ASTM - Melting of Superalloys

L. W.
Lherbier^
Melting of Superalloys
REFERENCE: Lherbier, L. W., "Melting of Superalloys," MiCon 78: Optimization of Processing, Properties, and Service Performance Through Microstructural
Control, ASTM STP 672, Halle Abrams, G. N. Maniar, D. A. Nail, and H. D.
Solomon, Eds., American Society for Testing and Materials, 1979, pp. 514-525.
ABSTRACT: Melting of superalloys is the initial, and perhaps most important, step
in the production of materials used in critical high-temperature applications.
Increasing demand for high-quality superalloys with specific characteristics has
resulted in various combinations of primary, melting, refining, and secondary
remelting operations. Specific characteristics of each of these process operations
are used to produce superalloys that meet customer quality requirements for (1)
chemistry, (2) product form, and (3) structural uniformity.
Various combinations of melting processes can be used to obtain a desired
primary chemistry not only in terms of the primary elements, but also for residual
and tramp elements. Product forms frequently dictate a combination of melting
processes that give importance to the shape of ingots, the end product of superalloy
melting processes. Additionally, it is frequently important to choose melting
combinations that achieve ingot structure control for optimum primary phase
distribution, cleanliness or hot workability, or both.
KEY WORDS: steels, microstructure, superalloys, melting, vacuum induction
melting, argon oxygen decarburization, vacuum arc remelting, electric furnace
melting, vacuum degassing, vacuum oxygen decarburization, election beam melting, electroslag remelting
In most analyses of superalloy developments throughout the past 20

years, attention is usually focused on the end productgas turbines,
ever growing in size and efficiency. The increase in' efficiency has been
due to both materials and design advances. The increase in hightemperature properties of materials generally referred to as iron, cobalt,
and nickel superalloys has been astounding. Most everyone, and especially those directly involved with the manufacture and use of superalloys, will attest to the importance of alloy development efforts during the
past two decades. However, fewer of us accept and even less recognize
the fact that achievements in the gas turbine industry would not have
' Manager, Powder Metallurgy, Universal-Cyclops Specialty Steel Division, Bridgeville,
Pa. 15017.
514
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LHERBIER ON MELTING OF SUPERALLOYS
515
occurred except for the concurrent development of special melting

methods that made possible the manufacture of superalloys for use in
products that we so much take for granted today. In view of this situation,
it seems appropriate to partially modify generally held views concerning
superalloys and point up through several examples the overriding importance of melting and casting a high-quality starting material.
Definition of Superalloy
Superalloy is a generic term that can be applied to a wide variety of

materials. To help narrow the focus of this effort concerning melting
processes of commercial significance, I would initially like to define
superalloys as a group of iron-, nickel-, or cobalt-base alloys, which
provide useful strength capabilities at temperatures exceeding 426C
(800F). Additionally, these alloys generally exhibit excellent oxidation
resistance at service temperatures. Examples of commercial significance
that fit this definition are listed in Table 1.
In addition to the nominal composition for the various alloys. Table 1
also groups the alloys listed by classifying them as to structure: austenitic
and martensitic. The austenitic and martensitic groups are further broken
down into specific types that are determined by some characteristic of
that material: composition, strength, strengthening mechanism, etc. In
the austenitic category. Type I precipitation hardening materials are
typically the M/cA:e/-base alloys, characterized by gamma prime
strengthening and carbide precipitation. The Type II precipitation hardening austenitic materials are typically the iron-nickel alloys also
strengthened by gamma prime, NigCb, or NijTi precipitation. The Type II
materials contain carbides and are prone to precipitation of intermetallic
compounds such as Laves and Mu phases. Both the Type I and Type II
materials are used for structural parts whose primary function is to supply
strength at elevated temperatures. Generally speaking, the Type II
materials are used up to 648C (1200F) while the Type I materials have a
higher temperature capability approaching 760C (1400F). The Type III
solid solution strengthened materials in the austenitic category are nickelor cobalt-h&^t alloys or both whose strengthening is achieved by solid
solution hardening and carbide precipitation. Much of this material is
fabricated from sheet into structural parts that require extremely good
oxidation resistance. As such, these materials can generally be used at
temperatures up to 926C (I700F) but at reduced strength levels.
The three types of materials listed in the martensitic stainless category
are all jVon-base materials and are generally employed at a temperature
ranging from 426 to 538C (800 to 1000F). The Type I straight chromium
material is the basic composition used to obtain adequate strength and
nominal oxidation characteristics at minimum cost. The Type II
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LHERBIER ON MELTING OF SUPERALLOYS
517
chromium modified alloys achieve higher strength levels through the

