Lecture - 4

Superalloys
 Outline of the Lecture
Superalloys – Applications, definition, historical
development, types and composition

Nickel base superalloys

Strengthening Mechanisms

Role of Gamma Prime Precipitates

Case Study – Nimonic PE16 – Types of Microstructures,

Fatigue, Deformation and Damage behaviour

Technology Development Efforts – Melting and Casting

Routes, Coating Technology

Challenges and Future Directions

 Applications of Superalloys

Aircraft
Industrial gas turbines
Rocket engines
Space Vehicles
Submarines
Nuclear Reactors
Military Electric Motors
Chemical Processing
Vessels
Heat Exchanger Tubing Aeroengine
 Need for High Temperature Alloys

Conversion of thermal
energy into mechanical or
other forms of energy is
more efficient at elevated
temperature.
The gas turbine engine
employing this principle in
jet engine aircrafts laid the
foundation for the
development of high
temperature alloys -
SUPERALLOYS
Basic Criteria for High Temperature Materials

¾ High melting point

¾ Structural stability over very long periods

¾ Retention of mechanical properties at

service temperatures

¾ Resistance to oxidation and corrosion

¾ Ability to be fabricated into desired shapes

 Superalloys
“Superalloys as a class constitute the currently
reigning aristocrats of the metallurgical world.
They are the alloys which have made jet flight
possible, and they show what can be achieved by
drawing together and exploiting all the resources
of modern physical and process metallurgy in the
pursuit of very challenging objectives”.

R W Cahn,
The Coming of Materials Science, 2001
 Historical Developments
¾ The first gas turbines was conceived in 1648 by Bishop
Gibbons.

¾ Relatively advanced steam turbines began to appear

during 1800 – 1910; in 1904 a gas turbine was used for
industrial electric power in Europe.

¾ The period 1910-1915 saw the birth of Ni-Cr stainless

steel, the first high temperature steel.

¾ The concept of Jet engine powered aircraft came during

1920 - 1930. Small addition of Ti and Al was made in
80/20 Nickel Chromium by Bedford,Piling and Merica in
1929, which resulted in significant creep strengthening.
This was the first concept of Superalloys.

Continued…
 Historical Developments
¾ More heat resistant materials required for aircraft
engine turbo superchargers prompted the further
development of Superalloys during 1930 – 1940.
¾ Increasing demands of advancing gas turbine engine
technology accelerated Superalloy development
since 1940
¾ In 1940 Bradley and Taylor envisaged the existence of
γ′ (gamma prime), the tiny coherent phase, which is
the key to the superalloy’s high temperature strength.
¾ Significant understanding of Physical Metallurgy of
Superalloys was achieved during 1950 – 1970.
¾ Significant advances in Process development
occurred between 1970 – 1980, and developments in
processing are still continuing .

Continued…
Broad Classification of Superalloys
Superalloys are broadly classified as follows:

i) Based on chemical composition

a) Iron Base
b) Cobalt Base
c) Nickel Base

ii) Based on processing methods

a) Wrought alloys
b) Cast alloys
 Nickel Base Superalloys
• Nickel-base superalloys are defined as those alloys that have nickel
as the major constituent, with significant amounts of chromium.
• They also contain cobalt, iron, molybdenum, tungsten, and
tantalum as major alloying additions.
• They are strengthened by solid-solution and second-phase
intermetallic precipitation. The intermetallic forming elements are
aluminum, titanium and niobium.

Large number of
alloying elements are
added to derive the
best combination of
mechanical
properties at elevated
temperatures
Ni-base superalloys- versatile high temperature alloys

• Display stable FCC structure right from room

temperature up to melting point

• The FCC base structure is tough,ductile and has

considerable microstructural stability at elevated
temperature

• High tolerance of Ni to other alloying additions

without disturbing phase stability
Chemical Composition Establishes Various Phases
Strengthening Phases in Ni- base superalloys

Deleterious Phases

DIFFERENT PHASES CREATE THE MICROSTRUCTURE

PHACOMP approach for eliminating the deleterious
phases in Ni-base superalloy
• Compositional control by PHACOMP (a computer programme)
eliminated the risk of brittle phase precipitation
• PHACOMP is the first direct application of solid-state electron theory
to alloy science utilizing computer-driven compositional analysis
approach
• PHACOMP (Nv) calculations is used to optimize alloying additions
and predict formation of TCP phases (such as Laves, σ, µ, ζ), during
prolonged high temperature exposure.

