Spray Casting: Fundamentals
of 0.5 to 1. Therefore, for very large-scale production,
Spray forming is a near net shape casting process
carried out by the impact of gas-atomized metal
droplets onto a substrate. The metal flow rates are
high, of the order of 0.2 to 2 kg s−", and this is achieved
by starting from fully melted liquid as in conventional
gas atomization for powder production. Spray form-
ing can be distinguished from other ‘‘thermal spray’’
processes in which solid powder is melted by a source
of heat such as an electric arc or a combustion flame.
As a result, lower metal flow rates are achieved and the
aim of thermal spraying is in general to make coatings
on preformed shapes. It has been established, by
theoretical models and experimental investigations as
described below, that for successful operation the
metal droplets must be partially solid at impact on the
substrate. If the operating conditions are correctly set,
then the spray-formed casting has a predictable shape,
it is produced with high sticking efficiencies of over
90% and has a fine grain sized microstructure with
only a small fraction (1–2%) of fine gas pores, typically
1–2 µm in diameter. The spray-formed casting has
greatly reduced micro and macro-segregation com-
pared to similar products conventionally cast using
input material that is 100% liquid and, as a result,
spray-formed material has mechanical properties that
are closer to wrought alloy properties than to cast.
However, only a limited number of shapes have so far
been successfully produced. These shapes include
cylindrical billets, flat strip or plate, and perhaps most
importantly, hollow tubes with a wide range of internal
diameters. Other important products include thickly
coated bilayers, for example, of stainless steel on
carbon steel, and in an important early application,
high-carbon chromium steel roll surfaces sprayed onto
low carbon substrates to form near net shape metal
working rolls. Metal matrix composites have also been
produced, usually by injection of the strengthening
phase into the spray so that the metal and the
reinforcement impact together onto the substrate.
Detailed descriptions of the process can be found in
various reviews, for example, by Grant (1995), the
conference volumes edited by Wood (1990, 1993, 1996,
and 1999) and the book by Lavernia and Wu (1996)
on the two major steps in spray forming: spray
atomization and deposition.
1. Process Description
In the Osprey method of spray forming, which is the
dominant method used in current technology (see
Wood 1990), a stream of molten metal is ‘‘atomized’’
or broken into a high density spray of molten droplets
by impact with a high-velocity inert gas stream. The
gas used is typically nitrogen, although for appli-
cations where nitrogen contamination in the product
is unacceptable, argon gas is used. Large amounts of
gas are used, with gas \metal weight ratios of the order
gas recycling is an important part of the process
economics. Unlike modern powder production, it is
not usually essential to achieve very fine powder sizes.
In spray-forming the powder sizes have a maximum
weight fraction at diameters of about 50–100 µm but
with a large spread in sizes, typically with a log-normal
distribution. The spray forms a cone with a radial
variation in mass flux and at present it is necessary to
measure the particle size distribution (PSD) and the
radial mass flux (RMF) experimentally as a function
of the main process variables: gas pressure, metal flow
rate, alloy type, super heat, etc. The spray is directed to
impact a suitably designed and moving substrate and
on this substrate the spray-formed casting builds up.
The substrate motion is designed to ensure that, after
an initial transient, the point of impact of the spray on
the growing casting occurs at a fixed flight distance,
typically about 0.2 m, from the point of atomization
where the converging gas streams hit the stream of
liquid metal. The aim is to have the thermal conditions
at the surface of the growing casting, on which the
spray is arriving, nearly constant. For billets and strip,
the casting remains essentially under the spray at all
times. However, for tubes or rolls the rotation of the
substrate causes the surface to move under the spray
and out again, once on each rotation, and multiple
passes under the spray then take place to build up the
required casting thickness. In many cases, spray
oscillation is used in combination with substrate
motion to achieve the required shape. This is clear for
strip casting, where with a nonuniform RMF only by
oscillating the center of the spray across the width of
the strip can an approximately uniform thickness be
achieved. Alternative methods for producing strip or
plate are to have multiple sprays or to replace the
cylindrical initial liquid stream with a slit source of
liquid metal. Even for billets and discs it is usual to
have the impact point off-center to achieve a controlled
nearly cylindrical shape. To achieve the desired near-
net shape with a minimum of ‘‘over-spray powder’’
material that was sprayed but did not stick to the
substrate, the operating conditions must be controlled
to ensure that metal arrives at the required place and
that as little as possible of the flux of metal misses the
deposit.
