Melting and remelting phenomena

M. Rettenmayr
Melting processes influence the microstructure evolution in metal alloys during casting and heat
treatments. Melting is often treated as ‘inverse solidification’, which is only appropriate in a limited
number of cases. In the present article, asymmetry between solidification and melting is reviewed
in detail. The current state of the thermodynamic description of melting under diffusion control is
outlined. Kinetic aspects that break the symmetry between solidifi-cation and melting that are
discussed are solute partitioning, solute concentration gradients and solute transport in the
involved phases. The view on nucleation of liquid and pre-melting phenomena, mostly of pure
materials, based on experimental and theoretical work, is given. Emphasis is laid on aspects of
melting with technical relevance, i.e. melting of alloys. Particu-larities of thermally and solutally
controlled melting are introduced. Mechanisms that involve both melting and solidification
simultaneously are capillary driven coarsening, temperature gradient zone melting and liquid film
migration. The impact of these processes on microstructural evolution is discussed. Open
questions concerning modelling and simulation of melting, namely, the interaction of different
melting mechanisms and the role of the solid/liquid inter-face, are identified.
Keywords: Melting, Dissolution, Solidification, Microstructure evolution, Coarsening, Liquid film migration, Temperature gradient zone melting, Dendrite
fragmentation

Introduction continuous scientific interest in melting since liquid/solid

Solidification and melting are both phase transforma-
tions involving at least one liquid and one solid phase
respectively. As compared to solidification, research
work on melting documented in the literature is
relatively scarce. This is certainly due to the fact that
solidification is of higher interest for technical applica-
tions, as the properties of a cast material are directly
connected to the microstructure evolution during
solidification.
At first sight it is tempting to adapt know-how from
the further developed solidification theory to melting, as
melting and solidification could be expected to be
similar. It appears to be straightforward to treat these
phase transformations symmetrically, i.e. melting as the
inverse process of solidification. This may indeed be
correct for liquid/solid phase transformations with low
transformation rate when the assumption of local
equilibrium at the interface holds and nucleation
phenomena are unimportant.
However, it is a long known experimental fact that
upon cooling of liquid metals, an undercooling under
the equilibrium melting temperature can hardly be
avoided, but that upon heating, solid metals can only
be heated above their melting temperature while
remaining in the solid state with considerable experi-
mental effort. The lack of symmetry has caused
FSU Jena, Materials Science and Engineering Institute, Metallic Materials
Department, Löbdergraben 32, D-07743 Jena, Germany
*Corresponding author, email M.Rettenmayr@uni-jena.de
phase transformations were studied. Different nuclea-
tion behaviour of melt ‘on its own solid’ was identified
first as a reason for the asymmetry, but further aspects
concerning structure, thermodynamics and kinetics have
been pointed out over the past decades. Research work
is published in the literature where these aspects of
asymmetry are not considered, in almost all instances for
cases where solidification and not melting is the main
focus of the work. Simulation calculations for solidifica-
tion processes that include remelting should thus be
interpreted with care.1–3
The influence of melting on microstructural evolution
is manifold. In large castings, the solidification structure
on a macroscopic level will generally be strongly
influenced by melting, since convection can increase
local temperature and composition and thus alter the
solidification time and the temperature at which
solidification occurs locally. More importantly, solidifi-
cation and melting are not necessarily separated in space
and time. Several processes are known that involve
simultaneous melting and solidification in the mushy
zone of an alloy. Among those are dendrite arm
coarsening, temperature gradient zone melting
(TGZM) and liquid film migration (LFM). Up to
present, those processes can be described analytically,
often semi-empirically, without including detailed ther-
modynamics and kinetics of melting.
In the present article, after documenting the technical
importance of melting (the section on ‘Technical impor-
tance of melting’), the known asymmetries between
melting and solidification are elaborated; recent progress
in the thermodynamics of melting is summarised, and

ß 2009 Institute of Materials, Minerals and Mining and ASM International

Published by Maney for the Institute and ASM International
DOI 10.1179/174328009X392930 International Materials Reviews 2009 VOL 54 NO 1 1
Rettenmayr Melting and remelting phenomena
aspects of differences in solute partitioning and structure
as well as phase transformation kinetics are presented (the
section on ‘Asymmetry between solidification and melt-
ing’). The literature on nucleation related phenomena is
discussed in the section on ‘Nucleation and related
phenomena and pre-melting’. Thermal and solutal
melting are treated separately in the sections on
‘Thermal melting’ and ‘Solutal melting’. Finally, pro-
cesses that involve simultaneous melting and solidifica-
tion are introduced in the section on ‘Melting and
simultaneous solidification’.
Melting and remelting phenomena are related in the
present work to the context that is common knowledge
in the scientific community working on liquid/solid
phase transformations. The focus of the present article is
on melting of alloys and ‘real crystals’. The larger part of
the literature on mechanisms and kinetics of melting
deals with pure substances under laboratory conditions
or in ideal crystals in computer simulations. In
numerous instances, especially in simulations and the
development of theory, the published literature con-
siders a state of considerable superheating, particularly
close to the theoretical limit of superheating. While this
contributes to a basic understanding of melting pro-
cesses, the way to a practical application is far. Aspects
with at least some relationship to engineering cases will
be introduced here, the scientific literature dealing with
pure materials under special laboratory conditions and
or the corresponding simulations are not discussed. The
interested reader is referred to the reviews of Dash4 on
surface melting and the recent comprehensive review on
melting and superheating by Mei and Lu.5
Technical importance of melting
In recent years, the importance of melting phenomena
for technical processes has become more and more
recognised. (Local) remelting is a phenomenon that
occurs in a variety of casting processes and influences
the structure evolution to an important degree. Local
remelting can occur in non-stationary states even if in a
cast part overall the enthalpy is decreased. In fact, in his
book ‘Castings’, J. Campell6 states verbatim: ‘convec-
tion can cause remelting of large sections of a casting
over an extended period of time; models that do not
consider this effect are grossly erroneous’.
Local remelting is not limited to ‘exotic’ cases with
low technical impact. Melting of considerable volume
fractions in semi-solid or solid alloys has been identified
as an important factor during a variety of processes.
During continuous casting, remelting can cause surface
defects on the cast piece.7 Premature melting in recycling
of scrap steel consisting of different kinds of steel has
been investigated in Ref. 8. In multicomponent alloys,
diffusion of different solute elements with the respective
kinetic constant can lead to local melting during heat
treatments.9
Furthermore, local remelting can have drastic influence
on a solidifying micro-structure, even if the remelting
volume fraction is minor. During Czochralski growth of
single crystals, remelting has been observed at triple
points liquid/solid/gas and is a source of structural
defects.10 Considering that secondary dendrite arms are
generally thinner at the root than closer to the growth
front, one can easily imagine that local remelting leads to
the detachment of dendrite arms. Thus, remelting is
2 International Materials Reviews 2009 VOL 54 NO 1
discussed as the main mechanism for dendrite fragmenta-
tion which in turn leads to the columnar-to-equiaxed
transition (CET)11–15 and freckle formation in Ni base
superalloys16 or Sn alloys.17 In these latter cases,
secondary dendrite arms that melt off at the root are
potential nuclei for new grains.
Some technological processes that are based on
melting need to be mentioned here, even though
generally rather the technological impact than the
melting process is in the focus of interest in the related
literature. Particularly there are soldering, brazing and
welding as joining technologies. Additionally, surface
remelting by laser, electrical arc, electrons, etc., is used
as a tool to modify the surface structure and conse-
quently the properties of a material. As the melting
mechanisms are only scarcely discussed in these works
they are not part of the present review.
Asymmetry between solidification and
melting
In the present work, it is distinguished between thermal
and solutal phase transformations. A definition of
solutal and thermal phase transformations is not trivial,
as in many cases, there are aspects of both solutal and
thermal control. The definition is, however, straightfor-
ward when starting a phase transformation from a single
phase in thermodynamic equilibrium, i.e. in the absence
of supersaturations/undercoolings. In Fig. 1, a sche-
matic of a part of a phase diagram is shown where the
two types of phase transformation are illustrated.
If starting with a single phase, thermal melting or
solidification are induced by a continuous increase or
decrease in temperature (more precisely in enthalpy),
cases (1) in Fig. 1 (solid line for melting, dotted line for
solidification). It should be noted, however, that even
though a change in enthalpy is the cause for the phase
transformation, its kinetics might still be controlled by
solute diffusion in the phases. Pure thermal control
would only be acting during rapid heating/cooling.
Nevertheless, in the present work, experiments that are
conducted by introducing heat into a sample and that
start single phase are treated as thermal melting, even
though solutal control might play an important role.
Solutal melting or solidification is due to driving
forces that can in principle persist under isothermal
conditions, i.e. where mainly a change in composition
yields a subsequent phase transformation. An example
where in an experiment starting from the single-phase
field the two-phase field in the phase diagram is entered
by one of the phases due to solute diffusion is the
constitutional undercooling/superheating ahead of a
solidifying/melting interface [cases (2) in Fig. 1, solid
line for melting, dotted line for solidification]. The phase
transformation behaviour in this case is likely to be
influenced by nucleation in the undercooled/superheated
region.
Additionally, melting or solidification can be con-
trolled solutally, if initially both a liquid and a solid
phase are present, but the composition of at least one of
the phases is not the equi-librium composition at the
interface; thus, a reaction between the phases will occur
at the interface, yielding a change of interfacial
compositions and a migration of the interface. Cases
(3) in Fig. 1 show the situation at the interface during

