U.S. patent number 3,639,179 [Application Number 05/007,895] was granted by the patent office on 1972-02-01 for method of making large grain-sized superalloys.
This patent grant is currently assigned to Federal-Mogul Corporation. Invention is credited to Steven H. Reichman, John W. Smythe.
United States Patent |
3,639,179 |
Reichman , et al. |
February 1, 1972 |
METHOD OF MAKING LARGE GRAIN-SIZED SUPERALLOYS
Abstract
A process for making nickel-base superalloys possessing superior
high-temperature properties which employs powder metallurgical
techniques and includes the steps of densifying the powdered alloy
into a blank approaching 100 percent theoretical density, cold
working the blank at a controlled temperature, recrystallizing the
cold-worked blank for a period of time sufficient to nucleate new
grains and thereafter heat treating the recrystallized blank at a
controlled temperature for a period of time sufficient to attain
the desired magnitude of grain growth.
Inventors: |
Reichman; Steven H. (Ann Arbor,
MI), Smythe; John W. (Ann Arbor, MI) |
Assignee: |
Federal-Mogul Corporation
(N/A)
|
Family
ID: |
21728689 |
Appl.
No.: |
05/007,895 |
Filed: |
February 2, 1970 |
Current U.S.
Class: |
75/246; 148/428;
148/514; 148/677; 419/28; 419/29; 419/66 |
Current CPC
Class: |
C22F
1/10 (20130101); C22C 1/0433 (20130101) |
Current International
Class: |
C22F
1/10 (20060101); C22C 1/04 (20060101); C21d () |
Field of
Search: |
;148/11.5
;75/.5,171 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Bizot; Hyland
Assistant Examiner: Stallard; W. W.
Claims
What is claimed is:
1. The method of forming a dense mass of a nickel-based superalloy
which comprises the steps of confining and densifying a powder of
said superalloy into a billet, cold working said billet by
effecting deformation thereof at a temperature below the
recrystallization temperature of the alloy, recrystallizing the
cold-worked said billet by heating it to a temperature above its
recrystallization temperature and below the gamma-prime solvus
temperature for a period of time sufficient to effect nucleation of
new grains, and thereafter heat treating the recrystallized said
billet at a temperature above the gamma-prime solvus temperature
and below the incipient melting point of the gamma matrix for a
period of time sufficient to effect growth of the grain to the
desired size.
2. The method as defined in claim 1, wherein said powder is of a
particle size ranging from about 60 mesh to about 1 micron and
contains less than about 100 p.p.m. oxygen.
3. The method as defined in claim 1, wherein said billet formed by
said confining and densifying is substantially of a 100 percent
theoretical density.
4. The process as defined in claim 1, wherein said cold working is
performed so as to provide a degree of cold working to said billet
equivalent to that resulting from a reduction in its cross
sectional area of from several percent up to about 50 percent.
5. The method as defined in claim 1, wherein said cold working is
performed on said billet which is preheated to a temperature
ranging from about 1,000.degree. F. to about 1,700.degree. F. in a
manner to impart a working thereof equivalent to that resulting
from about a 30 percent to about a 50 percent reduction in its
cross-sectional area.
6. The method as defined in claim 1, wherein said recrystallizing
the cold-worked said billet is accomplished for a period of time
ranging from about 2 hours up to about 12 hours at a temperature of
about 1,700.degree. F. to about 2,100.degree. F.
7. The method as defined in claim 1, wherein the recrystallization
temperature of said superalloy ranges from about 1,700.degree. F.
to about 2,100.degree. F.
Description
BACKGROUND OF THE INVENTION
Modern superalloys of the general types to which the present
invention is applicable contain large amounts of second-phase
gamma-prime and complex carbides in a gamma matrix which contribute
significantly to their high-temperature properties. The presence of
these constituents, however, has made such alloys exceedingly
difficult to form subsequent to casting. Additional problems are
further introduced as a result of the tendency of such alloys to
undergo segregation, which significantly detracts from their
high-temperature strength characteristics. The elimination of such
segregation is virtually impossible due to the extend of it.
