Professional Documents
Culture Documents
Melt reactions
1.1 Gaseous interactions with the melt considerable quantities of moisture in its lining
materials. Most refractories are hygroscopic and will
A liquid metal is a highly reactive chemical. It will absorb water up to 5 or 10 per cent of their weight.
react both with the gases above it and the solid This water is released into the body of the furnace
material of the crucible which contains it. If there is over the next few days of operation. It has to be
any kind of slag or flux floating on top of the melt, it assumed that the usual clay/graphite crucible ma-
will probably react with that too. terials are quite permeable to water vapour and/or
The driving force for these processes is the hydrogen, since they are designed to be approxi-
striving of the melt to come into equilibrium with its mately 40 per cent porous. Additionally, hydrogen
surroundings. Its success in achieving equilibrium is, permeates freely through most materials, including
of course, limited by the rate at which reactions can steel, at normal metallurgical operating tempera-
happen, and by the time available. tures of around 70O0C and above.
Thus reactions in the crucible or furnace during This moisture from linings or atmosphere can
the melting of the metal are clearly seen to be react in turn with the melt M:
serious, since there is usually plenty of time for M + H2O -» MO + H2 (1.2)
extensive changes. The pick-up of hydrogen from
damp refractories is common. Similar troubles are Thus a little metal is sacrificed to form its oxide, and
often found with metals which are melted in the hydrogen is released to equilibrate itself
furnaces heated by the burning of hydrocarbon fuels between the gas and metal phases. Whether it will,
such as gas or oil. on average, enter the metal or the gas above the
The chemical composition of hydrocarbons can be metal will depend on the relative partial pressure of
denoted QH^, and thus represent the straight chain hydrogen already present in both of these phases.
compounds such as methane CH4, ethane C2H6 and This reaction in turn is:
so on, or aromatic ring compounds such as benzene H2 = 2[H] (1.3)
C6H6 etc. (Other more complicated molecules may
contain other constituents such as oxygen, nitrogen, and the equation which allows prediction of the
and sulphur, not counting impurities which may be partial pressure of hydrogen which will be in
present such as arsenic, vanadium etc.) equilibrium with a given concentration of hydrogen
For our purposes we will write the burning of fuel in solution in the melt is:
as [H]2 = kPm (1.4)
QHy + (x + — JO 2 -> *CO2 + -H2O (1.1) where the constant k has been the subject of many
experimental determinations for a variety of
Clearly the products of combustion of hydrocarbons gas-metal systems (Brandes, 1983; Ransley and
contain water, so the hot waste gases from such Neufeld, 1948). It is found to be affected by alloy
furnaces are effectively wet. Even electrically additions (Sigworth and Engh, 1982) and tempera-
heated furnaces are not necessarily free from the ture. When the partial pressure of hydrogen P=I
problem of wet environment: an electric resistance atmosphere, then it is immediately clear from this
furnace which has been allowed to stand cold over a equation that k is numerically equal to the solubility
weekend will have had the chance to absorb of hydrogen in the metal at that temperature. Figure
Temperature (0C) 1.1 shows how the solubility of hydrogen in
aluminium increases with temperature.
It is vital to understand fully the concept of an
equilibrium gas pressure associated with the gas in
solution in a liquid. We shall digress to present a few
examples to illustrate the concept.
Consider a liquid containing a certain amount of
hydrogen atoms in solution. If we place this liquid in
an evacuated enclosure then the liquid will find itself
out of equilibrium with respect to the environment
Solubility of hydrogen (ml/kg)
Medium initial
gas content
1 atmosphere
addition of deoxidizer therefore still leaves hydro- the metal oxide is reduced, and carbon is oxidised to
gen at near saturation. This problem is, of course, CO, is that at which the free energies for the
less severe if electric melting is used. formation of CO exceed that of the metal oxide, i.e.
