Advanced Materials

Intermetallics for Manufacturing

February 2005

INTERMETALLIC MATERIALS are a

unique class of materials having characteristics of
both metals and ceramics. They differ from
conventional metal alloys in that they generally
possess long-range-ordered crystal structures. The
predominant bonding patterns found in ceramics are
highly directional covalent and ionic bonds,
whereas the unique deformation properties of
metals are due to non-directional metallic bonding.
Intermetallics contain both metallic and covalent
bonds, depending on the constituent metals. Mixed
bonding provides mechanical properties that are
Ordered Structure

Non-Ordered Structure

between metals (which are generally softer and

more ductile) and ceramics (which are generally
harder and more brittle).
High-temperature strength and superior oxidation
resistance make intermetallic materials exceptional
candidates for use in high temperature component
design providing not only longer equipment servicelife but the potential to operate at above normal
temperatures. Promising applications include heattreating fixtures, transfer rolls for hot metal
processing, forging dies, radiant burner tubes, or
pyrolyzer parts. The high-temperature strength and
superior oxidation resistance of these materials
would allow increases in operating temperature for
many industrial processes, with resulting dramatic
improvements in thermal energy efficiency and
reduced residence time of chemical reactants at
critical temperatures.

INTERMETALLIC DEVELOPMENT
The Department of Energy (DOE) began funding
the investigation of intermetallic materials at the
Oak Ridge National Laboratory (ORNL) in 1981.1
It has been one of the longest continuously funded
materials development programs ever undertaken.
Initial work focused on basic investigations of the
effects of microstructure, identification of alloying
elements, and the development of thermochemical
and thermomechanical property databases.
The DOE Office of Energy Efficiency and
Renewable Energys Industrial Technologies
Program (ITP) recognized that the unique properties
of intermetallic compounds could enable the
development of new, energy-efficient technologies
and process systems. ITP began funding R&D on
nickel aluminide intermetallics in the early 1990s.
As a result of cost-shared R&D with industrial
partners, intermetallic alloys have been deployed
commercially in a variety of manufacturing
applications.
NICKEL ALUMINIDE INTERMETALLICS
ORNL identified the nickel aluminide intermetallic
(Ni3Al) as having unique high-temperature strength
and oxidation resistance. Its highly ordered crystal
structure provides increased creep and yield
strengths with peak yield strength approximately 30
to 40% higher at 1475 to 1650F (800 to 900C)
than at room temperature. Since nickel aluminide
alloys contain up to 12 wt % excess aluminum, they
form a protective aluminum oxide (Al2O3) coating
which slows oxidation. This results in exceptional
resistance to carburization and coking at high
temperatures a characteristic making it ideal for
use in heat treating furnaces, steelmaking, and other
manufacturing processes.

BARRIERS TO USE

Despite the useful properties inherent to the Ni3Al

structure, the brittle texture of the material long
limited its usefulness in industrial settings.
Industrial materials need to be able to absorb and
respond to sudden pressure changes and mechanical
impacts without catastrophic failures typical of
ceramic or brittle materials. In addition, an
intermetallic's unique structural benefits can be lost
when using traditional metal fabrication techniques,
particularly forming and welding. The commercial
application of Ni3Al to industrial processes required
the development of Ni3Al alloys with reduced
brittleness and an increased capability for shape
casting, forming and welding into useful structures.
PATHWAY TO SUCCESSFUL

COMMERCIALIZATION

By adding boron and controlling the nickel-to

aluminum ratio, ORNL scientists were able to
develop Ni3Al alloys exhibiting ductility at room
temperature. Further chemistry modifications
improved intermediate-temperature ductility and
high-temperature oxidation resulting in
compositions that were potentially useful for
industrial applications.
Controlled composition ductile alloys were difficult
to make, and commercialization was hindered until
the early 1990s when ORNL developed a process
suitable for producing industrial quantities of the
intermetallic materials. The Exo-Melt process
uses a specialized furnace-loading arrangement to
control the exothermic heat from the reaction of
aluminum with nickel; energy is provided more
rapidly to the materials while the ideal composition
concentrations are maintained. This process
reduces melting and holding times and minimizes
silicon pick-up and other reactions with furnace
refractories. Exomelt also addressed important cost
and safety concerns in making Ni3Al. The process
received a 1995 R&D 100 Award and has been
widely adopted by industry.2
Ni3Al and other intermetallics, especially iron and
titanium aluminides, showed promise in a wide
variety of industrial applications. The metallurgical