2. Thermal Conditions
In any thermal process it is essential to know the
temperatures of the material as it passes through the
various stages in the process. This is needed both to
control the individual steps of the process and also to
predict the final microstructure of the product. Atom-
ization takes place with the metal stream at a tem-
perature close to the imposed superheat (temperature
above the liquidus). The superheat is set by the
conditions in the melt and is typically about 100 mC to
1
Spray Casting: Fundamentals
avoid risk of the metal stream freezing off in the
atomizer. After atomization the metal passes through
three different stages: (i) the spray, (ii) the deposit
surface, and finally (iii) within-sprayed billet strip or
tube. Each of these stages needs to be understood.
Ideally we would like to be able to measure the
conditions in each of these situations but this is difficult
and major progress has been made by numerical
modeling, for example by Mathur et al. (1989),
supplemented by experiments to calibrate and validate
the models.
2.1 Thermal Conditions and Droplet Microstructure
in the Spray
In order to model the thermal conditions in the two-
phase, gas–metal, spray, two empirically measured
variables must first be known. These variables are the
PSD and the gas velocity field. Although the particle
velocities and particles sizes can be measured in flight
in real time by various diagnostic techniques, such as
phase doppler anemometry, it is more common to
measure these in separate experiments. The gas flow
field can be measured in the absence of metal by
standard Pitot tube methods and the PSD and the
RMF after collection of powders in cylindrical tube
collectors. The collection must be done in the absence
of a substrate and with the collectors at a sufficient
flight distance to ensure full solidification. It is not
correct to sample the over-spray powders for their
PSD in a normal spray forming run, since the powders
that do not stick to the substrate have been shown not
to be representative of the PSD before impact. High-
velocity particle collisions with the deposit give a much
higher fraction of small particles than was present
before impact. That is, droplet fragmentation seems to
occur on impact. In addition, the smallest, and thus
lightest, droplets are carried away from the casting by
the defected gas stream without coming into contact
with the deposit.
Current thermal models consider the behavior of
individual droplets, of different sizes. Each droplet,
after atomization, is accelerated by the gas flow field
until it matches the velocity of the gas stream. The gas
velocity, however, falls with distance from the atomiz-
ation point, so the droplet will subsequently be
decelerated by the gas. Heat loss from the droplets
depends on the local heat transfer condition. The heat
transfer is a strong function of the relative velocities of
the gas and the droplet. Using these assumptions, the
loss of heat from an individual droplet at different
flight distances is modeled. This calculation is then
repeated for particles of all sizes to predict the average
heat content of the spray. Unknowns in this cal-
culation include the under-cooling at which a droplet
of a given size is expected to nucleate solid and reheat
back towards the liquidus temperature. Solidification
growth in under-cooled metallic alloys is very rapid.
2
The under-cooling required for nucleation of small
droplets is known to be large. This arises since suitable
catalysts for solidification are unlikely to be present in
most small droplets. Indeed observation of large
under-cooling in small droplets was a classic early
result in physical metallurgy that established the
validity of the homogeneous nucleation models in
structural metallurgy over 50 years ago. Early experi-
ments by Mathur were able to confirm this by
intercepting droplets of different sizes at different
flight distances onto glass slides passed quickly
through the spray. It was shown that there were large
under-coolings. However, the average under-cooling
fell as the droplet size increased. This data was
subsequently used for a validation test for a spray
nucleation model as described by Cai et al. (1993). In
their model it was assumed that the smallest droplets,
typically 20 µm or less in diameter, cool very quickly
and are unlikely to have any nucleation catalysts.
Therefore, the smallest droplets nucleate at the large
undercoolings (200–300 mC) predicted for homogen-
eous nucleation. This assumption is confirmed by the
previously measured under-coolings in the smallest
droplets. The critical new assumption was that, given
the large differential velocities of droplets of different
sizes, then larger droplets will, once they cooled below
the liquidus temperature, be nucleated by impact of
smaller, solidified, droplets. Microstructural evidence
supporting this idea was clearly confirmed by met-
allographic studies of over-spray droplets. Using this
assumption, Cai et al. were able to match successfully
the previously measured results for the decrease of
under-cooling with increasing droplet size. This match
confirms that in the condition of high droplet density
of gas atomization, characteristic of spray forming
and also of metal powder production, the dominant
nucleation process is the impact of small solidified
particles onto larger, slower-moving and under-cooled
liquid droplets.
