Indian Institute of Technology Indore

Department of Metallurgy Engineering and Material Science

CONTAINERLESS SOLIDIFICATION
Raineesh Babu KP (1902105016)
Mtech - Metallurgy Engineering
 OUTLINE

● Introduction
● Why containerless solidification?
● Nucleation and Crystal growth in undercooled melts
● Drop tubes and levitation
● Summary
 INTRODUCTION
● Containerless processing is an effective tool for undercooling metallic
melts far below their equilibrium melting temperatures.
● By this method heterogeneous nucleation on container walls is
completely eliminated
● Heterogeneous nucleation on free surfaces can also be prevented if the
experiments are carried out at clean environmental conditions
● In this way, large undercooling can be reached even for bulk solids that
are otherwise achieved only by the droplet emulsion technique.
● This can be achieved either by levitation techniques or drop tube
techniques.
 Why containerless solidification?
● Containerless processing is important in investigations where elimination
of the the influence of container walls is essential like
○ Fluid flow dynamics
○ Glass formation
○ Preparation of pure substances
○ Undercooling and solidification
● Containerless processing opens the possibility to achieve large degrees
of undercooling
● The state of an undercooled melt gives access to solidification into solid
states far from equilibrium.
● The undercooled liquid - i.e. the liquid below its freezing point is called
the metastable liquid.
● At a particular level of undercooling, liquid - solid transformation begins
and forms a solid phase which may be different from what is formed at
equilibrium melting temperature. They are referred to as Metastable solid
states.
● The spectrum of such metastable states comprises a broad variety of
material classes including:
○ Metastable crystalline phases
○ Quasicrystals
○ Bulk Metallic glasses
○ Supersaturated solid solutions
● Conventionally, these metastable phases are produced by fast cooling
techniques like melt spinning and splat cooling
● Even though a variety of novel products have emerged from these methods,
they are not suitable for direct analysis.
● Rapid quenching is a method that
allows little control over the
conditions during processing.
● Undercooling can be used as an
alternative here. For undercooled
melts, the driving force will be higher
Figure : Melt Spinning and hence the rate of solidification
also will be higher.
● The production of heat (latent heat) due to rapid crystallisation, occurs
much rapidly than transfer of the heat of the sample to the environment.
● This leads to a temperature rise during the initial crystallization of the
sample known as recalescence.
● The non-equilibrium process of rapid solidification is accessible to direct
analysis by investigating the recalescence profile.

Figure : In situ recalescence behavior captured by the HSV when the

Al2O3–ZrO2 eutectic melt is solidified spontaneously. The time interval
between two consecutive frames is 50 ms.
Nucleation and crystal growth in undercooled melts
Crystal Nucleation
● Crystal nucleation is the first step in crystallization of undercooled melts.
It selects the crystallographic phase, may it be stable or metastable.
● This nucleation may be homogeneous or heterogeneous nucleation.
● For homogeneous nucleation, the constraint is surface energy of the
nuclei.
● σ = the solid-liquid
interfacial energy
● ΔGv = GL − GS, the
difference of Gibbs
free energy

Figure : Free energy change with radius of cluster of atoms.

 (By Turnbull assumption, Cp = 0)

Figure : Free energy - Temperature The steady state nucleation rate, Iss, is computed by:
diagram for liquid and solid phase

● N0 and, hence, KV, are drastically reduced in case of heterogeneous

nucleation, as compared with homogeneous nucleation.
● So the rate of nucleation will be higher for homogeneous nucleation.
● For homogeneous nucleation No = Na/Vm which will be very large.
● The solidification of an undercooled metallic melt is a two-stage process

A fraction of the sample, fr, The remaining melt, fpr = 1 − fr,

solidifies during solidifies under near-equilibrium
recalescence under a conditions during
non-equilibrium condition post-recalescence period
● This fr increases with degree of undercooling and becomes unified (fr = 1) if
ΔT ≥ ΔThyp (where, ΔThyp = Hyper Cooling limit)
● The hyper cooling limit, ΔThyp, is reached if the heat of fusion ΔHf is just
sufficient to heat the sample with its specific heat Cp up to TL
● ΔThyp = ΔHf/Cp
Figure : Temperature-time-profile measured on pure Zr sample in the electrostatic levitator
Figure : Principle of nucleation triggering of a metastable bcc phase in Fe76Ni24 alloy by using a nucleation trigger
made of Fe95Mo5 bcc phase
Crystal Growth

● Crystal growth in undercooled melts leads to a heating up the solid-liquid

interface due to the release of the heat of crystallization
● As a consequence, a negative temperature gradient will be established in
front of the interface
● In alloys, a concentration gradient will be built up in addition
● These two gradients lead to the instability of solidification front.
● This destabilisation of initially planar interface leads to dendrite growth.
● Dendrites consist of the main stem and side-branches, which grow into
the melt.
● The values of dendritic growth rate are described by LKT (Lipton, Kurz,
Trivedi) and follow
● This is again validated by K.Drews Et al using cobalt metal.
 Supersaturated solid solutions
● Consider an alloy of composition Ci < CO composition - It has two options

It can split into liquid and It can directly transform into

solid of compositions CL solid phase of composition Ci
and CS respectively. (If transformation occurs
(Under Equilibrium cooling) below TO temperature)

Ci
Ci
● This happens in eutectic systems also.
● If we cool the liquid system below the To temperature, eutectic mixture
will not be formed, rather single phase 𝛼 or β will be formed based on
initial composition.
 Drop Tubes and levitation techniques
● Molten droplets are allowed to cool and solidify while falling freely down a
tube within which there is a controlled atmosphere.
● Tube is evacuated and single droplets 1-5 mm in diameter are melted by an
electron beam.
● After release, the droplet is monitored photodiodes along the length of the
tube to detect recalescence. (Undercooling can be found this way if time of
flight and cooling rate is known.)
● Heterogeneous nucleation on surface can be prevented by using high
vacuum.
● U (Under vacuum)

● (If an inert atmosphere is present)

● Drop tubes are limited to the solidification of small droplets.
● In drop tubes it is extremely difficult to perform direct diagnosis of
undercooling.
● These difficulties are overcome if a bulk melt can be suspended in a
quiescent state and a stable position by application of levitation techniques.
● Major levitation techniques are:
○ Aerodynamic levitation
○ Electromagnetic Levitation
○ Acoustic Levitation

Figure: Electromagnetic levitation setup

 Summary
● Containerless solidification is one the methods available to study the
homogeneous nucleation.
● Bulk metallic glasses can be formed even by small cooling if containerless
solidification is employed.
● It is possible to get extended solid solutions even by slow cooling.
● The nucleation rate is found to increase with increase in undercooling.
● The recalescence rate is also found to increase with increase in
undercooling.
● Copious nucleation is found during containerless solidification
 References
1. K. Drewes, K. Schaefers, M. Rosner Kuhn, M.G. Frohberg (1998), Measurements of
dendritic growth and recalescence rates in undercooled melts of cobalt, Materials
Science and Engineering A241 (1998) 99–103
2. Mingjun Li, Kosuke Nagashio, Kazuhiko Kuribayashi (2004), Containerless
solidification of undercooled oxide and metallic eutectic melts, Materials Science
and Engineering A 375–377 (2004) 528–533
3. D. M. Herlach, R. F. Cochrane, I. Egry, H. J. Fecht, and A. L. Greer (1993),
Containerless processing in the study of metallic melts and their solidification,
International Materials Reviews 1993 Vol. 38 No.6
4. Dieter M. Herlach (2014), Non-Equilibrium Solidification of Undercooled Metallic
Melts, Metals 2014, 4, 196-234