and mechanical properties of intermetallic alloys

were to be improved by enhancing ductility,
toughness, strength, creep and oxidation resistance.
Intermetallic casting studies determined
solidification behavior, mold interactions, fluidity,
hot shortness, and other casting properties.
Welding studies evaluated cracking susceptibility,
weld properties, process development, and thermal
and environmental aging behavior. Metalworking
issues were addressed through hot ductility testing.
The results of these studies were used to predict and
adjust alloy compositions for specific industrial
applications and fabrication techniques including
the casting, welding and coating/cladding of
intermetallics with properties suitable for
conventional code-approved structures.
In 1992, a specific industrial application was
identified to exploit the excellent thermal and
corrosion resistance properties of Ni3Al cast
materials and reduce energy consumption.3 Nickel
aluminide heat-treating trays (upper fixtures, lower
fixtures, and support posts) were cast. Each tray
assembly could carry 340 kg (750 lb) through a
furnace. Over 65
fixtures were
successfully
fabricated and
installed in 1995 in a
continuous
carburizing furnace at
GM Delphi Saginaw
Steering Systems.
The nickel aluminide
furnace assemblies provided greater carburization
and oxidation resistance, as well as higher elevated
temperature strength and creep strength than steel
alloys. The trays lasted more than three times as
long, reducing both scheduled and unscheduled
down-time considerably. In addition, the lower
mass of the assemblies reduced energy requirements
for heat-treating by 11% and continue to save over
60 million Btu annually at the Saginaw plant. If
utilized across the entire heat treating industry,
roughly 30 trillion Btu could be saved annually in
the United States.
In 2000, a Ni3Al application was initiated that
required both the casting and welding of
intermetallics to make large industrial furnace

continuous caster rollers.4 Traditional roller surfaces

warp, crack and blister. Ni3Al properties minimize
off-spec product that results from roller surface
defects and minimizes furnace maintenance.
Techniques to centrifugally cast large rolls, 17-inch
diameter by 160-inch long, and to weld trunnions
on both ends of the roll were developed.

Benefits derived from the use of intermetallics in

this application include increased service life of
rolls, elimination of the water cooling requirement,
decreased materials rejection rate, and reduced
energy use. Furthermore, efficiency is improved as
a result of not needing to: (1) shut down
austenitizing furnaces for frequent grinding of
current rolls to remove blister, (2) shut down
continuous casters to grind roll surfaces because of
thermal fatigue cracking, (3) replace rolls as
frequently in austenitizing furnaces and continuous
casters and thus casting significantly fewer rolls,
and (4) remelt and process out-of-specification steel
plates due to marring by blisters on current rolls in
the austenitizing furnaces or continuous cast
systems. It is estimated that, if the technology was
broadly adopted, the resulting energy savings will
be over 32 trillion Btu per year.
A total of 101 rolls were fabricated and installed at
the Burns Harbor Plate Mill in 2002. These have
provided over two years of uninterrupted superior
service.5 Continuous operation at this mill has
resulted in an additional 210 operational days,
product yields of consistently high quality and a
35% increase in energy efficiency. A total of
215,000 tons of steel plate (3 times the amount of
steel used in the Empire State Building) have been
heat treated. Duraloy (an ORNL licensed
manufacturer of Ni3Al) will soon manufacture 110
new rolls for installation at another U.S. mill.

Project partners have advanced the development of

other Ni3Al applications that include both casting
and welding techniques. Annealing furnaces
frequently use radiant burner tubes that fail due to
creep deformation and oxidation mechanisms.
Ni3Al tubes eliminate these failures. Forging dies
built of cast Ni3Al alloy can remain in service ten
times as long as those fabricated from commercially
used die material. Nickel aluminide forging dies
have been used to successfully forge 100,000 pieces
of a part known as a "brake spider."

New industrial applications of intermetallics are

continuing to emerge. For example, cast or wrought
high-alloy stainless steels used for ethylene furnace
tubes are subject to coke buildup and carburization.
Coke buildup results in lower furnace efficiency
and productivity. Removal of coke from the furnace
tubes is a frequent and energy-intensive operation.
The hydrocarbon feed is stopped, and natural gas
and air are fed into the furnace to combust the coke
deposits. This operation results in the loss of the
fuel value of both the natural gas and the coke.
Elimination of the need for decoking could result in
annual energy savings of over 200 trillion Btu while
simultaneously improving the furnace productivity.
The unique oxide surface chemistry of Ni3Al
hinders the rate of carburization and coke buildup.
Use of Ni3Al for ethylene furnace tubes and
development of novel tube manufacturing and
welding techniques are being investigated.6
FUTURE DEVELOPMENTS AND THE

SUCCESS OF INTERMETALLICS WORK

Other intermetallic alloys developed at ORNL are

showing promise in a variety of industrial settings.
FeAl intermetallics have resistance to carburization
and sulfidation that far exceeds that of most
commercial metal alloys. Ni3Si alloys have good
mechanical properties coupled with excellent

resistance to oxidizing conditions, such as in

sulfuric acid and seawater, and to ammonia at
temperatures up to 900C. Ni3Al and TiAl are also
being characterized and evaluated for potential uses
and commercialization.

