K/mm and
v = 1.2 μm/s (The nearly flat eutectic interface is at the
eutectic temperature.
3. Cast structures
• Alloys can be classified into three types based on their freezing ranges:
➢ Short: liquidus-to-solidus interval <50 °C (skin forming alloys)
➢ Intermediate: interval of 50 to 110 °C
➢ Long: interval > 110 °C (mushy forming alloys)
Pure metal (or eutectic alloys) Short freezing range alloy Intermediate (most Long freezing range alloy
(no freezing range) T s-TL =0
structural alloys)
Progressive solidification Mushy/pasty solidification

skin forming alloys: low carbon steels, low alloys steels, aluminum bronze, manganese bronze
Mushy forming alloys: aluminium alloys, magnesium alloys, some brasses
ASM Metals Handbook. Vol. 15: Casting 1990, ASM International
3. Cast structures
Effect of casting parameters on microstructure

▪Superheat : ↑ superheating (pouring temperature) increases the extent of
columnar growth
▪Composition: ↑ alloying content tends to decrease the extent of columnar region
▪Fluid flow (natural or forced): ↑ fluid flow decreases the extent of the columnar
region.
▪Mechanical vibration: ↑ mechanical vibration promotes grain refinement and can
extend the equiaxed zone
Al–2 wt-%Cu alloy. a)40ºC superheat; b) 80ºC superheat

Al–4,5 wt-%Cu alloy, effect of pouring temperature
Spittle, International Materials Reviews 51 (4) 2006
Effect of casting parameters on microstructure
▪ Inoculation and grain refining: Grain-refining additions can reduce the extent of
columnar growth (grain size depends on cooling rate)
▪ Size: ↑ cross section yields higher propertion of equixed grains
▪ Freezing range: short freezing range promotes more progressive solidification front
which tends to increase the size of the columnar zone
▪ Melting point: High melting point promotes high thermal gradients which tends to
increase the size of the columnar zone
▪ High thermal gradients: promote progressive solidification front that promotes
columnar growth
Al–5 wt-%Cu alloy solidified with a chill plate at its base

(solidification is left to right). Decreasing temperature
gradient in the range of 113-234 K/m → increase of
equiaxed zone
3. Cast structures
Contours of equal grain size shown on plot of solidification

velocity versus thermal gradient together with locus for CET
(Columnar to Equiaxed Transition)
Spittle, International Materials Reviews 51 (4) 2006
4. Defects in Casting
Defects in Castings are due to:

•Segregation: microsegregation or macrosegregation
•Surface tension
•Volume shrinkage during solidification
•Viscosity (fluidity)
•Inclusions (oxides, nitrides)
•Wide solidification temperature range
•Convection
•Incorrect mold selection and design
CHEMICAL DEFECTS
• Microsegregation
• Macrosegregation (normal, inverse, by gravity)
PHYSICAL DEFECTS
• Trapped gases
• Shrinkage and Pipes
• Incorrect shape
4. Defects in Casting: Segregation
Microsegregation: microscopic scale

There is a concentration gradient in the
liquid grains due to solute rejection during
(1455 o C) liquidus
solidification
Temperature
l+s
solidus
(1083 o C)
Solid solution
Ni 50% Cu
%Cu
4. Defects in Casting: Segregation
Macrosegregation: Macroscopic differences in composition through-out the

cast
Normal segregation Inverse segregation Gravity segregation
In planar growth solidification In dendrite structures: liquid metal Higher density

front: The centre of the casting (with higher concentration of inclusions or
(last metal to solidify) has high alloying elements of low melting compounds sink
concentration of alloying point) enters cavities in-between and lighter
elements with lower melting dendrite arms. Center of the casting elements float
point. has lower concentration of alloying
elements with low melting point.
4. Defects in Casting: Trapped gasses
▪Liquid metals have > solubility for gases than solids. When metal cools and
solidifies gases are expelled
▪Gases can result from reaction of molten metal with mold (example: H2O in sand
with Fe C Al Si)
Microporosity (interdendritic)
Problems Cavities: blowholes, pinholes

i.e. 3H2O+2Al = Al2O3+3H2
Formation of solids and oxides  embrittlement Thermodynamically
favourable
Pitting (due to water wapour)
4. Defects in Casting: Trapped gasses
Solutions:
1. Reduce amount of gases OR/AND
2. Facilitate gas evacuation
• Lower pouring temperature
• Keep melt in laddle as long as possible
• Inert gas flushing
• Vacuum melting and pouring
• Reduce humidity
• Increase permeability of mold and cores
• Make adequate provision for evacuation of
air and gas from the mold cavity
• Reduce pouring height
• Proper mold design (gating, runner height)
Pinholes
Blowhole defect
in a cast iron
part
Blowholes
4. Defects in Casting: Shrinkage
Contraction occurs in three stages:
1. Liquid contraction: Shrinkage of the liquid
from Tpouring to Tmelting
2. Solidification contraction: Solidification
shrinkage as liquid turns to solid
3. Solid contraction during cooling to RT
In general, for metals: liq< sol :

• (e.g.) Cobalt (Tm=1495ºC) : liq= 7,19 sol=7,66 
Volumetric contraction: -16,55%
• Total contraction: liquid contraction +

solidification contraction + solid contraction
• Solidification shrinkage ranges from 3 to 8% for pure metals
• Shrinkage : Can cause defects at a macroscopic and/or microscopic level