1 Schematic of a phase diagram for the definition of thermal
and solutal phase transformations; circles are for an
initial single-phase state, squares for an initial two-phase
state; solid lines depict melting cases, dotted lines solidi-
fication cases; (1) phase transformation due to a continu-
ous change in enthalpy (thermal melting/solidification), (2)
phase transformation due to diffusion in a single phase,
e.g. constitutional superheating/undercooling ahead of an
interface (solutal melting/solidification), (3) phase trans-
formation due to a concentration gradient at the interface
(solutal melting/solidification), (4) phase transformation
due to solute enrichment/depletion in one of the phases
(solutal melting/solidification)
plane front directional melting/solidification: diffusion
in the parent phase effectuates an increase/decrease in
composition of the parent phase, with the trend of
entering the two-phase field and consequently migration
of the interface.
A further well-known example for solutal melting is a
solid being in contact with a liquid that is solutally
enriched, i.e. the composition of the liquid is higher than
the liquidus composition and in the one-phase field in
the phase diagram. Under this condition, solutal melting
is often called dissolution [case (4) in Fig. 1]. For
example, at a given temperature below the freezing point
of water pure ice will dissolve in a water/ethanol
mixture, if the ethanol composition is higher than the
liquidus composition. For dissolution, the composition
in the solid phase only plays a less important role,
provided there is solute enrichment in the liquid melting
will occur for any solid composition.
Thermodynamic aspects of (non-equilibrium)
solidification and melting of alloys
Liquid/solid phase transformations with low or moder-
ate front velocities occur under diffusion control. It is
assumed that the interface is in local equilibrium, the
phase transformation rate is then governed by mass
transport in the adjacent phases. As long as the local
equilibrium assumption holds and melt nucleation at
defects is unimportant, the composition of the phases
at the interfaces can be taken from the phase diagram at
the relevant temperature, the phase transformation be
modelled symmetrically for solidification and melting.
Recent progress in the formulation of thermody-
namics of migrating phase interfaces allows pointing out
Rettenmayr Melting and remelting phenomena
differences between solidification and melting.
According to Boettinger and Corriell,18 there is a
hierarchy concerning the thermodynamics of phase
transformations:
N full diffusional equilibrium: uniform chemical poten-
tial and composition of all species in all of the phases
respectively, throughout the sample
N local equilibrium: concentration gradients in (one of)
the phases, equal chemical potentials of all species at
the interface
N metastable equilibrium: one of the involved phases
cannot nucleate
N interfacial non-equilibrium: jumps in the chemical
potentials, equal compositions left and right of the
interface.
At about the same time, when this classification was
established, it was shown19 that there is a transition
between the idealised conditions of interfacial local
equilibrium and non-equilibrium, as the partition
coefficient during alloy solidification evolves from the
equilibrium value to unity.
For establishing this hierarchy qualitatively, no
explicit statement about the nature of the interface
concerning structure or width, etc., is contained. As
soon as a quantification of the transition from equal
potential to equal composition at the interface is
attempted, some assumptions need to be made about
the interface. For liquid/solid interfaces, the interface
thickness and the ‘interface diffusion coefficient’ were
introduced,19 requiring some insight into the role of the
interface during the phase transformation. However,
more detailed insight into moving interfaces was mainly
gained in the field of solid/solid phase transformations,
as different interface models with finite extension were
established20,21 to account for effects like solute drag,
rearrangement of the lattice, etc.
Before the emerging of phase field models, liquid/solid
phase transformations have successfully been modelled
with a mathematically sharp interface. Without ques-
tioning the advantages of a diffuse interface, it can be
stated that solid/liquid interfaces are not prone to be
affected by segregation of impurities or by elastic
strains, so that complex interfaces need not be intro-
duced. It is generally accepted that the sharp interface
model can yield realistic results.
A classical phase transformation model will solve a set
of heat and/or mass transport equations in all of the
phases and connect the phases by assumptions or
separate models about the thermodynamic state of the
interface. The simplest yet widely applicable set of
conditions at the interface would be local thermody-
namic equilibrium. This implies that in a binary alloy,
the interface compositions will be given by the equili-
brium phase diagram, or, in a more general definition,
that chemical potential of all species is equal at the
interface in the adjacent phases.
In the fundamental work of Baker and Cahn,22 the
basic principles of non-equilibrium (interfacial) thermo-
dynamics are expounded with special emphasis on
solidification. General formulations of irreversible ther-
modynamics23,24 are discussed and considered. It is
shown under what conditions local equilibrium is lost
and the interface compositions will not be those defined
by the equilibrium phase diagram any more. The
interface compositions decide on the driving force that
International Materials Reviews 2009 VOL 54 NO 1 3
Rettenmayr Melting and remelting phenomena
2 Tangent-to-tangent construction in a molar Gibbs free
energy diagram for determining the energy change (dissi-
pation) DG upon a solid/liquid phase trans-formation;22 the
possible composition range DXa for solidifying a-phase
during a liquid/solid phase transformation starting from a
composition XL is also shown
is dissipated at the interface by either interface migration
or other processes occurring at the interface.
Baker and Cahn22 show how the change (dissipation)
DG in Gibbs energy is determined graphically by a
tangent-to-tangent construction, if an infinitesimally
thin layer with composition Xi out of a solid with
composition Xa is transferred to the liquid with
composition XL (Fig. 2). Note that the composition of
the transferred layer Xi is not necessarily that of one of
the involved phases.
By the intersection points of the tangent to the liquid
phase with the Gibbs energy curve of the a-phase, also a
range DXa of thermodynamically possible compositions
of the a-phase is specified that can solidify from a
supersaturated liquid with composition XL (Fig. 2). A
unique solution for Xa is not defined. As from
thermodynamic principles, compositions can be
excluded, but not positively and precisely defined, the
term ‘science of the impossible’ was coined.
In the formulation of the Gibbs energy dissipation
upon solidification, it is assumed that at the same time as
a layer of liquid transforms into a, it has changed its
composition from XL to Xa, a change that is made
possible by diffusion inside the liquid phase, implying
that there is no diffusion inside the a-phase. This latter
statement means that either diffusion in a is infinitely
slow or a precipitates with constant composition in a
steady-state. It also means that the composition of the
interface layer is not the generalised Xi (Fig. 2) any
more, but the composition Xa of the solidifying phase.
The transfer of atoms through the migrating interface
occurs by movement of a combination of A and B atoms
with the new composition, Xa, from a liquid reservoir
into the a-phase under a change of their chemical
potentials mA and mB respectively, yielding a total
decrease in Gibbs energy DG of



DG~ð1{X a Þ mLA {maA zX a mLB {maB (1)
Equation (1) shows that the phase transformation can
occur and DG will decrease even if the chemical potential
of one of the components is increasing. In fact, for rapid
4 International Materials Reviews 2009 VOL 54 NO 1
solidification, the chemical potential of the solute B will
always increase (for an equilibrium partition coefficient
keq,1), an effect that is overcompensated by a decrease
of the chemical potential of the matrix element A.
Still for the case of steady-state solidification,
equation (1) can be reformulated as20




DG~ 1{X L mLA {maA zX L mLB {maB



z X L {X a mLA {maA {mLB zmaB (2)
In this form, according to the sharp interface model, the
first two terms can be interpreted as the driving force for
the migration of the interface DGm. DGm can be used to
overcome various kinds of resistance to the migration of
the interface, e.g. pressure due to interfacial energy and
friction. The last term in equation (2) may be regarded
as the change of Gibbs energy DGt due to an adjustment
of the composition from XL to Xa by exchange of A and
B atoms between the two phases by diffusion across the
interface. This process is generally called trans-interface
diffusion. Thus, the total driving force for the phase
transformation is subdivided into




DG m ~ 1{X L mLA {maA zX L mLB {maB (3)