Nv = Σni=1 (X*i r) (Nv)i

X*i r - residual atomic fraction of each element
Nv - electron vacancy number of respective
element

• Mean Nv of <2.5 for the alloy was found to eliminate precipitation of

Topologically Close Packed (TCP) phases such as σ, µ and Laves
Strengthening Mechanisms in Nickel Base Superalloys

• Solid Solution Strengthening (Ti, Cr, Mo, W)

• Precipitation Hardening (γ′, γ′′, Carbides, Borides)
• Oxide Dispersion Strengthening (Yttria)
 Factors Responsible for observed Hardening of
austenitic superalloys by coherent particles (γ′)

¾ Coherency Strains
¾ Differences in elastic moduli between particle and
matrix
¾ Existence of order in the particles
¾ Differences in SFE of particle and matrix
¾ Energy to create additional particle – matrix interface
¾ Increases in lattice resistance of particles with
temperature

1. In case of particle cutting, the shear strength derived by the alloy, theoretically,
is the sum of above mentioned mechanisms
2. The two major factors that contribute to strengthening by γ′ are coherency
strains and the presence of order in particles
 Solid Solution Strengthening

Titanium is the strongest solid solution strengthener for

nickel base superalloys
Classification of nickel-base alloys according to degree of
mismatch, Coherancy strains contribute to strengthening.
 Illustration of γ’ Morphology in Nickel- base Alloys
Various Conditions and Heat Treatment (S-R = stress rupture)
UDIMET 500 IN 100

IN 713C

Matrix-precipitate lattice mismatch dictates precipitate shape

(<0.2% - spheres, 0.5-1.0% - cubes, >1.25% plates)
 Precipitation Hardening
Ni-20% Cr
Major contribution to
strength - coherent
stable intermetallic
compounds such as
γ' [Ni3(Al,Ti)] and γ''
[Ni3(Nb,Al,Ti)]

• Other phases such as borides and carbides

– Provide little strengthening in low temperature applications due
to small volume fractions.
– Significant effect on creep properties, rupture life, and rupture
strain through their influence on grain boundaries
 Effect of γ’ morphology on flow stress of Udimet 700

¾Yield strength depends on morphology of strengthening phase.

¾Temperature dependence of yield strength is also governed by morphology
¾Increased coherency strains of plate morphology contribute to higher strength
Experimental relationship between gamma prime particle size
and alloy strength in a Ni-20%Cr base alloy
 Influence of volume fraction of gamma prime on rupture strength of
Ni-base alloys
As the temperature is increased the size of gamma prime increases,
Creep rupture strength decreases with increase in size of gamma prime at a given
volume fraction
 Theoretical Relationship between γ’ particle size and
alloy strength
Particle Cutting

∆τ ∝ f 1/ 2 r01/ 2 Γ 2 / 3
Orowan looping mechanism

∆τ ∝ λ−1 ln(r0 / b)
f – volume fraction of γ′
ro - γ′ particle radius
Γ - Anti Phase Boundary
energy
∆τ - increase in yield
strength
b = burgers vector
¾ Relation ship between γ′ size and alloy strength is determined by the way in
which the dislocations bypass the particles
¾ When γ′ is below a critical size particle cutting occurs and strength is
proportional to r01/2
¾ when γ′ is above the critical size dislocation looping around γ′ occurs. In this
case strength is inversely proportional to particle radius
 Strengthening Mechanisms
When the mean radius of γ′ particles is below a critical value, these particles are
sheared by the moving dislocations. Under this conditions the following mechanisms
contribute towards strengthening of the alloy
Shearing
Shearingof
ofPrecipitates
Precipitates
Anti Phase Boundary Hardening : ∆σ γ A ∝ f 1/ 3 r 1/ 2 rA3 / 2
3/ 2
Coherency Hardening : ∆σ ε ∝ f 1/ 2 r 1/ 2ε
Flow Stress Mismatch : ∆σ FS∝ f 1/ 3r 1/ 2 (σ γ ′ − σ γ )

Modulus mismatch Hardening : ∆σ G ∝ λ −1 (1 − E12 / E22 )1/ 2

When γ′ particles coarsen beyond a certain value of r, dislocations bypass γ′ either
by looping of by climbing. The increment of flow stress due to the Orowan looping
mechanism is given by
Looping of Precipitates
Orowan looping mechanism : ∆σ 0 ∝ λ−1 ln(r / b)

f : Volume fraction ε : lattice mismatch σγ : flow stress of γ

r: mean radius of γ′ particles λ : Inter particle spacing E1 : Modulus of soft phase
b: burgers vector σ γ′ : flow stress of γ′ E2 : Modulus of hardphase
Heat Treatment cycles employed for Nickel-Base superalloys
(after forming and before employing in-service)