• Macro-shrinkage: macroscopic level contraction
• Micro-shrinkage: microscopic level contraction (it appears in interdendritic spaces
when liquid filling them solidifies)
Shrinkage defects:
– Pipes (shrinkage cavities, macroscopic): As the surface of
the cast begin to solidify funnel like cavities that develop
at the center of the cast
– Caved surface: shallow cavities that form across the
surface of the casting
– Macroporosity (macroscopic): large shrinkage cavities
formed within the casting
– Microporosity (or microshrinkge): liquid metal solidifies
and shrinks between dendrites
Microporosity
Caved Pipe
surface
Macroporosity
Shrinkage cavities produced by skin

forming alloys or pure metals Shrinkage porosity in the sand castings of alloys
that freeze in a mushy/pasty manner
Pipe in pure metal or casting in metallic Pipe in metal with wide solidification
mold (strong cooling) range or casting in sand mold
ASM International-Casting Design and Performance (2008)
Dpt. Materials Sci. and Eng. and Chemical Eng. UC3M Aerospace Materials41II
– Solutions:
▪ High thermal conductivity molds
▪ Use chills (internal or external)
▪ Adequate metal feeding (risers)
▪ Hot isostatic pressing (expensive)
Sprue/Riser: liquid metal reservoir in the mould, designed to provide liquid metal to
the casting and compensate for solidification shrinkage .
▪ They must be hot during all casting process.
▪ If they are open, atmospheric pressure effect can help to avoid the formation of micro-
shrinkage.
▪ Refractory material.
Chills:
External chills: pieces of a high-thermal conductivity material that are placed into
the mold and increase solidification rate in critical regions
Internal chills: pieces of a metal that are placed within the mold cavity to absorb
heat and increase solidification rate. Must be from the same material as cast
to get faster cooling. Small metal pieces, in a cavity or outside
Other defects:
•Metallic projections (fins, flash, swells)
•Cavities (gases, shrinkage)
•Discontinuities (cracks, lack of filling)
•Defective surfaces (folds, scars, sand, oxides)
•Incomplete casting (lack of material)
•Incorrect dimensions or shape
•Inclusions
Flash
(International Committee of Foundry Technical Associations)
References
• ASM Handbook Volume 15: Casting

• Doru Michael Stefanescu (auth.)-Science and Engineering of
Casting Solidification-Springer International Publishing (2015)
• John Campbell-Castings-Butterworth-Heinemann (2003).pdf

Metallic Materials Topic 2. Solidification of Metals

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Universidad

Carlos III de Madrid AEROSPACE MATERIALS II

Solidification: transformation from the liquid (melt) to the solid state

Solid forms from liquid in an interface

Variation of free energy G with temperature

4 Gint erface = 4r 2 LS

2· LS 2· LS ·Tm ΔH: latent heat of fusion

• At higher udercooling, lower critical radius, higher nuclei number

• Existing surfaces provide low energy nucleating sites

Lower undercooling is necessary for

- Fine structure (Chill zone)

Growth parallel and

Which is the direction of the heat flow?

Growth: incorporation of atoms from the liquid to the solid

Development of a preferred texture at a cool

Heterogeneous nucleation typically initiates at the mold walls

( I ) Positive thermal gradient ( I I ) Negative thermal gradient

For a pure metal solidification takes place at constant temperature Tm .

If the liquid ahead of the interphase is

Solute is partitioned into the liquid ahead of the

solidification front → corresponding variation in the

planar Constitutional supercooling

G/v ~ 1010 -1012 : planar solidification front

G: thermal gradient (102-103 K/m)

D diffusion coefficient of solute the liquid. (For most metallic

ΔT: frezzing range (TL-TS) → GRADIENT

G: thermal gradient (102-103 K/m) → ACTUAL

v: velocity (rate) at which the liquid/solid interface

Vcr = ? 2x10^(-6) m/sec

▪Secondary Dendrite Arm Spacing

Effect of solidification time on secondary dendrite spacing

Ice dendrite formation on a snowflake

Al-Si alloy (A356)

➢ A region of roughly spherical equiaxed crystals at the center of the casting

Cooling curve for solidification of pure metals:

Chill zone (equiaxed)

Chill zone (equiaxed)

l+s Tsolidus Equiaxed

t r= real(local) solidification time Solidification range (approx.):

No costitutional supercooling in Costitutional supercooling in

Microstructures of hypo- and hyper

Formation of cells with intercellular eutectic in the

Progressive solidification Mushy/pasty solidification

Effect of casting parameters on microstructure

Al–2 wt-%Cu alloy. a)40ºC superheat; b) 80ºC superheat

Effect of casting parameters on microstructure

Al–5 wt-%Cu alloy solidified with a chill plate at its base

Contours of equal grain size shown on plot of solidification

Spittle, International Materials Reviews 51 (4) 2006

Defects in Castings are due to:

Microsegregation: microscopic scale

Macrosegregation: Macroscopic differences in composition through-out the

In planar growth solidification In dendrite structures: liquid metal Higher density

Problems Cavities: blowholes, pinholes

In general, for metals: liq< sol :

• Total contraction: liquid contraction +

• Shrinkage : Can cause defects at a macroscopic and/or microscopic level

Shrinkage cavities produced by skin

• ASM Handbook Volume 15: Casting

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