A second reported method is melting under CO becomes more stable. This is where the lines
reducing conditions to decrease losses by oxidation. cross on the Ellingham diagram). However, it is as
Hydrogen removal is then attempted just before well to remember that charcoal contains more than
casting by adding copper oxide or by blowing dry air just carbon. In fact, the major impurity is moisture,
through the melt. Normal deoxidation is then even in well-dried material which appears to be
carried out. The problem with this technique is that quite dry. An addition to the charge at an early stage
the hydrogen-removal step requires time and in melting is therefore relatively harmless because
requires the creation of free surfaces, such as the release of moisture, and the contamination of
bubbles, for the elimination of the reaction product, the charge with hydrogen and oxygen, will have time
water vapour. Waiting for the products to emerge to be reversed. An addition of charcoal at a late
from the quiescent surface of a melt sitting in a stage of melting will flood the melt with fresh
crucible would probably take 30-60 min. Fumes supplies of hydrogen and oxygen which may not
from the fuel-fired furnace would be ever-present to have time to evaporate out before casting. Any late
help to undo any useful degassing. This technique additions, even alloying additions, introduce the risk
cannot be recommended at all. of unwanted gases.
The second technique described above would Reliable routes to melted metal with low gas
almost certainly have used a cover of granulated content include:
charcoal over the melt to provide the reducing
conditions. This is a genuinely useful way of 1. Electric melting in furnaces which are never
reducing the formation of drosses (dross is a mixture allowed to go cold.
of oxide and metal, so intimately mixed that it is 2. Controlled use of flaring for zinc-containing
difficult to separate) as can be demonstrated from alloys.
the Ellingham diagram (Figure 1.5). The oxides of 3. Controlled dry atmosphere above the melt.
the major alloying elements copper, zinc and tin are Charcoal is satisfactory, if added at an early
all reduced back to their metals by carbon, which stage, preferably before melting. (Late additions
preferentially oxidizes to carbon monoxide (CO) at of charcoal or other sources of moisture are to be
this high temperature. (The temperature at which avoided).
Standard free energy of formation (kJ)
In summary, the gases which can be present in the cupola furnace used in the melting of cast iron for
various copper based alloys are: use in iron foundries.) The CO reaction is so
Pure copper H2, H2O vigorous and violent that it is called a 'carbon boil'.
Brasses, gunmetalsH2, H2O, Zn, Pb After the carbon is brought down into specific-
Cupro-nickels H2, H2O, CO, (N2?) ation, the excess oxygen which remains in the steel is
lowered by deoxidizing additions of manganese,
1.1.3 Iron alloys silicon or aluminium. In modern practice a complex
cocktail of deoxidizing elements is added as an
Like copper-based alloys, iron-based alloys are also alternative or in addition. These often contain small
complicated by the number of gases which can react percentages of rare earths to control the shape of the
with the melt, and which can cause porosity on non-metallic inclusions in the steel.
subsequent evolution on solidification. Again, it Hydrogen is soluble as in Equation 1.3, and exists
must be remembered that all the gases present can in equilibrium with the melt as indicated in Equation
add to the total pressure in equilibrium with the 1.4. However, a vigorous carbon boil will reduce
melt. any hydrogen in solution to negligible levels by
Oxygen is soluble, and reacts with carbon, which flushing it from the melt.
is one of the most important constituents of steels In many steel foundries, however, steel is melted
and cast irons. Carbon monoxide is the product, from scrap steel (not made from pig iron, as in
following Equation 1.8. steelmaking). Because the carbon is therefore
In steelmaking practice the CO reaction is used to already low, there is no requirement for a carbon
lower the high carbon levels in the pig iron produced boil. TTius hydrogen remains in the melt. There is no
by the blast furnace. (The high carbon is the result quick chemical fix for hydrogen as there is for
of the liquid iron percolating down through the coke oxygen by the use of a deoxidizer. Hydrogen can
in the furnace stack. A similar situation exists in the only be encouraged to leave the metal by providing
an extremely dry and hydrogen-free environment. If leave it as the product of concentrations, as being
a carbon boil cannot be artificially induced, and if accurate enough to convey the concepts which we
environmental control is insufficiently good, or is wish to discuss.
