Superalloys

UNIT-I: Introduction to superalloys

Guide to selection of superalloys, wrought superalloys, Heat Resistant alloys. Physical Metallurgy:-
Microstructure of wrought Heat-Resisting Alloys, Microstructure of Ni-base & Co-base heat-resistant
casting alloys. Temperature and Time-dependent Transformation. Application to Heat Treatment of High
Temperature Alloys.
UNIT-II: Relationship of properties to microstructure in superalloys.
Fracture properties of superalloys. High temperature corrosion and use of castings for protection. Effect of
Physical Metallurgy and process variables on the microstructure of wrought superalloys. Process and
Metallurgical factors affecting on superalloys and other high temperature materials.
UNIT-III: Melting Process
Melting of Superalloys; Principles and practices of Vacuum Induction Melting and Vacuum Arc melting.
UNIT-IV: Forming Methods
Forming and Fabrication of superalloys; Recent developments in P/M of superalloys-Production of
components by Hot-Isostatic Pressing.
UNIT-V: Casting Methods
Improving turbine blade performance by solidification control-the development of single crystal turbine
blades. Quality of superalloys castings; Heat Treating of Heat resistant alloys

TEXT BOOKS:
1. Superalloys: Source book; Mathew J. Donachie. Jr. Editor; 1984.
2. The Superalloys: Edited Chester T. Sims and William C Haagel; 1972
REFERENCE:
1. High Temperature MATERIALS - Campbell IE, John Wiley and Sons Inc.;1956
2. The Superalloys: Fundamentals and Applications - Roger C. Reed
3. Superalloys: A Technical Guide - Elihu F. Bradley - 1988 - 280 pages
4. Super alloys: A Technical Guide, Mathew J. Donachie, Stephen J. Donachie
 Heat Treatment of Superalloys
Superalloy components are hardened and strengthened by heat treatment. At other times, stress relieving or
annealing treatments are required.
Examination of relevance of various Heat treatments
Stress Relieving (S.R.)
S R of wrought materials is confined to alloys that are not precipitation strengthened.

Time-Temperature cycles will depend on the metallurgical characteristics of the alloy and on the type and
magnitude of residual stresses developed by previous fabrication process.

S R temperature: Usually below the annealing or recrystallization temperatures.

Examples of Wrought alloys requiring S R treatment

Superalloys S R Temperature Annealing Temperature (Heat 1 h/inch cross-section)
A 286 (Fe-based) Full Annealing 980 ºC
recommended.
Intermediate Temp.
cause Ageing
Hastelloy (Ni-based) -- ” -- 1175 ºC

L-605 (Co-based) -- ” -- 1230 ºC

Note: Alloys such as A 286, Hastelloy X can be reduced by as much as 90% before a softening treatment
is required.
 Heat Treatment of Superalloys
Cast Superalloys require Stress Relieving (S.R.) treatment
Several superalloy castings are placed in service in the as-cast conditions without going for S R. However,
castings can be stress relieved provided:

 They are of an extremely complex shape that might crack during initial heating up period in service.
Their dimensional tolerances are stringent.
They have been welded.

There is no specific S R cycle for Cast Superalloys because S R cycles are dependent on geometry and
prior processing. It is to be developed by Empirical Studies.

Annealing
In Superalloys  Annealing is full annealing = Complete Recrystallization and Maximum softness.
Applied to Wrought products of the Non-Precipitation Strengthening type.

Purpose of Annealing
Increase ductility (reduce hardness) to facilitate forming or machining.
Relieve stress after welding.
Produce specific microstructure
Soften Age-hardened structures by re-solution process.

Most wrought alloys can be cold formed.

Severe cold forming may require intermediate annealing.
Full Annealing must be followed by rapid cooling.
 Heat Treatment of Superalloys
Quenching
 Quenching retains the alloying elements in supersaturated
condition at RT.
Quenching permits a finer γ’ particle size to be achieved on
ageing.

Ageing Treatment

Ageing Treatments strengthen superalloy by causing

precipitation of one or more phases from the supersaturated
solid-solution matrix.

