The 69th WFC Paper

November 2010

The mystery of molten metal

*Natalia Sobczak1, Jerzy Sobczak1, Rajiv Asthana2 and Robert Purgert3
(1. Foundry Research Institute, 30-418 Cracow, Poland; 2. Department of Engineering & Technology, University of Wisconsin-Stout,
Menomonie, WI 54751, USA; 3. Energy Industries of Ohio, Cleveland, OH 44131, USA)

Abstract: Recent advances in scientific understanding of high-temperature materials processing using novel
experimental methodologies have shed light on the complex role of surface and interface phenomena. New in-situ
studies on molten metal/solid ceramic interactions using a unique experimental complex at the Foundry Research
Institute, Krakow, have revealed a number of unusual observations in materials processing at high temperatures.
We present some such unusual observations and their explanation with reference to liquid metal processing of Al,
Ni, and Ti, and their alloys in contact with oxide ceramics. In particular, we focus on the following aspects: primary
oxidation of Al from residual water vapor or oxygen, capillary purification to remove surface oxide, substrate
protection by CVD carbon, roughening due to spinel whisker formation, inclusions in castings due to mechanical
detachment, floatation due to buoyancy forces, and segregation due to directional solidification, modification of the
solid surface morphology by metal vapor ahead of the liquid, and the complication due to multi-component alloys
melted in crucibles made from complex oxide-based ceramics. In the case of Ti, rapid reactions with oxides result
in undesirable volumetric changes that create difficulty in casting high-quality Ti parts, particularly by investment
casting. Nanoscale (e.g., colloidal) coatings based on Y2O3 protect crucibles and hold ladles against such attack.
Practical insights and recommendations for materials processing emerging from the fundamental studies on high-
temperature interfacial phenomena have been described.

Key words: molten metal; high-temperature phenomena; in-situ observation; casting defects
CLC number: TG146 Document code: A Article ID: 1672-6421(2010)04-425-13

1 Introduction Since at high temperatures everything reacts with everything,

Many important techniques of materials processing require the such interactions can be accompanied by a number of
contact between molten metals and refractory materials (i.e., complex chemical reactions at liquid metal/atmosphere and
casting processes, liquid metal handling, brazing ceramics, liquid metal/solid interfaces, leading to significant changes in
and fabrication of metal-ceramic composite materials). For interface structure and chemistry thus affecting the properties
such techniques, the resulting properties of final products are of final products. Therefore, it is highly desirable to develop
closely related to high-temperature properties of a liquid metal experimental techniques and equipment that allow in-situ
and, particularly, high-temperature surface and interfacial observation and analysis of high-temperature behavior of
phenomena. Thus the interaction between a liquid metal and liquid and semi-liquid alloys. This could be accomplished in a
a solid material and the nature of interfaces formed play a key unique experimental complex developed by the Center for High
role in selecting suitable material or processing parameters. Temperature Studies at the Foundry Research Institute ( Poland).
In this paper, methodological, scientific and practical aspects
*Natalia Sobczak
of high-temperature studies using the above experimental
Female, born in 1956, Prof., DSc, PhD, PI. Specialist in the field of high temperature
liquid state materials science, composite synthesis and joining dissimilar materials complex are discussed from viewpoints of production of
by liquid-assisted processes, casting of advanced and specialty materials. Head of advanced cast materials with special attention to high-
the Center for High Temperature Studies at the Foundry Research Institute (Cracow)
and Scientific Adviser at the Motor Transport Institute (Warsaw). She received her temperature phenomena affecting quality of castings due to
MSci and Ph.D degrees from St Petersburg State Polytechnic University and DSci formation of different casting defects.
from the Polish Academy of Sciences. Visiting professor at University of Wisconsin-
Milwaukee (1994-1996), Hokkaido University (2000), Osaka University (2000-2001),
University of Wisconsin-Stout (2002), Institute for Energetics and Interphases IENI-
CNR in Genova (2007, 2008, 2009). Head of Section 8.1. Cast Composites of Word 2 Experimental complex for high-
Foundry Organization (since 2001). Member of Polish Foundrymen Association, Polish
Society of Composite Materials, Polish Society for Materials Science, ASM. Winner
temperature characterization of
of numerous national and international awards including Gold Medal Award of Polish
Foundrymen's Association, Third Prize at Int. Metall. Contest, IMS & ASM, First Prize
liquid materials
Award of Polish Agency for Enterprise Development in the category “Polish Product Among methods for examination of properties of liquid
of the Future”, Award of Polish Academy of Sciences for young scientists, Awards
from Polish Ministry of Industry for Innovative products, Silver Medal at Salon Int. des metals and alloys as well as accompanying high temperature
Inventions in Geneva, Gold and Bronze Medals of the Belgian Chamber for Innovation, phenomena, the sessile drop method is widely used because
Brussels Expo. Autor and co-author of 4 books, more then 200 papers and 14 patents.
of its relative simplicity coupled with opportunity to extract
E-mail: natalie@iod.krakow.pl
Received: 2010-07-13; Accepted: 2010-08-20 fundamental information of practical importance. In the

