Nickel-Based Superalloys: Alloying Methods and

Thermomechanical Processing$
JH Weber, Special Metals Corporation, Huntington, WV, USA
YE Khalfalla, University College Dublin, Dublin, Ireland
KY Benyounis, Dublin City University, Dublin, Ireland
r 2016 Elsevier Inc. All rights reserved.

1 Introduction 1
2 Cast Alloy Processing 1
2.1 Melting 2
2.2 Investment Casting 3
2.3 Heat Treatment 3
3 Powder Metallurgy Processing 4
3.1 Powder Production 4
3.2 Consolidation 4
3.3 Thermomechanical Processing 5
3.4 Heat Treatment 5
4 Wrought Superalloys 5
4.1 Melting and Remelting 5
4.2 Hot and Cold Working 5
4.3 Heat Treatment 6
4.4 Finishing Processes 6
References 6
Further Reading 6

1 Introduction

Nickel-based alloys are multicomponent alloys with carefully balanced compositions. These alloys are used under severe operating
conditions and must function at temperatures that are high percentages of their melting temperatures. Such compositions with
high levels of active and hardener elements are inherently more difficult to produce. Composition control is critical and
mechanical working capabilities are often very limited. In addition to the processing limitations, achievement of the desired
properties requires unique alloy microstructures that are carefully designed and require sophisticated manufacturing technologies.
The goal of alloy processing and manufacture is to produce parts that incorporate the appropriate combinations of shape
configuration with the required composition and designed microstructures to meet the needs of the selected application.
The production of nickel-based superalloys includes several production paths. These sequences of processes are dependent on
the alloy composition and the part or product form being produced. Three general methodologies are used: investment casting,
powder metallurgy, and the more conventional wrought processes. Investment casting is used for complex shape parts made from
alloys with high levels of active elements. The alloys are directly cast into near-net or net shapes. With variation of the solidification
practices, the microstructural grain morphology can be equiaxed, directional, or even single crystal. Powder metallurgy is used to
produce alloy compositions that are either difficult to cast or cannot be made by any type of conventional melt þ cast practice. An
additional complication when using powder metallurgy is the need to consolidate the powder produced into useful forms with
acceptable properties. Conventional wrought manufacturing practices are used to produce the simplest, that is, lean, superalloy
compositions. Wrought manufacturing processes for nickel-based superalloys must be more carefully controlled than those for
nickel engineering alloys. However, the range of products for superalloys includes all of the generic forms – plate, sheet, strip, and
sections such as rounds and octagons. Figure 1 shows a schematic for the overall material flow and production steps for the
manufacture of cast, powder metallurgy, and wrought nickel-based superalloys.

2 Cast Alloy Processing

Alloys that are used as complex shapes such as gas turbine engine blades and vanes are normally produced by direct casting to
finished shape. These applications also have severe service requirements. This combination of shape and performance severity can

☆
Change History: October 2015. Y.E. Khalfalla and K.Y. Benyounis added an Abstract, a list of Keywords, expanded the text with review of additional articles
and extended the list of references accordingly.

Reference Module in Materials Science and Materials Engineering doi:10.1016/B978-0-12-803581-8.03383-X 1

2 Nickel-Based Superalloys: Alloying Methods and Thermomechanical Processing

Figure 1 General process flow for manufacture of nickel-based superalloy product forms.

only be met by the highly alloyed compositions. These alloys have limited ductility at both ambient and elevated temperatures
and, thus, are not amenable to mechanical working processes to form the desired part geometries. The general processing sequence
to manufacture these cast parts includes the following steps: primary melting, remelting, investment casting, heat treatment, and
final surface conditioning or coating.