 Factors that influence the selection of the number of ageing
steps and ageing temperatures include:
Type and number of precipitating phases available.
Anticipated service temperature
Precipitate size
Combination of strength and ductility required
IN 718: Details of delta phase crystals.
Gamma prime precipitate is visible in the
gamma matrix. Replica electron
micrograph, 10,000×
Condition: Solution treated and aged—
solution annealed 1 h at 955 °C,
air cooled, aged 8 h at 720 °C and furnace
cooled in 10 h to 620 °C.

Primary precipitating phases in superalloys:

γ’ - Ni3Al or γ’ - Ni3(Al, Ti)  η - Ni3(Al, Ti) at > 801 ºC in CM-7

γ” - Ni3Nb  δ - Ni3Nb due to overageing/extended ageing in IN 718

 Heat Treatment of Superalloys

Hastelloy X: The structure is IN 718: Structure is δ - Ni3Nb in a Incoloy 901: Ni-rich solid- Incoloy 901: The needle-like
primary M6C and needle-like gamma matrix. OM 1000×. Condition: constituent is η-phase
solution matrix, eutectic
M23C6 carbides that have Solution treated and aged—solution with M3B2 formed by fusion (Ni3Ti); the remainder of the
precipitated at dislocations annealed 1 h at 955 °C ,air cooled, at 1205 °C, large crystals of structure is gamma prime in
generated around primary carbide. aged 8 h at 720 °C and furnace cooled
MC, and M23C6 carbide at a gamma matrix. Negative-
The matrix is γ solid solution. in 10 h to 620 °C
grain and twin boundaries. replica electron micrograph,
OM500×. Condition: As 15,000x
Secondary precipitating phases in superalloys: forged)
M23C6, M7C3, and M6C and MC , MN (nitrides), MCN (carbo-nitrides), M3B2 (borides)
M2Ti (Laves phase), δ - Ni3Nb (orthorhombic)

The above phases occur principally in Ni-based superalloys

The primary phases in Fe-based superalloys are similar to those in Ni-based superalloys, although η is
more apt to the present in Fe-based alloys because of generally high Ti-Al ratio found in Fe alloys than in
Ni alloys.
 Heat Treatment of Superalloys

Haynes 25: Structure is precipitates of

M6C and “Co2W” intermetallic in a fcc
M7C3 and M23C6 carbides in a predominantly fcc
matrix. OM 500×. Condition: Solution
matrix with some hexagonal close-packed
treated and aged—solution annealed at
crystals. OM500×. Condition: Solution treated
1205 °C and aged 3400 h at 870 °C .
and aged—solution annealed at 1230 °C and
aged 8 h at 900 °C

Secondary precipitating phases in superalloys:

The primary phases in Co-based superalloys: M23C6, M7C3, and M6C and MC
Alloy Base Form γ ′ solvus temperature, °C Table : Approximate
A-286 Ni-Fe Wrought 855 solvus temperature of γ ′
Incoloy 901 Ni-Fe Wrought 940
for selected superalloys
Astroloy LC Ni Wrought 1120
B-1900 Ni Cast 1150
C263 Ni Cast 925
CMSX-4 Ni Cast 1305
CMSX-10 Ni Cast 1345
Inconel 100 Ni Cast 1180
Inconel 713LC Ni Cast 1180–1200
Inconel 738 LC Ni Cast 1160–1175
Inconel 792 Ni Cast 1100–1150
M-252 Ni Wrought 1010
MAR-M 200 Ni Cast 1180–1200
MM-006 Ni Cast 1180–1200
Nimonic 80A Ni Wrought 960–980
Nimonic 90 Ni Wrought 980–1000
René 41 Ni Wrought 1050–1070
René 95 Ni Wrought 1120–1160
René 80 Ni Cast 1150
UC01 Ni Wrought 1170
Udimet 500 Ni Wrought 1050–1100
Udimet 700 Ni Cast 1140
Udimet 700 Ni Wrought 1130–1150
Waspaloy Ni Wrought 1025–1040
Alloy Form Type Solutioning Aging Table : Common
A-286 Wrought Ni-Fe 980°C/1h/OQ 720°C/16h/AC
superalloys heat
Discaloy Wrought Ni-Fe 1010°C/2h/OQ 730°C/20h/AC + 650°C/20h/AC
treatments
N-155 Wrought Ni-Fe 1175°C/1h/WQ 815°C/4h/AC
1175°C/4h/
Astroloy Wrought Ni
AC+1080°C/4h/AC 845°C/24h/AC + 760°C/16h/AC AC = Air Cool
Inconel 901 Wrought Ni 1095°C/2h/WQ 790°C/2h/AC + 720°C/24h/AC
Inconel 625 Wrought Ni 1150°C/2h/RQ   FC = Furnace
Used in as-cast
Inconel 713 Cast Ni
condition   Cool,
Inconel 718 Wrought Ni 980°C/1h/AC 720°C/8h/FC + 620°C/8h/FC
Inconel 718 Cast Ni 1095°C/1h/AC
955°C/1h/AC + 720°C/8h/FC + GFQ = Gas
620°C/8h/AC
Furnace Quench,
Inconel 738 Cast Ni 1120°C/2h/AC 845°C/24h/AC
Nimonic 80A Wrought Ni 1080°C/8h/AC 705°C/16h/AC RAC = Rapid
Waspaloy Wrought/cast Ni 1080°C/4h/AC 845°C/24h/AC + 760°C/16h/AC Air Cool,
Haynes 25 Wrought Co 1230°C/1h/RAC …
Haynes 188 Wrought Co 1230°C/0.5h/RAC
… RQ = Rapid
S-816 Wrought Co 1175°C/1h/RQ 720°C/12h/AC
Quench to below
CMSX-2 Cast Ni (single crystal) 1315°C/3h/GFQ 980°C/5h/AC + 870°C/20h/AC
540°C,
PWA-1480 Cast Ni (single crystal) 1290°C/4h/GFQ 1080°C/4h/AC + 870°C/32h/AC
CMSX-10 Cast Ni (single crystal)
1316°C/1h + 1152°C/6h/AC + 871°C/24h/AC+ WQ = Water
1329°C/2h + 760°C/30h/AC
Quench
1327°C/2h +
       
1340°C/2h +
1346°C/2h +
       
1352°C/3h,
1357°C/5h +
       
1360°C/3h +
1363°C/10h +
       
1365°C/15h
 Heat Treatment of Ni-based Superalloys
Wrought superalloys:
 In the solution treated condition, wrought alloys consist
mainly of the matrix and MC carbides.

 Solution Temperature: Usually in the range of 1040ºC -

1230ºC.

It prepares the matrix for uniform precipitation of γ’ on

subsequent ageing.

Rene 41. Particles of M6C (white), metal carbide

(gray), and M23C6 (at grain boundaries). Grain-
boundary borders are darkened by γ ′.

In Rene 41 (Ni – 55%, Cr – 19%, Co – 11% , Mo – 10%, Al – 1.5%, Ti – 3.1%, C – 0.09%, Others)

 Solutionizing at about 1070ºC causes formation of M6C, which can decrease other subsequent
carbide reactions.

 M23C6 does not normally form during solution treatment.

 Two-step Ageing is adopted to precipitate and develop major strengthening phases.

 I-step Ageing carried in the range of 840ºC - 1100ºC will precipitates γ’.
II-step Ageing carried out at 760ºC will complete γ’ development.
 Heat Treatment of Ni-based Superalloys
Wrought superalloys: Heat Treatment of Udimet 500
(Ni – 52%, Cr – 18%, Co – 19% , Mo – 4.2%, Al – 3.0%, Ti – 3.0%, C – 0.07%, Others B, Zr)
 Following Heat treatment cycle establishes the optimum relationship b/w Heat Treatment, γ’ morphology and
strengthening:
 Primary Solutionizing: 1120ºC / 2 h / AC
 1120ºC  dissolves γ’.
 Air Cooling  form fine γ’.

 Secondary Solutionizing: 1085ºC / 2 h / AC

 1085ºC  re-dissolves most of γ’ formed earlier.
 Air Cooling  form additionally finer γ’ at lower temperatures =>
 This finer γ’ effective strengthener than that formed at 1120 ºC.
 Further, the remaining original γ’ particles formed at 1120 ºC grow slightly.

 Primary Ageing: 925ºC / 24 h / AC

 Produces growth of both I stage cooled and agglomerated
 II stage cooled γ’ with slight additional precipitation of γ’

 Primary Ageing: 760ºC / 16 h / AC

 Final ageing at 760ºC generated little further change.
 The structure has a contribution of moderate Tensile strength and Creep-rupture life
well suited for long-lived industrial turbine blades.