The foregoing problems have been overcome by employing powder
metallurgical techniques for making bodies of such superalloys. In
accordance with this technique, the superalloy is microcast or
atomized to a powder state and then consolidated in a substantially
oxygen-free environment to a blank of the desired size and
configuration, which is substantially free from segregation. A
continuing problem experienced in superalloy components made by
such powder metallurgical techniques has been the severe limitation
in effecting any appreciable grain growth in the resultant
densified component. It is believed that such grain growth
restriction is in part attributable to oxides and other relatively
insoluble impurities which are present on the surfaces of the
powder particles. Various precautions taken to reduce the presence
of such insoluble impurities have not been successful since the
problem in achieving such grain growth has been encountered even
with powdered alloys containing as little as 30 parts per million
(p.p.m.) oxygen.
In accordance with the process comprising the present invention,
the problem of effecting grain growth in densified powder
components has now been overcome providing for a metallurgical
structure which is of superior homogeneity and of superior physical
properties at elevated temperatures than cast and wrought forms of
the same superalloy compositions.
SUMMARY OF THE INVENTION
The benefits of the present invention are achieved by an improved
process for making large grain-sized nickel-base superalloys in
which the alloy is initially microcast or otherwise subdivided into
a powder form of controlled size and is thereafter confined and
densified into a body or blank approaching substantially 100
percent theoretical density. The dense body is subjected to cold
working at a temperature below the recrystallization temperature of
the alloy and thereafter is recrystallized at a temperature between
the recrystallization temperature and the solvus of the gamma-prime
phase for a period of time sufficient to nucleate new grains. The
recrystallized body is thereafter heat treated at a temperature
above the solvus of the gamma-prime phase and below the incipient
melting temperature of the alloy for a period of time sufficient to
effect grain growth and the attainment of the desired ultimate
grain size.
The nickel-based superalloys made in accordance with the process
comprising the present invention are characterized as being of
exceptionally large grain size and possessing superior tensile
strength and stress rupture life at elevated temperatures, that is,
temperatures in excess of about 1,400.degree. F. in comparison to
similar-type alloys heretofore known.
Further advantages and benefits of the present invention will
become apparent upon a reading of the description of the preferred
embodiments taken in conjunction with the accompanying
drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic flow sheet illustrating the sequence of steps
in accordance with the preferred practice of the process comprising
the present invention;
FIG. 2 is a photomicrograph of a Kalling's etched sample taken at a
magnification of 500 times of the grain structure of a superalloy
after densification from loose powder to a density corresponding
substantially to 100 percent theoretical density;
FIG. 3 is a photomicrograph of the same alloy shown in FIG. 2 at
the same magnification after being cold worked and subjected to
recrystallization; and
FIG. 4 is a photomicrograph of the grain structure of a Kalling's
etched tensile specimen taken at a magnification of 10 times
prepared from the alloy shown in FIGS. 2 and 3 after heat treatment
to effect grain growth.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring now in detail to the drawing, and as diagrammatically
shown in FIG. 1, the process comprising the present invention
consists of five basic steps which are performed in the same
sequence as illustrated in the flow sheet. As shown, a nickel-based
superalloy of the desired composition is initially comminuted or
microcast so as to form a powder of the desired configuration and
particle size which thereafter is confined and densified, forming a
body or blank having a density approaching a 100 percent
theoretical density. The resultant blank is thereafter cold worked,
that is, subjected to deformation at a temperature below the
recrystallization temperature of the alloy, followed by a
recrystallization step in which nucleation of new grain occurs.
Thereafter, the recrystallized blank is subjected to a heat
treatment at a controlled temperature, during which a growth in the
grain size is effected and by proper control, can be increased up
to almost a single crystal structure.
The provision of the nickel-based alloy in the form of a metallic
powder in which each of the powder particles is of substantially
the same nominal composition can be achieved by a variety of
techniques, of which microcasting, such as achieved by atomization
of a melt of the alloy, constitutes the most convenient and
preferred technique. The microcasting of the molten alloy can be
achieved, for example, by an atomization process employing an
atomization nozzle and technique as described in U.S. Pat. No.
3,253,783, which is assigned to the same assignee as the present
invention and is incorporated herein by reference.
Due to the deleterious effects of oxygen and oxides of the metals
comprising the alloy, the atomization of the superalloy and the
collection of the powder particles is achieved under conditions
whereby oxygen and oxygen-containing substances, including water,
are not permitted to contact the powder particles for any
appreciable time to minimize oxidation and/or oxygen entrapment.