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classical sessile drop procedure, the metal/substrate couple are evidenced by periodic increases of the drop volume and solid
is contact heated to the experimental temperature while the precipitates floating on the surface of the liquid drop. Obviously,
recorded images of liquid drops are used for measurements this ceramic material is not suitable for melting or casting this
of surface tension (σ lv), density of the liquid, characterization particular alloy since the reactively formed porosity and non-
of its wetting and spreading properties by measurements metallic inclusions are unavoidable. Figure 1(b) presents the
of the contact angle (θ ) and work of adhesion [Wa = σ lv (1 + behavior of a liquid Al drop contacting a MgO single crystal
cosθ )] between the liquid and the solid substrate. Despite plate during periodic cooling and heating. In this test, the Al drop
the small quantity of liquid metal used in the sessile drop was produced by squeezing the liquid metal melted in a ceramic
method, the observations of wetting and spreading behavior capillary situated above the MgO plate at a constant distance.
are useful in various liquid-assisted manufacturing processes [1]. During interaction, strong adhesion between the Al drop and the
Moreover, visualization accompanying the sessile drop method MgO plate was established while during cooling and heating,
may be utilized for observation of metal behavior during melting, metal shrinkage and expansion resulted in movement of the
heating or cooling as well as experimental estimation of metal MgO plate vertically either upward or downward.
expansion during heating or metal shrinkage during cooling. These The significant methodological and practical issues in
thermophysical properties are particularly important for computer wettability measurements at elevated temperatures by the
simulation and modeling of liquid-assisted processes. sessile drop method have been discussed in references [1–3]
Figure 1 illustrates two examples using the sessile drop while some useful recommendations for its application have
test for observation of critical phenomena that are common been summarized in references [4, 5]. In order to fulfill all
in foundry practice and significantly affect the structure and requirements, an experimental complex (Fig. 2) with unique
properties of castings. Figure 1(a) shows a high-temperature operating capabilities was developed [6]. Its design in Fig. 3(a, b)
interaction between a liquid alloy and a ceramic substrate permits multiple complex functions to be performed including,
accompanied by the formation of gaseous reaction products that among others, ‘pushing’, ‘smearing’ and ‘rubbing’ a spreading
drop, thus making it possible to mimic the behavior of liquid
or semi-solid alloys in real technological processes. For this
propose, special manipulators were developed and utilized
for an up and down movement of both a ceramic support
and a ceramic capillary filled with molten metal; a rotation
or side movement of the support; and a drop movement or
removal by either pushing or sucking. As a result, besides
classical sessile drop and large drop procedures, new testing
procedures and methods can be realized simultaneously or
independently as shown in Fig. 3(c,d). The tests of different
materials (metals, alloys, ceramics, glass, fluxes, dross) can be
done at a temperature of up to 2,100℃ under vacuum of up to
10-7 hPa or in protective atmosphere (static or flowing gas with
controlled rate at required level of pressure).
The experimental complex with its unique design, as shown
in Fig. 3 (a, b), was built on the concept of LEGO blocks.
It integrates several apparatuses having unique possibilities
for complex materials characterization at high temperatures
by different testing methods and various procedures for
simultaneous estimation of different characteristics in one
test under high vacuum or flowing inert gas. Its central part
employs a chamber for the transfer of the samples between
different apparatuses without opening and dehermetization, so
that there is no contact with air.
Vacuum of 10-7-10-10 mbar is produced by turbomolecular
and ionic pumps. The chamber for sample treatment and
(a) (b) surface characterization (chemistry, impurities, and oxidation)
Fig. 1: Visualization of high-temperature phenomena in is equipped with an Auger spectrometer and an ion gun (for
a sessile drop test: (a) interaction between a liquid alloy surface cleaning or for neutralization of electrical charges at
and ceramic substrate accompanying with the formation of
the surfaces of ceramic samples).
gaseous and solid products responsible for structural defects in
ready castings (porosity and non-metallic inclusions); (b) liquid The main part of the complex is a high-temperature chamber
Al shrinkage and expansion during subsequent cooling and (up to 2,100℃), working under high vacuum or flowing inert
heating resulting in the movement of the MgO plate contacting gas. It is equipped with a quadropole residual gas analyzer (for
with the Al drop produced by squeezing the metal from a
capillary situated above the MgO plate. characterization of gases formed during materials heating),

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November 2010

(a) (b)

Fig. 2: Experimental complex

for high temperature
studies (a) and scheme
of its movable elements
allowing examination by
different testing methods
and procedures (b)

a manipulator for the movement of the experimental table 2,000 frames per second), and it is used for direct visualization
in an XY plane or its rotation up to 270°, a manipulator for of behavior of liquid metals and alloys at high temperatures
loading, removal and transfer of the samples between different
chambers and apparatuses, a manipulator located above the (c)
drop in order to transfer from the top an additional substrate or
capillary with liquid metal, which can also permit squeezing of
a metal through a capillary in order to realize the in-situ drop
cleaning from an initial oxide film by the capillary purification
procedure or dispensed drop method. This chamber has four
windows and it is operated with a high speed CD camera (up to

(a) (b)

(d)

Fig. 3: Schemes of experimental complex design (a, b) and methods and procedures that can be applied in a new complex (c) [6],
including recently developed procedure for interface “opening” by the drop replacement using a special design of ceramic
support (d) [17]:
(1) Vacuum chamber for the first stage of sample preparation by preheating in vacuum up to 200°C in order to remove adsorbed gases;
(2) Chamber for transferring the samples between the chambers using a manipulator that allows to bring the samples of different sizes and various shapes;
(3) Analytical chamber containing Auger spectroscope for surface characterization of examined materials before and after high temperature treatment, ion
beam for etching/cleaning samples and removal of surface films from examined samples;
(4) Portable chamber (vacuum “traveling-bag”) for storage and collection of specimens after testing under vacuum;
(5) Experimental chamber for high-temperature studies of materials in solid, semi-solid or molten states, containing experimental table (metallic or ceramic support)
with rotation and up-and-down movement, the heater and screens with up-and-down movement, additional windows for observation and recording, quadropole
residual gas analyzer for real time recording of chemical composition of atmosphere in a vacuum chamber, capillary with up-and-down movement (for capillary
purification procedure or for removal of a drop after testing directly at high temperature in a vacuum chamber, for example in order to “open” the interface or the
reaction products formed at the interface), manipulator, located under a drop/substrate couple, which allows to delivery another substrate (for sandwiched drop
procedure) or alloying additions (for in-situ alloying in vacuum chamber), automatic real-time temperature control by 4 thermocouples located in selected positions.

