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Superalloys: A Primer and History

INTRODUCTION
The term "superalloy" was first used shortly after World War II to
As a supplement to The Minerals, describe a group of alloys developed for use in turbosuperchargers and
Metals & Materials Society's site aircraft turbine engines that required high performance at elevated
dedicated to the 9th International temperatures. The range of applications for which superalloys are used
Symposium on Superalloys, this
page was developed by Randy
has expanded to many other areas and now includes aircraft and land-
Bowman of NASA Lewis Research based gas turbines, rocket engines, chemical, and petroleum plants. They
Center. are particularly well suited for these demanding applications because of
their ability to retain most of their strength even after long exposure
times above 650C (1,200F). Their versatility stems from the fact that
they combine this high strength with good low-temperature ductility and excellent surface stability.

Superalloys are based on Group VIIIB elements and usually consist of various combinations of Fe, Ni,
Co, and Cr, as well as lesser amounts of W, Mo, Ta, Nb, Ti, and Al. The three major classes of
superalloys are nickel-, iron-, and cobalt-based alloys.

NICKEL-BASED SUPERALLOYS
Nickel-based alloys can be either solid solution or precipitation strengthened. Solid solutioned
strengthened alloys, such as Hastelloy X, are used in applications requiring only modest strength. In the
most demanding applications, such as hot sections of gas turbine engines, a precipitation strengthened
alloy is required. Most nickel-based alloys contain 10-20% Cr, up to 8% Al and Ti, 5-10% Co, and
small amounts of B, Zr, and C. Other common additions are Mo, W, Ta, Hf, and Nb (often still referred
to as "columbium" although the name "niobium" was adopted by the International Union of Pure and
Applied Chemistry in 1950 after more than 100 years of controversy). In broad terms, the elemental
additions in Ni-base superalloys can be categorized as being i) formers (elements that tend to partition
to the matrix, ii) ' formers (elements that partition to the ' precipitate, iii) carbide formers, and iv)
elements that segregate to the grain boundaries. Elements which are considered formers are Group V,
VI, and VII elements such as Co, Cr, Mo,W, Fe. The atomic diameters of these alloys are only 3-13%
different than Ni (the primary matrix element). ' formers come from group III, IV, and V elements and
include Al, Ti, Nb, Ta, Hf. The atomic diameters of these elements differ from Ni by 6-18%. The main
carbide formers are Cr, Mo, W, Nb, Ta, Ti. The primary grain boundary elements are B, C, and Zr. Their
atomic diameters are 21-27% different than Ni.

The major phases present in most nickel superalloys are as follows:

 Gamma ( ): The continuous matrix (called gamma) is an face-centered-cubic (fcc) nickel-based


austenitic phase that usually contains a high percentage of solid-solution elements such as Co, Cr,
Mo, and W.

 Gamma Prime ( '): The primary strengthening phase in nickel-based superalloys is Ni3(Al,Ti),
and is called gamma prime ( '). It is a coherently precipitating phase (i.e., the crystal planes of the
precipitate are in registry with the gamma matrix) with an ordered L12 (fcc) crystal structure. The
close match in matrix/precipitate lattice parameter (~0-1%) combined with the chemical
compatability allows the ' to precipitate homogeneously throughout the matrix and have long-
time stability. Interestingly, the flow stress of the ' increases with increasing temperature up to
about 650oC (1200oF). In addition, ' is quite ductile and thus imparts strength to the matrix
without lowering the fracture toughness of the alloy. Aluminum and titanium are the major
constituents and are added in amounts and mutual proportions to precipitate a high volume
fraction in the matrix. In some modern alloys the volume fraction of the ' precipitate is around
70%. There are many factors that contribute to the hardening imparted by the ' and include ' fault
energy, ' strength, coherency strains, volume fraction of ', and ' particle size.

