Nickel Based Superalloys 6/2/17, 3)27 PM

Nickel Based Superalloys

H. K. D. H. Bhadeshia

A superalloy is a metallic alloy which can be used at high temperatures, often in excess of 0.7 of the absolute melting
temperature. Creep and oxidation resistance are the prime design criteria. Superalloys can be based on iron, cobalt or
nickel, the latter being best suited for aeroengine applications.

The essential solutes in nickel based superalloys are aluminium and/or titanium, with a total concentration which is typically
less than 10 atomic percent. This generates a two-phase equilibrium microstructure, consisting of gamma () and gamma-
prime ('). It is the ' which is largely responsible for the elevated-temperature strength of the material and its incredible
resistance to creep deformation. The amount of ' depends on the chemical composition and temperature, as illustrated in
the ternary phase diagrams below.

The Ni-Al-Ti ternary phase diagrams show the and ' phase field. For a given chemical composition, the fraction of '
decreases as the temperature is increased. This phenomenon is used in order to dissolve the ' at a sufficiently high
temperature (a solution treatment) followed by ageing at a lower temperature in order to generate a uniform and fine
dispersion of strengthening precipitates.

The -phase is a solid solution with a cubic-F lattice and a random distribution of the different species of atoms. Cubic-F is
short for face-centred cubic.

By contrast, ' has a cubic-P (primitive cubic) lattice in which the nickel atoms are at the face-centres and the aluminium or
titanium atoms at the cube corners. This atomic arrangement has the chemical formula Ni3Al, Ni3Ti or Ni3(Al,Ti). However,
as can be seen from the (+')/' phase boundary on the ternary sections of the Ni, Al, Ti phase diagram, the phase is not
strictly stoichiometric. There may exist an excess of vacancies on one of the sublattices which leads to deviations from
stoichiometry; alternatively, some of the nickel atoms might occupy the Al sites and vice-versa. In addition to aluminium
and titanium, niobium, hafnium and tantalum partition preferentially into '.

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Crystal structure of Crystal structure of '

The phase forms the matrix in which the ' precipitates. Since both the phases have a cubic lattice with similar lattice
parameters, the ' precipitates in a cube-cube orientation relationship with the . This means that its cell edges are exactly
parallel to corresponding edges of the phase. Furthermore, because their lattice parameters are similar, the ' is coherent
with the when the precipitate size is small. Dislocations in the nevertheless find it difficult to penetrate ', partly because
the ' is an atomically ordered phase. The order interferes with dislocation motion and hence strengthens the alloy.

The small misfit between the and ' lattices is important for two reasons. Firstly, when combined with the cube-cube
orientation relationship, it ensures a low /' interfacial energy. The ordinary mechanism of precipitate coarsening is driven
entirely by the minimisation of total interfacial energy. A coherent or semi-coherent interface therefore makes the
microstructure stable, a property which is useful for elevated temperature applications.

The magnitude and sign of the misfit also influences the development of microstructure under the influence of a stress at
elevated temperatures. The misfit is said to be positive when the ' has a larger lattice parameter than . The misfit can be
controlled by altering the chemical composition, particularly the aluminium to titanium ratio. A negative misfit stimulates the
formation of rafts of ', essentially layers of the phase in a direction normal to the applied stress. This can help reduce the
creep rate if the mechanism involves the climb of dislocations across the precipitate rafts.

The transmission electron micrographs shown below illustrate the large fraction of ', typically in excess of 0.6, in turbine
blades designed for aeroengines, where the metal experiences temperatures in excess of 1000oC. Only a small fraction
(0.2) of ' is needed when the alloy is designed for service at relatively low temperatures (750oC) and where welding is
used for fabrication.

Transmission electron micrograph showing a small

Transmission electron micrograph
showing a large fraction of cuboidal '
particles in a matrix. Ni-9.7Al-1.7Ti-
17.1Cr-6.3Co-2.3W at%. Hillier, Ph.D.
Thesis, University of Cambridge, 1984.
fraction of spheroidal ' prime particles in a matrix.
Ni-20Cr-2.3Al-2.1Ti-5Fe-0.07C-0.005 B wt%. Also
illustrated are M23C6 carbide particles at the grain
boundary running diagonally from bottom left to top
right.