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that is particularly helpful for understanding of different oxidation of aluminum takes place even under ultra high
mysterious high-temperature phenomena accompanying vacuum at temperatures below ~1,000℃[11]. Figure 5 shows
different liquid-assisted processes. a change in the amounts of residual gases in the vacuum
chamber equipped with a gas spectrometer which is operated
during the test. When an oxide-free AlSi12 alloy drop was
3 Several examples of high
produced at 900℃ by squeezing the alloy through graphite
temperature tests
capillary, a sudden decrease in amount of water vapor was
In order to demonstrate the wide testing possibilities of a new recorded together with remarkable increase in amount of
experimental complex and applicability of such studies in hydrogen that represents experimental evidence of the liquid/
foundry practices, several examples of high temperature tests gas reaction: 2Al + 3H2O(g) → Al2O3 + 3H2(g). Subsequently,
with molten Al, Ni and Ti alloys are discussed below. this reaction results in secondary oxidation of the initially
oxide-free aluminum drop (and was confirmed during real-time
3.1 Al alloys observation of the drop surface since the drop surface became
Pure aluminum and its alloys are known to be sensitive to matte with time) and it is also responsible for the formation of
oxidation and the presence of even negligibly small amounts bubbles inside the drop. In foundry practice, the same reaction
of oxygen are sufficient to instantaneously (~10-23 s) form between molten metals and residual water vapor in the
a monolayer of aluminum oxide at room temperature. The furnace’s atmosphere or from foundry appliances presents one
presence of this primary oxide film on aluminum is the main of the most common factors responsible for structural defects
reason for a large scatter in experimental data on wetting in castings such as oxide inclusions and gas porosity.
properties in all Al/ceramic systems [7-11]. Consequently, Furthermore, the studies [7-11] showed that even a continuous
primary oxidation generates many problems for practitioners and tenacious oxide film few nanometers thick covering the
and engineers since it leads to contradictory recommendations, liquid aluminum significantly affects macro-scale properties of
depending on the data selected as the correct one. It might be Al/ceramic couples such as wetting and shear bond strength;
illustrated with an example of Al/alumina system shown in
Fig. 4. At 700℃, the highest contact angle is θ = 162° that
corresponds to the lowest value of work of adhesion Wa =
41.6 kJ·m-2, showing non-wetting and very weak bonding in
the system. Thus one may recommend alumina as a suitable
material for crucibles, molds and protective coatings. However,
if for the same temperature the lowest value of θ = 88° is taken
to be the true contact angle and corresponding highest value of
Wa = 880 kJ·m-2 were selected, then one may conclude that it
is possible to produce well-bonded Al/alumina joints at 700℃
and hence this system is a good candidate for low-temperature
cast composite synthesis even though alumina is not suitable
for foundry appliances.
It is not only oxygen in the furnace atmosphere that plays
an important role in interactions between molten Al and
refractory ceramics, but also water vapor in the chamber, Fig. 4: Literature data on temperature dependence of
which is almost unavoidable. In the presence of water vapor, contact angle values in Al/Al2O3 system

Fig. 5: Change in the amount of residual gases in a vacuum chamber during wettability test of AlSi12/TiO2 system at
900ºC for 120 min by capillary purification procedure; inserts show a design of a graphite capillary and steps
of squeezing metal [11]

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November 2010

these properties are particularly important in the practice of Many problems in foundry practice are related with the
metal matrix composite synthesis and joining ceramics. It was fact that oxidized aluminum exhibits different wetting
demonstrated that compared to the classical contact heating behavior and wetting-bonding relationship depending upon
procedure (CH), the removal of the primary oxide film from the reactivity of Al/ceramic system [7-11]. This creates also
the aluminum drop in CP procedure results in improvement contradictory interpretation of experimental data on contact
of both wetting (Fig. 6a) and bonding (Fig. 6b) in Al/Al2O3 angle measurements or even questions on its validity. One
couples. This effect is used in the practice of cast composite such example is interaction between molten Al and SiO 2;
synthesis by the application of different methods to effectively this reaction is particularly important because of the wide
remove primary oxide films from the metal/ceramic interface application of silica in many refractory ceramics used for
mechanically (by intensive stirring of metal-ceramic slurry), melting technology products (molds, filters, crucibles, etc).
physically (through application of ultrasounds) or chemically The wetting in Al/SiO2 is reactive, promoted by the formation
(by the addition of Mg into molten matrix in order to consume of Al2O3 from redox reaction: 4Al + 3SiO2 → 2Al2O3 + 3Si.
the primary oxide by the formation of MgAl2O4). Despite the fact that literature data [12,13] have confirmed the

(b)
(a)