addition of molybdenum or some other solid solution hardening element
or both for a modest increase in cost. The Type III precipitation hardening
martensitic materials increase strength even further by altering the
composition so as to provide precipitation hardening in conjunction with
transformation hardening. Additionally, this material, because of higher
chromium and molybdenum contents, generally exhibits higher oxidation
resistance than the other two types in the martensitic alloy category. It
should be further pointed up that all of the examples listed in Table 1
involve wrought superalloys and represent the bulk of the production of
these materials in this country.
Factors Affecting Superalloy Performance
In analyzing the superalloys listed in Table 1, it should come as no
surprise that their characteristics in service depend primarily on their
chemical composition. As such, it is imperative that one uses a melting
procedure to obtain the right balance of primary elements in these
materials. However, it must be remembered that the characteristics
imparted by the primary element composition can be significantly affected
by other factors, such as residual gases, inclusions, and other impurities,
which may be metallic or nonmetallic in nature. The effect of sulfur on
elevated temperature ductility is well recognized as is the effect of
inclusions on fatigue strength. Even the presence of minute quantities of
various metallic elements can significantly affect superalloy properties.
The beneficial effect of boron on stress rupture and creep was reported
long ago. There can be negative effects also as shown by Fig. 1, which
illustrates the harm bismuth has on the rupture properties of an ironnickel (Fe-Ni) (Unitemp 718) superalloy.
Furthermore, desired characteristics in superalloys are not obtained by
chemical composition alone, and it is recognized that the other major
factor to be considered during initial production is the solidification
structure. In many instances, the final properties are determined by the
original cast structure, that is, grain size, phase distribution, and the
degree and amount of cast structure defects. One very important aspect of
structure involves the ability of the cast product to be satisfactorily hot or
cold worked into a usable shape. The importance of structure and surface
in altering the hot workability of a cobalt-base alloy is illustrated in Fig. 2.
It must be recognized that chemistry changes occurring during melting
operations aimed at improving structure can also influence hot workability. Recognition of the importance of both composition and structure has
consequently resulted in the specialty steel industry developing advanced
technology utilizing various combinations of melting and refining techniques to produce material capable of meeting quality requirements at the
lowest possible cost.
518
MICON 78
150
125
|,oo
50
^-fi*rt(/
25
2UiSE_
lite spec.
4
6
Bismuth
10
Content (pptn)
elong. spec.
ELONGATION
REDUCTION of ftREA
4
6
Bismuth
FIG. 1Effect
superalloy.
10
12
Content (ppm)
of bismuth on 649C/689 MPa stress rupture properties
of an Fe-Ni
Melting Techniques
If we could design an ideal melting process for the production of
high-quality superalloys, it would be necessary to have the following
attributes: (1) it must have the capability of using all varieties of scrap and
virgin raw materials; (2) it must be amenable to absolute control of
chemistry with high recovery of all alloying elements; (3) it must be both
flexible and adaptable to the production of all types of alloys, regardless
of class; (4) it must be totally controllable from the standpoint of efficient
refining reactions, and the solidification sequence; (5) it must be completely free from all sources of contamination from the standpoint of
gases, impurities, and nonmetallic inclusions; and (6) it must be capable of
high productivity at low operating cost.
It should be readily apparent that it is impossible to combine all of these
requirements into a single melting unit. Rather, the melting of superalloys
can be best understood by dividing the sequence into three separate
categories as illustrated in Fig. 3. First, is the primary melting processes,
which essentially makes the alloys from pure metals, ferro alloys, revert,
and scrap material. Refining processes fall into the second category and
can involve separate units or can be accomplished in the primary melting
LHERBIER ON MELTING OF SUPERAUOYS
519
Test Temperature PF)

70
1750
1850
1950
2050
2150
2250
60
\ESR
50
40
VAR
f. 30
20
oos 'Nomin al Strain R ate of 20

CHeoc Rote 2in 5cm) /sec
Jaw Spacing lin 2.5cm)
10
[
954
1010
.1066
i
1121
177
1232
Test Temperature (C)