ADDITIONAL KEY PUBLICATIONS

a.

V. K. Sikka, Processing of Aluminides, pp. 561-604 in

Physical Metallurgy and Processing of Intermetallic
Compounds, ed. N. S. Stoloff and V. K. Sikka (Chapman
and Hall, New York, NY, 1996).

The intermetallic alloy development program at

ORNL has contributed significantly to the
understanding of intermetallic materials and
processing technologies. The program has been
characterized by outstanding research and effective
coordination between basic and applied research
organizations. Finally, collaborative interactions
between DOE, ORNL and industrial participants
(metal producers and end-users) have contributed to
plant floor energy efficiency improvements through
the implementation of innovative alloy
compositions and processing methods.

b.

V. K. Sikka, M. L. Santella, and R. W. Swindeman,

Ni3Al-Based Alloys in Steel and Heat Treating Furnace
Industry, Materials Research Society, 2000.

c.

V. K. Sikka, S. C. Deevi, S. Viswanathan, R. W.

Swindeman, and M. L. Santella, Advances in Processing
of Ni3Al-Based Intermetallics and Applications, pp.
1329-1337 in Intermetallics 8 (2000): Materials Park,
OH: ASM International.

d.

V. K. Sikka, M. L. Santella, P. Angelini, J. Mengel, R.

Petrusha, A. P. Martocci, and R. I. Pankiw, Large-scale
manufacturing of nickel aluminide transfer rolls for steel
austenitizing furnaces, Intermetallics, Volume 12, pp.
837-844, 2004.

REFERENCES

PATENTS

1. "Industrial Materials of the Future (IMF) Program

Intermetallic Alloy Development"

The Ni3Al research work performed at ORNL is

protected under 27 patents in the United States.

http:/www.oit.doe.gov/imf/pdfs/intermetallicalloystudy8_9.pdf

2. V. K. Sikka, S. C. Deevi, and J. D. Vought, "Exo-Melt: A

Commercially Viable Process," Advanced Materials and
Processes, 147(6), pp. 29-31 (1995).
3. V. K. Sikka, "Newly Developed Ni3Al Heat Treating
Furnace Assemblies are Being Commercialized at
Delphi," April 2001.
http://www.oit.doe.gov/imf/pdfs/ni3alheatfurnace.pdf

4. V. K. Sikka, M. L. Santella, P. Angelini, J. Mengel, R.

Petrusha, A. P. Martocci, L. Fabina, and R. Chango,
Large-Scale Evaluation of Nickel Aluminide Rolls in a
Heat-Treat Furnace at Bethlehem Steel (now ISG) Burns
Harbor Plate Mill, Sept. 2004.
http:/www.oit.doe.gov/imf/pdfs/10_nickel_aluminide_final_report.pdf

5. V. K. Sikka, M. L. Santella, P. Angelini, J. Mengel, R.

Petrusha, A. P. Martocci, and R. I. Pankiw, Large-Scale
Manufacturing of Nickel Aluminide Transfer Rolls for
Steel Austenitizing Furnaces, Intermetallics, Volume 12,
pp. 837-844 (2004).
6. "Oxide-dispersion Strengthened Tubes Will Enable
Higher Operating Temperatures, Leading to More
Efficient Ethylene Production."
http://www.oit.doe.gov/imf/pdfs/1783ethylenetubessum.pdf

LICENSES
Six licensed companies are producing nickel
aluminide alloys for the manufacture of industrial
components in the United States.
CONTACT INFORMATION:
Dr. Vinod K. Sikka
Metals and Ceramics Division
Oak Ridge National Laboratory
P.O. Box 2008
Oak Ridge, TN 37831-6083
Telephone: (865) 574-5112 Fax: (865) 574-4357
E-mail: sikkavk@ornl.gov
Visit the Industrial Technologies Program Web site
at: http://www.eere.energy.gov/industry/
The EERE Information Center also answers
questions on EERE's products, services, and 11
technology programs. You may contact the EERE
Information Center by calling 1-877-EERE-INF (1
877-337-3463) or online at
http://www.eere.energy.gov/informationcenter/