Fig. 6: Effect of testing procedure (CH, CP) and temperature on wettability kinetics (a) and shear behavior (b)
of sessile drop Al/Al2O3 couple recorded as a change of shear stress τ = (F/S) with displacement l [7]

formation of a thick reaction product region (RPR) in Al/SiO2 = 53°) when the primary oxide film is in-situ removed under
even at low temperatures, and freshly formed Al2O3 should be vacuum by the formation of gaseous aluminum suboxide Al2O
wettable by liquid Al, there is some uncertainty regarding low- from the reaction: 4Al + Al2O3 = 3Al2O (g).
temperature wetting in Al/SiO2. Laurent et al. [12] suggested that In additional tests by CP at 1,273K, the oxide-free drop,
this uncertainty is related to the presence of oxide film on Al, deposited at 973K and then quickly heated to 1,273K (~ 40
which hinders spreading, while Zhou and Hosson [13] propose K·min-1), exhibits the highest decrease in contact angle (up to
that formation of surface cavities ahead of the triple line (TL) ~ 40° ) during an 80 min contact (Figs. 7a, 10a).
hampers the spreading. These cavities may form due to a 38 % Alloying Al with Si inhibited the Al/SiO 2 reaction, and
volume mismatch between the reactants and the products in led to higher contact angle values (Fig. 7b). The structural
the redox reaction mentioned above. examination of cross-sectioned Al/SiO2 couples did not show
Recent research [11] demonstrated a strong dependence of the any remarkable cavities at the TL, although numerous cracks
wettability kinetics in the Al/SiO2 testing procedure (CH, CP), were noted in the SiO2 substrates. A few cracks were also in
as shown in Fig. 7(a) for different temperatures together with the heterogeneous reaction product region (RPR), composed
the effect of Si alloying of an Al droplet. Similar to the data of of fine alumina particles surrounded with Si and Al(Si) phases;
the literature [12, 13] for 973K, the couple exhibited a lack of such cracks propagated even over the TL. These observations
low-temperature wetting for CH (θ = 114° > 90°). However, were found as experimental evidence for a key role of primary
for the same temperature, it becomes wettable (θ < 90°) for oxide film on Al drops on contact angle measurements [11].
CP, indicating θ = 59° similar to that recorded with CH at 1,273K (θ They prove also the fact that the wettability of the Al/SiO2

(a) (b)

11/SiO2 (b) [11]

Fig. 7: Effect of testing conditions on wettability kinetics in Al/SiO2 (a) and AlSi11

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system is controlled by the wettability of RPR (i.e., mainly reactive metal penetration of dense SiO2-rich ceramics with
aluminum oxide) and not by the wettability of SiO2 while this liquid Al at high temperatures [11]. However, if the starting
process is strongly affected by kinetic factors, particularly ceramic has high porosity, liquid Al does not flow inside the
in an oxidizing environment. This statement is in agreement porosity channels even at high temperatures when Al exhibits
with foundry practices and confirms that SiO 2-containing very good wetting. The porosity in the starting ceramic
refractories are suitable for short-times or low-temperature remains unfilled with molten metal because the reaction takes
contact with molten low-silicon Al alloys in air (e.g. molds). At place through the ceramic only (Fig. 8). Consequently, the
high temperatures, the lifetime of such materials significantly obtained IP composite is also porous and thus pressure-assisted
decreases and thus they should not be used as crucibles. processes are needed in order to produce a dense IP structure.
On the other hand, redox reaction taking place in the Al/SiO2 Similar behavior was observed with many SiO2-rich ceramics
system has been successfully utilized for the in-situ synthesis such as mullite, kaolin, and fly ash.
of interpenetrating composites (IP) of an Al-Al2O3 type by Another example is the effect of a carbon layer on ceramics

(a) (c)

(b)

Fig. 8: Pure Al drop after interaction with porous SiO2 preform (1,000ºC, 120 min, vacuum): (a) top-view; (b, c) cross-sections (OM)

when being wetted by Al alloys. As demonstrated in [14], speed CCD camera (Fig. 10b), after squeezing AlTi6 alloy
even a very thin carbon film deposited by a CVD method or through alumina capillary at 1,273K (there is no reactivity in
mechanically using soot or graphite as a paint (e.g. from a AlTi6/Al2O3 system at 1,273K [7,14]), the AlTi6 drop, falling from
pencil) results in better wetting and improved bonding in Al/ ~5 mm height, touches the CNT paper and immediately jumps
alumina systems (θ Al/Al2O3 = 96º contrary to θ Al/C/Al2O3 = 79º). up without wetting and spreading. The drop jumping repeats 4
Particularly, it is well-distinguished with Al alloys containing times and finally the drop settles without any spreading forming
carbon-forming additions, e.g. alloying with 6wt.% Ti results a high contact angle of ~140°.
in perfect wetting of carbon-coated alumina (θ = 17º) and More work is needed in order to understand this ‘mysterious’
more than twice increases in shear strength of AlTi6/C/Al2O3 behavior of Al-Ti alloy on nanostructured carbon material.
couple (τ = 42.8 MPa), contrary to non-wetting of an uncoated However, whatever the reason for the ‘jumping ball’ effect,
alumina substrate (for AlTi6/Al2O3: θ = 103º, τ = 17.8 MPa) it suggests that a nanoscience approach might be useful for
[14]
. These observations are in sound agreement with the development of a new generation of refractory materials
positive effect of alloying Al with Ti on wetting reported for resistant to aggressive attacks of reactive liquid alloys. This idea
both crystalline (graphite) and amorphous (vitreous carbon) has been successfully demonstrated by examples of interactions
carbon materials [1,10]. The above beneficial effect of a thin of Ni-based superalloy IN740 with ZrO2-based ceramics using
carbon coating may be successfully utilized in both composite additions of nanoparticles Y2O3np or Zr2O3np [15] showing that
synthesis or ceramic joining. But on the other hand, it may at 1,773K a much worse wetting (the contact angles are 150°
cause some problems in melting and casting of aluminum and 129°, respectively) along with a lack of bonding between
alloys containing Ti or other carbon-forming additions when the alloy and such ceramic substrates contrary to ZrO2-based
the surface of molds, crucibles or holders are stained with ceramic produced by conventional high temperature synthesis
carbon. However, absolutely ~
different behaviors of highly using 3% of micro-sized Y2O3 powder and characterized by
reactive and well wetting AlTi alloys in contact with a carbon θ = 95º coupled with certain degrees of reactivity (e.g. the
material was observed in the test, when under identical testing formation of oxygen-rich precipitates at the drop surface as well
conditions, the graphite substrate was replaced by carbon as at the substrate-side interface was recorded).
nanotubes (CNT) in the form of a paper. As recorded by high- Many unusual and apparently difficult to explain phenomena
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November 2010