These or similar principles are applied to virtually all alloys.

 Heat Treatment of Ni-based Superalloys
Wrought superalloys: Intermediate Carbide Heat treatments
 Adopted b/w Primary Ageing and Secondary Ageing creates favourable initial types and morphologies of
carbides before final ageing of γ’.
 Applicable for wrought alloys  M 252, Nimonic 80 A, Nimonic 1155, Rene 41, U500, U700 and
Waspalloy.
 This intermediate heat treatment will degenerate / transform initial MC carbide to lower carbides.
 MC  M23C6
 An also form residual C in the alloy matrix to M23C6.
 It may be remembered that MC carbides usually form in superalloys during freezing.
 They occur throughout the alloy, both intergranular and transgranular positions.

 Heat treatment of IN 738

 IN 738 = Cast Ni-based superalloy 
 (Ni – 61.5%, Cr – 16%, Co – 9% , Mo – 2.0%, Al – 3.75%, Ti – 3.7%, W – 2.8%, Ta – 2%, Nb – 1.1%,
C – 0.13%, B – 0.02%, Others)
Solution Treatment: 1125ºC / 2 h / Vacuum or Argon cooled to 500ºC, Forced Air, Argon cooled to RT.
Ageing Treatment: 850ºC / 24 h, Vacuum or Argon cooled to 500ºC, Forced Air cooled to RT.

 This heat treatment does not solutionise pre-existing γ’.

 Thus, we may see irregular particles along with a background of fine γ’ generated at 850ºC.

Since Wrought U500 superalloy already possesses a IV-part heat treatment.

Primary Ageing at 925ºC /24 h/AC produces the carbide degeneration reaction thereby giving an enhanced
creep-rupture life of U500 y providing some resistance to grain boundary sliding.
 Heat Treatment of Ni-based Superalloys
Cast superalloys:
Cast superalloys used in GTEs are given exhaustive heat treatments to strengthen γ’ , to improve
ductility, homogenize the structure and achieve a variety of other effects.

Homogenized or not the original dendritic structure is maintained even after service. Dendritic
boundaries contain some carbides and γ-γ’ eutectic.

Examples of Cast alloys:

IN 738 LC, IN 939, Rene 77, Udimet 500
 Heat Treatment of Co-based Superalloys
Co-Cr-Ni superalloys can be fully annealed or stress –relief because γ’ precipitation are not involved in the
strengthening of Co-based superalloys.
So called ageing treatment may be given, i.e. to modify the Carbide distribution.

Wrought alloys:
Generally wrought alloy, after fabrication can be Stress-relieved at a temperature nearly 55ºC below
annealing temperature.
Co-based alloy are welded either as fabricator or to repair weld  as a result cracks may appear in based
alloys after some time of operation.
To prevent this post weld stress-relief heat treatment is carried out.

Haynes 188:
It is also a solid solution strengthened wrought alloy having excellent weldability and workability and
outstanding oxidation resistance at temperature in Gas Turbine Combustion application.

Microstructure after annealing consist of intragranular M23C6. carbides which provide the require strength
to resist creep at high temperature.
 Heat Treatment of Co-based Superalloys
Cast Co-based superalloy
Most of the Co-based superalloys in high temperature application such as in Gas Turbines are
investment casting.

These are carbide strengthened alloys where the Tensile strength and Creep –rupture strength are
essentially a direct function of %C and resultant % wt of carbide in the matrix.

Upto 982ºC, it lacks substantially lower creep strength due to lack of high temperature, ordered, coherent
particle strengthening mechanism.

The greater stability of carbide especially (M6C and MC) Vs (γ’) of Ni-based superalloy yield a strength
advantage at higher temperatures.

This is the prime reason why Co-based superalloys are utilised in the lower strength, high temperature
stationary vanes in gas turbine (FSX 414).

Annealing of the Cast Co-based superalloy is often avoided because of the undesirable precipitation of
coarse carbides that occur during slow cooling after annealing. They can only be stress-relief at 870ºC
900ºC for 2 - 4 h.
Heat Treatment of Co-based Superalloys