too slow, then the comparatively expensive last Nitrogen is also soluble in liquid iron. The
resort is vacuum degassing. This option is common reaction follows the normal law for a diatomic gas:
in the steelmaking industry, but less so in steel
melting for the making of castings. N2 -> 2[N] (1.10)
A carbon boil can be induced in molten cast iron, and the corresponding equation to relate the
providing the silicon is low, simply by blowing air concentration in the melt [N] with its equilibrium
onto the surface of the melt (Heine, 1951). Thus it is pressure J0N2 is simply:
clear that oxygen can be taken into solution in cast
iron which already contains high levels of carbon, so [N]2 = A:PN2 (1.11)
releasing CO gas at (or actually slightly above) As before, the equilibrium constant A: is a function
atmospheric pressure. During solidification, as of temperature and composition. It is normally
carbon and oxygen are concentrated still further, it determined by careful experiment.
is easy to envisage how, from relatively low initial
contents of these elements, they can increase 1.1.4 Transport of gases in melts
together so as to exceed a critical product [C].[O] to
cause CO bubbles to form in the casting. The Gases in solution in liquids travel most quickly when
equilibrium equation, known as the solubility the liquid is moving, since, of course, they are
product, relating to Equation 1.8 is: simply carried by the liquid.
However, in many situations of interest the liquid
[C].[O] = kPco (1.9) is stationary, or nearly so. This is the case in the
We shall return to this important equation later. It is boundary layer at the surface of the liquid. The
worth noting that the equation could be stated more presence of a solid film on the surface will hold the
accurately as the product of the activities of carbon surface stationary, and because of the effect of
and oxygen. However, for the moment we shall viscosity, this stationary zone will extend for some
Reciprocal absolute temperature (103 K'1)
Liquid
Figure 1.7 Diffusion coefficients for elements
0 in iron (see Figure 1.6 (caption) for sources of
Temperature ( C) data).
the rates of diffusion of elements which are apparent of their oxides, and thus the ease with which they
in the solid become less marked. are reduced back to the metal.
These relative rates of diffusion will form a It is interesting to note that cast iron is an
recurrent theme throughout this book. The reader intermediate case, occupying an intermediate pos-
will benefit from memorizing the general layout of ition in the Ellingham diagram. It therefore has a
Figures 1.6 and 1.7. complicated behaviour, sometimes having films,
whose changing compositions change them from
1.2 Surface film formation solid to liquid as the temperature falls. Its behaviour
is considered in detail later.
1.2.1 Films in general Certain casting alloys are characterized by the
When the hot metal interacts with its environment stability of the products of their surface reactions.
many of the reactions result in products which Although part of the reaction products, such as
dissolve rapidly in the metal, and diffuse away into hydrogen, diffuse away into the interior, the
its interior. Some of these processes have already noticeable remaining product is a stable surface
been described. film. Film-forming alloys include alloy systems
In fact, is worth bearing in mind that the two based upon aluminium, magnesium, and titanium.
important film-forming reactions, the formation of A wide range of other important alloys exist
oxide films from the decomposition of moisture, and whose main constituents would not cause any
the formation of graphitic films from the decom- problem in themselves, but which form troublesome
position of hydrocarbons, both result in the increase films in practice because their composition includes
of hydrogen in the metal. The comparative rates of just enough of the above highly reactive metals.