in foundry practices are caused from roughness of real substrate was rotated and the second drop was deposited
surfaces, particularly when there is a certain degree of in a new place, kept 5 min and sucked-up again (Fig. 9b).
reactivity between the liquid metal and the contacting of solid In this case, a good contact and adhesion were established,
material. It is illustrated by an example of wetting behavior of accompanied by the formation of SiC due to reaction between
AlSi22 alloy on a rough graphite substrate at 1,000℃ using Si from the alloy and graphite. Consequently, both drop
the experimental complex described above as shown in Fig. 9. sucking and detachment were more difficult and a large
After deposition of an oxide-free drop using a CP procedure amount of the alloy remained on the substrate but this second
and ~30 s contact, the drop does not wet the substrate (θ>>90º) drop did not wet the substrate (~150º) despite strong adhesion.
and it is easily removed by sucking it into an alumina capillary In the next step (Fig. 9c), the substrate was rotated once more
due to the weak adhesion between the drop and the substrate and the third drop was deposited without detachment from the
while the remaining “daughter” droplet exhibits good wetting capillary and sucked after ~30 s. The daughter droplet again
since it forms the contact angle of ~60º (Fig. 9a). Then the formed a small contact angle of ~60º. The next or fourth drop

(a)

(b)

(c)

(d)

(e)

(f)

(g)

Fig. 9: Visualization of the behavior of AlSi22 drops deposited on rough graphite substrate by squeezing
the metal through alumina capillary at 1,273K (a-f) and subsequent cooling (g)

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(Fig. 9d) was deposited by low positioning of the capillary contact angles formed on a rough surface of the graphite
and by simultaneously rotating the substrate causing metal substrate used (Ra: ~150 – 400 μm, depending on location).
smearing along the substrate and resulting in the formation of These observations clearly showed the role of physical
the lowest contact angle of ~30º. Then a fifth large drop (Fig. heterogeneity of real surfaces on wetting and spreading
9e) was deposited by the high positioning of the capillary behavior of liquid metals that resulted in different adhesion
coupled with substrate rotation in such a way that the freshly and bonding and caused disagreement between practice and
produced and smeared drop with an artificially low contact experimental literature data that are almost always obtained on
angle touched the second drop. It caused immediate metal perfectly smooth, flat and non-deformable substrates.
breaking into two drops but the situation became reversible, There are also at least two other questions that resulted
i.e. former fifth drop became non-wetting while former second during the last step of the above tests (Fig. 9g) to be answered
non-wetting drop became wetting. After a few minutes (Fig. which is the reason that more fundamental research is
9f) the drops images were observed by substrate rotation and needed: (1) “Why during solidification of all AlSi22 drops
no significant change in contact angles were recorded. did they exhibit a noticeable extension in a vertical direction
The question is: “Why does the same alloy on the same corresponding to the direction of drops’ tension, independently
substrate and at the same temperature form such different of the values of the contact angles?” (2) “How may we utilize
contact angles vary from 150º to 30º and what is the true these observations in foundry practice?”
contact angle?” In this test, all recorded contact angles present Moreover, the most confusing observations are noted in Al/
apparent values corresponding to receding and advancing

(a) (b) (c) (d)

Fig. 10: Visualization of the behavior of different metals on ceramic substrates during wettability test using CP procedure:
(a) Al/SiO2, squeezing at 973K and fast headed to 1,273K, total contact time 80 min; (b) AlTi6/CNT-paper, 1,273K, 5
min, (c) NiW10 and (d) NiCr10 alloys on MgO(100) single crystal at 1,773K, 10 min

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ceramic systems of high reactivity on rough ceramics when central part of the drop, compared to its periphery (Fig. 11).
the effect of physical surface heterogeneity is coupled with the As explained in [16], this unusual shape of RPR is related
effect of primary oxide films. Such an example is shown in with the effect of the competition between the kinetics of the
Fig. 11(a-e) that illustrates wetting behavior of liquid Al placed chemical reaction and the kinetics of deoxidation of liquid Al
between two vertical yttria plates of different roughness at taking place at high temperatures under a vacuum due to the
1,000℃ under high vacuum [16]. On a polished (Ra: ~ 120 μm) formation of gaseous aluminum suboxide Al2O. Consequently,
surface, the contact angles are 72º and 70º, measured for both the kinetics of the removal of Al2O from the drop/substrate
a liquid and solidified drop, respectively. On a rough surface interface presents a key factor and it depends on the type of
(Ra: ~ 400 μm), they are 97º and 77º, correspondingly, and the Al/substrate contact. In the case of polished substrate,
present advancing contact angles caused mainly from physical this contact is continuous (“hermetic”) and the primary oxide
heterogeneity of the substrate surface. But what is interesting film on Al specimen remains undestroyed thus preventing
is that despite identical testing conditions the shape of the the formation of a true drop/substrate contact for longer time.
reaction product region (RPR) formed inside the substrate is In the case of rough substrate, the Al/substrate contact is
different. For rough surface, it has a classical leaf-like shape discontinuous, allowing much easier and faster removal of
typical for reactive systems. On the contrary, for polished gaseous product Al2O from the interface in the contact area.
substrate the RPR is unusually more than twice thinner in the

