Ellingham diagrams – their use and misuse

P. Stratton*
Ellingham diagrams can be very useful in the trouble shooting of heat treatment problems related
to the use of protective atmospheres especially for determining if a particular atmosphere is
oxidising or reducing to the metal or alloy in question. However, use without understanding can
lead to incorrect conclusions. It is important to understand that the diagram relates to the
equilibrium condition and takes no account of kinetics. It also assumes that there is sufficient
oxidising species present for the reaction to continue. How these properties can affect the
interpretation of results is illustrated by some industrial examples.
Keywords: Atmospheres, Oxidation, Ellingham diagrams

Introduction (iv) to determine the ratio of hydrogen to water

vapour that will be able to reduce the oxide to
An Ellingham diagram is a plot of DG (Gibbs fee energy metal at a given temperature.
change) versus temperature for the formation of an
oxide, sulphide, chloride, etc. Since DH (enthalpy
change) and DS (entropy change) are essentially
Ease of reduction
constant with temperature unless a phase change occurs, The position of the line for a given reaction on the
the free energy versus temperature plot can be drawn as Ellingham diagram shows the stability of the oxide as a
a series of straight lines, where DS is the slope and DH is function of temperature. Reactions closer to the top of
the y intercept. An example for iron oxide is shown in the diagram are the most ‘noble’ metals (for example,
Fig. 1. The slope of the line may change when any of the copper), and their oxides are unstable and easily
materials involved melt or boil. reduced. As we move down towards the bottom of the
Free energy of formation is negative for most metal diagram, the metals become progressively more reactive
oxides, and so the oxide diagram – by far the most and their oxides become harder to reduce. Aluminium
common and the only one used for heat treatment – is for example cannot be reduced in practice.
usually drawn with DG50 at the top of the diagram, and
the values of DG shown are all negative numbers. Equilibrium partial pressure of oxygen
Temperatures where either the metal or oxide melts or
The nomograph scale on the right side of the diagram
boils are marked on the diagram although this is not labelled ‘Po2’ is used to determine what partial pressure
often an issue in heat treatment applications except of oxygen will be in equilibrium with the metal and
perhaps for zinc in the heat treatment of brasses. The metal oxide at a given temperature. The significance of
oxygen partial pressure is taken as 1 atmosphere, and all this is that, if the oxygen partial pressure is higher than
of the reactions are normalised to consume one mole of the equilibrium value, the metal will be oxidised, and if it
oxygen. is lower than the equilibrium value, then the oxide will
Many examples of comprehensive Elligham diagrams be reduced.
have only two nomograph scales to the right of the To use this scale, first determine the temperature you
diagram, but the one shown in Fig. 2 after Darken and are interested in, and the point where the oxidation line
Gurry1 has three including that for H2/H2O ratio which of interest crosses that temperature. Then draw a line
is important in protective atmosphere heat treatment. through both that point and the point labelled ‘0’ (upper
At present, there are four main uses of the Ellingham left corner of the diagram). Now read off the oxygen
diagram in heat treatment: partial pressure (in atmospheres) where the extension of
(i) to determine the relative ease of reducing a the line crosses the ‘Po2’ scale to get the equilibrium
given metallic oxide to metal partial pressure.
(ii) to determine the partial pressure of oxygen that
is in equilibrium with a metal oxide at a given Ratio of CO/CO2 or H2/H2O needed for
temperature
(iii) to determine the ratio of carbon monoxide to reduction
carbon dioxide that will be able to reduce the When using carbon as a reducing agent, there will be a
oxide to metal at a given temperature minimum ratio of CO to CO2 that will be able to reduce
a given oxide. The harder the oxide is to reduce, the
greater the proportion of CO needed in the gas mixture.
Matscribe UK, Bingley BD16 4SD, UK To determine the CO/CO2 ratio needed to reduce a
*Corresponding author, email [email protected] metal oxide at a particular temperature, use the same

ß 2013 IHTSE Partnership

Published by Maney on behalf of the Partnership
70 International Heat Treatment and Surface Engineering 2013 VOL 7 NO 2 DOI 10.1179/1749514813Z.00000000053
 Stratton Ellingham diagrams – their use and misuse