Solution Treatment :
To dissolve all the γ′ and some of the carbides

Double Ageing Treatments :

Intermediate Ageing Treatment

To precipitate the carbides in optimum distribution

Final Ageing Treatment

To precipitate the γ′ as a fine homogeneous precipitate
 Nimonic PE-16 – A Case Study
Chemical Composition of NIMONIC PE-16 Superalloy
Cr Ti C Al Mo Zr S B Mn Cu Ni Fe

Wt 16.5 1.2 0.07 1.2 3.3 0.03 0.004 0.0015 0.04 0.06 43.2 33.83
%

Treatments Employed
Treatment Designation

1313 K/ 4h A fine grain microstructure free from Microstructure A

carbide and γ′ (Solution
Annealed)
1313 K/ 4h + A microstructure with intra and Microstructure B
1073 K/ 2h + intergranular M23C6 and uniform (Peak Aged)
973 K/ 16h distribution of spherical γ′ of 18 nm
dia
1313 K/ 4h + A microstructure with intra and Microstructure C
1173 K/ 1h + intergranular MC and M23C6 type (Over Aged)
1023 K/ 8h carbides and γ′ of 35 nm dia
 NIMONIC PE-16

M23C6 MICROSTRUCTURE B fine γ′

¾Intermediate Ageing Treatment at 1073 K/2h precipitates M23C6 along

high angle grain boundaries

¾ Final Ageing Treatment at 973 K/16h produces uniform distribution of

spherical γ′ of 18 nm average diameter
 NIMONIC PE-16

MICROSTRUCTURE C
coarse γ′
TiC

¾Intermediate Ageing Treatment at 1173 K/1h precipitates Titanium rich

MC particles along grain boundaries
¾Final Ageing Treatment at 1023 K/8h produces Spherical γ′of 35 nm
average diameter in Matrix
LCF of Nimonic PE-16 Superalloy in Different Heat Treatment
Conditions

Strain –Life Plots at 923 K

¾SA alloy exhibits better fatigue resistance
¾Microstructure B shows two-slope behaviour in strain-life plots
Deformation Modes during Fatigue of Nimonic PE-16 with
Various Microstructures

¾Alloy without gamma prime exhibited planar array of single dislocations

¾Planar slip promoted higher fatigue resistance of Microstructure A
 Deformation Modes during Fatigue of Nimonic PE-16 with
Various Microstructures

Planar
dislocation
arrangement Orowan looping
and dislocation (+1.0%) at 923 K
pairs indicating
gamma prime
shearing
(+0.4%)

Mechanism of Orowan
Looping

Operation of orowan looping at high strain amplitudes and dislocation shearing at

low strain amplitudes in Microstructure B resulted in two-slope behaviour of
strain-life plots
 Deformation Modes during Fatigue of Nimonic PE-16 with
Various Microstructures

Dislocation
loops around
Super
coarse gamma
dislocation
prime (Orowan
pairs
loops) at 923 K
(+1.0)

Mixed mode deformation

indicating gamma prime
shearing and Orowan
looping

Presence of coarse γ′ initially and subsequent precipitation of fine γ′during LCF

testing in Microstructure C promoted operation of Orowan looping as well as
dislocation shearing of γ′. The combined action of these processes caused
facetted fracture and lower fatigue resistance
Crack Initiation and Propagation Modes during Fatigue of
Nimonic PE-16 with Various Microstructures

Microstructure A, 923 K, 3 x 10-3 s-1

Transgranular propagation
Transgranular Initiation marked by striations

¾Fatigue life is related to prevailing deformation and fracture modes

¾Microstructure A showing no gamma prime exhibits Transgranular crack
initiation and propagation with highest fatigue resistance
 Crack Initiation and Propagation Modes during Fatigue of
Nimonic PE-16 with Various Microstructures

Microstructure B, 923 K, 3 x 10-3 s-1

Transgranular crack Mixed mode propagation, +0.25%

Propagation, +1.0%

Transgranular crack initiation and propagation at high strains and mixed mode
propagation at low strains in Microstructure B caused the two-slope behaviour,
leading to lower life at low strain amplitudes
Crack Initiation and Propagation Modes during Fatigue of
Nimonic PE-16 with Various Microstructures
Microstructure C, 923 K +0.6%