(a) (b) (c) (d) (e)

(f) (g) (h)

Fig. 11: (a-e) Visualization of the behavior of pure Al placed between two dense yttria plates, during melting (a),
heating to (b) and at (c,d) 1,000ºC followed by cooling (e); (f) scheme of the examined assembly; (g,h) Cross-
sections of assembly showing the formation of regular shape of RPR with polished yttria plate (g), contrary to
unusual RPR shape with rough (grounded) yttria plate (h)

3.2 Ni alloys separate the Ni drop from the sapphire substrate. However,
Liquid pure Ni shows non-wetting and a non-reactive (no new contrary to expectations for most non-reactive and non-
reactively produced phases) character in contact with all oxides wetting systems, during drop sucking, a well-adhered sapphire
used for the manufacture of ceramic products for melting substrate was picked up along with the drop thus preventing
and casting of Ni-alloys. Nevertheless, the high melting a drop-substrate separation, as shown in Fig. 12. Likewise, it
temperature of Ni influences its interaction with oxides due to was impossible to reposition the drop to another location using
an increased role of ceramic dissolution in liquid Ni. Since the the drop pushing procedure of Fig. 3(c), because the whole
surface tension of liquid Ni strongly depends on the amount drop/sapphire couple, and not just the Ni drop, moved on the
of dissolved oxygen [17], one may expect some changes in alumina support [18]. Strong adhesion and problems with drop
wetting and spreading behavior of liquid Ni during any long- de-bonding by either drop pushing or drop sucking procedures
time contact with a ceramic substrate. Moreover, despite non- were also noted for non-reactive and non-wetting Ni and
wetting and its non-reactive character, pure Ni and some of its NiW10 drops with MgO [18], ZrO2 and Y2O3 substrates.
alloys show good adhesion to many bulk oxides. In a recent Therefore, for such systems, a special support fixture was
study [18] on a Ni/Al 2O 3(sapphire) system the Ni drop was designed to separate the oxide substrate from the drop for
sucked via an overhead alumina capillary (using the procedure either partial or complete in-situ opening of the interface at the
shown in Fig. 3c) after 10 min contact at 1,773 K in order to test temperature as shown in Fig. 3(d). Using this improved

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behavior in the Ni/MgO system (θ = ~112°) coupled with

the significant density difference of MgO and Ni cause the
enhanced floatation of the MgO particles and their collection
to the top of the melt. Therefore, it is reasonable to use a
bottom metal pouring instead of pouring by crucible tilting.
Furthermore, during solidification the introduced MgO
inclusions could be pushed by the non-wetting solidifying
alloy and hence directional solidification is the preferred
casting process for Ni-base alloys in order to remove these
inclusions.
The study [18] also provided evidence for the pristine
ceramic surface modification by metal vapor from Ni-base
Fig. 12: Visualization of a good adhesion of Ni drop alloys ahead of an advancing triple line (TL). Such surface
to sapphire substrate (transparent) at 1,773 K
resulting in up movement of the substrate during modifications take place even when metal vapor neither reacts
drop sucking into the alumina capillary with nor condenses at TL but nevertheless causes significant
changes in surface morphology resulting in the formation
drop pushing procedure several interesting observations were of numerous cavities that might affect the surface quality of
made with Ni and NiW10 drops on single crystal MgO(100) the final cast products. If volatile additions in the alloy react
substrates described in detail in [18]. Figure 10(c) presents with the oxide ceramic the formation of new oxide crystals
the visualization of the behavior of the NiW10 alloy on a at the oxide substrate ahead of an advancing triple line takes
perfectly smooth MgO(100) single crystal substrate (8 Å place by a mechanism similar to the CVD process. Such an
roughness) at 1,773K, forming a contact angle of 118°. After example is shown in Fig. 13(a) for Ni-Al/MgO couple at 1,773
a 15 min hold in the 1st position, the NiW10 drop was pushed K where Al vapor was responsible for growth of MgAl2O4
and partially deposited onto polycrystalline alumina support spinel whiskers around the drop. These results are important
(Al2O3PC) in such a way that only ~2/3 of the drop’s bottom in view of possible crucible degradation above the level of
surface was “seated” on the support. However, it was observed molten metal affecting the lifetime of foundry appliances and
that the drop returned almost to the same position on the the formation of non-metallic inclusions, particularly in metal
MgO(100) substrate immediately after upward movement of pouring by tilting a crucible.
the alumina pusher, despite the fact that only ~1/3 of the drop Interestingly, the formation of the same spinel whiskers was
base was on the MgO(100). In the second attempt, the drop also observed in case of wettability test with Ni-Al alloy on
was pushed again, positioned wholly on the support and kept for an alumina substrate if the alloy was pre-melted in a crucible
15 min. Since the alumina support surface had a much higher made from MgO-based ceramic. In this case, Mg was first
roughness, the difference between the left and the right angles introduced into alloy due to redox reaction of MgO with Al.
on Al2O3 PC was noticeable (~15°) while average contact angle Next in the wettability test, it evaporated and reacted with the
value was 27° higher compared to reference sapphire substrate alumina substrate to form spinel whiskers around the drop.
(θ sapphire = 112°, θ Al2O3 = 139° [18]). The growth of whisker-like crystals is possible also directly at
These observations were found to be consistent with the the drop surface due to interaction between the drop and the
calculations of work of adhesion (Wa) as for NiW10/MgO, Wa gaseous compounds evacuated from the substrate. An example
is more than twice that for NiW10/Al2O3PC. They suggest also is shown in Fig. 13(b) for interaction between Al alloys with
the reason for quite common MgO-rich inclusions in Ni-based a rough graphite substrate without prior heat treatment since
castings since during processing, small MgO particles could pre-heating at 1,273K causes the decomposition of residual
be detached from the surface of foundry appliances made from organic compounds from the substrate.
polycrystalline MgO-rich ceramics which come into contact Another example of an unusual behavior, shown in Fig.
with the liquid alloy. For such systems, the role of dissolutive 10(d), was recorded during high-temperature wettability
character of interaction contributing to establishment of a good tests at the Foundry Research Institute with NiCr10 alloy on
bonding between the melt and the ceramic should be taken MgO(100) single crystal at 1,773K under flowing high-purity
into consideration in the development of melting and casting Ar. During an isothermal hold at the test temperature, the drop
processes because it facilitates mechanical detachment of slowly spreads and wets the substrate to form a contact angle
oxide particles from the surface of crucibles, filters and molds, of ~70º. Next, sudden de-wetting takes place and the drop
especially if it is accompanied with any movement of the melt returns to almost its initial shape of a high contact angle of
during processing (e.g. mixing, flowing, pouring). ~140º. This wetting-de-wetting process repeats periodically
Another reason of such inclusions is related with an oxide 5 times during 15 min contact. In the final step, the drop was
substrate ridging around small gas bubbles easily formed pushed into another position by the alumina pusher. However,
at the melt/crucible interface. These ‘hills’ also might be during picking up of the pusher, unexpectedly, the drop was
mechanically destroyed and introduced into the melt during easily detached from the substrate and moved together with the
conventional pouring. In foundry practice, the non-wetting rising pusher. Based on these observations, one may conclude
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November 2010