2.1 Melting
The highly alloyed nickel-based superalloys are almost always produced by vacuum induction melting (VIM). Melting, alloying,
purification, and solidification are all carried out under vacuum. Metallurgical considerations and the required alloy cleanliness
dictate this method. Chemistry control is required for major alloying elements, for active elements such as aluminum, titanium,
niobium, and vanadium, and for tramp contaminants including lead, bismuth, tin, and others. Excellent alloy cleanliness and
deoxidation are required to achieve acceptable performance in use.
Vacuum induction melting is a highly flexible process that allows independent control of bath temperature, chamber pressure,
melt bath stirring, and cycle time. The VIM practice begins with melting of the prepared charge. This initial charge typically
contains the major alloying elements that are not reactive. After meltdown, the bath temperature is adjusted. The deoxidation
reaction, sometimes called the ‘carbon boil,’ begins. This gas evolution, refining reaction is the result of the combination of carbon
with oxygen from the molten bath to form carbon monoxide gas. It is a heterogeneous reaction that occurs preferentially along the
walls of the vessel and is promoted by electromagnetic stirring of the bath. The nitrogen content of the bath may also be decreased
at the same time due to scavenging by the CO gas as it passes through the bath. Volatilization of certain tramp elements such as
lead, silver, bismuth, selenium, and tellurium occurs due to the vacuum environment above the molten bath. The final stage of the
melting process is the addition of the active elements such as aluminum, titanium, zirconium, and hafnium, followed by
temperature adjustment in preparation for pouring and casting.
Pouring and casting are performed under vacuum. Casting is usually performed in a second chamber adjacent to the melting
one. The molten alloy is conveyed to the molds using a ceramic-lined trough. The pouring rate is restricted to allow heterogeneities
to rise to the surface in the molds before solidification. When higher pouring rates are desired or the bath exhibits gross cleanliness
problems, ceramic foam filters are sometimes used to clean the molten stream before casting. Remelt bars for investment casting
are the most common form for the VIM cast product. In a few instances, the VIM bath is directly converted into castings or
atomized powder.
 Nickel-Based Superalloys: Alloying Methods and Thermomechanical Processing 3

Separate VIM remelting furnaces are commonly used for the investment casting process and production of atomized alloy
powders. This separation facilitates better control of the subsequent secondary casting and atomization processes. The casters and
atomizers are sometimes at separate facilities or even different companies.

2.2 Investment Casting

Development of investment casting process has been always a challenge for manufacturers of complex shape parts with
thin elements. Particularly, misruns often occur in the as-cast complex shape parts due to the formation of solid skin by freezing of
melt in contact with colder ceramic mould (Rahimian et al., 2015). Production of complex shapes with good dimensional control
is achieved using the investment casting process. Investment casting is the casting of parts into ceramic shell molds. Preparation of
the molds for investment casting includes: manufacture of dies having negative images of the part shapes; wax injection to form
positive images of the parts; assembling wax forms with casting gates and risers; multiple sequences of slurry coating and addition
of dry ceramic powder to the wax assemblies; heating to remove the wax forms; and firing the ceramic to produce a rigid shell
mold. These molds are then placed in a vacuum chamber where the alloys are melted and poured into the molds. After casting the
parts are separated, cleaned, straightened, and inspected.
Cast parts with microstructures comprising equiaxed grains, directional grains, or single crystals can be produced
using variations in the process parameters. Equiaxed parts are produced by using mold face coats to enhance grain nucleation,
low pouring temperatures, and control of the mold preheat temperature, mold thickness and assembly configuration,
and cooling rate after casting. Directionally solidified structures are produced by incorporating a secondary withdrawal
furnace during casting and using chill plates at the ends of the molds. These allow careful control of the thermal gradient
in the mold and crystal growth rate. Production of single crystal cast parts is the most complex. Here all of the controls for
producing directional structures are augmented by seed crystals or helical segments in the mold to promote the crystal growth
orientation.
Hot isostatic press (HIP) densification is an optional step in the production of equiaxed cast parts. Solidification of these
parts can allow the formation of porosity due to shrinkage in the mold. Such porosity can be deleterious to part performance
in service. Closure of this porosity is achieved by undergoing HIP at controlled combinations of temperature, pressure,
and time. Rahimian et al. (2015) have presented a new tool for physical simulation of skin formation during investment
casting. Special ceramic tubes are designed and fabricated from the material used for the manufacturing of ceramic moulds for
investment casting. Melting/solidification experiments are carried out in the thermo-mechanical simulator, where the melt is
contained in the ceramic tube, which is heated to the temperature of ceramic mould in investment casting. Detailed micro-
structural characterization of the solidified specimens is performed; the obtained results predict the thickness of skin and its
microstructure. This concept is applied to investment casting of complex shape nozzle guide vanes from the Mar-M247 Ni-based
superalloy.