FIG. 2Effect of remelt practice on the Gleeble hot ductility values for a
superalloy.
cobalt-base
equipment to obtain specified requirements in terms of gas content,

impurity removal, alloy recovery, etc. The third category involves the
secondary melting processes where primary emphasis is placed on
solidification control to produce ingots of high structural integrity and also
to obtain additional specific purification aims without introducting undesirable contamination from either refractories or the atmosphere. Although there are many variations within these three categories of primary
melting processes, refining processes, and secondary melting processes,
this effort will discuss only those of significant commercial importance for
today's production of superalloys.
Primary Melting Processes
The basic electric arc furnace (EFM) was the first large-scale primary
production unit for the melting of superalloys in this country. The
520
MICON 78
EFM
VIM
FIG. 3Advanced melting and refining technology for superalloys.
procedure involves charging of solid scrap, virgin raw materials, ferro

alloys, or all three within a refractory lined shell and melting in an air
environment via the generation of heat resulting from an electric arc
between graphite electrodes and the charge. Slags are added for refining
purposes and the impurities removed as gases or as liquid slag. Generally,
gaseous oxygen is used to lower the carbon, hydrogen, and nitrogen
contents of the melt. The molten metal is generally cast into ingots for
processing to various mill products or into electrodes for remelting to
obtain further refinement and improved ingot structure. Principal advantages of the electric furnace include a wide flexibility in charge material
(chemistry and shape), good temperature control, a fluid reactive slag for
metallurgical refining, slag reactions adaptable to particular needs, and,
perhaps most important of all, high productivity at low cost. Disadvantages include the presence of the refractories, ambient air, slag, and
generally a lack of good stirring that leads to longer refining times and
poor melt homogenization. However, years of experience have enabled
producers to develop basic arc melting practices for high-temperature
alloys by carefully tailoring the procedures of the equipment to meet
specific material requirements.
The secondary primary melting process of commercial significance is
vacuum induction melting (VIM). This process developed from a laboratory curiosity in the 1950's to a process that is today the dominant method
of producing superalloys that must meet consistently stringent material
specifications. The procedure involves charging solid scrap, virgin raw
LHERBIER ON MELTING OF SUPERALIOYS
521
materials, ferro alloys, or all three into a refractory-lined crucible under

vacuum and then generating the heat required for melting via eddy
currents induced within the charge. In view of the reduced pressure
during the melting process, some impurities are removed as gases and
there is generally no contamination from air or slag or both. The refined
molten metal is cast under vacuum into ingots for processing to mill
products or into electrodes for melting to obtain further refinement and
improvement in ingot structure.
The vacuum induction melting process is quite flexible and provides the
best control over the entire melt chemistry, in terms of primary elements,
beneficial trace elements, and harmful impurities. In fact, the reproducibility of chemical composition from heat to heat approaches for a number
of elements the accuracy limits of present analytical techniques. The high
degree of flexibility is made possible by induction stirring and the vacuum
environment that allows the entire system to be treated in a thermodynamic sense. Control of the pressure in this process results in strong
degassing, good carbon deoxidation, and highly favorable reaction kinetics. A significant advantage of the process, induction stirring, allows melt
homogenization, complete control over refining times, and excellent temperature control during all phases of the operation. A major disadvantage
is that it requires relatively good charge materials and cannot handle some
of the charge materials used in the electric furnace. Other disadvantages
are the potential reaction of the molten alloy with the refractory lining and
the loss of high vapor pressure alloying elements. Consequently, the cost
of production via vacuum induction melting is somehwat higher than
electric furnace melting.
Refining Processes
Three basic refining processes have been applied to superalloys melted
initially by the electric furnace process. Vacuum degassing (VD) was
introduced as the first stage of up-grading the quality of electric furnace
product. In this refining process, molten metal is degassed in a separate
vessel by exposure to pressures substantially below atmospheric. Under
these conditions, dissolved gases such as carbon monoxide, hydrogen,
and nitrogen are reduced. Efficiency is increased by stirring the molten
metal so as to maximize the exposure of the entire bath to the vacuum/
metal interface. Some of the more sophisticated facilities have been
equipped with graphite electrodes or induction coils to reheat the molten
metal during or following the degassing operation. This refining process
was soon followed by more complex metallurgical technologies involving
carbon deoxidation and compositional adjustments under vacuum.
Degassing developments led to the vacuum oxygen decarburization
process (VOD) in which stainless and superalloys could be treated in
522
MICON 78
specially designed equipment under closely controlled conditions. In this