Faceted Fracture in Microstructure C

Facetted fracture resulting from localised deformation led to increased crack

propagation rate and poor LCF life in Microstructure C
Paradigm Shift in the Technology Development of Superalloys
 Advantages of Remelting (VIM + VAR)
- Low oxygen/better cleanness
– Increased uniformity, top to bottom and centre to edge of ingot
– Reduced anisotropy in mechanical properties
– Reduced micro/macro segregation
– Greater cast to cast reproducibility
– Improved forgeability
– Less forging required to achieve consolidation
– low inclusion content and fine size

0.2% Yield Strength, MPa

% Reduction in area

Potential of vacuum remelting is high with the usage of virgin metals

compared to scrap
 Cast Alloys for Higher Temperatures
¾ To enhance high temperature performance of superalloys
extensive addition of refractory elements is carried out; this
makes the alloys practically impossible to hot work.
¾ To over come this difficulty, advances have been made in
vacuum melting and casting technologies towards
development of near net shaped products with complex
profiles, such as turbine blades and vanes.
All cast superalloys can be grouped as
™ Conventionally Cast (CC) Superalloys.
™ Directionally Solidified (DS) Superalloys.
™ Single Crystal (SC) superalloys.

Examples: CM247, ReneN6, CMSX4,TMS 162, TMS 138,

CMSX 10 etc.,
 Structures of Cast Aerofoils

Gas Turbine Blades and Vanes

Equiaxed
Directionally solidified Single Crystal
polycrystalline
columnar grains
 LPT- Vane
HPT- Vane
LPT- Blade
HPT- Blade

Directionally Solidified CM247 Aerofoil

Components for Indian Kaveri Engine

Courtesy: RCMA & DMRL

Creep Rupture Lives of Typical Superalloys at 850 oC, 350 MPa

Single
Crystal
Directionally
Solidified

Wrought

Reduction in transverse grain boundaries by direction solidification and

elimination of grain boundaries in single crystal alloys improves creep rupture
strength and lives
 Evolution of Superalloys Over the Years

Single crystal alloys offer improved fatigue, creep-rupture, oxidation and coating
properties, resulting superior turbine engine performance and durability
 Turbine Blade Alloy Development

Year

Development of directionally solidified and single crystal alloys enabled

operation of turbine blades at higher temperatures
 Processing of Materials to Optimise Properties
Location – By – Location

Dual property turbine discs has coarse grains in the rim to provide better
creep properties while the bore is fine grained to optimise fatigue life.
 Protective Coatings Development

¾Property requirements for gas turbines will also include resistance to

oxidation, hot corrosion and erosion
¾Alloying additions that allow the improvements in creep strength, fatigue
resistance and toughness do not generally improve surface properties
¾Both structural requirements and surface property requirements are met
through the use of coatings.
 Challenges in the Development of
High Temperature Materials and Processes
• Multi-Scale and Multi-Physics Modeling and Simulation
Tools.
• Effects of multiple stimuli (mechanical, thermal and
chemical effects) for new materials and processes
• Thermal barrier coatings technology
• Processing of the materials by tailoring the
microstructure location–by–location
• In-situ sensors for assessing in-service performance
• Prediction of component behaviour with respect to all
possible material degradation modes
• Development of cost-effective, new material system
requires multiple partners (industry, universities and
laboratories) across the globe
 Understanding the Superalloys
• The Major Strengthening Phase in Nickel Base Superalloys containing Ti
& Al
(a) γ′ (b) γ′′ (c)M23C6 (d) TiC

• Major Factor Controlling the Morphology of γ′

(a) Melting Route (b) Modulus Mismatch
(c) Heat Treatment Temperature (d) Coherency Strains

• Undesirable Phases in Nickel Base Superalloys

(a)Primary Carbides (b) TCP Phases (c) Secondary Carbides (d) γ′′

• Double Ageing Treatments are given to superalloys

(a) For Control of Grain Size (b) for Dissolution of Primary Carbides
(c) To precipitate desirable Carbides and γ′ at appropriate Locations (d) To control
Morphology of γ′

• Factor dictating the shearing of γ′ precipitates

(a) Mean radius of γ′ particles alone (b) Volume fraction of γ′ particles alone
(c) flow stress mismatch between γ and γ′ (d) Both (a) & (b)

• Superalloys are generally produced by employing

(a) Air Induction Melting (b) Electric Arc Melting Route
(c) Vacuum Induction Melting and Vacuum Arc Refining (d) Air Induction Melting followed by
Electro Slag Refining

• Directional Solidification is employed for improving

(a) Creep Strength (b) Ductility (c) Impact Strength (d) castability
Understanding the Superalloys

1. (a)
2. (d)
3. (b)
4. (c)
5. (d)
6. (c)
7. (a)