Superalloy

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A superalloy, or high-performance alloy, is an alloy that exhibits excellent mechanical

strength and resistance to creep (tendency for solids to slowly move or deform under
stress) at high temperatures; good surface stability; and corrosion and oxidation
resistance. Superalloys typically have a matrix with an austenitic face-centered cubic
crystal structure. A superalloy's base alloying element is usually nickel, cobalt, or nickeliron. Superalloy development has relied heavily on both chemical and process
innovations and has been driven primarily by the aerospace and power industries.
Typical applications are in the aerospace, industrial gas turbine and marine turbine
industries, e.g. for turbine blades for hot sections of jet engines, and bi-metallic engine
valves for use in diesel and automotive applications.

Nickel superalloy jet engine

(RB199) turbine blade

Examples of superalloys are Hastelloy, Inconel (e.g. IN100, IN600, IN713), Waspaloy, Rene alloys (e.g. Rene 41, Rene 80,
Rene 95, Rene N5), Haynes alloys, Incoloy, MP98T, TMS alloys, and CMSX (e.g. CMSX-4) single crystal alloys.
Superalloys are commonly used in parts of gas turbine engines that are subject to high temperatures and require high strength,
excellent high temperature creep resistance, fatigue life, phase stability, and oxidation and corrosion resistance.
Superalloys develop high temperature strength through solid solution strengthening. The most important strengthening
mechanism is through the formation of secondary phase precipitates such as gamma prime and carbides through precipitation
strengthening. Oxidation and corrosion resistance is provided by the spraying of a thermal barrier coating (TBC). Oxidation or
corrosion resistance is provided by elements such as aluminium and chromium.
Air cooling (such as the air cooling holes seen in the picture above) can cool the components and allow them to operate under
oxidising or corrosive conditions. The air cooling protects the base material from thermal effects as well as from corrosion and
oxidation. If air cooling is used it is usually used for the high-pressure turbine, where air-cooled blades can face temperatures
200 C above the melting temperature of the superalloy used.
Turbine Inlet Temperature (TIT), which is a direct parameter controlling the efficiency of a gas turbine engine, depends on the
temperature capability of 1st stage high-pressure turbine blade. This component is exclusively made of nickel base superalloys.
Turbocharger turbines also use superalloys, typically electron beam welded to a steel shaft. Common superalloys in this
application are for instance Inconel 713 and Mar-M 247. The latter is particularly useful for gasoline engines as it reduces the
need for fuel enrichment at high loads, which improve engine efficiency.
They are also used where corrosion by media would rule-out other metal materials (e.g.) instead of stainless steel in acidic or
saltwater environments.
Superalloys (such as Nimonic 80A) are also used in the poppet valves of piston engines, both for diesel and gasoline engines.
This is either in the form of a single solid valve or as a bi-metallic valve. The corrosions resistance is particularly useful when
dealing with the high temperatures and pressures found in a diesel engine. The superalloys resist pitting and degradation allowing
operating conditions that would not be possible with regular stainless steel.
Additional applications of superalloys include: gas turbines (commercial and military aircraft, power generation, and marine
propulsion); space vehicles; submarines; nuclear reactors; military electric motors; racing and high-performance vehicles,
chemical processing vessels, bomb casings and heat exchanger tubing.

Contents

1 Chemical development
2 Process development
3 Metallurgy of superalloys
4 Coating of superalloys
4.1 Pack cementation process
4.2 Gas phase coating
4.3 Bond coat
5 Research and development of new superalloys
6 See also
7 References
7.1 Bibliography
8 External links