2.3 Heat Treatment

Multistage heat treatments are given to superalloy products and parts to develop alloy microstructures appropriate for the
intended service application. Typically, this involves a sequence of a solution anneal followed by one or more precipitation
aging treatments. The solution anneal is performed to allow some or all of the carbides, and other constituents such as g0
and g00 phases, to go into solid solution. This anneal is usually followed by some type of rapid cooling to prevent dissolution
and reprecipitation. This prepares the alloy for later heat treatments where control of temperature, time, and cooling rate
promotes selective precipitation of the various phases to the desired locations in the microstructure. For example, precipitation
of carbides is often directed toward grain boundaries, whereas precipitation of the intermetallic phases g0 and g00 is primarily within
the grain interior. Duplex aging treatments can be used to develop hierarchies of precipitates with different size and
size distributions within the grains. Phase transformations in prototype high strength polycrystalline nickel-based superalloys
of varying Ti/Nb ratio are studied using time-resolved, high resolution X-ray synchrotron diffractometry. The dissolution
kinetics of the ordered phase Ni3(Al, Ti, Nb, Ta) upon heating to the solutioning temperature of B1200 1C and its reprecipitation
on cooling are deduced; effects of varying Nb and Ti alloy composition on the reaction kinetics are identified. Heating to
800 1C does not alter substantially the fraction of the strengthening phase Ni3(Al, Ti, Nb, Ta) but further heating causes its
rapid dissolution. At higher temperatures, evidence is provided for the formation of further ordered phases; Ni3(Ti, Ta) is
proposed and possibly Ni0.45Ta0.55; cooling causes their dissolution and reprecipitation of Ni3(Al, Ti, Nb, Ta), so that it seems
probable that the reactions are coupled. The unforeseen high temperature precipitation of further ordering by phases other
than Ni3(Al, Ti, Nb, Ta) implies the possibility of a contribution by them to the high temperature mechanical behavior of
these materials, which until now has been thought to be solely due to Ni3(Al, Ti, Nb, Ta). The MC carbide, probably TiC,
is stable even at the solution heat treatment temperature; no evidence of reactions involving other carbides such as M23C6 was
found (Collins et al., 2015).
4 Nickel-Based Superalloys: Alloying Methods and Thermomechanical Processing

3 Powder Metallurgy Processing

Powder metallurgy (P/M) methods are used to manufacture nickel-based superalloys that are very highly alloyed and are difficult
to cast or cannot be made by conventional casting technologies. Powder metallurgy can overcome casting and processing lim-
itations and can produce a finer controlled grain size. Disadvantages attendant with using powder metallurgy are concerns
regarding gas content of the powders produced via atomization, the potential for nonmetallic inclusions, and the existence of prior
particle boundary (PPB) oxides and carbides in the consolidated product. The general processing sequence for the manufacture of
powder metallurgy components includes powder production, powder screening and cleaning, consolidation, thermomechanical
processing, and heat treatment. Isothermal forging was a critical step process to fabricate the high-performance nickel-based
superalloy. The temperature and strain rate served the most critical role in determining its microstructure and mechanical
properties. He et al. (2015) have employed the hot compression to simulate the isothermal forging process upon the temperature
ranging from 1000 to 1100 1C in combination with a strain rate of 0.001–1.0 s1 for a new P/M nickel-based alloy. The activation
energy was determined as 903.58 kJ mol1 and the processing maps at a strain range of 0.4–0.7 were developed. The instability
domains were more inclined to occur at strain rates higher than 0.1 s1 and manifested in the form of adiabatic shear
bands. The map further demonstrated that the regions with peak efficiency of 55% were located at 1080 1C/0.001 5 s1 and
1095 1C/0.014 s1, respectively. Obvious dynamic recrystallization could be detected at the strain rate 0.01 s1 leading to a
significant flow stress drop and the grain growth was remarkably triggered under 1100 1C. The findings can shed light on the
forging processing optimization of the new nickel-based superalloy.

3.1 Powder Production

Atomization is powder production using melting techniques. The most common form of atomization is inert gas atomization.
Remelt bars from primary VIM melting are remelted in a secondary VIM furnace. The molten alloy is poured into a ceramic lined
tundish with a small orifice in the bottom. Alloy flowing through the orifice at a controlled rate is disintegrated into fine droplets
by impingement of high-pressure inert gas, typically argon. The alloy droplets freeze during their fall to the bottom of the
atomizing chamber. Powder size and size distribution are controlled by varying the chamber pressure, gas pressure, gas flow rate,
and gas nozzle configuration.
Atomized powder is also produced using centrifugal methods. An alloy feed electrode is melted on the end by an electric arc or
plasma. Centrifugal force is created either by high rotational speed of the electrode being melted, or by high rotational speed of a
chill plate under the electrode. In either situation, powder is formed by the controlled melt of the electrode and the disintegrating
force of the rotating component.
Mechanical and chemical methods of producing powder are the only practical means to produce oxide dispersion-strengthened
(ODS) nickel-based superalloys. The only mechanical powder production method in commercial production is mechanical
alloying (MA). MA is used to incorporate a controlled fine dispersion of oxides into complex, highly alloyed alloys. This process
can yield essentially any composition as long as one of the input components is slightly compressively deformable. It is a dry
milling process wherein the input raw material powder components are subjected to repetitive welding and fracture. The resultant
composite powder has the nominal composition of the raw material charge containing the uniformly dispersed oxides. To preserve
cleanliness, the milling is performed in a controlled atmosphere. Very close chemistry control can be obtained using MA. Chemical
processing involves precipitation of fine alloy powder from aqueous solutions. The compositions of these powders are limited to
simple matrices such as nickel–chromium and a single oxide such as thoria. Complex compositions with high levels of active
elements are not possible via chemical processing.
Sizing and cleaning are performed on the powders after manufacture. Sizing is done by sieving to remove the coarsest and/or
finest powder fractions. This process optimizes the size distribution of the powder materials for subsequent consolidation. Selected
sieving is sometimes used to remove contaminated powder particles. Chemical cleaning of powders may be used to remove
contaminated powder surface layers and minimize later PPB effects.