diffusion of hydrogen and other elements in solution These include the following:
in various metals are shown in Figures 1.6 and 1.7. Liquid lead exhibits a dull grey surface oxide
These reactions will be dealt with in detail later. consisting of solid PbO. This interferes with the
In the case of liquid copper in a moist, oxidizing wetting of soldered joints, giving the electrician the
environment, the breakdown of water molecules at feared 'dry joint', which leads to arcing, overheating
the surface releases hydrogen which diffuses away and eventual failure. This is the reason for the
rapidly into the interior. The oxygen released in the provision of fluxes to exclude air and possibly
same reaction (Equation 1.5), and copper oxide, provide a reducing environment (the corrosive
Cu2O, which may be formed as a temporary fluxes to dissolve the oxide are now less favoured)
intermediate product, are also soluble, at least up to and the use of pre-tinning of the parts to be joined,
0.14 per cent oxygen. The oxygen diffuses and since tin stays free from oxide at low temperature.
dissipates more slowly in the metal so long as the The addition of 0.01 per cent Al to lead is used to
solubility limit in the melt is not exceeded. It is reduce oxidation losses during melting. However, it
clear, however, that no permanent film is created would be expected to increase wettability problems.
under oxidizing conditions. Also, of course, no film From the Ellingham diagram it is clear that lead can
forms under reducing conditions. Thus liquid copper be kept clear of oxide at all temperatures for which
is free from film problems in most circumstances. it is molten by a covering of charcoal: the CO
(Unfortunately this may not be true for the case atmosphere will reduce any PbO formed back to
where the solubility of the oxide is exceeded at the metallic lead.
surface, or in the presence of certain carbonaceous Zinc alloys: Most zinc-based castings are made
atmospheres, as we shall see later.) from pressure die casting alloys which contain
Liquid silver is analogous to copper in that it approximately 4 per cent Al. This percentage of
dissolves oxygen. In terms of the Ellingham diagram aluminium is used to form a thin film of aluminium
(Figure 1.5) it is seen that its oxide, Ag2O, is just oxide which protects the iron and steel parts of the
stable at room temperature, causing silver to tarnish casting machines from attack by zinc. From the
(together with some help from the presence of point of view of the casting quality, the film-
sulphides), as every jeweller will know! However, formation problem does give some problems,
the free energy of formation of the oxide is positive assisting in the occlusion of air during the extreme
at higher temperatures, appearing therefore above surface turbulence of filling. Nevertheless, these
zero on the figure. This means that the oxide is problems generally remain tolerable because the
unstable at higher temperatures. It would therefore melting and casting temperatures of zinc pressure
not be expected to exist except in cases of transient die casting alloys are low, thus probably restricting
non-equilibrium. the development of the film.
Liquid tin is also largely free from films. Other zinc-based alloys which contain higher
The noble metals such as gold and platinum are, quantities of aluminium, the ZA series containing 8,
for all practical purposes, totally film-free. These 12 and 27 per cent Al, become increasingly
are, of course, all metals which are high on the problematical as film formation becomes increas-
Ellingham diagram, reflecting the relative instability ingly severe.
Alloys such as the AI-Mg family, where the in which films can become incorporated into a
magnesium level can be up to 10 weight per cent, are casting so as to damage its properties. These are
widely known as being especially difficult to cast. vitally important issues. They are dealt with below.
Along with aluminium bronze, those alloys contain-
ing 5-10 per cent Mg share the dubious reputation 1.2.2 Films on aluminium alloys
of being the world's most uncastable casting alloys!
Aluminium bronze itself contains up to approxi- A solid film grows from the surface of the liquid,
mately 10 per cent Al, and the casting temperature atom by atom, as each metal atom combines with
is of course much higher than that of aluminium newly arriving atoms or molecules of the surround-
alloys. The high aluminium level and high tempera- ing gas.
ture combine to produce a thick and tenacious film For the case of pure aluminium the oxide film is
which makes aluminium bronze one of the most initially y-alumina. This is a thin film which inhibits
difficult of all foundry alloys. Some other high- further oxidation. After an incubation period this
strength brasses and bronzes which contain alu- oxide transforms to a-alumina, which allows oxid-
minium are similarly difficult. ation at a faster rate. The alloying elements iron,
Ductile irons (otherwise known as spheroidal copper, zinc and manganese have little effect on the
graphite or nodular irons) are markedly more oxidation process (Wightman and Fray, 1983).