Extremely small ' precipitates always occur as


spheres. In fact, for a given volume of
precipitate, a sphere has 1.24 less surface area
than a cube, and thus is the preferred shape to
minimize surface energy. With a coherent
particle, however, the interfacial energy can
be minimized by forming cubes and allowing
the crystalographic planes of the cubic matrix
and precipitate to remain continuous. Thus as
the ' grows, the morphology can change from
spheres to cubes (as shown in this figure) or
plates depending on the value of the
matrix/precipitate lattice mismatch. For larger
mismatch values the critical particle size where the change from spheres to cubes (or plates)
occurs is reduced. Coherency can be lost by overaging. One sign of a loss of coherency is
directional coarsening (aspect ratio) and rounding of the cube edges. Increasing directional
coarsening for increasing (positive or negative) mismatch is also expected.

 Carbides: Carbon, added at levels of 0.05-0.2%, combines with reactive and refractory elements
such as titanium, tantalum, and hafnium to form carbides (e.g., TiC, TaC, or HfC). During heat
treatment and service, these begin to decompose and form lower carbides such as M23C6 and
M6C, which tend to form on the grain boundaries. These common carbides all have an fcc crystal
structure. Results vary on whether carbides are detrimental or advantageous to superalloy
properties. The general opinion is that in superalloys with grain boundaries, carbides are
beneficial by increasing rupture strength at high tempeature.

 Topologically Close-Packed Phases: These are generally undesirable, brittle phases that can
form during heat treatment or service. The cell structure of these phases have close-packed atoms
in layers separated by relatively large interatomic distances. The layers of close packed atoms are
displaced from one another by sandwiched larger atoms, developing a characteristic "topology."
These compounds have been characterized as possessing a topologically close-packed (TCP)
structure. Conversely, Ni3Al (gamma prime) is close-packed in all directions and is called
geometrically close-packed (GCP).

TCPs ( , , Laves, etc.) usually form as plates (which appear as needles on a single-plane
microstructure.) The plate-like structure negatively affects mechanical properties (ductility and
creep-rupture.) Sigma appears to be the most deleterious while strength retention has been
observed in some alloys containing mu and Laves. TCPs are potentially damaging for two
reasons: they tie up and ' strengthening elements in a non-useful form, thus reducing creep
strength, and they can act as crack initiators because of their brittle nature.

APPLICATIONS
Nickel-based superalloys are used in load-bearing structures
to the highest homologous temperature of any common alloy
system (Tm = 0.9, or 90% of their melting point). Among the RELATED LINKS
most demanding applications for a structural material are
those in the hot sections of turbine engines. The preeminence Superalloy-Related Companies
of superalloys is reflected in the fact that they currently
comprise over 50% of the weight of advanced aircraft  Axel Johnson Metals

engines. The widespread use of superalloys in turbine engines  Cannon-Muskegon Corp.

coupled with the fact that the thermodynamic efficiency of  Carpenter Technology Corporation

turbine engines is increased with increasing turbine inlet  Chromalloy

temperatures has, in part, provided the motivation for  Dynamet

increasing the maximum-use temperature of superalloys. In  Haynes International

fact, during the past 30 years turbine airfoil temperature  Howmet Corp.

capability has increased on average by about 4F per year.  INCO

Two major factors which have made this increase possible are  Ladish
 PCC Airfoils
1. Advanced processing techniques, which improved alloy  Special Metals
cleanliness (thus improving reliability) and/or enabled  Teledyne Allvac
the production of tailored microstructures such as  Utica Corporation
directionally solidified or single-crystal material.  Wyman-Gordon