The degree of precautions required to prevent oxidation of the
superalloy during the atomization process is dependent to a large
extent on the specific alloying constituents present in the alloy.
For example, the presence of aluminum and titanium require
particular precautions due to their susceptibility to oxidation
attack at the high temperatures encountered in conventional
microcasting techniques. Under such conditions, it is conventional
to effect microcasting in the presence of inert atmospheres such as
argon or helium, which are substantially moisture free.
Commercially available argon containing minimal amounts of
conventional impurities has been found particularly satisfactory
for providing a nonoxidizing, substantially dry inert atmosphere
for microcasting such superalloys. In accordance with conventional
practice, the interior of the equipment to be employed is initially
evacuated and thereafter back-flooded with the substantially dry,
nonoxidizing atmosphere prior to initiation of the atomization of
the melt. Regardless of the specific technique employed for forming
the powder, the oxygen content of the powder as finally densified
is preferably controlled to a level of less than about 100
p.p.m.
In accordance with conventional atomization or microcasting
procedures, the superalloy is transformed into a metallic powder in
which the particles preferably are of a generally spherical
configuration and wherein each powder particle is of substantially
the same or similar alloy chemistry. The metallic powder is
thereafter recovered and is subjected to a screening operation so
as to segregate the powder particles which are suitable for forming
the densified body or billet of superalloy. Conventionally,
particles of a size less than about 60 mesh United States Standard
Sieve Size (250 microns) can be satisfactorily employed down to a
particle size as small as about 1 micron. Particularly satisfactory
results are obtained when the powder particles range from about 100
mesh (150 microns) to about 10 microns, and wherein the particles
are further randomly distributed over the aforementioned range.
This provides for optimum packing density of the free-flowing
powder, facilitating subsequent densification thereof.
The resultant superalloy powder, having the desired composition and
particle size, is thereafter confined and densified at elevated
temperatures so as to form a body or billet approaching 100 percent
theoretical density. The densification of the metallic powder can
be achieved by any one of the variety of techniques well known in
the art, including extrusion, hot upsetting, vacuum die pressing,
hot isostatic compaction, explosive compaction, etc. The
densification process is preferably done at an elevated temperature
to facilitate a bond of the powder particles and to facilitate
compaction and deformation thereof into a billet approaching
substantially 100 percent theoretical density. For most nickel-base
superalloys, preheat temperatures ranging from 1,900.degree. F. up
to about 2,500.degree. F. can be satisfactorily employed. The
specific temperature used within the aforementioned range is
dictated by that temperature approaching the solidus or just below
the incipient melting point of the powder particles. The
aforementioned explosive compaction technique in which the powder
is subjected to violent densification is usually done without any
appreciable preheat. In the extrusion and hot upsetting compaction
techniques, it is conventional to confine the powder within a
suitable container which is evacuated and subsequently sealed.
Optimum packing of the interior of such containers with the loose
powder can be achieved by subjecting the containers to sonic or
supersonic frequencies wherein packing densities ranging from about
60 percent to about 70 percent of a theoretical 100 percent density
can be attained. It is also contemplated that the loose powder
particles can be confined in the cavity of a die, subjected to
vacuum and compacted so as to make a preform approaching 85- 90
percent theoretical density. Such a preform can also be attained by
compacting the powder in vacuum and sintering it at an elevated
temperature, forming a self-sustaining body or billet which
subsequently can be subjected to further compaction to attain
substantially 100 percent density.
Of the foregoing compaction techniques, hot extrusion of the powder
while contained within an elongated deformable container has been
found convenient and satisfactory for producing the improved
superalloy in elongated rod form. Such containers may comprise any
metal having sufficient ductility to enable their deformation by
extrusion at elevated temperatures without rupture of the
sidewalls, thereby maintaining the sealed integrity of the powder
particles therein. Typical of such ductile metals which are
compatible with the superalloy powder and which can be
satisfactorily employed for the practice of the present invention
are various of the so-called conventional stainless steels such as
AISI-type 304 or an AISI 1010 mild steel.