difficult to cast free from oxides and other defects Other alloys mentioned below appear to exert
when compared to grey (otherwise known as flake important changes.
graphite) cast iron. This is the result of the minute Where the aluminium alloy contains a trace of
concentration of magnesium which is added to magnesium (above approximately 0.005 weight per
spherodize the graphite. cent) the surface oxide is the mixed oxide
High-temperature alloys: These nickel and cobalt- MgO.Al2Os known as spinel. When the magnesium
based materials for turbine blades contain alu- content of the alloy is raised to above approximately
minium and titanium as the principal hardening 2 per cent, then the oxide film is expected to be pure
elements. Because such castings are produced by magnesia, MgO (Ransley and Neufeld, 1948).
investment (lost wax) casting, the running systems In fact, the majority of aluminium alloys have
have been traditionally poor, the top pouring some magnesium in the intermediate range so that a
introducing severe surface turbulence. Scrap levels spinel film is to be expected as the norm. When such
are therefore normally high. In an effort to reduce an oxide film is viewed under the microscope, the
the scrap, the alloys have been cast in vacuum. It surface resembles a jumble of separate trigonal
seems clear, however, that this is not a complete shaped crystals.
solution, which is to be expected from the fact that Rough measurements of the rate of thickening of
alumina is only prevented from forming in a vacuum the film on holding furnaces show its growth to be
around 10~30 torr, which is a better vacuum than impressively fast, approximately 7 x 10~7(kg/m2)/
exists in outer space! The real solution is, of course, s, which is orders of magnitude faster than rates of
to avoid top pouring and so avoid the incorporation growth of protective films on solid metals. Since the
of the oxide films. oxide itself is almost certainly fairly impervious to
Steels are an interesting and complicated case. the diffusion of both metal and oxygen, how can
The normal carbon and manganese steels form films further growth occur after the first molecular
which do not appear to be too troublesome to the thickness?
manufacture of castings. This is a welcome benefit It seems that this happens because the film is
where turbulent running systems are the norm, and permeated with liquid metal. Fresh supplies of metal
difficult to correct because of the necessity to cast arrive at the surface of the film not by diffusion,
from bottom-poured ladles, where the overlying which is slow, but by flow of the liquid along
head of metal causes high and effectively uncontroll- capillary channels, which is, of course, far faster.
able velocities in the running system. In higher- The structure of the film as a porous assembly of
alloyed steels containing chromium and/or alu- oxide crystals percolated through with liquid metal,
minium, including stainless steels, the solid oxide as coffee percolates through ground beans, is an
forms a thick film which tends to give problems essential concept for the understanding of its
when making castings. behaviour.
With regard to all these film-forming alloys, it has to
be kept in mind that although a surface film can be 1.2.3 Effect of alloying elements
harmless whilst it is on the surface, it also has the The presence of other alloying elements significantly
potential to become one of the most severely affects the character and growth of the oxide on
damaging defects if somehow introduced into the aluminium alloys.
interior of the finished casting. It is essential, We have already seen that progressive magnesium
therefore, to understand film formation and the way additions change the oxide from alumina, to spinel,
and finally to magnesia. A cursory study of the Sodium is also added to modify the microstructure
periodic table to gain clues of similar behaviour of the eutectic silicon in Al-Si alloys. In this case the
which might be expected from other additives effect on the existing oxide film is not clear, and
quickly indicates a number of likely candidates. The requires further research. Sodium will have much
other group UA elements, the alkaline earth metals less of an effect in sensitizing the melt to the effect of
including beryllium, calcium, strontium and barium, moisture because it is less reactive than strontium.
and the neighbouring group IA elements, the alkali In addition, sodium is lost from the melt by
metals lithium, sodium and potassium, would be evaporation because the temperature is close to its
expected to be similar. The Ellingham diagram also boiling point of 8830C. Wightman and Fray (1983)
confirms that these elements have similarly stable find that all alloys which vaporize disrupt the film
oxides, so stable in fact that alumina can be reduced and increase the rate of oxidation. The additions
back to aluminium and the new oxide take its place include sodium, selenium and (above 90O0C) zinc
on the surface of the aluminium alloy. (Figure 1.8).