These models then predict that just before impact
on the substrate, the smallest droplets are fully
solidified, the largest ones fully liquid, while the bulk
of the droplets are only partially solidified. Since the
cooling rates are high and the solidification times
short, typically a few milliseconds, the dendrite arm
spacing in the droplets is very fine—typically 1 µm or
less. This is confirmed by observations of the fine
dendritic structure in the over-spray powders and in
conventional powder metallurgy.
2.2 Thermal Conditions and Microstructural
DeŠelopment on Impact with the Deposit
The droplets travel at velocities of the order of the gas
velocity, 10 to 50 m s−", and so impact onto the deposit
at these speeds causes extensive deformation of the
partially molten particles. These conditions appear to
produce the dendrite fragmentation typically seen

during stir casting. Stir casting usually yields grains
fragmented to the size of a few dendrite arm lengths.
For spray forming, these initial grains, seen in regions
of the casting that is rapidly chilled, appear to be only
5–10 µm in size. The details of how fragmentation
occurs is not fully agreed. However, the mechanism
proposed for stir casting (Doherty et al. 1984) seems a
reasonable possibility. This involves the following
steps: plastic, dendrite arm bending, recrystalliza-
tion to produce high-angle grain boundaries which
are wetted by the liquid metal, producing grain
break-up.
These ideas have been experimentally supported for
stir casting. A high-speed video of the impact at the
surface does indicate considerable liquid movement at
the substrate surface. This movement seems typical of
liquid on liquid impact, indicating that the solid–liquid
mixtures do seem to have the liquid-like viscosities
found during high shear rates in stir casting. The
surface movement is not the solid-like behavior of
solid–liquid mixtures that can readily sinter together at
solid fractions greater than about 0.3. Immediately
below the surface, when impact-induced movement
has died out, there should be solid-like behavior.
This must, in fact, occur or the partially solid deposit
would break up during the high rotation rates
usually imposed in most billet and tube spray-forming
processes.
The thermal models of the material under the spray
indicate that the material should achieve, in a few
milliseconds, a locally uniform temperature deter-
mined by the enthalpy content calculated for the
spray. That is, the colder small solid particles, the hot
fully liquid large droplets and the intermediate par-
tially solid droplets quickly equilibrate in temperature.
This is expected by virtue of the high thermal con-
ductivity of metallic alloys and the small heat diffusion
distances in the droplets that are flattened by high
velocity impact. For a deposit surface under a station-
ary spray, the models indicate that the temperature
should, after a short period of metal build-up on the
substrate, be that determined by the enthalpy of the
spray. For sprays that oscillate and for rotating
castings such as tubes that move in and out of the
spray, there is additional cooling by the gas.
This additional cooling will reduce the fraction
liquid of the deposit significantly below that calculated
from the enthalpy content of the metal in the spray just
before impact. Reliable thermal models of the complex
geometry in, for example, rotating tubes have not yet
been fully developed to quantify this effect. Experi-
ments by Doherty et al. (1997) indicate that the
temperature on the deposit surface and thus the
fraction liquid on the deposit are vital factors in
successful spray-forming. These experiments also indi-
cate that the deposit surfaces of spray-formed tubes
are indeed colder than billets formed under the
equivalent sprays. Therefore, reliable thermal models
of complex spray-formed billets are clearly needed.
Spray Casting: Fundamentals
2.3 Thermal Conditions and Microstructural
DeŠelopment within the Deposit
Thermal models for simple shapes such as spray-
formed billets are available and these have been
validated by temperature measurements. For billets
formed continuously under the spray the surface
temperatures match the predicted liquid fractions, fl,
predicted for the spray, typically fl " 0.30. Under such
situations the casting is successful in producing ma-
terial with a high yield and a low amount of fine gas
porosity (Doherty et al. 1997). Grain sizes of 20–50 µm
are produced with very limited microsegregation with
a length scale of the grain size. There is no sign of the
usual dendritic structure seen when the segregation is
on a scale finer than the grain size. The grain size scales
directly with the solidification time, indicating that
this is controlled by grain coarsening (Annavarapu
and Doherty 1995). A critical result for the deve-
lopment of the fine spherical grain structure appears to
be particle or gas pore inhibited grain coarsening.