At the completion of the compaction or densification operation, the
resultant densified billet is allowed to cool and is thereafter
cold worked by subjecting it to a mechanical deformation, such as
by passing it between a pair of rolls or by subjecting it to a
further extrusion operation. The cold working of the densified
billet can be achieved in one or more successive passes to impart
he desired degree of cold work to the billet, which is dictated by
that amount necessary to provide for a substantially complete
recrystallization of the alloy at the specific temperature used
during the following recrystallization step. For most nickel-base
superalloys, it has been found that the magnitude of cold working
expressed in terms of percentage reduction of the cross-sectional
area of the densified body or billet during such cold working can
range from only several percent up to about 50 percent or more. The
maximum degree of cold working imparted to the densified billet is
dictated by practical considerations, including equipment
limitations and time. Usually, 50 percent reductions in
cross-sectional area in one pass have been found satisfactory and
cross-sectional area reductions or the equivalent cold working in a
range of about 30 percent to about 50 percent at moderate
temperatures ranging from about 1,000.degree. F. to about
1,700.degree. F. constitutes a preferred practice.
During the cold-working step, the densified blank or billet is
preferably heated to facilitate deformation thereof and as
previously indicated, can be heated to moderate temperatures which
approach but are below the recrystallization temperature of the
specific alloy. For most nickel-based superalloys of the type to
which the process comprising the present invention is applicable,
the recrystallization temperature generally is in the range of from
about 1,700.degree. F. to about 2,100.degree. F. In view of this,
it is preferred to heat the densified billet to a temperature of
from about 1,000.degree. F. to about 1,700.degree. F. during such
cold reduction.
For the purpose of the present invention, the terminology
"recrystallization temperature," as employed in the specification
and subjoined claims, is defined as that temperature above which a
nucleation and growth of new strain-free grains occurs accompanied
by consumption of the cold-worked matrix as a result of the growth
of such grains.
The resultant densified and cold-worked billet is thereafter
subjected to recrystallization at a temperature above the minimum
recrystallization temperature but below the gamma-prime solvus
temperature. The gamma-prime solvus temperature, as herein used, is
defined as the temperature at or above which the gamma-prime phase
dissolves in the gamma phase matrix. The gamma-prime phase in turn
is defined as a variety of intermetallic compounds which are
generally expressed by the formula Ni.sub.a (X,Y,Z).sub.b, in which
X, Y and Z represent, for example, aluminum, titanium, cobalt,
etc., and wherein "a" and "b" are integers. These intermetallic
compounds at temperatures below the gamma-prime solvus temperature
are dispersed throughout the gamma matrix and act as a
strengthening agent.
In accordance with the preceding definitions, recrystallization of
the cold-worked and densified billet is achieved at a temperature
generally ranging from about 1,700.degree. F. up to about
2,100.degree. F. for a period of time sufficient to effect a
nucleation of new strain-free grains in the cold-worked billet.
Recrystallization is continued for a period of time sufficient to
effect substantially full recrystallization of the billet, which,
for most nickel-based superalloys which are cold worked in an
amount ranging from about 10 percent to about 50 percent in terms
of reduction of cross-sectional area or the equivalent thereof at
recrystallization temperatures of from 1,700.degree. F. up to about
2,100.degree. F., requires about 2 to about 12 hours. It will be
noted that the recrystallization of a cold-worked billet can be
performed at any time after the cold working and similarly, the
heat-treating step can be performed at any time after the
recrystallization step. The absence of any criticality in time with
respect to the performance of the several process steps provides
further advantages in connection with the versatility and
processing flexibility afforded.
At the completion of the recrystallization step, the densified,
cold-worked and recrystallized billet is subjected to a heat
treatment in which grain growth occurs. The heat-treating operation
is carried out by heating the recrystallized billet to a
temperature above the gamma-prime solution or solvus temperature
and below the incipient melting point of the gamma matrix. The
incipient melting point of the gamma matrix for nickel-based
superalloys of the general type to which the process is applicable
conventionally ranges from about 2,200.degree. F. up to about
2,500.degree. F. The duration of heat treatment can be varied so as
to provide the desired degree of grain growth. Normally,
heat-treating periods of from about 30 to about 60 hours at
heat-treatment temperatures ranging from about 2,100.degree. F. to
about 2,400.degree. F. for nickel-based superalloys of the general
type evaluated have been found satisfactory to produce a resultant
microstructure in which the grain size is approximately one-eighth
inch in diameter. It is feasible, by continuing the heat treatment
of the billet over prolonged periods of time, to effect further
increases in grain size until ultimately a billet of a single grain
crystal is attained.