Fig. 13: (a) Ni-Al/MgO couple after wettability test at 1,773K showing the formation of whisker-like MgAl2O4 crystals
at the substrate around the drop. Note similar effect was recorded on alumina substrate with Ni-Al alloy
prior melted in MgO crucible; (b) Al alloy on raw graphite material without prior heat treatment showing the
formation of whisker-like crystals at the drop surface due to interaction between the alloy with gaseous
products formed due to decomposition of residual organic compounds in the substrate.

that adhesion of NiCr10 alloy with MgO is weaker than that to conventional mold materials [20].
with alumina. But the reason for this is not clear, particularly Among different alloying additions to Ti, Al exhibits the
when taking into account the wetting character in NiCr10/ strongest effect on reactivity and wetting behavior of oxides,
MgO contrary to the non-wetting character in NiCr10/Al2O3. resulting in nonwetting-to-wetting transition from Ti/oxide
Presumably, interaction with NiCr10 alloy is strongly affected to Ti-Al/oxide. Alloying Ti with 50% Al results in perfect
by the evaporation from the alloy as evidenced by a green and immediate wetting of alumina mold at 1,773K (θ ~38º).
color (typical for chromium oxide) on the area under as well At the same temperature, it forms θ ~30º on ZrO2 mold after
as near the drop. Possibly it was formed by the consumption 2 min and θ ~50º on MgO-containing ZrO2 after 5 min [21].
of oxygen from MgO by Cr evaporated and deposited on the The highest contact angles were reported on Y2O3-containing
substrate surface in the vicinity of the drop. Research is under ZrO 2 (θ ~75º after 25 min) and on pure Y 2O 3 mold (θ ~85º
progress to explain this unusual behavior. after 23 min) [21]. These data are consistent with practical
In foundry practice of high-temperature melting of multi- recommendations on use of Y 2 O 3 -based colloidal (nano
component Ni-base alloys in crucibles made from complex approach) protective coating on crucibles or containers in high
oxide-based ceramics, the situation would become even more temperature measurements of thermophysical properties of
complicated because of the confluence of vapors of different liquid reactive alloys [20].
compositions and history, and formation of whisker-like Further alloying of Al-rich titanium alloy with such reactive
crystals of new oxides, usually deposited at cooler parts of additions as Nb or Ta (e.g. in alloys suitable for casting of
the furnace. These observations demonstrate the importance large turbine blades for aero-engines and stationary gas
of information on melting history of not only the Ni alloy and turbines) increases its melting temperature and as consequence,
the crucible but even the furnace used for its melting in order its reactivity [22]. It creates many difficulties in processing
to understand the reasons for expected structural defects in the liquid phase in a crucible. As an example in Fig. 14,
castings of Ni-base alloys. the Ti46Al46Nb8 alloy starts to wet the Al2O3 substrate even
before complete melting of the alloy (drop formation stage)
3.3 Ti alloys has occurred, and immediately after melting, it forms θ ~57º
Pure liquid Ti easily reacts with many oxide-based ceramics and θ ~42º, at ~1,920K and ~2,020K, respectively. Covering
by forming different interfacial Ti-rich oxides, depending alumina substrate with Y2O3-based colloidal protective coating
on the processing conditions. Contrary to most industrially increases the contact angle of the alloy, showing after 5 min of
important systems, high reactivity of Ti with these oxides contact, θ ~120º at 2,008 K. Interestingly, for the same contact
is not accompanied by good wetting (θ = 130-60º [19]) thus time, an increase in the temperature of only ~20K results in θ
making possible a selection of suitable mold materials for dropping to 77º (2,030K).
casting Ti. However, one of the main problems in foundry These results suggest the possibility to prepare accurate
practice of Ti is related with volumetric increase of oxide tests for determination of thermophysical properties of liquid
ceramic during interaction with liquid Ti and caused due to the TiAlX-based alloys (X: Nb or Ta) by utilizing kinetic factors,
formation of reaction products inside the ceramic, as reported i.e. under certain conditions and time, even extremely reactive
in [6]. Particularly for investment castings, such dimensional alloys are ‘kinetically’ stable thus allowing reliable data on
changes generate difficulties in manufacturing final Ti high temperature measurements to be experimentally accessed.
products of high quality. An application of a nano approach in This concept was utilized in the study on measurements of
manufacturing of oxide-based ceramics with additions of Y2O3 surface tension and density of TiAlX-based alloys [21] using
nano-particles was found to reveal beneficial effects, compared two methodologies in a single test (i.e. the pendant drop and