DG t ~ X L {X a mLA {maA {mLB zmaB (4)
In the sharp interface model, it is usually assumed that
the interface migration and the trans-interface diffusion
are two independent physical processes. Following this
assumption, it is straightforward that each of the
processes can only occur if the driving force is positive.20
This limits the range DXa of possible compositions that
can precipitate from the liquid.25
However, the simplification that the interface compo-
sition Xi is that of one of the adjacent phases is
acceptable for solidification, but not for melting.25 The
reason is that not only in the parent phase (solid), but
also in the product (liquid) phase, concentration
gradients can lead to diffusion toward the interface
and modify the interface composition. Accepting the
assumption of independent trans-interface diffusion and
migration and re-introducing an interface composition
Xi that is different from that in the adjacent phases,
equation (2) becomes for melting



DG~ð1{X a Þ maA {mLA zX a maB {mLB



z X a {X i maA {mLA {maB zmLB (5)
The first two terms in equation (5) are again the driving
force for migration DGm, the last term is the trans-
interface diffusion DGt.
Similar to the construction in Fig. 2, DGm and DGt
can be represented graphically25 (Fig. 3). Even though
the Gibbs energy dissipation during both thermal and
solutal melting is given by equation (5), the different
compositions that lead to the melting processes require a
specific graphical construction for the two cases. The
total driving force DG is again defined by a tangent-to-
tangent construction at composition Xi. DG is the sum of
the two parts DGm and DGt. For thermal melting, the
composition Xi will always be in between the composi-
tions of the adjacent phases (Fig. 3a). For solutal
melting, there are more degrees of freedom. In the case
of melting of a solute depleted solid in contact with a
solute enriched liquid, Xi can be lower than the solid

3 Tangent constructions for a thermal melting and b solutal melting of a solute depleted solid in contact with a solute
enriched liquid25
composition Xa (Fig. 3b). Note that there are concen-
tration gradients in both of the phases, implying that
diffusion in the two phases in the vicinity of the interface
will yield a change from Xi to XL as one layer of solid
with Xa melts.
Solute rejection and solute absorption
In alloys, solute partitioning yields different conditions
for solidification and melting.
For alloys with melting point depression (keq,1),
there is an excess of solute at the interface during
solidification. Solute is rejected into the parent phase
(liquid) by the product phase (solid). The highest solute
content in both the liquid and the solid is at the
interface. Any amount of solute that the product phase
rejects can be accommodated in the liquid and is then to
be transported away from the interface for the process to
continue (or the temperature needs to be lowered so that
the concentration of the solute enriched liquid reaches
the liquidus line again).
During melting, on the other hand, there is solute
depletion at the interface. Solute needs to be transported
towards the interface for the process to continue. The
lowest solute content is at the interface only for thermal
melting from a superheated solid, for solutal melting,
there are more degrees of freedom. If solidification and
melting were symmetric, during melting solute should be
ejected from the parent phase (solid) in any amount that
the product phase (liquid) requires. This is obviously not
the case: the amount of solute that can be released from
the solid at the interface is certainly limited, as it needs
to be transported to the interface by solid diffusion.
Structural aspects
The qualitatively different crystallographic structure
between liquid and solid, i.e. short range order v. long
range order, entails further aspects of asymmetry. While
it can be assumed that an atom that is released from the
solid during melting can be accommodated in the liquid
at any location along the interface, there are unfavour-
able locations on the solid for an atom that arrives from
the liquid. This aspect of asymmetry has been worked
out in detail by Chalmers.26 As a result, the entropy of
fusion has been identified as an important characteristic
Rettenmayr Melting and remelting phenomena
entity governing the growth of a crystal during
solidification. The similar solidification morphology of
the majority of metal alloys is attributed to the similar
entropy of fusion (DSf/R<1, with the gas constant R).27
The asymmetry effects of atomic accommodation are
enhanced for solidification of complex crystal structures,
e.g. non-cubic structures or molecule structures. The
non-dimensionalised entropy of fusion for such struc-
tures is larger than unity, and the tendency for faceted
crystal growth will increase with increasing entropy of
fusion.27 Faceted growth requires additional under-
cooling. This is a well known and experimentally shown
fact and has also been shown by molecular dynamics
simulations (for a recent example, see Ref. 28). On an
atomically smooth faceted interface, the fraction of sites
that are unfavourable for solidification is substantially
higher than on a rough interface. Atoms that are melting
will on the other hand always see a rough interface and
will still be accommodated in the melt easily.
Semiconductors are known to solidify both with faceted
and rough interface, depending on the growth condi-
tions, as documented in recent studies.29,30 The same can
be true for some intermetallic phases, as shown for the
intermetallic eutectic phase solidifying in Al–Fe–Si.31
It is straightforward that the dynamics of the melt
structure will be different from that in the solid, leading to
further aspects of asymmetry. The low range order in the
melt (the nearest neighbour distance, coordination num-
ber) is a function of temperature32 and can be permanently
changed by a pronounced superheating. Additionally,
ordering in the melt in the vicinity of the solid is an effect
that has been studied experimentally and theoretically.33
All of the mentioned effects cannot be characteristic for
solids. Thus, solidification and especially nucleation of a
solid will be affected by the structural effects in the parent
phase (liquid). As the parent phase for melting does not
show such structural changes and effects, the melting
process cannot be dependent on them.
Link between thermodynamics and kinetics
It is well known that in most metal alloys, mass
transport by diffusion in the melt is faster by 3–4 orders
of magnitude than in the solid. It is one of the basic
aspects of asymmetry between solidification and melting
International Materials Reviews 2009 VOL 54 NO 1 5
Rettenmayr Melting and remelting phenomena

that the melt with the faster mass transport (that can be
further accelerated by buoyancy) is the parent phase for
solidification, but the product phase for melting. For
solidification, the slow diffusion in the product phase
(solid) yields that equation (1) (that is actually derived
neglecting the flux Ja in the solid) is still a good
approximation for the Gibbs energy change at the
interface, even if concentration gradients in the solid are
present; the interfacial compositions and the interface
velocity are hardly influenced by processes in the solid.
On the other hand, in the case of melting, slow diffusion
in the parent phase (solid) will move the interface
composition of the product phase (liquid) towards or
into the two-phase field.25 This can change the
concentration gradient in the liquid (that governs the
melting process) and thus influence the interface velocity
drastically.
The kinetics of a phase transformation process is
linked via equaiton (5) with the thermodynamics.
The term Xa2Xi in equation (5) can be defined
considering the mass balance as25
X a {X L
X a {X i ~ (6)
1{J L =J a
where JL and Ja are the fluxes of B in the liquid and a-
phase respectively. If the diffusion in the parent phase a
is negligible, the trans-interface term DGt becomes zero,
there will be no adjustment of composition by trans-
interface diffusion.25 For melting, (almost) all of the
available driving force can be spent for the migration
of the interface; for solidification, a part of the
available driving force is dissipated by trans-interface
diffusion.
By equation (6), thermodynamics and kinetics are
coupled, the thermodynamic state of the interface is no
longer ‘science of the impossible’, but fully defined.
Considering the thermodynamic constructions in
Fig. 3, schematic representations of concentration pro-
4 Schematic composition profiles for thermal and solutal
files in the liquid and solid phase for both thermal and
solid/liquid phase transformations: a thermal solidifica-
solutal liquid/solid phase transformations can be pro-
tion, b thermal melting (situation corresponding to
vided (Fig. 4). In all parts of Fig. 4, there is the solid
Fig. 3a) and c solutal melting (dissolution of solute
phase on the left, the liquid phase on the right, the
depleted solid in a solute enriched melt, corresponding
interface is moving in the direction of the arrow, i.e.
to the initial conditions as shown in Fig. 3b
solidifies towards the right and melts towards the left.
For solidification, both thermally and solutally con-
trolled (rapid) processes yield interface compositions may enter the two-phase field in the phase diagram an
inside the two-phase field in the phase diagram, i.e. Xa thus be lower than XeL. In this case, the composition of
above the solidus composition Xea and XL below the the solid will be in the one-phase field in the phase
liquidus composition XeL, this latter condition implying diagram below Xea.
that the driving force must be some undercooling of the
liquid (Fig. 4a). Nucleation and related phenomena and
For melting, there are more degrees of freedom. pre-melting
Supersaturation (superheat) of the solid will be the
driving force for thermal melting (Fig. 4b, correspond- It has long been known that solids even in the form of
ing to Fig. 3a). Generally, thermal melting will occur high purity, low defect single crystals exhibit little kinetic
with increasing temperature and thus decreasing inter- inhibition for melting. This is believed to result form the
face compositions. Solutal melting can either occur absence of a nucleation barrier. Not only is superheating
during directional melting in a steady-state with uniform avoided by the easy nucleation of liquid, but the melting
concentration in the melt (not shown in Fig. 4), or if temperature at the surface is even somewhat depressed.
solute enriched liquid is in contact with a solid that is This effect is referred to as pre-melting.
saturated with solute or solute depleted (initial situation A heuristic explanation for pre-melting states that
as in Fig. 3b). However, the solute enriched liquid will atoms at the surface of a solid crystal have a lower
be diluted at the interface by the dissolving solid, leading coordination number and are thus thermally less stable
to a concentration profile as shown in Fig. 4c.25 For than bulk atoms. Thus, the surface of a crystal can
solutal melting, the interface composition in the liquid transform to a (thin) liquid layer already below the

