Analysis of individual metallic alloys

employed in aeronautics.

UNIT 8
Chapter 1 – Steels
Chapter 2 – Aluminium alloys
Chapter 3 – Titanium alloys
Chapter 4 – Superalloys
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 Fe, Co or Ni, the latter being best suited for
aeroengine applications.

The essential solutes in Ni-based superalloys are Al and/or Ti<10 at%.

This generates a two-phase equilibrium microstructure, consisting of:
γ (FCC solid solution) and γ' (intermetallic).

γ' has a primitive cubic lattice in which the Ni atoms are at the face-centres and the
Al or Ti atoms at the cube corners: Ni3Al, Ni3Ti or Ni3(Al,Ti).
In addition to Al and Ti, Nb, Hf and Ta partition preferentially into γ'.
γ' is largely responsible for the elevated-T strength of the material and extremely
high resistance.

γ γ´
For a given chemical composition, the fraction of γ' decreases as T increases.
This phenomenon is used in order to dissolve γ' 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.

In is worth noting that, as can be seen from the (γ+γ')/γ' phase boundary,
the γ' phase is not strictly stoichiometric.
Two main reasons for this:
(i) an excess of vacancies on one of the sublattices
(ii) site-exchange of Ni and Ti/Al atoms.
The γ phase forms the matrix in which the γ' precipitates. Since both the phases have
a cubic lattice with similar lattice parameters,
the γ' precipitates in a cube-cube orientation
relationship with the γ. This means that the
cell edges are exactly parallel.

Furthermore, the γ' is coherent with the γ when the precipitate size is small.
Dislocations in the γ nevertheless find it difficult to penetrate γ',
because the γ' is an atomically ordered phase (a whole array of pinning sites).
γ matrix γ’ precipitate

order hardening

↓
dislocations
find it difficult
to penetrate γ’
 -The γ'-phase hardens the alloy through an unusual mechanism.
In γ the Burgers vector is a lattice vector and it does not alter the crystal structure.
However for γ’, it is no longer a lattice vector: it follows that the motion of a dislocation
into γ’ will disrupt the order, leaving behind a so called “anti-phase domain boundary”:
however, the passage of a second such dislocation through γ’ on the same slip plane
restores the order.
As a consequence, the penetration of γ’ has to occur by pairs of γ dislocations, called
“superdislocations”. This requirement for pairing makes it more difficult for
dislocations to penetrate γ’.

intact γ’ lattice γ’ lattice with superdislocation re-establishes

antiphase boundary intact γ’ lattice
superdislocation
Strength vs Temperature
The strength of most metals decreases as the temperature is increased,
because assistance from thermal activation makes it easier for dislocations to
surmount obstacles. However, Ni-based superalloys containing γ' are particularly
resistant to temperature because of a range of dislocation-hindering processes are
present.
Among others, a typical dislocation-hindering process is the following trapping one:
- At high T, the free energy associated with the anti-phase boundary is considerably
reduced if it lies on a particular plane, which is not a permitted slip plane, thus the
dissociated dislocation is effectively locked.
- By this mechanism, the yield strength of γ'-phase Ni3Al actually increases with
temperature up to about 1000 °C, giving superalloys their currently unrivalled high-
temperature strength.
The strength only
Tcrit Tcrit decreases beyond a
critical T where the
thermal activation is
sufficient to allow the
dislocations to
high γ’ fraction low γ’ fraction overcome obstacles.
(~60%) (~20%)
The small misfit between the γ and γ' lattices – that can be controlled through the
chemical composition - is important in superalloys for two reasons:
i) It ensures a low γ/γ' interfacial energy. The key mechanism of precipitate
coarsening is driven by the minimisation of interfacial energy ⇒ a coherent interface
makes the microstructure stable towards particle growth in high-T applications.
Coarsening is driven by surface energy.
For a spherical particle, S/V=3/r. The particle therefore
has an extra energy of 3σ/r per unit area. It follows
that the equilibrium compositions will be altered so that
there will be a diffusion flux from the small to the large
particles, leading to coarsening.
To minimise coarsening it is necessary to reduce the
interfacial energy, to minimise the diffusion
coefficient and to minimise the solubility of solute in
the matrix so that diffusion gradients are small.

ii) Magnitude and sign of 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 γ' has a larger lattice parameter than γ.
A negative misfit (i.e. when the γ' has a smaller lattice
parameter than γ) stimulates the formation of layers
of γ‘ (called “rafts”) in a direction normal to the applied
tensile stress. (mismatch wrt matrix reduced by
compression in this direction): this reduces the creep by
imposing climb of dislocations in the matrix layers.
Large fraction of γ' (>60%) in turbine blades designed for aeroengines, where the metal
experiences T>1000°C.
Only a small fraction of γ' (~20%) is needed when the alloy is designed for service
at relatively low temperatures (750°C).

TEM micrograph: large fraction of TEM micrograph: small fraction of spheroidal γ'
cuboidal γ' particles in a γ matrix. particles in a γ matrix.
Ni-9.7Al-1.7Ti-17.1Cr-6.3Co-2.3W at%. Ni-20Cr-2.3Al-2.1Ti-5Fe-0.07C-0.005 B wt%.

M23C6 precipitates
at grain boundary
Other strenghtening mechanisms
When greater strength is required at lower T (e.g.
turbine discs), alloys can be
strengthened using another phase known as γ''.
With additions of Nb or V: γ'' is Ni3Nb or Ni3V.

The crystal structure of γ'' is based on a BCC lattice with

an ordered arrangement of
Ni and Nb atoms (Inconel 718).