Similarly the H2/H2O ratio is determined from the ‘H’

point (just above the ‘C’ point) using the ‘H2/H2O’ scale.
As H2/H2O ratio is so important in heat treatment, a
‘simplified’ version of the Ellingham diagram is some-
times used.4 Such a diagram is shown in Fig. 3. As in the
original, environments above the line are reducing and
those below it oxidising to the element concerned.
From this diagram, it is simple to deduce which metals
are easy to reduce at low temperatures such as copper
and metals difficult to reduce such as chromium which
can only be reduced at high temperatures. This has a
significant impact on heat treatment processes such as
annealing of easily oxidisable metals where, as the
1 DG0 versus temperature for oxidation reaction temperature falls, the atmosphere, which is protective at
2FezO252FeO high temperatures, can easily become oxidising.

procedure as that for determining the equilibrium

Alloys
pressure of oxygen, except that the point marked ‘C’ It is worth noting that in selecting the constituent of an
(centre of the left side of the diagram) is now the point of alloy element that is the most easily oxidised in alloys to
origin of the line and the ratio is read off of the scale be annealed, hardened, brazed, etc., it is usual to
marked ‘CO/CO2’. discount constituents that have concentrations less than

2 Ellingham diagram1–3

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Stratton Ellingham diagrams – their use and misuse

3 Oxidation boundaries of various elements: environ-

ments above line are reducing and those below it oxi-
4 Copper brazing stainless steel
dising to element concerned5

case, the critical metal element with regard to the

about 1% as they are not able to form continuous oxide
atmosphere requirements is chromium as for alloys the
films.
most easily oxidised element is usually selected because
it forms the surface oxide layer. Using the method
Examples of use described above, Fig. 2 shows that at 1130uC, even using
Let us consider gaseous carburising. If we are carburis- 100% hydrogen, a dewpoint of 237uC is required to
ing a mild steel at 900uC at a carbon potential of 0?8% in suppress oxidation of chromium. However, practical
a typical endothermic type atmosphere with 23%CO, experience indicates that to produce good joints,
then the CO2 would be 0?34%. This is a CO/CO2 ratio of dewpoints better than 250uC are required for complete
676. If we now note that the point at which the line reduction of the small amounts of chromium oxide
between ‘C’ and 676 on the CO/CO2 scale crosses the initially present on the parts during the available process
900uC line, we see that it is well below the iron oxide line time.
and is thus reducing to iron. However, it is well above This is because the Ellingham diagram considers only
the manganese and silicon lines. This is the cause of thermodynamics, not kinetics. Chromium oxide is
internal oxidation in carburised steel and cannot be reduced only slowly so that, although an atmosphere
avoided in endothermic type atmospheres. The only with an H2/H2O ratio just above the line will reduce it
solution is to use low pressure carburising where the eventually, a larger driving force is required for
atmosphere contains no oxygen bearing species. reduction at a high rate.
Next, let us consider a continuous furnace annealing It should also be noted that temperature has a huge
brass. A typical hydrogen content for such a furnace effect on kinetics. Thus, although the Ellingham
would be 30%, yet, typically, the product will emerge diagram says that stainless steel oxidises in air at room
with a fine white coating of zinc oxide that must be temperature, the oxide layer formed is very thin and
polished off before the product is used. If we draw a line does not grow enough to be visible even after long
through ‘H’ and the melting point of zinc we find that exposure.
the H2/H2O ratio is approximately 26105. This equates Copper annealing
to a dewpoint of approximately 280uC, a level almost
impossible to reach in this type of furnace. Even raising Figure 2 gives a Po2 of approximately 10214 (1028 ppm)
the hydrogen level to 100% would only reduce the at 600uC for reducing conditions. This is equivalent to a
required dewpoint to 272uC and even this would be dewpoint of 18uC in a 3% hydrogen atmosphere. This
oxidising to zinc below its melting point. In practice, it would lead to the conclusion that hydrogen was
is only possible to achieve bright annealing of brass necessary to keep copper bright during annealing. A
in high integrity bell furnaces using 100% hydrogen study of the oxidation of copper was carried out using
atmospheres. copper tube which had been prereduced in an atmo-
sphere of nitrogen/3% hydrogen to ensure consistent
starting conditions. The samples were exposed to
Examples of avoiding misuse different simple nitrogen/oxygen atmospheres with no
Ellingham diagrams can be very useful for trouble hydrogen present at 800uC for times of between 30 s and
shooting heat treatment problems related to the use of 30 min. The time at which visible surface oxidation first
protective atmospheres particularly for determining if a occurred was noted for each oxygen level. Subsequent
particular atmosphere is oxidising or reducing to the X-ray photoelectron spectroscopy analysis showed that
metal or alloy in question. They also have uses in the oxide became visible when the copper to oxygen
pyrometallurgy that are not addressed here. However, ratio in the surface layers of the tube was less than about
use without understanding can lead to incorrect conclu- 6 : 1 with all the copper either in the 0 or z1 oxidation
sions as illustrated by the following four examples. state. The results which were consistent with previous
work6 are summarised in Fig. 5.
Stainless steel brazing As the time at high temperature in a typical induction
Copper alloy brazing of stainless steel (Fig. 4) is carried heated inline copper tube annealing furnace is around
out at a temperature in the range 1120–1150uC. In this 3 s. This is equivalent to a maximum allowable oxygen