6 International Materials Reviews 2009 VOL 54 NO 1


equilibrium melting temperature Tm. Besides this
‘mechanistic’ view, the unstable surface is sometimes
explained in textbooks34 by a balance of interfacial
energies: the sum of solid/liquid and liquid/vapour
energies is supposed to be smaller than the solid/vapour
surface energy, also entailing the formation of a liquid
layer at temperatures slightly below Tm. It is worth
noting that not all materials feature a combination of
interfacial energies that lead to pre-melting.35
The origin of the idea that a solid may have a liquid
layer on its surface stems from observations of
Faraday36 on ice as early as 1859. Further experimental
evidence was provided when preparation techniques
were available to generate well defined surfaces of high
purity crystals and when measurement techniques were
available to detect the ultra-thin liquid layers at the
onset of melting. Direct evidence of surface melting on
metals is documented for Pb37 and for Al.38 A summary
of further experimental findings can be found in Ref. 39.
It is worth noting that surface melting is crystal face
dependent and thus not observed for all crystal surface
orientations. It appears that close packed {111}-surfaces
of fcc metals do not pre-melt. Less densely packed
{110}-surfaces show complete surface melting,5 whereas
intermediate packing densities lead to incomplete sur-
face melting.
From the theoretical side, it is nowadays assumed that
specific modes of vibrations, fluctuations and changes of
electronic structures at a free surface are connected with
an excess free energy that leads to pre-melting.40 It is
generally accepted that various processes occur at a
crystal surface as it is approaching its melting tempera-
ture from far below. At low temperatures, there is no
surface liquid layer. As temperature increases, above a
critical temperature, a disordered surface region forms
on the crystal with properties in between those of solid
and liquid. Before melting, the surface region grows in
thickness until pre-roughening, roughening and wetting
are initiated. Wetting is an early stage of surface melting
and equivalent to the wetting as described by the energy
balance above.
The thickness of the liquid surface layer increases
significantly as Tm is approached. Close to Tm some 20
atomic layers have been detected to be liquid. At Tm the
thickness of the liquid layer diverges. For the ‘equili-
brium thickness’ of the liquid layer, a power law
temperature dependence has been deduced.41
For a surface strained in a direction parallel to the
surface, there is an additional free energy contribution
to the surface energy that modifies the formation of a
liquid surface layer at temperatures near Tm.42 The
surface strain enhances the free energy of the solid, but
leaves the liquid unaffected, thus favouring melting
independently of the nature and direction of the strain.
However, the onset temperature for surface melting is
also influenced by the strain, and under certain
conditions, increased up to Tm. In this case, incomplete
surface melting may be observed or surface melting may
be entirely suppressed for a material where a strain free
surface exhibits complete surface melting.
A practically important question is to what degree
pre-melting and nucleation of liquid at an internal
surface or interface are comparable to a free surface.
Pre-melting at grain boundaries has been observed in Al
4 K below Tm.43 However, in in situ observation of
Rettenmayr Melting and remelting phenomena
melting of Al in the transmission electron microscope on
a hot stage,44 no evidence was found for pre-melting
below Tm. It should be noted that in this and other
work, superheating near a grain boundary was not
observed.
Various models of pre-melting at grain boundaries45
have been proposed. Computer simulations by molecu-
lar dynamics,46,47 Monte-Carlo48,49 and phase field50
methods suggest grain boundary melting below the
melting point. In highly symmetric tilt boundaries, some
superheating of a grain boundary could be achieved in a
simulation.51 It is pertinent to note that computer
simulations dealing with grain boundaries only give
hints on the behaviour of real grain boundaries, as
segregated impurities will change their properties
drastically. Owing to the common melting point
depression upon alloying, it is highly probable that
pre-melting is more pronounced in real crystals (see the
HRTEM and Auger spectroscopy studies in Ref. 52).
Pre-melting can also occur at line defects (disloca-
tions).53–55 Detailed observations of melting behaviour
within bulk colloidal crystals56 illustrate that there is a
‘hierarchy’ of defects as far as the nucleation of liquid is
concerned. With increasing temperature, pre-melting
starts at grain boundaries, then affects dislocations and
finally partial dislocations. In molecular dynamics
simulations, the role of different defects on melting57,58
has also been found, even though the occurrence of pre-
melting has not been confirmed.59,60
From the experiments and the corresponding theore-
tical interpretation on pre-melting, it can be concluded:
N pre-melting occurs on loosely packed surfaces,
arbitrary surfaces do not necessarily form a liquid
layer below the melting temperature
N in experiments that are not especially designed for
studying pre-melting, melting starts close to or at the
melting temperature; the liquid layer on a surface is
not relevant for practical purposes
N surface or interfacial strains can influence local
remelting processes (TGZM, LFM, see below); it
remains unquantified to what degree this influence is
significant
N easy nucleation of a liquid layer is not restricted to
free surfaces, internal two-dimensional defects like
grain boundaries or interfaces can act similarly.
Thermal melting
Slow heating of pure substances and alloys
Literature describing melting due to (slow) heating is
scarce. In the few instances, melting is treated symme-
trically to solidification, which may be justified for the
majority of cases. Since melting is controlled by the
kinetics in the liquid, convection may play an important
role. Hence, due to the difficulties in quantifying the
effects of convection precisely, it is difficult to draw
conclusions on details of the thermodynamic state of the
interface. Purely diffusion controlled melting experi-
ments conducted under microgravity conditions with
pure transparent materials yield close agreement with
conventional phase transformation theory. The melting
processes occurs for flat interfaces at Tm, the melting
kinetics is governed by the heat flow in the liquid
phase.61 For curved interfaces, the melting temperature
needs to be corrected for the melting point depression
International Materials Reviews 2009 VOL 54 NO 1 7
Rettenmayr Melting and remelting phenomena
5 Concentration profiles in a sample after homogenisa-
tion in the two-phase region and after subsequent heat-
ing (left) and corresponding phase diagram (right): the
solid at the higher temperature is superheated
(hatched) at all locations64
due to the Gibbs–Thomson effect.62 Melting of the
strongly anisotropic pivalic acid shows a peculiarity: a
locally enhanced melting rate is due to steep gradients in
the mean curvature, a thermo-capillary heat flux in the
solid phase is induced.63
In alloys, the situation during slow heating is more
complex, since it is hard to characterise to what degree
superheating in the solid can be achieved in a practical
case. Raising the temperature in a semi-solid alloy with
uniform concentration in both the liquid and solid phase
will inevitably lead to a constitutionally superheated
solid (Fig. 5). Such types of profiles have been predicted
in Refs. 1 and 3. Note that if there is uniform
composition in the liquid due to the faster diffusion,
the solid fraction is larger than the equilibrium solid
fraction predicted by the lever rule, while during
solidification, the lever rule predicts the maximum
possible solid fraction. It will be discussed below that
more mechanisms than just diffusion are available to
reduce superheat in the solid, especially if other
interfaces are in the vicinity of the considered interface.
The difficulty of achieving a superheated solid experi-
mentally is presented in the section on ‘Theory on
melting and superheating of pure solids’.
Rapid heating of alloys
A few experiments are documented in the literature
where it is attempted to superheat a solid alloy by rapid
heating.
Bulk samples of Sb–Bi alloys were heated with heating
rates up to 30 000 K s21 by an electrical current.65,66 A
plateau in the heating curve is found above the solidus
temperature, but below the T0 temperature. The T0
temperature is defined as the temperature at which solid
and liquid phase possess the same Gibbs free energy,
allowing for a partitionless phase transformation. The
estimated melting front velocity from a grain boundary to
the centre is given as 2–7 mm s21 for superheatings of 40–
60 K. The sample temperature is measured with a thermo-
couple: averaging effects of the thermocouple are not
discussed. The author shows that there can be repreciptia-
tion of solid phase with equilibrium composition, i.e. a
melting/resolidification mechanism that assists the process
of reducing supersaturation: a liquid film migrates from
the grain boundary through the supersaturated grain;
behind the film the equilibrium concentration resolidifies
to form a non-supersaturated crystal.
Heating experiments using small Sn–Bi particles with
5–20 mm diameter with heating rates between 0?1 and
8 International Materials Reviews 2009 VOL 54 NO 1
50 K s21 (Ref. 67) demonstrate that melting can occur
partitionless at the T0 temperature. One of the peculia-
rities of the chosen alloy system is that the solid
diffusion of Bi in Sn close to the melting temperature
is two orders of magnitudes slower than that of the
majority of metal alloys. Also, due to the small size of
the powder particles, less defects are to be expected in
the particles than in a bulk sample. An endothermal
signal is detected near the T0 temperature for various
heating rates. A deflection of the heating curve close to
the T0 temperature is found at heating rates as low as
0?1 K s21. It is concluded that the solid is super-heated
until partitionless melting occurs at T0.
Rapid heating of Nb–Ti wires (1?3 mm diameter) has
been performed with heating rates between 100 and
10 000 K s21.68 Before collapsing, the Nb–Ti wires reach
liquid fractions of 0?4–0?9. The temperature is determined
by simultaneous measurement of the radiance temperature
and the normal spectral emissivity. The authors propose a
model with diffusion control and local equilibrium at the
interface. By this model, the heating curves of material
with different grain sizes are well reproduced. Maximum
melting front rates are estimated to 2 mm s21.
In conclusion of the rapid heating experiments of
alloys, it can be stated that melt nucleation in alloys will
occur independently of the heating rate close to the
solidus temperature at the free surface and internal
interfaces. With rapid heating, a finite amount of
superheating can be achieved: direct measurement of
the superheating appears to be problematic, and the
documented values are rather estimates than precise
values. Different bulk melting temperatures with respect
to solidus T0 and liquids temperature have been found.
Thus, there is different melting kinetics depending on the
alloy system. The dependency on the alloy system
appears to be more prominent for melting than for
solidification. Reasons for the different behaviour of
different alloy systems include
(i) the defect structure of the solid crystals
(ii) the structure of the solid/liquid interface
(iii) the viscosity of the melt
(iv) the kinetics in the solid.
Theory on melting and superheating of pure
solids
In addition to the different nucleation behaviour of
liquid as compared to a crystalline solid, further criteria
have been introduced in the literature that add further
aspects of asymmetry between solidification and melting
regarding the migration of the interface.
The most quoted early concept of a melting mechan-
ism that is different from the classical nucleation/growth
mechanism of solidification is that of Lindemann,69,
even though the idea has been introduced in the
literature earlier.70 It is supposed that at the melting
point a surface instability of the oscillating atoms
occurs, i.e. that the atoms acquire enough energy and
free volume ‘to slip past one another’ (the root mean
square displacement of the atoms reaches a critical
fraction of the interatomic distance), or the crystal
’shakes itself to pieces’. The Lindemann criterion has
been further elaborated in the following decades5 and is
still occasionally used. However, thermodynamically the
Lindemann criterion is incomplete, since the free energy
of the liquid is not taken into account.