refining process molten metal from the electric furnace containing relatively high levels of carbon and chromium is decarburized under vacuum
by lancing with oxygen. Under these conditions, it is possible to remove
carbon with minimal oxidation of chromium. This permits the use of a
lower cost high-carbon-containing raw materials (especially chromium) in
the production of some superalloys. Efficiency is greatly increased by
stirring the molten metal during decarburization using argon or induction
stirring or both. Dissolved gases are reduced during exposure to pressures
below atmospheric.
The latest refining process to be adopted by the industry is argon/
oxygen decarburization technique (AOD). Duplex processing combining
the electric furnace and the AOD process marks a new era in specialty
steelmaking whereby an alloy and scrap charge is melted in the basic
electric furnace to the melt in composition, transferred to a slag-free
argon/oxygen reactor, decarburized, the resulting slag reduced to recover
chromium, etc., a new slag added for desulfiirization, if required, and the
material refined to a final high-quality product. The molten metal is
usually decarburized by the injection of argon and oxygen. The argon/
oxygen mixture is injected through separate tuyeres or nozzles, and the
ratio of argon to oxygen is increased as refining or decarburization occurs.
Slag metal reactions such as the reduction of chromium and desulfurization, if necessary, are enhanced by stirring with pure argon after the
desired carbon level has been achieved. Injection of argon also promotes
the removal of other dissolved gases.
The AOD process has received wide acceptance rapidly because of its
simplicity and flexibility of operation, its easy control and reproducibility,
and its superior quality over conventional electric furnace practices. This
process can be termed as one of revolutionary significance in specialty
steelmaking and offers unlimited potential for the production of nickelbase and other superalloys requiring low-carbon contents and nominal
reactive element contents. This process permits the use of lower cost
high-carbon ferrochrome and other less expensive raw materials in the
production of many alloys. The simple construction of the AOD vessel
makes it relatively free of maintenance or operating problems. The high
consumption of argon has been partially reduced by the substitution of
nitrogen in the early stage of decarburization. Admittedly, most of the
AOD activity currently involves stainless steels, however, there are a
number of firms using the process of corrosion-resistant and hightemperature nickel-base alloys.
The only refining process that has been applied to vacuum induction
melted materials has been the electron beam technique (EBM). Although
not commercially viable at the present time, it does seem appropriate to
discuss the technique because a large unit was built and put into operation
523
LHERBIER O N MELTING OF SUPERALLOYS
for several years. In the electron beam refining process, molten metal
from the vacuum induction furnace is further refined by passing it through
a very hard vacuum in a water-cooled copper trough during which it is
heated locally to very high temperatures by electron beam guns. The
refining efficiency is extremely high due to the combination of the hard
vacuum and the intense localized heating. During this part of the
process, there is no contamination from the air, slag, or crucible. The
refined molten metal is continuously cast under vacuum for processing to
mill products or for remelting to obtain an improved ingot structure.
Remelting Processes
It soon became apparent in the early days of vacuum induction melting
that the achievement of closely controlled chemical composition in terms
of both primary and residual elements was not sufficient to meet the
quality requirements demanded by many applications, specifically those
in the gas turbine industry. This situation resulted in the development of
the remelting processes with the primary goal of further refining the
molten metal from gases, nonmetallic and metallic impurities, and the
production of larger ingots of uniform composition with dense homogeneous structures free of metallurgical defects.
The first remelting process developed on the commercial basis was the
vacuum arc remelting process (VAR) in the late 1950's. Figure 4a
illustrates the basic characteristics of the process. As-cast electric furnace
Electrode Composition
and Quolity
Electrode Composition
and Quality
Electrode Shape ,
Electrode Stiope
Electrical Energy
Volts/ Amps
Slag Characteristics
Viscosity, Resistivity etc.
[Slog Volume |
Slog Composition
Chonqes
Additions to Slog
Mg. It etc.
:x:
I Atmosphere |
Electrical Energy
Volts/Amps
Electrode/Ingot
Diameter Ratio
Electrode/Ingot
Diameter Ratio
Power Mode
Power Mode
Electrode Immersion
itt_SlflS.
^MuJliphasej.';^'":!'!
Pool Depth
ond Shape
Power
Consumption
I Melt
Rotel
Ingot Composition
ond Quolity
Cooling Efficiency
Temperoture Grodient
Electromagnetic
Fields
Arc Lengfh
Electrode Tip to Pool
DC
Pool Depth
and Shape
(straight)
Power
Consumption
I Melt Rote I
Cooling Efficiency
Temperature Gradient
:z:
Electromagnetic
Fields
[ Ingot Composition
I
ond Quality
FIG. 4A comparison of electroslag and vacuum are remelting process
characteristics.
524
MICON 78
melted or vacuum induction melted electrodes are progressively remelted