The particles of γ'' are in the form of discs with

specific crystal orientations between γ and γ”.

Overall, strengthening occurs therefore by both

coherency hardening (γ’) and order hardening (γ”).
Alloy compositions
In addition to the key alloying elements Ni, Al and Ti, commercial superalloys contain
Other alloying elements playing different roles.
i) Oxidation resistance: Cr favours the formation of protective scales and Y helps the
oxide scale to cohere to the substrate.
ii) Grain-boundary stabilisers for polycrystalline superalloys: B and Zr, which
segregate to the grain-boundary, reducing the grain boundary energy.
iii) Carbide-formers: C, Cr, Mo, W, C, Nb, Ta, Ti and Hf. Carbides precipitate at grain
boundaries and hence reduce the tendency for grain boundary sliding.
iv) Solid-solution strengtheners: Co, Fe, Cr, Nb, Ta, Mo, W, V both in γ and γ'.
The limits to the concentrations of alloying elements are dictated by:
(a) precipitation; (b) avoidance of embrittling phases (such as σ).
There are no simple rules governing the critical concentrations, the classical
approach is to calculate or measure the appropriate part of a phase diagram.

N.B. Co-based superalloys

Traditional Co-based superalloys lack the γ’ precipitation strengthening.
Nevertheless Co is attractive because it exhibits a higher TM.
Metastable γ’-Co3(Al,W) intermetallics allow to obtain
Co-based alloys with coherent cuboidal γ’ embedded in a continuous γ matrix
(morphologically identical to Ni-based systems).
See “Microsctructure and Heat Treatment”
Compositions of some commericial Ni-based superalloys (wt%)

PM: powder metallurgy, SX: single-crystal,

MA/ODS: machanically alloyed, oxide dispersion strengthened
Single-crystal superalloys (role of Re)
The single-crystal superalloys are often classified into 1st, 2nd and 3rd generation
alloys wrt Re additions: 1st: absent; 2nd 3%, 3rd 6%.
Re was found to improve creep strength, for a series of reasons:
i) it partitions into γ making the lattice misfit more negative and thus promoting
“rafting”;
ii) it forms atomic clusters in γ;
iii) it reduces the diffusion rate in both γ and γ’.
4th, 5th and 6th generation superalloys have been developed which incorporate Ru
additions, with similar effects.

N.B. Re can give rise to undesirable phases: the topologically close-packed (TCP)
phase precipitates.
In these phases, some of the atoms are arranged as in Ni, 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.
Such phases: (i) are brittle; (ii) their precipitation depletes the matrix from elements
which are added for different purposes.
Since Re additions promote TCP formation, Re-containing alloys must have Cr, Co W
and Mo concentrations reduced to minimise precipitation. In particular, reduction of
Cr can led to insufficient formation of protective oxides ⇒ use of coatings.
Microstructure and Heat Treatment
Ni-based superalloys, after solution treatment, are
often heat treated at two different temperatures within
the γ/γ' phase field. The higher-T treatment
precipitates coarser particles of γ'. The second,
lower-T treatment leads to further precipitation, as
expected from the phase diagram, giving rise to a
finer, secondary dispersion of γ'. The net result is a
bimodal distribution of γ'.

The solution heat treatment temperature determines not only the amount of γ' that
dissolves, but also the grain size of the γ. The size becomes coarser if all the γ' is
dissolved, since there is then no pinning effect of the precipitate particles on the
movement of the γ/γ boundaries.

treated at treated at
T<Tsolvus T>Tsolvus
Oxide dispersion strengthened superalloys
Can be produced starting from alloy powders and Y2O3, using the mechanical
alloying process. Yttria, a very stable oxide, becomes finely dispersed in the final
product, making it particularly suitable for elevated-T applications.

MA6000
Applications of Ni-based superalloys
Aeroengine turbine blades
Superalloy blades are used in aeroengines in regions where T>400°C ,
with Ti blades in the colder regions (Ti ignition danger).
GRAIN STRUCTURE
Boundaries are easy diffusion paths and therefore reduce the resistance of the material
to creep deformation.
A single-crystal blade is free from γ/γ grain boundaries.
Many of the grain boundary strengthening solutes are thus removed and 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 at temperatures
in the range 1240-1330°C, allowing the dissolution of coarse γ' which is a residue of
the solidification process. Subsequent heat treatment can therefore be used to achieve
a controlled and fine-scale precipitation of γ'.
The primary reason why single-crystal superalloys can be used at higher-T
than the directionally solidified ones, was because of the ability to heat-treat
the alloys at a higher-T.

The directionally solidified columnar grain structure has many γ 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 (cast polycrystalline) structure.
single-crystal directionally equiaxied
solidified polycrystalline
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. 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. 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 or voids that can initiate fatigue fracture.

Powder metallurgical aeroengine disc.

 Melting processes
Superalloys contain reactive elements such as Al and Ti and it is necessary to melt
the alloys under vacuum, with the added advantage that detrimental trace elements
are removed by evaporation.
Vacuum induction melting is commonly used because the inductive stirring
encourages homogenisation and helps expose more of the liquid to the melt-vacuum
interface, optimising the removal of undesirable gases and volatile impurities.

Many alloys are then vacuum arc remelted in order to achieve

a higher purity and better solidification microstructure.
(a) The ingot is made an electrode: 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.
(b) There is a liquid pool where further purification occurs by
the floatation of solid impurities.
(c) The solidified metal has a desirable directional
microstructure.