In 1939, Born71 introduced his concept of the
‘rigidity catastrophe’, a shear instability introduced
through the elastic constants that also shows that the
temperature range for which the crystal can be stable is
limited. The melting point is thus defined as the
temperature at which the rigidity of a crystal becomes
zero. Similar to the Lindemann criterion, the Born
criterion is a one-phase theory. It was also challenged
by observations of elastic moduli that failed to vanish
at Tm.72–75
Frank76 introduced in 1939 more of a thermodynamic
approach by comparing melting with a solid state order/
disorder transition. He postulates critical temperatures
above (and below) Tm that limit the range of existence of
the superheated (or undercooled) state. These tempera-
tures are not symmetric to Tm, which is assumed to
explain that superheating is more difficult to attain than
undercooling.
The concept of upper limits for the stability of a
superheated solid has subsequently be extended. The
hierarchy of stability limits includes the isochoric
(temperature at which liquid and superheated solid have
the same volume),77 the isenthalpic (equal enthalpy)78
and eventually the isentropic (equal entropy) condi-
tions.78 Subsequently it has been postulated, that before
(i.e. at temperatures below) one of the above mentioned
instabilities would occur, thermally activated nucleation
of liquid inside the superheated crystal occurs.79
The role of vacancies for the lattice instability is
discussed in different contexts. Gorecki80 systematically
studied the possible role of vacancies for melting. He
showed that in metals the equilibrium concentration of
vacancies at the melting point reaches a value of 0?37%
at the onset of melting, independently of the crystal
structure (fcc, bcc and hcp) of the metal. In a subsequent
paper,81 further correlations of the property changes due
to vacancies and the melting temperature are pointed
out. These correlations include latent heat of melting,
volume change upon melting and the change of electrical
resistivity.
An extension of the view of melting as being vacancy
induced is presented in Ref. 82. The authors study the
role of vacancy diffusion rather than vacancy concen-
tration. They find that close to Tm a vacancy migrate to
such an extent that it interacts with several lattice
positions at the same time (‘is decomposed by neigh-
bouring atoms’), leading to lattice disordering. Recently,
it has been shown82 that at the equilibrium melting
temperature, the vacancy concentration close to a free
surface is approximately three times higher than in the
bulk. This phenomenon is interpreted as a hint for the
role of vacancies for pre-melting.
Molecular dynamics simulations suggest that both
heterogeneous and homogeneous melting processes are
mediated by atoms with defective coordination. Their
concentration in the crystalline regions close to the
surface at the equilibrium melting point was found to be
approximately the same as in the bulk system at the limit
of superheating.84,85
Further defect controlled melting mechanisms are
discussed in Ref. 5. In a context of studying liquid/solid
phase transformations in ‘real crystals’, results on
melting close to the theoretical limit of superheating
are not applicable. Work on the number of atoms in a
liquid nucleus is thus not discussed here.
Rettenmayr Melting and remelting phenomena
Experiments on superheating
Whether superheating of crystals, particularly metal
crystals, can be achieved experimentally has been
questioned for many decades. In fact, still in the 1960s,
authors state that ‘superheating of bulk solid metals
above their melting point is not observed’.86
However, already in the 1930s, it was concluded from
observations of Ga irradiated with a light source that
superheating of solid Ga by 0?1 K is possible.87 Later
on, several pure substances that form viscous melts
(different modifications of SiO2,88 P2O5,89 Na2O.SiO2,90
Na2S2O5.5H2O,91 As2O392) were reported to be observed
in a superheated state.
Superheating of ice has been described in Ref. 93. It is
shown that superheating of ice of up to 0?4 K is possible
by dielectric heating: the ice is used as the dielectric in a
capacitor, liquid water nucleates at different locations
(‘Tyndall figures’) in the bulk of the solid ice. The
superheating is on the one hand directly measured by a
thermocouple; on the other hand, it also becomes evident
indirectly through the ongoing growth of the liquid nuclei
after the external heating is stopped. Further evidence
and quantification of Tyndall figures caused by light
radiation into the bulk is documented in Ref. 94. The
growth of the liquid regions follows conventional growth
kinetics and thermodynamics, i.e. it can be described with
the aid of transport of latent heat, interfacial tension, and
the anisotropic interfacial kinetics of ice.
Superheatings and melting rates have also been
quantified carefully in Ga single crystals.95 The melting
kinetics of thin Ga rods in a capillary (0?5 mm diameter)
was studied as a function of the crystallographic
orientation. Superheatings of 0?1 K were measured
through the change of electrical resistivity. A quantita-
tive relationship between melting rate and superheating
is given. It is distinguished between dislocation-free and
dislocation-assisted conditions.
An important step in the achievement of higher super-
heatings over an extended period of time is described in
Ref. 96, following an idea of Turnbull97 to coat the
surface of a crystal in order to prevent contact of solid
with vapour. Ag spheres of 120–160 mm diameter were
produced and coated with Au of 11 mm thickness by
electrodeposition. The Ag spheres were heated to 25 K
above Tm for 1 min. Some of the Ag spheres had melted
at Tm, which can be easily identified by the Au from the
coating that is dissolved in the Ag. Other spheres
remained solid, as shown by the diffusional Au profile in
the Ag in the vicinity of the Au layer.
Subsequently, substantial superheatings have been
achieved with smaller and smaller particles down to the
size in the nanometre range. For free particles, a size
dependent melting point depression is expected and also
found experimentally in numerous cases. Embedded
particles can exhibit superheating, an effect that can be
more pronounced for non-spherical particles than for
spherical ones. The crucial role of interfaces and strains
in superheating experiments of nanoparticles has been
demonstrated in Ref. 98 where freezing temperatures
above Tm have been observed upon resolidification of
melted particles. Ample literature is available in the field
of superheated nanoparticles. The interested reader is
referred to the review in Ref. 5.
For documentation of ultrafast heating by shock wave
loading (Fe, Mo, V, Ta, W) and intense laser irradiation
International Materials Reviews 2009 VOL 54 NO 1 9
Rettenmayr Melting and remelting phenomena
(Al, Pb) with superheatings up to the order of 0?5Tm, see
Ref. 99.
Solutal melting
Constitutional superheating during directional
melting experiments
Constitutional undercooling and the stability of a planar
solidifying solid/liquid interface were a prominent
research topic since the 1950s. Later on, a series of
papers was published attempting to transfer the progress
in this field both theoretically and experimentally to
melting. Experiments on melting thin layers of K–Na
alloys100 showed that melting starts at grain boundaries
(presumably due to impurities) and that there are
independent melt nuclei ahead of the melting front,
suggesting that a superheated region in the solid should
exist.
Stability analysis similar to the Mullins-Sekerka
analysis for solidification is developed in Ref. 101. It
predicts a constitutional superheating criterion for
melting, similar to the constitutional undercooling
criterion for solidification. The comparison with the
experiment is not fully meaningful, as the theory is
applicable to steady state, but the experiments with the
K–Na alloy are with transient melting.
Directional melting experiments are documented for
Sn–Sb alloys in Ref. 102 and for Sn–Bi alloys in
Ref. 103. The microstructures are carefully analysed
‘post-mortem’ after quenching and compared with EDX
measurements. The authors conclude on constitutional
supercooling ahead of the melting interface of up to
3?3 K over a length of up to 0?3 mm for the Sn–Sb alloy.
It is stated that it is impossible to attain temperature
gradients experimentally that render the melting front
stable (in the order of 104 K mm21 for melting rates of
0?2 mm s21), and the breakdown of the front as well as
melt nuclei ahead of the front are observed for the faster
melting rates and lower temperature gradients. For the
Sn–Bi alloys, the superheating is not confirmed; over the
length of the solid that is predicted by theory to be
superheated, (former) liquid droplets that are assumed
to ‘relieve the superheating’ are found.
The stability analysis for melting is refined in
Ref. 104. The authors point out that constitutional
superheating predicts that a melting interface would be
less stable than a solidifying interface, but that stability
analysis predicts that it would be more stable. The
reason is that morphological instability is governed by
diffusion in the liquid for both solidification and
melting, but that constitutional superheating is governed
by solid diffusion for melting and liquid diffusion for
solidification. This is another point demonstrating the
asymmetry between solidification and melting.
Directional melting experiments with organic succi-
nonitrile–water alloys are presented in Ref. 105.
Diffusion control for melting and local equilibrium at
the interface is assumed, and consistency between
observed melting rates and a solution of the diffusion
equation is found. Composition distributions are not
assessed or discussed, but for some cases, the authors
assume a superheated solid. They suggest that their
experimental procedure can be used for determining the
liquid diffusion coefficient. Another series of experi-
ments on directional melting with a transparent alloy
10 International Materials Reviews 2009 VOL 54 NO 1
system (succinonitrile–acetone) is documented in
Ref. 64. The authors focus on the morphology of the
liquid regions. They observe nucleation first at grain
boundaries, spherical nuclei in the solid ahead of the
melting front and dendrite-like melting morphology.
Concluding the section on superheating of solid
alloys, the following can be stated.
Superheating a solid alloy is certainly more easily
possible than for a pure substance. It appears that
superheating is facilitated if the melt is viscous. Thus,
results obtained from organic alloys should not be
directly applied on metal alloys. The nucleation events
of liquid in the solid bulk ahead of the melting front64,100
show that the conditions for nucleation from a super-
heated solid are satisfied, but the amount of super-
heating or supersaturation can so far only be estimated.
The interpretation of the directional melting experi-
ments with Sn–Sb and Sn–Bi alloys102,103 suffers from
the low spatial resolution of the concentration measure-
ments and the only vaguely known position of the
interface at the time of the quench. As a consequence,
the interface composition is not measured, but con-
cluded on.
For quantifying superheating unambiguously, it
would be desirable to have precise information about
both local temperature and local composition in the
solid. Experiments with organic alloys provide readily
the necessary temperature information, with metal
alloys (post mortem) good composition information.
At present, information about the spatial distribution of
both temperature and composition in one and the same
system is not available.
Dissolution in a solute-rich melt
Dissolution of a solute depleted solid in a solute
enriched melt is prone to be governed by convection.
Hence, it is difficult to specify the experimental
conditions directly at the interface, and quantification
of experimental results is tedious.
In Ref. 106, melting experiments with transparent
systems and with Pb–Sn and Sn–Pb alloys are docu-
mented. Depending on the initial conditions of the
experiments, the authors observe convection and diffu-
sion controlled dissolution. Convection assisted melting
occurs with a rate that is approximately two orders of
magnitude faster than diffusion controlled melting.
Gradients or interfacial conditions are not quantified
in detail. Literature concerned with the effects of
thermosolutal convection on dissolution rates relevant
to oceanographic and geological contexts is quoted, e.g.
the melting of icebergs and reactions in magma
chambers.107,108 It is found that the mixing enthalpy
upon dissolution of a solid exerts a certain influence on
the melting rate and needs to be considered. Detailed
simulation calculations considering convection and
mixing enthalpy are carried out in Ref. 109. The
simulation results are compared with experiments on
melting of ice and dissolution of Si in Fe-rich melts.
Small solid particles (r<10 mm) of transparent
organic alloys that float in hot melt are observed in
Ref. 110. The melting process is assumed to occur in an
adiabatic environment, i.e. with solute or temperature
gradients around the melting particles. The melting
kinetics of the particles is assumed to be due to the
kinetics of solute or heat in the liquid phase. The authors
distinguish between alloys with high and low solubility