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Strength versus Temperature

The strength of most metals decreases as the temperature is increased, simply because assistance from thermal
activation makes it easier for dislocations to surmount obstacles. However, nickel based superalloys containing ', which
essentially is an intermetallic compound based on the formula Ni3(Al,Ti), are particularly resistant to temperature.

Ordinary slip in both and ' occurs on the {111}<110>. If slip was confined to these planes at all temperatures then the
strength would decrease as the temperature is raised. However, there is a tendency for dislocations in ' to cross-slip on to
the {100} planes where they have a lower anti-phase domain boundary energy. This is because the energy decreases with
temperature. Situations arise where the extended dislocation is then partly on the close-packed plane and partly on the
cube plane. Such a dislocation becomes locked, leading to an increase in strength. The strength only decreases beyond
about 600oC whence the thermal activation is sufficiently violent to allow the dislocations to overcome the obstacles.

To summarise, it is the presence of ' which is responsible for the fact that the strength of nickel based superalloys is
relatively insensitive to temperature.

The yield strength of a particular

superalloy containing only about 20% of
'. The points are measured and the curve
is a theoretical prediction. Notice how the
strength is at first insensitive to
temperature.

When greater strength is required at lower temperatures

(e.g. turbine discs), alloys can be strengthened using
another phase known as ''. This phase occurs in nickel
superalloys with significant additions of niobium (Inconel
718) or vanadium; the composition of the '' is then
Ni3Nb or Ni3V. The particles of '' are in the form of
discs with (001)''||{001} and [100]''||<100>

The crystal structure of '' is based on a body-centred

tetragonal lattice with an ordered arrangement of nickel
and niobium atoms. Strengthening occurs therefore by
both a coherency hardening and order hardening
mechanism. The lattice parameters of '' are
approximately a=0.362 nm and c=0.741 nm

X-ray Powder Diffraction

A comparison of the diffraction patterns indicated below reveals many more peaks from the '. The additional reflections
are quite weak in intensity. They arise because the ' lattice is primitive cubic, which means that planes such as {100} give
rise to diffracted intensity, whereas the reflections from the corresponding {100} planes of have zero intensity (destructive
interference with the {200} planes). The additional reflections from the ' prime are termed superlattice reflections and are
weak because they depend on the difference in scattering power between the Ni and Al atoms.

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X-ray diffraction pattern from , for a particular set of

diffraction conditions.

X-ray diffraction pattern from ', for a particular set of

diffraction conditions.

Movies
Crystal structure of , cubic-F lattice.
Crystal structure of ', cubic-P lattice.
Crystal structure of '', body-centred tetragonal lattice.

Electron Diffraction
The figures below show a superimposed electron diffraction pattern from , ' and M23C6 carbide. The and ' phases
have their cubic-lattice edges perfectly aligned.

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Alloy Compositions
Commercial superalloys contain more than just Ni, Al and Ti. Chromium and aluminium are essential for oxidation
resistance small quantities of yttrium help the oxide scale to cohere to the substrate. Polycrystalline superalloys contain
grain boundary strengthening elements such as boron and zirconium, which segregate to the boundaries. The resulting
reduction in grain boundary energy is associated with better creep strength and ductility when the mechanism of failure
involves grain decohesion.

There are also the carbide formers (C, Cr, Mo, W, C, Nb, Ta, Ti and Hf). The carbides tend to precipitate at grain
boundaries and hence reduce the tendency for grain boundary sliding.

Elements such as cobalt, iron, chromium, niobium, tantalum, molybdenum, tungsten, vanadium, titanium and aluminium
are also solid-solution strengtheners, both in and '.

There are, naturally, limits to the concentrations that can be added without inducing precipitation. It is particularly important
to avoid certain embrittling phases such as Laves and Sigma. There are no simple rules governing the critical
concentrations; it is best to calculate or measure the appropriate part of a phase diagram.

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Alloying element effects in nickel

based superalloys. The "M" in
M23C6 stands for a mixture of
metal atoms. Click on chart to
enlarge.

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Nominal chemical compositions, wt%. MA/ODS mechanically alloyed, oxide dispersion-strengthened.

PM powder metallurgical origin. The alloy names are proprietary. SX single crystal.