Chemical development
Because these alloys are intended to be used for high temperature applications, in addition to these materials being able to
withstand loading at temperatures near their melting point, their creep and oxidation resistance are of primary importance. Ni
based superalloys have emerged as the material of choice for these applications.[1] The properties of these Ni based
superalloys can be tailored to a certain extent through the addition of many other elements, both common and exotic, including
not only metals, but also metalloids and nonmetals; chromium, iron, cobalt, molybdenum, tungsten, tantalum, aluminium,
titanium, zirconium, niobium, rhenium, yttrium, vanadium, carbon, boron or hafnium are some examples of the alloying additions
used. Each of these additions has been chosen to serve a particular purpose in optimizing the properties for high temperature
application.
Creep resistance is dependent on slowing the speed of dislocation motion within a crystal structure. In modern Ni based
superalloys the -Ni3(Al,Ti) phase present acts as a barrier to dislocation motion. For this reason, this intermetallic phase,
when present in high volume fractions, drastically increases the strength of these alloys due to its ordered nature and high
coherency with the matrix. The chemical additions of aluminum and titanium promote the creation of the phase. The
phase size can be precisely controlled by careful precipitation strengthening heat treatments. Many superalloys are produced
using a two-phase heat treatment that creates a dispersion of cuboidal particles known as the primary phase, with a fine
dispersion between these known as secondary . In order to improve the oxidation resistance of these alloys, Al, Cr, B, and Y
are added. The Al and Cr form oxide layers that passivate the surface and protect the superalloy from further oxidation while B
and Y are used to improve the adhesion of this oxide scale to the substrate.[2] Cr, Fe, Co, Mo and Re all preferentially partition
to the matrix while Al, Ti, Nb, Ta, and V preferentially partition to the precipitates and solid solution strengthen the matrix
and precipitates respectively. In addition to solid solution strengthening, if grain boundaries are present, certain elements are
chosen for grain boundary strengthening. B and Zr tend to segregate to the grain boundaries which reduces the grain boundary
energy and results in better grain boundary cohesion and ductility.[3] Another form of grain boundary strengthening is achieved
through the addition of C and a carbide former, such as Cr, Mo, W, Nb, Ta, Ti, or Hf, which drives precipitation of carbides at
grain boundaries and thereby reduces grain boundary sliding.
While Ni based superalloys are excellent high temperature materials and have proven very useful, Co based superalloys
potentially possess superior hot corrosion, oxidation, and wear resistance as compared to Ni based superalloys. For this
reason, efforts have also been put into developing Co based superalloys over the past several years. Despite that, traditional Co
based superalloys have not found widespread usage because they have a lower strength at high temperature than Ni based
superalloys.[4] The main reason for this is that they appear to lack the precipitation strengthening that is so important in the

high temperature strength of Ni based superalloys. However, there has been a recent discovery of a stable -Co3(Al,W)
intermetallic compound with the L12 structure. The two-phase microstructure consists of cuboidal precipitates embedded in
a continuous matrix and is therefore morphologically identical to the microstructure observed in Ni based superalloys. Like in
the Ni based system, there is a high degree of coherency between the two phases which is one of the main factors resulting in
the superior strength at high temperatures. This provides a pathway for the development of a new class of load-bearing Co
based superalloys for application in severe environments.[5] In addition to the fact that many of the properties of these new Co
based superalloys could be better than those of the more traditional Ni based ones, Co also has a higher melting temperature
than Ni. Therefore, if the high temperature strength could be improved, the development of novel Co based superalloys could
allow for an increase in jet engine operation temperature resulting in an increased efficiency.

Process development

The historical developments in superalloy processing have brought about considerable increases in superalloy operating
temperatures. Superalloys were originally iron based and cold wrought prior to the 1940s. In the 1940s investment casting of
cobalt base alloys significantly raised operating temperatures. The development of vacuum melting in the 1950s allowed for very
fine control of the chemical composition of superalloys and reduction in contamination and in turn led to a revolution in
processing techniques such as directional solidification of alloys and single crystal superalloys.[6]

There are many forms of superalloy present within the gas turbine engine. In order to have fracture resistance, the disks of the
high pressure turbine are polycrystalline, which are usually cast and then forged into shape. The cast discs have a large columnar
grain structure and contain chemical segregation. The polycrystalline discs can also be made by powder metallurgy, where fine
powders are hot-isostatically pressed, extruded, and forged into shape. On the other hand, turbine blades are usually
monocrystalline or single crystal. Single crystal blades are free of / grain boundaries, which allow for increase in creep
resistance. Turbine blades can also be polycrystalline, which are made via investment casting. The polycrystalline blades can
contain either columnar grains or equiaxed grains. Columnar grain structured blades are created using directional solidification
techniques and have grains parallel to the major stress axes while equiaxed grain structured blades are prone to creep
deformation.
Single-crystal superalloys (SX or SC superalloys) are formed as a single crystal using a modified version of the directional
solidification technique, so there are no grain boundaries in the material. The mechanical properties of most other alloys depend
on the presence of grain boundaries, but at high temperatures, they would participate in creep and must be replaced by other
mechanisms. In many such alloys, islands of an ordered intermetallic phase sit in a matrix of disordered phase, all with the same
crystalline lattice. This approximates the dislocation-pinning behavior of grain boundaries, without introducing any amorphous
solid into the structure.