6 Melting front velocities of succinonitrile particles as a
function of temperature110
of the solvent. For alloys with high solubility, the onset
of thermally controlled melting is above the liquidus
temperature, but below the melting temperature of the
solvent. A sharp transition between lower solutally and
higher thermally controlled dissolution and melting
rates respectively, is found (Fig. 5), confirming theore-
tical results in Ref. 111.
In a series of papers,112–114 solutal melting is studied
systematically. A pure metal is brought into contact with
a solute rich binary alloy at a temperature where the
pure metal is still solid and the binary alloy is liquid with
a solute composition distinctly above the liquidus
composition. Thus, both parts of the sample were in
their one-phase field in the phase diagram respectively.
A high reliability of the experimentally determined front
velocity has been achieved despite the convection
control of melting.
In the dissolution experiments,112 a surprisingly low
composition at a formerly melting interface was mea-
sured. However, the reliability of the measurement of the
low composition is limited, as discussed in Ref. 115. In
Ref. 114, the possibility of an interface composition in the
liquid that is lower than the equilibrium composition, i.e.
inside the two-phase field in the phase diagram, is
introduced. Good agreement between experimental and
simulated shapes of the melting front is achieved (Fig. 7).
In Ref. 115, simulation calculations based on an extre-
mum principle confirm qualitatively the possibility of
interface compositions in the liquid inside the two-phase
field for the case of high interface mobilities. A high
mobility is certainly characteristic for liquid/solid inter-
faces. The quantitative disagreement about the time span
to reach local equilibrium in Refs. 114 and 115 may be
attributed to the fact that the case for an instantaneous
(short) disturbance of local equilibrium is treated in
Ref. 115, while the disturbance persists over a longer time
span in Ref. 114.
As a result of the solutal melting experiments112–114
and the subsequent discussion,116,117 the thermody-
namics of Baker and Cahn was further elaborated,
yielding the possibility for the quantification of the
interfacial compositions in the adjacent phases, as
described above and in Ref. 25. Quantification of the
interfacial compositions based on Ref. 25 has been
attempted for rapid solidification.118,119 In Ref. 119, the
same initial conditions as in Ref. 115 are treated and
similar results concerning the time span to re-adjust
Rettenmayr Melting and remelting phenomena
7 Former melting front of pure Al that was in contact
with Al–Mg, and simulated concentration distribution of
Mg in the melt and shape of the front114
local equilibrium after an instantaneous disturbance are
obtained.
First calculations based on the thermodynamics25 for
initial conditions leading to melting120 indicate that the
interface properties need to be different for solidification
and melting in order to find a consistent solution.
Calculations for steady-state directional melting121 yield
interface compositions that are influenced by friction, if
during melting, the same interface mobility is assumed
as for earlier solidification calculations. Molecular
dynamics and kinetic Monte-Carlo calculations, mostly
on solidification, confirm the existence of different
characteristics of interfaces.122 The dependence of
the interface mobility in pure Ni123 and pure Mg124 on
the growth direction also demonstrates the impact of the
interface on growth.
As a result of the solutal melting experiments and the
subsequent development, it can be stated:
N concentration gradients in the liquid must be con-
sidered when describing the kinetics of a melting
process
N structure and properties of a solid/liquid interface
appear to be different for solidification and melting
N under diffusion control, non-equilibrium interfaces
will approach equilibrium within microseconds,
under convection control non-equilibrium interfaces
may exist longer.
Melting and simultaneous solidification
Dendrite arm coarsening and dendrite
fragmentation
Dendrite arm coarsening is an effect that is driven by the
reduction of surface energy, involving a remelting/
resolidification mechanism. In the literature, coarsening
is generally described in terms of a change of secondary
dendrite arm spacing. For this, several morphological
changes have been proposed (Fig. 8). A secondary arm
can melt back radially,125 axially,126 melt off at its
root,126,127 or two secondary arms can coalesce.128 By
definition, a coarsening process does not involve any
change of the phase fractions. The melting of secondary
International Materials Reviews 2009 VOL 54 NO 1 11
Rettenmayr Melting and remelting phenomena
8 Coarsening mechanisms as proposed by
authors
arms in the context of coarsening must thus be
accompanied by simultaneous solidification at regions
with low curvature convex shape and/or concave
shape.
In real dendritic microstructures, all of the above
mentioned mechanisms have been observed, even
though the melting off at the roots126 is rarely seen
during steady state dendritic growth. It should be noted
that in the majority of cases, coarsening only occurs
once the secondary arms are overgrown by their
neighbours, or the growth is stopped by the neighbour-
ing dendrite(s). Once the large turnover of energy due to
solidification comes to an end, the weaker contributions
of interfacial energy become effective, and the over-
grown dendrite arms start melting back, generally at the
same time radially and axially.
Coarsening increases the diffusion distances during
solidification in the liquid and solid phases. This might
lead to a less homogeneous microstructure, since the
homogenising effect of back diffusion is reduced. On the
other hand, the remelting/resolidification mechanism of
coarsening leads to the opposite, homogenising effect,
since the compositions of the remelting/resolidifying
phase fractions are slightly different. Generally, the net
effect of coarsening is a homogenising one. There is also
an influence on the solidification path and potentially on
the type of secondary phases that crystallise toward the
end of solidification.129 Various work is concerned with
these aspects of coarsening in binary130 and multi-
component alloys.131,132
Both melting of secondary dendrite arms at the root
and mechanical breakdown have been discussed as cause
for dendrite fragmentation and thus for the columnar-
to-equiaxed transition in castings and for microstruc-
tural defects like freckles or stray crystals.
In early experiments on fragmentation, it has been
found that local remelting is the most likely cause for
fragmentation.133 The authors find evidence that
excludes mechanical shear forces as major cause: when
they start mechanical stirring in the liquid phase of their
transparent system, there is a delay between the onset of
stirring and the generation of dendrite fragments. In
further studies on transparent alloys,134,135 local melting
was confirmed as fragmentation mechanism. However,
later on, some work was published where at least in
certain melt, velocity ranges a correlation between melt
flow and fragmentation was found.136,137 Other authors
assume a stronger influence of melt flow and state that
grain refinement is not controlled by the breaking of
dendrites by shear forces alone.138 Fragmentation is
12 International Materials Reviews 2009 VOL 54 NO
observed in a transparent alloy under forced convection
conditions, with the conclusion that ‘shear forces cannot
be completely discounted’ in Ref. 139. In solidification
experiments from undercooled droplets in levita-
tion,140,141 different causes for fragmentation in Ni–Cu
alloys at low and high undercoolings are assumed: while
constitutional melting is effective at low undercoolings,
mechanical shearing is suggested to govern the frag-
mentation process at high undercoolings. Other authors
assert that only remelting can be the cause for dendrite
fragmentation.142
Melting at the dendrite root leading to fragmentation
different is prevalent if the solidification front velocity is
decelerated.133,142–144 While recalescence is assumed to
be responsible for the fragmentation in Ref. 133, no
evidence is found for thermal recalescence in Ref. 144. It
is thus concluded that an increase in solute composition
in the mushy zone causes the detachment of dendrite
arms.
Calculations considering fluid flow around a dendrite
revealed that under non-forced convective conditions,
fragmentation is unlikely to occur. This has been shown
in an analytical model145 and simulation calcula-
tions.14,146 Under rapid solidification conditions, the
forces of strong fluid flow on fine structures may be
sufficient for at least mechanical deformation of dendrite
arms.147 By mechanical deformation (bending), a
dendrite arm would reduce its cross-section toward the
flowing melt and thus avoid to be sheared off. Further
conditions for mechanical deformation have been
identified,148 and experimental evidence for bent den-
drites is given in Cu–Sn and Cu–O alloys. Subsequently,
it has been shown149 that misorientations in dendrites
due to bending are far from being a rare incidence.
In recent experiments in Al–Cu that were documented
with high resolution synchrotron radiation,150 fragmen-
tation could be observed in situ. It is shown how solute
flow into the mushy zone, solute advection and solute
rejection due to local growth lead to solute pile-up at the
roots of the secondary dendrite arms. This solute pile-up
alters the local compositional balance at the solid/liquid
interface at the root, causing the root to remelt, which in
turn results in further branch detachment.
In conclusion, it appears that melting phenomena are
the most prominent and most frequently observed cause
for dendrite fragmentation. However, being aware of
this, dendrite fragmentation is still hard to be quantified,
as several causes for melting can be named that might
occur on different time scales. All of these mechanisms
have been evidenced experimentally. Particularly, there
are
(i) capillary driven adjustment of local
radii14,133,151
(ii) solute rejection due to local solidification in the
vicinity of the dendrite arm roots150
(iii) flow of solute rich melt into the mushy zone150
(iv) flow of melt from hot regions toward the mushy
zone
(v) recalescence14,133
(vi) back diffusion in the solid dendrite in multi-
component alloys that changes the local solidus
temperature.9
Fully understanding and predicting the interplay of the
six mechanisms mentioned above will require sophisti-
cated simulation calculations.
1