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sessile drop) and an advanced experimental complex described mbar vacuum, 2,100℃) to mimic the behavior of liquid or semi-
above. In order to make the measurements with pendant solid materials (metals, alloys, ceramics, glass, fluxes, dross) in
drop method highly reliable, special testing conditions were real technological processes. In this paper, new interfacial studies
created by reduction of alloy/ceramic true contact through relevant to the production of advanced cast materials of three
the presence of native primary oxide film on the Al45.5Ti46.5X8 groups of alloys: Al, Ni, and Ti were presented.
alloys during their melting in an alumina capillary. For the Aluminum is known to exhibit extreme sensitivity to
next-step involving sessile drop test on oxide-free droplets oxidation and the presence of even minute amounts of oxygen
produced by squeezing the alloy through the capillary, the (e.g., water vapor) lead to a primary oxide film on Al and
yttria-based porous barrier layer on alumina substrate (formed considerable dispersion in wetting properties. Aluminum
from colloidal yttria spray) was found to have sufficient oxidizes even under ultra high vacuum at temperatures below
stability. The results obtained showed a good agreement with ~1,000℃. Reaction between molten metals and residual water
those obtained by container-less method. vapor in a furnace atmosphere or from foundry appliances is
the most common factor for structural defects in castings such
as oxide inclusions and gas porosity. In addition, even a few
nanometers thick tenacious oxide films on liquid Al adversely
affects the wetting and joint strength, factors important in
cast MMCs. Removal of oxide films via capillary purification
improves both wetting and bonding, and this provides the basis
for application of oxide removal methods for MMCs, such as
intensive stirring, ultrasound, or addition of Mg to Al melts, to
transform primary oxides into MgAl2O4.
Likewise, reactions between molten Al and SiO 2 are
particularly important because of extensive use of silica
in many refractory ceramics used for melting technology
products such as molds, filters, crucibles, etc. Tests show
that wettability in the Al/SiO2 system is controlled by the
wettability of Reaction Product Region (RPR) and not by the
Fig. 14: Wettabilty kinetics of Ti46Al46Nb8 alloy (mole %) wettability of SiO2. Thus, SiO2-containing refractories are
on pure Al2O3 substrate (PC-polycrystalline; suitable for short-time or low-temperature contact with molten
SC-single crystal) and the values of contact low-silicon Al alloys in air. At high temperatures, the lifetime
angles formed after 5 min contact on Y2O3
-coated alumina at 1,735ºC and 1,755ºC. of such materials significantly decreases and they should not
be used in crucibles. In another example, the effect of CVD
carbon films (or mechanically smeared soot or graphite paint)
4 Summary and conclusions results in better wetting and bonding. However, it may cause
The field of high-temperature liquid-state materials science some problems in melting and casting of Al alloys containing
impacts a number of advanced processing and manufacturing Ti or other carbide-forming solutes when the surface of
technologies such as casting, soldering, brazing, welding, molds, crucibles or holders is stained with carbon. Many
liquid-phase sintering, and cast composites. The production unusual interfacial phenomena are caused by roughness and
of advanced materials is impacted by wettability, spreading, whiskering, and lead to large dispersion in contact angles on
infiltration, volumetric changes, nonmetallic inclusions, smooth and rough surfaces.
refractory degradation, roughening, whiskering, and metal Nickel is non-wetting and non-reactive in contact with
oxidation. The properties of the final product depend upon oxides used in the manufacture of ceramic products for melting
these factors and are related to high-temperature properties of and casting of Ni-alloys; however, Ni dissolves oxides and the
liquid metal and, particularly, high-temperature surface and surface tension of liquid Ni depends upon dissolved oxygen.
interfacial phenomena. Thus interactions between liquid metals Ni alloys show good adhesion to bulk oxides such as MgO;
and solids, and the nature of interfaces formed play a key role this leads to the frequent occurrence of MgO-rich inclusions
in selecting suitable materials and processing parameters. in Ni-base castings that get mechanically detached from the
Recent advances in methodological, scientific and surface of foundry appliances made from polycrystalline MgO-
technological aspects of high-temperature processing using rich ceramics, especially if accompanied by a fluid flow (e.g.
new, sophisticated experimental techniques have begun to mixing, flowing, pouring). Such inclusions could also form
unravel the complex role of fundamental phenomena. A unique because of a detachment of oxide substrate ridges that develop
experimental complex designed and developed at the Foundry around tiny gas bubbles formed at the melt/crucible interface.
Research Institute, Krakow, allows in-situ studies at high The non-wetting behavior of Ni and MgO coupled with
temperatures. Its unique design and multiple features permit the significant density difference between them causes MgO
complex functions such as ‘pushing’, ‘smearing’ and ‘rubbing’ of floatation and segregation at the top thus necessitating bottom
sessile drops to be done under stringent test conditions (10-7-10-10 pouring during casting. Furthermore, as MgO inclusions
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November 2010

could be pushed by non-wetting solidifying alloys, directional [3] Eustathopoulos N, Sobczak N, Passerone A, Nogi K.
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http://www.tms.org/pubs/journals/JOM/0001/Asthana/Asthana-
0001.html

(The paper was presented at the 69th World Foundry Congress (WFC), Hangzhou China 2010, republished in China Foundry with the
author's kind permission)

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