The disruption or wholesale replacement of the The effect of volatile elements, sodium, selenium
protective alumina or spinel film may have impor- and zinc, in the melt is complicated. In addition to
tant consequences for the melt. the direct effect on the oxide film, the environment
In the case of additions of beryllium at levels of above the melt will be protected to some extent
only 0.005 per cent, the protective qualities of the from the approach of water vapour by the outflow-
film on Al-Mg alloy melts is improved, with the ing wind of metal vapour.
result that oxidation losses are reduced. Experience of handling melts to which sodium has
When, however, strontium is added (usually to been added indicates that the character of the oxide
modify the eutectic silicon in Al-Si to improve the film is changed to become more tenacious. The
ductility of those alloys above 7 per cent or so beneficial effects found for the improved ductility of
silicon), the enhanced rate of oxidation of the Al-Si alloys treated with sodium may be due not
strontium means that any moisture in the environ- only to the refined silicon particle size, but also
ment is quickly converted to surface oxide, and the partly to the changed distribution of oxide films.
hydrogen is released into the melt (Equation 1.2). In
open furnaces therefore the addition of strontium is
usually accompanied by an increase of porosity. The 1.2.4 Films on cast iron
porosity naturally increases with increasing stron-
tium content, temperature, time, and environmental When cast iron is held at a high temperature (e.g.
water. This makes it practically impossible to add 150O0C) in a furnace or ladle lined with a traditional
strontium in most foundry melting systems, unless refractory material such as ganister, its surface is
the time for absorption of hydrogen is reduced by seen to be continuously marked by bright patches
pouring of the whole melt immediately after the which suddenly appear and spread from nothing to
strontium treatment. their full size of several centimetres within about a
Strontium is, however, successfully used in low second. The patches drift around, coalesce with
pressure casting systems where the melt is transfer- other patches, and finally attach themselves to the
red immediately after treatment into an enclosed wall of the vessel where they add to the solidified
furnace. It may then be held indefinitely, provided rim of slag. These patches are droplets of liquid
that the pressurizing gas which is introduced into the refractory, melted from the walls and bottom of the
furnace from time to time is dry or inert, and that vessel. As the vessel is tipped and emptied, the
the furnace lining is already saturated with stron- upstanding 'stalactites' on the base which mark the
tium from previous additions. These numerous sites where drops detached, and the upward runs
factors explain the confusion which has existed over and drips on the walls, can usually be clearly seen.
whether strontium can be successfully added with- In common with all the components of molten
out the deleterious effect of hydrogen pick-up. (As a metal systems, the slag will be changing its
further aside, the oft-quoted quantity of hydrogen composition rapidly as it interacts with the molten
which is added with the strontium alloy addition, metal. At high temperature its contents of iron,
and which is often blamed for this problem, is manganese and silicon will be reduced from their
almost certainly negligible.) respective oxides and taken into solution in the
It is worth mentioning that this explanation of the liquid iron, whereas the remaining stable oxides,
action of strontium is not agreed with by all. such as those of aluminium and calcium, will remain
Gruzleski (Dimayuga 1988, Mulazimoglu 1989) has to accumulate as a dry slag, often called a dross.
carried out careful measurements on Al-TSi-0.36Mg These reactions will be explained further in the next
alloy and found no increase in the rate of absorption section.