9 Schematic diagram of the solute distribution in a den-
drite arm along the line AB during solidification in a
temperature gradient161
Temperature gradient zone melting
In the presence of steep temperature gradients, a
melting/resolidification mechanism can occur involving
either a liquid droplet migrating in the solid phase, or a
sequence of dendrite arms moving in the liquid phase, in
either case toward the hot zone of the sample. Not
considering thermotransport, the kinetics of TGZM is
controlled by diffusion in the liquid phase: solute atoms
diffuse in the liquid from colder regions with high
concentration toward regions with higher temperature at
lower concentrations. The consequence is a depletion of
solute atoms at the colder side (leading to local
solidification) and an enrichment at the warmer side
(leading to local remelting). As opposed to coarsening,
the process is not driven by the reduction of surface
area, but by solutal effects that are established due to the
adjustment of equilibrium concentrations at the inter-
face (Fig. 9).
TGZM was observed in arctic ice152 in 1926. For the
case of migration of dendrite arms TGZM was first
described by Pfann,153 for the case of the migration of
liquid droplets by Tiller.154
TGZM of dendrite arms leads to an asymetric (saw-
tooth like) concentration distribution in the dendrite
arms, as e.g. measured in unidirectionally cast copper
alloys,155 in investigations by different authors in
steels156–160 or in Al alloys.161 In organic alloys, it has
been reported that secondary dendrite arms migrate
along the primary stem towards the dendrite tip up to a
distance of four dendrite arm spacings.162
An equation is given for the migrating velocity of the
geometric centre of the dendrite arm vm as162
DGT
vm ~ (7)
mL X L (1{keq )
where D is the diffusion coefficient in the liquid, GT is
the temperature gradient and mL is the slope of the
Rettenmayr Melting and remelting phenomena
liquidus line. TGZM is not an important mechanism for
the coarsening of dendritic structures for technical
casting conditions,163 while it may be significant for a
combination of a high temperature gradient and a low
solidification velocity.
Besides the effects on dendrite arms and liquid
droplets, TGZM can contribute to the formation of
macroscopic concentration gradients in a mushy zone in
a (steep) temperature gradient. This mechanism is first
discussed in Ref. 164. The transport of solute atoms
out of the mushy zone in the liquid is described in
Ref. 165.
Direct observation of TGZM by synchrotron radia-
tion is reported for Al–Ni166 and for Sn–Bi.167 Samples
are partially melted in a (steep) temperature gradient,
and resolidification of the mushy zone to form solid
phase with a macroscopic concentration gradient is
tracked. In some cases, detachment of secondary
dendrite arms is observed.167 The evolution of the
macroscopic concentration gradient is characterised for
the purpose of defining good initial conditions for
subsequent directional solidification.168 It is shown that
the boundary condition at the outer boundary of the
mushy zone toward the liquid is dependent on convec-
tion in the melt. The evolution inside the mushy zone
yields similar concentration profiles for experiments on
earth and in space. After similar melting experiments in
a temperature gradient,169 post-mortem analysis of the
concentration distribution and estimation of the rate of
the kinetic processes, the amount of solute that diffuses
out of the mushy zone lead to the conclusion that
TGZM and liquid diffusion cannot be the only physical
processes that lead to the macroscopic gradients.
Liquid film migration
The movement of a thin liquid zone in a mostly solid
structure is being referred to as LFM. It is generally
accepted that grain boundaries are favourable sites for
the nucleation of liquid. Considering that melting starts
by the formation of a liquid layer between the grains, it
is expected that at the interface in both the liquid and the
solid phase the equilibrium compositions as given by the
phase diagram are found (Fig. 10). If the local geometry
is perfectly symmetric, the liquid layer should be
stationary at constant temperature. If the symmetry is
broken, it starts to migrate. Reasons for the broken
symmetry might be fluctuations, concentration differ-
ences across the liquid layer, coherency strains or
anisotropic interfacial energy.
It is generally taken as evidence for LFM if a grain
boundary is growing against the curvature pressure, or if
there are regions positive and negative curvature along
one and the same grain boundary (Fig. 11). Triple
junctions are occasionally mentioned as a cause of
curved grain boundaries, as the triple junctions are
assumed to be less mobile than the ordinary straight or
slightly curved boundary. This is not in accordance with
grain growth theory where it is assumed that grain
growth is controlled by triple junctions at low tempera-
ture only.
It is worth noting that the liquid film is highly mobile,
as enthalpic effects are not involved in the process: the
latent heat needed for melting the solid at one side of the
film is provided by solidification at the other side.
Different mechanisms are discussed in the literature
that lead to a migration of the liquid film. Initially,
International Materials Reviews 2009 VOL 54 NO 1 13
Rettenmayr Melting and remelting phenomena
10 Concentration distribution at a liquid layer between two grains moving to the right, suggested with coherency strains
as driving force171 (left), suggested with supersaturation as driving force180 (right)
coherency strains in the solid phase on one side of the
film were assumed to be the driving force for LFM.
However, an estimation170 leads to the conclusion that
solely the reduction of coherency strains is not sufficient
to drive the liquid layer. It is pointed out that coherency
strains can only be responsible for the film migration at
the initial state, and that the anisotropy of interfacial
energy can be symmetry breaking.171
Impurities appear to influence the migration rate
significantly.172 An Inhomogeneous distribution of Fe
impurities in Al–Cu–Mg alloys is assumed to be the
cause for a reduction of the migration rate and for
the detachment of liquid droplets that remain behind the
liquid film. The authors in Ref. 172 speculate about
effects of Fe on the coherency strain. Recent analytical
models for LFM173,174 also assume coherency strains as
driving force and include the anisotropy of the inter-
facial energy.
11 Resolidified microstructure in Al–Cu with curved grain
boundary after LFM (right arrow) and former position of
grain boundary (diffuse ‘ghost boundary’, left arrow)
14 International Materials Reviews 2009 VOL 54 NO 1
In several works, it is assumed that different
coherency strains in two adjacent grains are due to
composition differences across the grain boundary. The
higher solute content in the dissolving grain entails a
higher coherency strain that is reduced by the liquid film
and reprecipitation in the growing grain with a different
composition. Similar effects as LFM are diffusion
induced grain boundary migration (DIGM),175 chemi-
cally induced grain boundary migration (CIGM)176 or
discontinuous precipitation.177 It is assumed that they
are similarly based on different coherency strains in the
adjacent grains due to a varying composition.
It is, however, likely that chemical driving forces
should be the stronger ones as compared to interfacial
pressure or coherency strains close to the melting point.
In alloy systems with finite solubility of the solute, for
thermodynamic reasons, there must be a temperature
dependence of the solubility. In a precisely known
solidus temperature as a function of solute composition
in the phase diagram the solid can thus be slightly
superheated, so that melting occurs only at the grain
boundaries and not in the interior of the grains. This has
been used in Ni alloys to generate migrating liquid
films.178 The liquid film grows in thickness if there is a
superheated region around the liquid film,179 since the
excess solute of the solid phase will remain in the liquid
as the liquid film passes by.
Processes similar to LFM, but certainly driven by the
reduction of supersaturation, have been identified
during melting and resolidification in a (steep) tempera-
ture gradient.169,180 Different initial microstructures
(single crystal, equiaxed fine grained and columnar) give
insight in the role of LFM. LFM occurs both laterally,
i.e. isothermally perpendicular to the direction of the
heat flow, and longitudinally along the temperature
gradient. In the longitudinal direction, the temperature
gradient breaks the symmetry at the migrating film.
LFM along the temperature gradient occurs at a higher