It will be apparent from the foregoing that it is now feasible,
employing powder metallurgical practices, to form billets and
components composed of nickel-based superalloys which are of a
relatively large grain structure and possess superior
high-temperature physical properties in comparison to the same or
similar superalloys in a cast and/or wrought form. The benefits of
the process comprising the present invention are achieved with any
one of a variety of well-known superalloys which are nickel based,
that is, in which the major alloying constituent is nickel. Typical
of the various nickel-based alloys which are presently known and
which can be processed in accordance with the present invention are
the compositions as set forth in table 1. It will be understood
that the enumerated superalloy compositions are provided for
illustrative purposes and are not intended as being restrictive of
other suitable nickel-based alloy compositions that can be
satisfactorily processed to achieve the benefits of the present
invention. ##SPC1##
In order to further illustrate the process comprising the present
invention, the following typical examples are provided. It will be
understood that the examples are furnished for illustrative
purposes and are not intended to be limiting of the scope of the
invention as herein described and defined in the subjoined
claims.
EXAMPLE I
A nickel-based superalloy corresponding to the nominal composition
of Udimet 700, as set forth in table 1, was microcast into
spherical powder particles and were screened providing a randomly
sized powder ranging from 10 microns up to 60 microns in size. The
free-flowing powder was confined in an elongated cylindrical
container composed of a mild steel and compacted therein by
subjecting the container to supersonic vibrations. The container
was subsequently evacuated and sealed by welding and thereafter was
extruded to a fully dense rod, while heated to a temperature of
1,950.degree. F. The microstructure of the resultant densified
billet is illustrated in FIG. 2. The resultant extruded rod
thereafter was preheated to 1,700.degree. F., which is
approximately 200.degree. F. below its recrystallization
temperature. At this preheat temperature, the billet was cold
worked by passing it through a pair of rolls, effecting
approximately a 50 percent reduction in cross-sectional area in one
pass. The resultant cold-worked billet was thereafter
recrystallized for a period of 21/2 hours at a temperature at
2,100.degree. F., which is a temperature above the
recrystallization temperature but below the gamma-prime solvus
temperature for this alloy. The resultant recrystallized structure
of the cold worked and recrystallized billet is illustrated in FIG.
3. It is apparent that the cold-worked and recrystallized grain
structure of the billet as shown in FIG. 3 evidences a fine
recrystallized grain structure.
Following the recrystallization step, the billet was subjected to
heat treatment at a temperature of 2,150.degree. F. for a period of
about 72 hours. The heat treatment temperature employed is above
the gamma-prime solvus temperature but below the incipient melting
temperature of this alloy. The large grain structure attained as a
result of the heat treatment step is clearly evident in the
photomicrograph comprising FIG. 4 of the drawings which comprises a
Kalling's etched micrograph of a tensile specimen prepared from the
billet and photographed at a magnification of 10 times.
In comparison, a control specimen prepared from the same powder and
subjected to the same compaction by extrusion followed by
recrystallization and heat treatment, but omitting the cold-working
step, did not evidence any appreciable grain growth characteristics
and possessed high temperature physical properties substantially
inferior to that of the specimen as evidenced by the microstructure
shown in FIG. 4. Comparative room and elevated temperature tests of
the tensile properties of the alloy prepared in accordance with the
process comprising the present invention and the same alloy in a
cast-and-wrought condition revealed the alloy made in accordance
with the process comprising the present invention to be at least as
good, and in most cases, superior to that of the prior art
structures. In addition, stress rupture properties, a property
particularly important in alloys subjected to high temperature
stress applications, were measured at a temperature of
1,850.degree. F. and at a stress of 20,000 p.s.i. for the alloy
comprising the present invention and identical alloy compositions
of the cast-and-wrought type heretofore known. The alloy processed
in accordance with he present invention had a stress rupture life
to failure of 196 hours, whereas conventional cast-and-wrought
U-700 alloy of the same composition had a life of only 10 hours
under these same conditions.
While it will be apparent that the description of the preferred
embodiments of the present invention is well calculated to provide
the advantages and benefits of the process comprising the present
invention, it will be appreciated that the process is susceptible
to variation, modification and change without departing from the
spirit of the invention.
* * * * *