of hydrogen after additions of strontium. It may be, Such layers of slag on the surface of molten iron
however, that higher magnesium levels are required, can be anything from 0.1 mm thickness upwards. (In
possibly around 0.5Mg to 0.6Mg. the cupola, of course, the thickness is often around
Reciprocal absolute temperature (103 K'1)
1 Atmosphere
Boiling points
Vapour pressure (mm Hg)
100mm or more.) It is not intended to consider such composition of the iron; de Sy (1967) reports a range
surface-layer problems in this section. Practical of 1410-145O0C for the irons which he investigated,
solutions to deal with these macroscopic surface whereas the Ellingham diagram, Figure 1.5, predicts
problems are dealt with later in the sections on an inversion temperature for pure Fe-C alloys of
running systems and slag traps. This section about 150O0C. The agreement is, perhaps, as good
considers only the microscopically thin surface film as can be expected. Below approximately 140O0C,
which, under certain conditions, will form auto- therefore, SiO2 appears on the surface as a dry, solid
matically on the surface of the melt (no matter how film, rather grey in colour. This film cannot be
good is the melting resistance of the lining material removed by wiping the surface, since it constantly
of the holding vessel). reforms.
At a temperature of 130O0C, and in alloys which
1.2.4.1 Oxide films contain some manganese, it is clear from the
Ellingham diagram that MnO is the least stable,
Work by Heine and Loper at the University of SiO2 is intermediate, and CO the most stable. Thus
Wisconsin, dating from 1951, has done much to manganese is oxidized away preferentially, after-
explain the complex film formation in cast irons. It is wards followed by silicon, and finally by carbon.
convenient to explain the changes which occur as the The contribution of MnO may reduce the melting
temperature falls. point of the film, causing it to become liquid.
When the iron is at a high temperature, 155O0C, At around 120O0C, iron oxide, FeO, contributes
the Ellingham diagram indicates that CO is a more to the further lowering of the melting point at the
stable oxide than SiO2. Thus carbon oxidizes ternary eutectic between FeO, MnO and SiO2. If
preferentially, and is therefore lost at a higher rate sulphur is also present in the iron then MnS will
than silicon, as is well seen in Figure 1.9. Here the contribute to a complex eutectic of melting point
blowing of air on to the surface of a small crucible of 10660C (Heine and Loper, 1966).
molten metal serves to accentuate the effect. Silicon When casting grey iron in an oxidizing environ-
is observed to fall only after all the carbon has been ment, the falling temperature during the pour and
used up. Under these conditions no film is present the filling of the mould will ensure that the surface
on the melt - any SiO2 phase would be immediately film will be liquid. If it becomes entrained in the
reduced to silicon, which would be dissolved in the molten metal it will therefore quickly spheroidize
melt, simultaneously forming CO, which would into compact droplets. The droplets are of much
escape to atmosphere. lower density than the iron, and so will float out
At around 142O0C the stability of the carbon and rapidly. On meeting the surface of the casting they
silicon oxides is inverted. The exact temperature of will wet the existing liquid film, and so spread over
this inversion seems to be dependent on the the casting surface. The glassy sheen of some grey
Composition (wt per cent)
Time (h)
Composition (wt per cent)
Time (h)
w/
Figure 1.9 The change in composition of 3.6kg of molten grey iron held in a silica
crucible, whilst air was directed over its surface at the rate of 22 mils (a) melt at
155(TC; and (b) melt at 130O0C. Data from Heine (1951).
iron castings may be this solidified skin. The at the upper surface of the dross is the reason for the
harmless dispersal of the oxide film in this way is the dross growing so quickly and copiously. The dross is
reason for the good natured behaviour of cast iron the bain of the ductile iron foundryman, forming
when cast into greensand moulds; it is one of the films, and agglomerating into dry, non-wetting
very few metal-mould combinations which is heaps, spoiling the surface of otherwise excellent
tolerant of surface turbulence. castings. Ductile iron is renowned for being difficult
In ductile irons it is quite another matter. The to cast cleanly, without such unsightly dross defects.
small percentage of magnesium which is required to Liquid steel probably forms an analogous series of
convert the iron from flake to the spheroidal complex films. An aluminium addition has been
graphite type dramatically alters the nature of the recommended to reduce MnO and FeO, which
oxide film. contribute to slag-type defects (Rouse, 1987).