3.2 Consolidation
Compacting the powder particles into solid forms involves three steps: encapsulation of the powder in a container; evacuation of
the sealed container to remove contained gas; and the compaction process itself. The container for the powders is normally made
of mild steel, but glass and ceramic containers are also used. After sealing, the containers are evacuated to remove interparticle
gases and reduce particle surface contamination. Evacuation made be done at either ambient or elevated temperatures.
The most common consolidation practice for superalloy powders is hot isostatic pressing (HIP). This is performed in an
autoclave, a large pressure vessel, using isostatic gas pressure to densify the powder into a solid. The control parameters during HIP
are the temperature, gas pressure, and process time. The consolidated form is dependent upon the shape and design of the powder
container. Shapes range from simple round cylinders to relatively complex three-dimensional disk configurations. Canned
powders are also consolidated by hot extrusion and forging. The advantage of these mechanical working–consolidation practices is
 Nickel-Based Superalloys: Alloying Methods and Thermomechanical Processing 5

better interparticle bonding due to particle deformation and surface shearing. Extrusion and forge consolidation is typically
limited to relatively simple shapes. PM processing of nickel-based superalloys has been used for a wide range of near net-shape fine
grained products. Bai et al. (2015) have proposed a novel forming process, i.e., direct forging of unconsolidated powder super-
alloys. In this process, encapsulated and vacuumed powder particles are heated up to a forming temperature and forged directly at
high speed to the final shape, by using a high forming load. Experiments of direct powder forging have been conducted on an
upsetting tool-set.

3.3 Thermomechanical Processing

The fine grain structure and the lack of chemical heterogeneity allow consolidated powder metallurgy forms to exhibit higher hot
ductility and lower deformation stresses than their cast counterparts. Limited mechanical working is thus possible. Conventional
metalworking processes under controlled conditions are used to produce the desired shapes. A more detailed discussion of
metalworking is presented below in Section 4.

3.4 Heat Treatment

Multistage heat treatments are given to powder metallurgy superalloy products to develop alloy microstructures appropriate for the
application. Heat treatment involves a sequence of a solution anneal followed by one or more precipitation aging treatments. The
solution anneal is performed to allow carbides and precipitated constituents to go into solid solution. This anneal is usually
followed by some type of rapid cooling to prevent dissolution and reprecipitation. Directional heat treatments can be used for
ODS alloys to promote the formation of very coarse, elongated grains. These anneals and treatments prepare the alloy for later heat
treatments where control of temperature, time, and cooling rate promotes selective precipitation of the various phases to the
desired locations in the microstructure. Single or multistage aging treatments are then used to develop the desired precipitate size
and size distributions.

4 Wrought Superalloys

Wrought superalloys are produced using the same conventional processing techniques as the engineering nickel alloys. The general
process sequence includes melting, remelting, hot working, some cold working for sheet and strip products, and final heat
treatments. The discussion below will focus on the process differences compared with those for nickel alloys.

4.1 Melting and Remelting

Vacuum induction melting is the preferred melting method for superalloys due to the specifications for alloy chemistry and purity.
Commercial grade superalloys are melted using select raw materials, some foundry or other revert, and lower purity elemental raw
materials. Aerospace grade superalloys also use select materials, but the revert material, if used at all, is purposely cleaned prior to
melting. Premium quality grade alloys are produced only from the highest quality raw materials. In addition, premium quality
methods require very tight control of both the VIM melting and remelting procedures.
Superalloys may also be produced by electron beam melting. This specialized melt process involves melting the charge under
high vacuum using an electron beam. The charge is sequentially melted on a water-cooled hearth with no refractories. Very high
purities are achievable due to the vacuum, sequential melting, and slag flotation during melting. This newer melting process is
costly and its use to date is limited.