Metallurgy of superalloys
The microstructure of most precipitation strengthened nickel-base superalloys consists of the gamma matrix, and of intermetallic
' precipitates. The -phase is a solid solution with a face-centered crystal (fcc) lattice and randomly distributed different
species of atoms. By contrast, the '-phase has an ordered crystalline lattice of type LI2. Modern alloys typically contain about
70% by volume fraction of cube-like ' precipitates whose edge length is about 0.5 m.
In pure Ni3Al phase atoms of aluminium are placed at the vertices of the cubic cell and form the sublattice A. Atoms of nickel
are located at centers of the faces and form the sublattice B. The phase is not strictly stoichiometric. There may exist an excess
of vacancies in one of the sublattices, which leads to deviations from stoichiometry. Sublattices A and B of the '-phase can
solute a considerable proportion of other elements. The alloying elements are dissolved in the -phase as well. The '-phase
hardens the alloy through an unusual mechanism called the yield strength anomaly. Dislocations dissociate in the '-phase,
leading to the formation of an anti-phase boundary. It turns out that at elevated temperature, the free energy associated with the
anti-phase boundary (APB) is considerably reduced if it lies on a particular plane, which by coincidence is not a permitted slip

plane. One set of partial dislocations bounding the APB cross-slips so that the APB lies on the low-energy plane, and, since this
low-energy plane is not a permitted slip plane, the dissociated dislocation is now effectively locked. By this mechanism, the
yield strength of '-phase Ni3Al actually increases with temperature up to about 1000 C, giving superalloys their currently
unrivalled high-temperature strength.
Initial material selection for blade applications in Gas Turbine engines included alloys like the Nimonic series alloys in the
1940s.[7] The early Nimonic series incorporated ' Ni3(Al,Ti) precipitates in a matrix, as well as various metal-carbon
carbides (e.g. Cr23C6) at the grain boundaries[8] for additional grain boundary strength. Turbine blade components were forged
until vacuum induction casting technologies were introduced in the 1950s.[7] This process significantly improved cleanliness,
reduced defects, and increased the strength and temperature capability of the material.
Modern superalloys were developed in the 1980s with the advent of single crystal, or monocrystal, solidification techniques
(see Bridgman technique) for superalloys that enable grain boundaries to be entirely eliminated from a casting. Because the
material contained no grain boundaries, carbides were unnecessary as grain boundary strengthers and were thus eliminated.
Additionally, the volume fraction of the ' precipitates increased to about 50-70%. The first generation superalloys incorporated
increased Aluminium, Titanium, Tantalum, and Niobium content in order to increase the ' volume fraction in these alloys.
Examples of first generation superalloys include: PWA1480, Ren N4 and SRR99.[7]
The second and third generation superalloys introduced about 3 and 6 weight per cent Rhenium, for increased temperature
capability. Examples of second generation superalloys include PWA1484, CMSX-4 and Ren N5. Third generation alloys
include CMSX-10, and Ren N6. Fourth, Fifth, and even Sixth generation superalloys have been developed which incorporate
Ruthenium additions, making them more expensive still than the prior generation's Re-containing alloys.
The current trend is to avoid very expensive and very heavy elements. A possible remedy to this is Eglin steel, a budget material
with compromised temperature range and chemical resistance. It does not contain rhenium or ruthenium and its nickel content is
limited. To reduce fabrication costs, it was chemically designed to melt in a ladle (though with improved properties in a vacuum
crucible). Also, conventional welding and casting is possible before heat-treatment. The original purpose was to produce highperformance, inexpensive bomb casings, but the material has proven widely applicable to structural applications, including
armor.

In addition, it is often beneficial for grain boundaries that the nickel-base superalloy contains carbides (or boron or zirconium)
for improvements in creep strength. Where the carbides (e.g. MC where M is a metal and C is a carbon atom) are precipitated
at the grain boundaries, they act to pin the grain boundaries and improve the resistance to sliding and climbing and migration that
would occur during creep diffusion. However if they precipitate as a continuous grain boundary film, the fracture toughness of
the alloy may be reduced, together with the ductility and rupture strength.

Coating of superalloys
Superalloy products that are subjected to high working temperatures and corrosive atmosphere (such as high pressure turbine
region of jet engines) are coated with various kinds of coating. Mainly two kinds of coating process are applied: pack
cementation process and gas phase coating. Both are a type of chemical vapor deposition (CVD). In most cases, after the
coating process near-surface regions of parts are enriched with aluminium, the matrix of the coating being nickel aluminide.

Pack cementation process

The pack cementation process is carried out at lower temperatures, about 750 C. The parts are loaded into boxes that contain
a mixture of powders: active coating material, containing aluminum, activator (chloride or fluoride), and thermal ballast, like
aluminum oxide. At high temperatures the gaseous aluminum chloride is transferred to the surface of the part and diffuses inside

(mostly inward diffusion). After the end of the process the so-called "green coating" is produced, which is too thin and brittle for
direct use. A subsequent diffusion heat treatment (several hours at temperatures about 1080 C) leads to further inward
diffusion and formation of the desired coating.