Above 14540C Heine and Loper (1966) find that However, the solid alumina film will not be without
the surface of liquid ductile iron remains clear of any its associated problems. Later we shall see how
film. Below this temperature a film starts to form, improved running systems can help to solve this
increasing in thickness to 135O0C, at which point the problem.
surface exhibits solidified crusty particles. By the
time the temperature has reached 129O0C the entire
surface is covered with a dry dross. Magnesium 1.2.4.2 Graphite films
vapour distils off through dross since the molten iron The liquid film present on cast iron at low
is above the boiling point of magnesium. Presum- temperature in an oxidizing environment has made
ably the oxidation of the vapour to a powdery oxide iron easy to cast free from serious defects. This
unique property of cast iron when cast into moulds be assisted in keeping its place by being held against
made from sand bonded with clay and water must the surface of the sand grains by the pressure of the
have played an important part in the success of the liquid.
industrial revolution. Later this benefit was to be The only explanation which fits all the facts is that
extended to moulds made from sodium silicate- the graphitic film forms on the surface of the molten
bonded sand. However, the arrival of modern metal itself. Photographs of lustrous-carbon defects,
chemical binders was to change all this. particularly those seen on the fracture surfaces of
Polyurethane resin binders were heralded as the parts which have suffered brittle failure, beautifully
binder breakthrough of the century. Indeed, the reveal their origin as the surface film on the liquid
new binder had many desirable properties, making metal (Bindernagel et al. 1975; Naro and Tanaglio,
accurate and stable moulds, with excellent surface 1977). The caption to the photograph of the oxide
finish, and at good rates of production from simple skin on an aluminium alloy (Figure 1.10) could be
low-cost plant. changed to read that it was a graphitic skin on a grey
However, when iron was poured into poly- iron; the appearance of the two types of film is very
urethane-bonded moulds, a new defect was dis- similar.
covered. It became known as lustrous carbon. This Other work has revealed that even greensands can
shiny, black material resulted in casting skins generate a hydrocarbon environment for the liquid
wrinkled like elephant hide. Studies concluded that metal if sufficiently high concentrations of hydro-
it was pyrolytic carbon (a microcrystalline form) carbons are added to the sand mixture. Such
which was deposited from the gas phase on to hot additives help the mould to resist wetting by the
surfaces in the temperature range of at least metal, and so improve surface finish (Bindernagel et
650-1000°C (Draper, 1976). The hot surface was al. 1975). Excess additions give lustrous carbon
always assumed to be the sand grains of the mould, defects if the surface becomes turbulent.
and somehow the deposit was pushed ahead of the Lustrous-carbon films are a troublesome defect in
advancing liquid front, to become incorporated into lost foam castings where the foam consists of
the surface as folds (Naro and Tanaglio, 1977). polystyrene. In this situation the vaporization of the
The explanation is clearly problematical on polystyrene to styrene, and the subsequent decom-
several fronts: in many instances where lustrous position of the styrene to lower hydrocarbons,
carbon causes severe problems the sand surface is deposits thick carbonaceous films on the advancing
most likely to be rather cold, and thus incapable of surface of the iron (Figure 3.36, to be discussed
chemically 'cracking' the polymeric gases to precipi- later, shows the decomposition products). Gallois et
tate graphite. Also, it is difficult to imagine how a al. (1987) found the film to consist of three main
film deposited on the complex and rough sand grains layers: (1) an upper lustrous multilayered structure
could be detached from its grip on these three- of amorphous carbon; (2) an intermediate layer of
dimensional shapes before the arrival of the liquid sooty fibres consisting of strings of crystallites; and
metal. After the arrival of the metal the film would (3) a layer adhering strongly to the surface of the
1 cm