4.2 Hot and Cold Working

Hot and cold working of nickel-based superalloys is used to change the shape of the cast ingots into the final product form. All
ingots are subjected to hot working. Three types of hot working are used: forging, rolling, and extrusion. Hot working destroys the
ingot structure and replaces it with an improved one having better grain structure and chemical homogeneity. The highly alloyed
compositions of superalloys limit the hot working temperature range and several reheats are typically used during the working
process. In addition to uniform section rod, hot forging is used to produce shapes having varying section size along the workpiece
length. Extrusion of nonround or rectangular sections is quite common. These sections are sometimes cut into short lengths and
forged into complex shapes.
Cold rolling of superalloys produces sheet and strip with good dimensional control and a smooth surface finish. These product
forms are only obtained with the leaner superalloy compositions. Even with these alloys, the amount of cold work between
softening anneals is limited and numerous anneals are required.
6 Nickel-Based Superalloys: Alloying Methods and Thermomechanical Processing

4.3 Heat Treatment

Wrought superalloys are given the same multistage heat treatment sequences as are cast and powder metallurgy superalloys. The
overall heat treatment sequence involves a solution anneal followed by one or more precipitation aging treatments. Carbides and
precipitated constituents are dissolved into the solid solution during annealing. Anneals are followed by some type of rapid
cooling to prevent reprecipitation. Single or multistage aging treatments with controlled temperature, time, and cooling rate cycles
promote precipitation of the various phases in the microstructure.

4.4 Finishing Processes

Finishing operations for all types of nickel-based superalloys include not only the typical pickling, machining, and blasting but
also sophisticated coatings. The severe conditions these materials must endure often require protection of the parts with even more
highly alloyed or ceramic coatings to prevent environmental surface degradation. Nitriding (gas nitriding, plasma nitriding, glow
discharge, ion implantation, etc.) improves the mechanical, tribological, or corrosion resistances of Ni-based superalloys. When
performed at ‘high’ temperature (4450 1C), the ‘internal nitriding’ leads to more or less fine nitride precipitates responsible for the
strengthening of the nitrided layer (Chollet et al., 2013).

References

Bai, Q., Lin, J., Jiang, J., et al., 2015. A study of direct forging process for powder superalloys. Materials Science and Engineering: A 621, 68–75.
Chollet, S., Pichon, L., Cormier, J., et al., 2013. Plasma assisted nitriding of Ni-based superalloys with various microstructures. Surface and Coatings Technology 235,
318–325.
Collins, D.M., Crudden, D.J., Alabort, E., Connolley, T., Reed, R.C., 2015. Time-resolved synchrotron diffractometry of phase transformations in high strength nickel-based
superalloys. Acta Materialia 94, 244–256.
He, G., Liu, F., Si, J., Yang, C., Jiang, L., 2015. Characterization of hot compression behavior of a new HIPed nickel-based P/M superalloy using processing maps.
Materials & Design 87, 256–265.
Rahimian, M., Milenkovic, S., Maestro, L., De Azua, A.E.R., Sabirov, I., 2015. Development of tool for physical simulation of skin formation during investment casting of
nickel-based superalloys. Materials & Design 87, 712–720.

Further Reading

Benjamin, J.S., 1986. Mechanical Alloy for Preparation of Superalloys, Advanced High Temperature Alloys: Processing and Properties. Materials Park, OH: American Society for
Metals, pp. 85−91.
Betteridge, W., Heslop, J., 1974. The Nimonic Alloys, second ed. New York, NY: Crane, Russak & Co., pp. 115−156.
Erickson, G.L., 1990. Polycrystalline cast superalloys. In: Metals Handbook, tenth ed., vol. 1. Materials Park, OH: ASM International, pp. 981−994.
Gell, M., Kortovich, C.S., Bricknell, R.H., Kent, W.B., Radavich, J.F., 1985. Superalloys 1984. Warrendale, PA: The Metallurgical Society of AIME.
Harris, K., Erickson, G.L., Schwer, R.E., 1990. Directionally solidified and single-crystal superalloy. In: Metals Handbook, tenth ed., vol. 1. Materials Park, OH: ASM
International, pp. 995−1006.
Stoloff, N.S., 1990. Wrought and P/M superalloys. In: Metals Handbook, tenth ed., vol. 1. Materials Park, OH: ASM International, pp. 950−980.