2. Alloy development resulting in higher-use-temperature


materials primarily through the additions of refractory Turbine Engine Manufacturers
elements such as Re, W, Ta, and Mo.
 AlliedSignal Aerospace
 Allison Engine Company
About 60% of the use-temperature increases have occurred
 CFM International
due to advanced cooling concepts; 40% have resulted from
 Daimler-Benz Aeorspace
material improvements. State-of-the-art turbine blade surface
 General Electric Aircraft Engines
temperatures are near 2,100F (1,150C); the most severe
 Lycoming
combinations of stress and temperature corresponds to an
 Pratt & Whitney (P&W Canada)
average bulk metal temperature approaching 1,830F (1,000
 Rolls Royce/BMW Rolls Royce
C).
 Snecma
 Volvo Aero Corporation
Although superalloys retain significant strength to
 Westinghouse
temperatures near 1800F, they tend to be susceptible to
environmental attack because of the presence of reactive Another listing of manufacturers is available
alloying elements (which provide their high-temperature from Gas-Turbines.
strength). Surface attack includes oxidation, hot corrosion,
and thermal fatigue. In the most demanding applications, such Turbine Engine Information
as turbine blade and vanes, superalloys are often coated to
improve environmental resistance.  How a Jet Engine Works (from NASA
Lewis)
Gas Turbine Primer (from Gas-Turbines)
PROCESSING 
The material and casting technique improvements that have Other Interesting Sites
taken place during the last 50 years have enabled superalloys
to be used first as equiaxed castings in the 1940s, then as  General Science
directionally solidified (DS) materials during the 1960s, and  Periodic Table of Elements
finally as single crystals (SC) in the 1970s. Each casting  Crystal Lattice Structures
technique advancement has resulted in higher use  Phase Diagrams
temperatures.  Materials/Metallurgy
 Materials Science Links
In DS processing, columnar grains are formed parallel to the  ASM's Metal Producers and
growth axis. In nickel-based alloys, the natural growth Suppliers Guide
direction is along the <100> crystallographic direction. This  Metal Suppliers Online
morphology is accomplished by pouring liquid metal into a  Mechanical Testing
mold that contains a water-cooled bottom plate. Solidification  Metal Forming and Forging
first occurs at the bottom plate, after which the mold is slowly  Metallurgy
withdrawn from the furnace, allowing the metal inside to  Aerospace
directionally solidify from bottom to top. The exceptional  Airliner Photo Index
properties of DS and SC alloys is due to  Boeing
 Aviation Week & Space

1. The alignment or elimination of any weak grain Technology


boundaries oriented transverse to the eventual loading
direction.

2. The low modulus associated with the <100> directions enhances thermal mechanical fatigue
resistance in areas of constrained thermal expansionparticularly turbine vanes. In general, the
lack of transverse grain boundaries coupled with the lower modulus can result in 3-5 times
improvement in rupture life.

SC casting were developed during the 1970s and were a spin-off from the technological advances made
in the DS casting processes. SC casting are produced in a similar fashion to DS by selecting a single
grain, via a grain selector. During solidification, this single grain grows to encompass the entire part.
Single crystals obtain their outstanding strength through the elimination of grain boundaries that are
present in both equiaxed and directionally solidified materials. In addition, the elimination of grain
boundary strengtheners such as C, B, Si, and Zr raises the single crystal's melting point. By increasing
the alloy's melting point, the homogenization heat-treat temperature can be increased without fear of
incipient melting, thus allowing for more complete solutioning of the ' and thereby increasing alloy
strength and maximum use temperature.

FURTHER READING
The first comprehensive book on superalloysand probably the best single source of information
related to superalloysis, appropriately, Superalloys, published in 1972 by John Wiley & Sons. Since
the book's original publication, it has become widely regarded as the standard reference in the field of
superalloys. The 1987 edition, Superalloys II, although based on the original version was thoroughly
updated to reflect the latest developments in the field.

Another good reference is "The Microstructure of Superalloys" by Madeleine Durand-Charre, published


by Gordon and Breach Science Publishers in 1998. With more than 100 illustrations, the 140-page text
explains all the transformation mechanisms involved in the formation of microstructures during
solidification and heat treatments (crystallization paths, segregation, crystal orientation, precipitation,
TCP, coarsening and rafting, etc.). It includes up-to-date information and data such as phase diagrams
and crystallographic structures. The nearly 300 references provide a valuable resource for further
investigation.

Additional information can also be gleaned from the following conference sites:

 The 4th International Symposium on 718, 625, 706, and Derivatives


 The 9th International Symposium on Superalloys

The content of this site was developed by Randy Bowman (randy.bowman@lerc.nasa.gov); your feedback is welcome.

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