Many results and theoretical models find accelerated
coarsening of solid grains in solid–liquid mixtures as
the fraction liquid, fl, decreases towards zero. Coarsen-
ing in solidifying spray-formed casting should occur
rapidly as fl falls from 0.3 to zero in times of the order
of 10–100 s. However, the grain sizes actually seen
after spray forming are much smaller than those
predicted from standard coarsening theory. The solu-
tion to this important discrepancy between theory
and experiment appears to come from grain-boundary
pinning by fine particles seen on the boundaries of all
fine-grained spray-formed alloys. These particles are
sometimes transition metal nitrides in high tempera-
ture alloys based on copper, iron or nickel or they are
iron impurity particles in aluminum alloys. The role of
these boundary-pinning particles has not yet been
fully analyzed but it is clear than the fine grain size
characteristic of successful spray forming arises from
their influence on inhibiting grain coarsening.
3. Other Aspects of the Structure of Spray-formed
Castings
The limited microsegregation in spray-formed ma-
terials directly arises from the unusual solidification
condition in spray-forming. The first 50–70% of
solidification occurs in a few ms in flight, giving
dendrite cells of the size of about 1 µm. These dendrites
break up to fine grains on impact and the remaining
solidification occurs at high fraction solid, and much
more slowly. Thermal equalization for a few seconds
near the surface of the deposit allows homogenization
of the solid particles giving a solid composition
corresponding to the low solidus temperature at a
solid fraction, fs, of " 0.7. This gives 70% solid at a
composition close to that of the alloy. During the
3
Spray Casting: Fundamentals
coarsening, as the grains grow in size by five- to 10-
fold before solidification is complete, the solid is being
continuously remelted and refrozen at temperatures
steadily approaching the solidus, resulting in a solid
even closer to the alloy composition. This yields the
minimal microsegregation characteristic of the pro-
cess. In addition, with only limited solidification in the
deposit (a change of fs of only 0.3) there is much
reduced solidification contraction. This combined
with inhibition of liquid flow, owing to the fine liquid
channels, greatly reduces the amount of contraction-
induced fluid flow. Such liquid flow is responsible for
macrosegregation, the chemical inhomogeneity on the
length scale of the casting, so this is also greatly
reduced in shaped castings made by spray forming.
The fine-scale porosity apparently resulting from
trapped atomizing gas is almost always present. The
only exceptions are for nitrogen atomization in high-
temperature alloys containing nitride-forming ele-
ments such as chromium, aluminum, or titanium. The
nitride particles can completely remove trapped ni-
trogen. Atomizing under an inert gas such as argon,
however, always leads to trapped porosity, as does
aluminum alloy spray forming at low temperatures,
where nitrogen reaction appears impossible. Fine gas
porosity from insoluble atomizing gases can be re-
duced by plastic working. This elongates the pores to
long tubes, which will break up by the Rayleigh
instability (see, for example, Martin et al. (1997)) to
small spheres. The increased capillarity pressure, ∆P,
owing to the solid surface energy, γ, of a pore of radius
r, for the smaller spheres, will reduce the volume of the
gas pores. For γ of 1 J m−#, and r of 0.1 µm, this gives a
pressure of about 100 atmospheres.
∆P l 2γ\r (1)
Copyright ' 2001 Elsevier Science Ltd.
All rights reserved. No part of this publication may be reproduced, stored in any retrieval system or transmitted
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otherwise, without permission in writing from the publishers.
Under these circumstances porosity can appear to
have vanished but it should be remembered that the
gas is still present and if the pores coarsen, for example,
by pore migration and coalescence during high tem-
perature processing, then the porosity will return. This
possible problem in the use of spray-formed com-
ponents has so far been little studied but its presence
should be kept in mind and for critical components be
subject to experimental testing.
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R. D. Doherty
Encyclopedia of Materials : Science and Technology
ISBN: 0-08-0431526
pp. 8776–8779