The single-crystal superalloys are often classified into first, second and third generation alloys. The second and third
generations contain about 3 wt% and 6wt% of rhenium respectively. Rhenium is a very expensive addition but leads to an
improvement in the creep strength. It is argued that some of the enhanced resistance to creep comes from the promotion
of rafting by rhenium, which partitions into the and makes the lattice misfit more negative. Atomic resolution experiments
have shown that the Re occurs as clusters in the phase. It is also claimed that rhenium reduces the overall diffusion rate
in nickel based superalloys.

The properties of superalloys deteriorate if certain phases known as the topologically close-packed (TCP) phases
precipitate. In these phases, some of the atoms are arranged as in nickel, where the close-packed planes are stacked in
the sequence ...ABCABC.. However, although this sequence is maintained in the TCP phases, the atoms are not close-
packed, hence the adjective 'topologically'. TCP phases include and . Such phases are not only intrinsically brittle but
their precipitation also depletes the matrix from valuable elements which are added for different purposes. The addition of
rhenium promotes TCP formation, so alloys containing these solutes must have their Cr, Co, W or Mo concentrations
reduced to compensate. It is generally not practical to remove all these elements, but the chromium concentration in the
new generation superalloys is much reduced. Chromium does protect against oxidation, but oxidation can also be
prevented by coating the blades.

Microstructure and Heat Treatment

To optimise properties (often of a coating--metal system), nickel based

superalloys are, after solution treatment, heat treated at two different
temperatures within the /' phase field. The higher temperature heat
treatment precipitates coarser particles of '. The second lower
temperature heat treatment leads to further precipitation, as expected
from the phase diagram. This latter precipitation leads to a finer,
secondary dispersion of '. The net result is a bimodal distribution of
', as illustrated in this figure (courtesy R. J. Mitchell).

The solution heat treatment temperature

determines not only the amount of ' that
dissolves, but also the grain size of the .
The size becomes coarser if all the ' is
dissolved, since there is then no pinning
effect of the precipitate particles on the
movement of the / boundaries. The
picture on the left has been heat treated
at a sub-solvus temperature, that on the
right at a super-solvus temperature.
(Image courtesy of R. J. Mitchell).

The The three-dimensional shape of the

grains has recently been determined by
Michael Uchic.

Oxide Dispersion Strengthened Superalloys

Oxide dispersion strengthened superalloys can be produced starting from alloy powders and yttrium oxide, using the
mechanical alloying process. The yttria becomes finely dispersed in the final product. It is also a very stable oxide, making
the material particularly suitable for elevated temperature applications. However, mechanical alloying is a very difficult
process so such alloys have limited applications. A transmission electron micrograph showing the oxide dispersion in a

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mechanically-alloyed nickel based superalloy is shown below.

ODS alloy MA6000

Applications of nickel based superalloys

Turbine Blades

A major use of nickel based superalloys is in the manufacture of aeroengine turbine blades. A single-crystal blade is free
from / grain boundaries. Boundaries are easy diffusion paths and therefore reduce the resistance of the material to creep
deformation. The directionally solidified columnar grain structure has many grains, but the boundaries are mostly parallel
to the major stress axis; the performance of such blades is not as good as the single-crystal blades. However, they are
much better than the blade with the equiaxed grain structure which has the worst creep life.

One big advantage of the single-crystal alloys over conventionally cast polycrystalline superalloys is that many of the grain
boundary strengthening solutes are removed. This results in an increase in the incipient melting temperature (i.e., localised
melting due to chemical segregation). The single-crystal alloys can therefore be heat treated to at temperatures in the
range 1240-1330C, allowing the dissolution of coarse ' which is a remanent of the solidification process. Subsequent
heat treatment can therefore be used to achieve a controlled and fine-scale precipitation of '. The primary reason why the
first generation of single-crystal superalloys could be used at higher temperatures than the directionally solidified ones,
was because of the ability to heat-treat the alloys at a higher temperature rather than any advantage due to the removal of
grain boundaries. A higher heat-treatment temperature allows all the ' to be taken into solution and then by aging, to
precipitate in a finer form.

Superalloy blades are used in aeroengines and gas turbines in regions where the temperature is in excess of about 400oC,
with titanium blades in the colder regions. This is because there is a danger of titanium igniting in special circumstances if
its temperature exceeds 400oC.