Gas phase coating

This process is carried out at higher temperatures, about 1080 C. The coating material is usually loaded onto special trays
without physical contact with the parts to be coated. The coating mixture contains active coating material and activator, but
usually does not contain thermal ballast. As in the pack cementation process, the gaseous aluminium chloride (or fluoride) is
transferred to the surface of the part. However, in this case the diffusion is outwards. This kind of coating also requires diffusion
heat treatment.

Bond coat
The bond coat adheres the thermal barrier coating to the superalloy substrate. Additionally, the bond coat provides oxidation
protection and functions as a diffusion barrier against the motion of substrate atoms towards the environment.
There are three major types of bond coats, the aluminides, the platinum-aluminides, and MCrAlY. For the aluminide bond
coatings, the final composition and structure of the coating depends on the composition of the substrate. Aluminides also lack
ductility below 750 C, and exhibit a limited by thermomechanical fatigue strength.
The Pt-aluminides are very similar to the aluminide bond coats except for a layer of Pt (5-10 m) deposited on the blade. The
Pt is believed to aid in oxide adhesion and contributes to hot corrosion. The cost of Pt plating is justified by the increased blade
life span.
The MCrAlY is the latest generation of bond coat and does not strongly interact with the substrate. The Chromium provides
oxidation and hot-corrosion resistance. The aluminum controls oxidation mechanisms by limiting oxide growth. The yttrium
enhances the oxide adherence to the substrate. Investigation indicates that addition of rhenium and tantalum increases oxidation
resistance.

Research and development of new superalloys

The availability of superalloys during past decades has led to a steady increase in the turbine entry temperatures and the trend is
expected to continue. Sandia National Laboratories is studying a new method for making superalloys, known as radiolysis. It
introduces an entirely new area of research into creating alloys and superalloys through nanoparticle synthesis. This process
holds promise as a universal method of nanoparticle formation. By developing an understanding of the basic material science
behind these nanoparticle formations, there is speculation that it might be possible to expand research into other aspects of
superalloys.
There may be considerable disadvantages in making alloys by this method. About half of the use of superalloys is in applications
where the service temperature is close to the melting temperature of the alloy. It is common therefore to use single crystals. The
above method produces polycrystalline alloys, which suffer from an unacceptable level of creep.
Future paradigm in alloy development focus on reduction of weight, improving oxidation and corrosion resistance while
maintaining the strength of the alloy. Furthermore, with the increasing demand for turbine blade for power generation, another
focus of alloy design is to reduce the cost of super alloys.

See also
Oxide dispersion strengthened alloy

Titanium aluminide

References
1. ^ Reed, Roger C. The Superalloys: Fundamentals and Applications. Cambridge, UK: Cambridge UP, 2006.
2. ^ Klein, L., Y. Shen, M. S. Killian, and S. Virtanen. "Effect of B and Cr on the High Temperature Oxidation Behavior of Novel
/Strengthened Co-base Superalloys." Corrosion Science 53 (2011): 2713-720.
3. ^ Shinagawa, K., Toshihiro Omori, Katsunari Oikawa, Ryosuke Kainuma, and Kiyohito Ishida. "Ductility Enhancement by
Boron Addition in CoAlW High-temperature Alloys." Scripta Materialia 61.6 (2009): 612-15.
4. ^ Sato, J. "Cobalt-Base High-Temperature Alloys." Science 312.5770 (2006): 90-91.
5. ^ Suzuki, A., Garret C. DeNolf, and Tresa M. Pollock. "Flow Stress Anomalies in / Two-phase CoAlW-base Alloys."
Scripta Materialia 56.5 (2007): 385-88.
6. ^ C. Sims, N. Stoloff, W. Hagel, Superalloys II: High Temperature Materials for Aerospace and Industrial Power, 1987, John
Wiley & Sons
7. ^ a b c R.C. Reed, The Superalloys. Fundamentals and Applications
(http://www.cambridge.org/gb/knowledge/isbn/item1173393/?site_locale=en_GB)
8. ^ D. Bomba, M. Fazarinc, G. Kugler, S. Spaji, Microstructure development of Nimonic 80A superalloys during hot
deformation, Materials and Geoenvironment, 55:3 (2008) 319-328.

Bibliography
Levitin, Valim (2006). High Temperature Strain of Metals and Alloys: Physical Fundamentals. WILEY-VCH.
ISBN 978-3-527-31338-9.

External links
Extensive resource on Superalloys, Cambridge University (http://www.msm.cam.ac.uk/phase-trans/2003/nickel.html)
TMS - Superalloys: A Primer and History
(http://www.tms.org/Meetings/Specialty/Superalloys2000/SuperalloysHistory.html)
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Categories: Metallurgy Superalloys Aerospace materials Emerging technologies
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