72 International Heat Treatment and Surface Engineering 2013 VOL 7 NO 2

 Stratton Ellingham diagrams – their use and misuse

5 Time limit for visible oxidation for copper tube exposed

to nitrogen/oxygen atmospheres7

content of 0?12% in order to obtain a bright product. 7 Selection of bright hardened tools
For bright annealing copper wire, where even shorter
exposure times are typical, an atmosphere containing Thus, not only do we need to consider if the
several per cents of oxygen can be used successfully, atmosphere is oxidising to the alloy in question, but if
once again demonstrating that it is necessary to take there is sufficient oxidising species present to form a
both thermodynamics and kinetics into consideration. visible oxide.

Bright annealing aluminium foil Vacuum hardening tool steels

Surprisingly, given that aluminium is very easy to At typical tool hardening temperatures, an oxygen
oxidise, it is magnesium, which is even easier, that is partial pressure of around 10219 is required to keep
chromium containing alloys bright. However, even using
the critical element in annealing aluminium foil alloys.
a vacuum – nitrogen purge – vacuum cycle down to
The Ellingham diagram suggests that to keep the foil
1025 torr, it is not possible to achieve an oxygen partial
bright a Po2 of 10290 is required. This is clearly
pressure much better than 2?5610214 because of the
impossible to realise in the large box furnaces used to
tiny amount of oxygen present in commercially available
anneal aluminium foil (Fig. 6), yet such foil reaches our
nitrogen.
kitchen shelves every day.
However, the tools still come out bright (Fig. 7)
In practice, bright annealing of aluminium foil can be
because the amount of oxygen availability is so small
achieved using an atmosphere containing 0?5% oxygen.8 that even for a low surface area load of tools, there is
At the start of the heating cycle, the oxygen is needed to insufficient oxygen to form a visible oxide layer.
react with and remove the rolling oil from the coils and
the free oxygen level falls. If this is not done, brown
deposits are formed on the foil as the less volatile
Summary
fractions of the rolling oil get baked on. During the Ellingham diagrams can be very useful for solving
latter part of the cycle, the oxygen level returns to 0?5%, protective atmosphere problems in heat treatment.
so why does it not oxidise the magnesium. The answer is However, it is important to understand that the diagram
that it does, but the total volume of oxygen available is relates to the equilibrium condition and takes no
insufficient to give a visible oxide film on the huge area account of kinetics. It also assumes that there is
of foil in the coil or coils in the furnace. This effect is sufficient oxidising species present for the reaction to
helped by the fact that the flowrates used are relatively continue.
low.
References
1. L. S. Darken and R. W. Gurry: ‘Physical chemistry of metals’;
1953, New York, McGraw-Hill.
2. H. J. T. Ellingham: J. Soc. Chem. Ind. (London), 1944, 63, 125.
3. F. D. Richardson and J. H. E. Jeffes: ‘The thermodynamics of
substances of interest in iron and steel making from 0uC to 2400uC:
I-Oxides’, J. Iron Steel Inst., 1948, 160, 261.
4. http://heattreatment.linde.com/International/Web/LG/HT/like35lght.
nsf/repositorybyalias/wp_semifnshd_21/$file/21.pdf
5. P. F. Stratton and A. McCracken: ‘Controlled atmospheres for
bright brazing’, Proc. 2nd Int. Brazing and Soldering Conf., San
Diego, CA, USA, February 2003, AWS.
6. B. Pilling and R. E. Bedworth: ‘The oxidation of metals at high
temperatures’, J. Inst. Met., 1923, 29, 529.
7. P. F. Stratton: ‘Atmospheres for bright copper’, Wire Cable
Technol. Int., 2002, 3, 116–117.
8. G. R. White, T. Plilips and R. N. Nayar: ‘Effect of oxygen
concentration in the annealing atmosphere on the surface quality of
aluminum alloys, gas metal interactions in non ferrous materials’,
6 Aluminium annealing Proc.TMS Conf., Anaheim, CA, February 1996, TMS, 95–106.

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