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Equiaxed
Single crystal Directionally solidified polycrystalline Engine materials (source: Michael Cervenka)
columnar grains

This movie has kindly been provided for

educational purposes by Professor Hongbiao
Dong of Leicester University. The simulation
shows only one crystal makes it through the spiral
selector so that the liquid above the selector
solidifies as a single crystals as the assembly is
lowered through a temperature gradient.

Turbine Discs

Turbine blades are attached to a disc which in turn is connected to the turbine shaft. The properties required for an
aeroengine discs are different from that of a turbine, because the metal experiences a lower temperature. The discs must
resist fracture by fatigue. Discs are usually cast and then forged into shape. They are polycrystalline.

One difficulty is that cast alloys have a large columnar grain structure and
contain significant chemical segregation; the latter is not completely eliminated
in the final product. This can lead to scatter in mechanical properties. One way
to overcome this is to begin with fine, clean powder which is then consolidated.
The powder is made by atomisation in an inert gas; the extent of chemical
segregation cannot exceed the size of the powder. After atomisation, Some
discs are made from powder which is hot-isostatically pressed, extruded and
then forged into the required shape. The process is difficult because of the
need to avoid undesired particles introduced, for example, from the refractories
used in the atomisation process, or impurities picked up during solidification.
Such particles initiate fatigue; the failure of an aeroengine turbine disc can be
catastrophic.

Powder metallurgical aeroengine disc.

Image provided by M. Hardy of Rolls-
Royce.

Turbochargers

An internal combustion engine generally uses a stoichiometric ratio of air to fuel. A turbocharger is a device to force more
air into the engine, allowing a correspondingly greater quantity of fuel to be burned in each stroke. This boosts the power
output of the engine.

The turbocharger consists of two components, a turbine which is driven by exhaust gases from the engine. This in turn
drives an air pump which forces more air into the engine. The typical rate of spin is 100-150,000 rotations per minute.
Because the turbocharger is driven by exhaust gasses, it gets very hot and needs to be oxidation resistant and strong.

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Turbocharger of nickel based superalloy Inconel 713C, Ni-2Nb-12.5Cr-4.2Mo-0.8Ti-6.1Al-

0.12C-0.012B-0.1Zr wt%.

Melt Processing
The superalloys contain reactive elements such as aluminium and titanium. It is necessary therefore to melt the alloys
under vaccum, with the added advantage that detrimental trace elements are removed by evaporation. Vaccum induction
melting is commonly used because the inductive stirring encourages homogenisation and helps expose more of the liquid
to the melt-vaccum interface. This in turn optimises the removal of undesirable gases and volatile impurities.

Many alloys are then vaccum arc remelted in order to

achieve a higher purity and better solidification
microstructure. The ingot is made an electrode (a). An
arc burns in the vacuum, thereby heating the front end
of the electrode. Droplets are formed which then trickle
through the vacuum and become purified. The molten
metal is contained by a water-cooled copper mould.
There is a liquid pool (b) where further purification
occurs by the floatation of solid impurities. The solidified
metal (c) has a desirable directional-microstructure.

The diagram for electroslag refining looks similar to that for vacuum arc remelting, except that the melt pool is covered by a
10 cm thick layer of slag (lime, alumina and flourite). The ingot is again an electrode in contact with the slag. The slag has
a high electrical resistivity and hence melts, the temperature being in excess of the melting point of the metal electrode.
The tip of the electrode melts, allowing metal to trickle through the slag into the liquid sump at the bottom. This refines the
alloy.

It is common for alloys destined for critical applications to go through two or more of these melting processes.

Casting of Blades
Nickel based superalloy blades are generally made using an investment casting process. A wax model is made, around
which a ceramic is poured to make the mould. The wax is removed from the solid ceramic and molten metal poured in to fill
the mould. The actual process is more complicated because of the intricate shape of the blade, with its cooling channels
and other features.

More information on nickel based superalloys.

Photograph of "superalloy", courtesy Franck Tancret.

Acknowledgment

I am grateful to Sammy Tin for arranging access to several of the micrographs.

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Neural Networks Creep Mechanicallly Alloyed Theses Retained Austenite
Kirkendall Dendrites Cementite Thermodynamics Kinetics

PT Group Home Materials Algorithms

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