velocity than laterally, leading to elongated grains.
Mean interface velocities in the order of 1 mm s21 have
been determined.
In conclusion of LFM, it can be stated that the
melting/resolidification mechanism will assist the reduc-
tion of superheat/supersaturation at a solid/liquid inter-
face, if other solid/liquid interface are in the vicinity. A
variety of symmetry breaking effects can cause a liquid
layer at a grain boundary to start migrating. For
modelling, the driving forces need to be identified
unambiguously. It is unlikely that there will be a
‘general LFM model’ that describes the migration of a
liquid film for different boundary conditions.
Conclusion and outlook
Melting and remelting phenomena are frequently
occurring in a variety of processes and exert a strong
influence on the microstructural evolution in numerous
cases. The technical relevance of melting is more and
more acknowledged, but until present, mostly scientific
questions are the subject of research. Most of the
research work deals with pure substances or binary
alloys, leaving numerous basic technical questions
unanswered.
Melting and solidification are not symmetric in several
structural, thermodynamic and kinetic aspects. This
becomes visible mostly for rapid processes under a loss
of local equilibrium. For slow melting front velocities
and diffusion control, diffusion in the solid is generally
sufficiently fast to warrant local equilibrium at the
interface. However, even in this case, symmetric treat-
ment of melting and solidification can lead to erroneous
results, as super-heating in the solid has been predicted
in casting simulations, but is unlikely to be observed in
reality. The kinetics of the process of reducing super-
heating in a solid alloy is not yet fully understood. This
concerns not only the melting/resolidification mechan-
ism as in LFM, but also defect controlled melting at a
liquid/solid interface.
The mobility of the solid/liquid interface appears to be
variable, depending on the alloy system and the
direction of migration of the interface. For solidifica-
tion, there is a dependence on the crystallographic
direction of migration. Furthermore, there is the
possibility that for a melting interface both thickness
and structure are different from a solidifying interface.
When modelling the thermodynamics of the interface
during a phase transformation, the difference of kinetic
coefficients in the adjacent phases needs special con-
sideration. It has been shown that a fast kinetics (high
kinetic coefficients) especially in the product phase can
change the interface compositions and thus concentra-
tion gradients at the interface and the kinetics of the
phase transformation process. Further clarification is
expected from continuum models based on the interface
kinetics25 and extremum principle models.
When modelling remelting during solidification in the
simulation of casting or microstructure evolution in
general, one should consider that:
N melting is controlled by the kinetics in the product
(liquid) phase
N superheating is unlikely to be observed in real
crystals; in addition to solute diffusion, there are
more mechanisms that assist to reduce superheating,
Rettenmayr Melting and remelting phenomena
particularly defect controlled melting and the melting/
resolidification mechanism as in TGZM or LFM
N further development of theories of melting and
interfaces as well as sophisticated simulation calcula-
tions are needed to predict microstructure evolution
directly, as in phase field models, if local remelting is
involved.
Open problems with technical relevance are effects in
multicomponent alloys, and detailed studies of the
interaction of temperature field, composition field and
capillarity that lead to fragmentation.
Non-equilibrium melting can at present only be
simulated for small deviations from local equilibrium.
Further development of irreversible thermodynamics
concerning larger potential jumps as during joining
processes with dissimilar materials (soldering, brazing) is
necessary to find consistent results. All continuum
models known to the author assume a linear relationship
between driving force and process rate, a relationship
that has been confirmed only for small driving forces.
No attempts are known to the author to model defect
controlled melting at very low superheatings, i.e. in a
practical context. Atomistic modelling for further
quantification of the influence of line defects (disloca-
tions) and area defects (internal interfaces, stacking
faults, etc.) could be a first step; for practical purposes, a
continuum theory considering defects would be highly
desirable. The theoretical development also needs to be
sustained by experimental progress.
Detailed studies with molecular dynamics or kinetic
Monte-Carlo simulations are required concerning the
structure of the interface. It appears that the variability
of the interface is a question that has so far not be
addressed sufficiently. It appears to be impossible to get
further insight into the structure of a moving interface
through direct observation in experiments. Atomistic
modelling or precise knowledge of the consequences of
varying interfaces structures is necessary.
Documented research on melting started more than a
century ago with the fundamental question why super-
heatings are generally not observed during melting. The
focus of research soon shifted to extreme cases and
conditions, e.g. suggesting the different ‘catastrophes’ to
be responsible for the asymmetry of melting and
solidification. While through the research on extreme
conditions certainly substantial progress has been made
in the basic understanding of melting, there are still
plenty of open questions concerning the details of the
first fundamental question and the quantification of
melting in practical cases.
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