and solidified in water-cooled copper mold under vacuum by an electric
arc generated between the electrode and the molten metal above the
solidifying ingot. Some refining occurs by removal of impurities in
gaseous form, and there is no further contamination from air, slag, or
refractory. The progressively solidified ingot is completely homogeneous
and free of shrinkage defects and can be processed directly to mill
products. The process grew rapidly in the 1%0's and found wide
acceptance in this country for the production of superalloys. The process
is the most important and dominant remelting process in the production of
double-vacuum melted advanced superalloys, which must meet the
specifications for most critical applications. A large number of widely
different alloys of almost any composition can be remelted and improved
by the vacuum arc remelting process.
Although developed many years ago, the electroslag remelting process
(ESR) did not find wide use in this country until the mid-1960's.
Characteristics of this process are also illustrated in Fig. 4b. In this
process, as-cast electric furnace melted, or vacuum induction melted
electrodes are progressively remelted and solidified in a water-cooled
copper mold under a blanket of molten flux to electric current passing
between the electrode and the solidifying ingot. Refining occurs as molten
metal passes through the flux and impurities are removed as gas or by
reaction with the flux to form slag. The progressively solidified ingot is
completely homogeneous and free of shrinkage defects and can then be
processed directly to mill products. The process has experienced very
rapid growth in the last ten years for the production of a wide variety of
materials and in particular many nickel- and cobalt-base alloys.
The electroslag process compliments vacuum arc remelt in several
areas and, in others, it is an alternative process in competition with the
highly perfected vacuum arc remelting technology. Nevertheless, each of
the two remelting processes have their own particular characteristics as
illustrated in Fig. 4 and should, therefore, be considered as complimentary to one another rather than competitive. An advantage of the
electroslag process includes the production of shaped ingots and slabs
with high aspect ratios. It also allows greater tolerance in the selection of
remelting parameters owing to the favorable thermal effects of the flux
bath by providing uniform heat distribution over the pool and reducing
thermal gradients. Minor disadvantages include the problem of chemistry
control in certain alloys attributable to mildly oxidizing conditions of the
liquid flux. Flux compositional changes also need close attention because
of possible control problems with certain highly reactive elements in the
remelted material.
A third and much less significant remelting process is the electron beam
remelting (EBR) technique. In this process, as-cast electric furnace
LHER8IER ON MELTING OF SUPERAUOYS
525
melted or vacuum induction melted electrodes are progressively remelted

and solidified under a very hard vacuum. Melting occurs from heat
generated in the electrode due to the inpingement of high-energy electrons
from electron beam guns. Refining efficiency is extremely high due to the
vacuum and the intense heat generated by the bombarding electrons.
Impurities are removed in gaseous form and there is no contamination
from air, slag, or refractory. However, higher costs and insufficient
quality improvements of this process have prevented it from becoming of
great commercial significance at this point in time.
Summary
Development of the various melting processes by the specialty steel
industry has resulted in cost effective methods of producing high-quality
superalloys. Ultimately, the choice of a melting sequence for the production of these materials is dependent upon the quality and cost of the final
product. Consequently, primary, refining, and remelted processes are
used in a variety of combinations to produce ingots capable of being
fabricated into reliable, cost effective products. The importance of
melting in the overall sequence from raw material to end product cannot
be overemphasized. No amount of highly sophisticated hot or cold
processing, heat treatment, etc., can produce today's required quality
level without a proper composition or structure in the cast ingot.

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L. W.

In most analyses of superalloy developments throughout the past 20

LHERBIER ON MELTING OF SUPERALLOYS

occurred except for the concurrent development of special melting

Superalloy is a generic term that can be applied to a wide variety of

LHERBIER ON MELTING OF SUPERALLOYS

chromium modified alloys achieve higher strength levels through the

of bismuth on 649C/689 MPa stress rupture properties

LHERBIER ON MELTING OF SUPERAUOYS

Test Temperature PF)

oos 'Nomin al Strain R ate of 20

Test Temperature (C)

equipment to obtain specified requirements in terms of gas content,

FIG. 3Advanced melting and refining technology for superalloys.

procedure involves charging of solid scrap, virgin raw materials, ferro

LHERBIER ON MELTING OF SUPERALIOYS

materials, ferro alloys, or all three into a refractory-lined crucible under

specially designed equipment under closely controlled conditions. In this

LHERBIER O N MELTING OF SUPERALLOYS

FIG. 4A comparison of electroslag and vacuum are remelting process

melted or vacuum induction melted electrodes are progressively remelted

LHER8IER ON MELTING OF SUPERAUOYS

melted or vacuum induction melted electrodes are progressively remelted

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