U.S. patent number 3,847,680 [Application Number 05/302,807] was granted by the patent office on 1974-11-12 for dispersion strengthened metals and alloys and process for producing same.
This patent grant is currently assigned to Sherritt Gordon Mines Limited. Invention is credited to Robert W. Fraser, David A. W. Fustukian, Bud W. Kushnir, Leon F. Norris.
United States Patent |
3,847,680 |
Fustukian , et al. |
November 12, 1974 |
DISPERSION STRENGTHENED METALS AND ALLOYS AND PROCESS FOR PRODUCING
SAME
Abstract
Wrought dispersion strengthened compositions having a metallic
matrix comprised of nickel, cobalt or alloys of nickel and cobalt
with each other and/or with chromium are prepared by first hot
working a solid, fine grained workpiece formed from a powder
composition containing uniformly dispersed, sub-micron refractory
oxide particles and one or more of the desired metal constituents
in the desired proportions to take at least a 15 percent reduction
in cross-sectional area. During the hot working, the workpiece is
maintained at an elevated temperature below the melting temperature
of the workpiece matrix but above the minimum temperature at which
dynamic recrystallization occurs in the workpiece microstructure.
The hot-worked workpiece is then heat treated at a sufficiently
high temperature and for a time sufficient to cause
recrystallization of the metallic matrix and growth of large,
equi-axed grains. The product is characterized by a coarse grained
micro-structure which exhibits improved high temperature service
characteristics and an absence of anisotropy.
Inventors: |
Fustukian; David A. W.
(Edmonton, Alberta, CA), Kushnir; Bud W. (Edmonton,
Alberta, CA), Norris; Leon F. (Fort Saskatchewan,
Alberta, CA), Fraser; Robert W. (Fort Saskatchewan,
Alberta, CA) |
Assignee: |
Sherritt Gordon Mines Limited
(Ontario, CA)
|
Family
ID: |
26699335 |
Appl.
No.: |
05/302,807 |
Filed: |
November 1, 1972 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
|
25135 |
Apr 2, 1970 |
|
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Current U.S.
Class: |
419/28;
148/514 |
Current CPC
Class: |
C22C
32/0026 (20130101); B22F 3/24 (20130101) |
Current International
Class: |
C22C
32/00 (20060101); B22F 3/24 (20060101); B22f
003/24 (); C21d 001/26 () |
Field of
Search: |
;148/11.5F
;75/.5AC,.5BC |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Stallard; W. W.
Attorney, Agent or Firm: Piper; Frank I. Fors; Arne I.
Parent Case Text
This application is a continuation-in-part of Ser. No. 25,135,
filed Apr. 2, 1970 and now abandoned.
Claims
What we claim as new and desire to protect by Letters Patent of the
United States is:
1. A process for producing wrought dispersion strengthened nickel,
cobalt and alloys of these metals with each other and with chromium
which comprises providing a sintered workpiece formed from a powder
composition containing uniformly dispersed submicron refractory
oxide particles and one or more of said metals in the proportion
desired in the final wrought product, said workpiece having a grain
structure characterized by the presence of a substantial proportion
of small grains whose greatest diameter is less than 30 microns,
hot working said workpiece to effect a cross-sectional area
reduction at least sufficient to ensure consolidation of the
workpiece to substantially full density and to effect at least a 15
percent reduction in cross-sectional area of the densified
workpiece, maintaining the temperature of said workpiece at an
elevated temperature below its melting temperature but no lower
than the minimum temperature at which dynamic recrystallization
occurs in the microstructure of said workpiece at least while
effecting the final 15 percent reduction in cross-sectional area of
the fully densified workpiece, heat treating said hot worked
workpiece at a temperature below its melting temperature but
sufficiently high and for a period of time sufficient to cause
recrystallization and growth of large equi-axed grains in the
workpiece microstructure.
2. The process according to claim 1 wherein the workpiece is a
sintered, non-dense billet and consolidation to full density and
reduction in cross-sectional area of the fully dense workpiece are
both conducted at a temperature below the melting temperature of
the workpiece, but above the temperature at which dynamic
recrystallization occurs in the workpiece microstructure.
3. The process according to claim 1 wherein the starting workpiece
is a substantially fully dense billet having a grain structure
characterized by a substantial proportion of grains whose greatest
diameter is less than about 10 microns.
4. The process according to claim 1 wherein the hot working is
carried out at a temperature above the recrystallization
temperature of the workpiece microstructure.
5. The process according to claim 1 wherein consolidation and
reduction in cross-sectional area are effected by a single hot
rolling reduction carried out at a temperature of about
1,200.degree. C.
6. The process according to claim 1 wherein the sintered workpiece
is sheathed in mild steel prior to the hot working operation.
7. The process according to claim 1 wherein the heat treating step
is conducted at a temperature in the range of about 1,200.degree.
C. to about 1,425.degree. C.
8. The process according to claim 1 wherein the fully dense
workpiece is worked in said hot working operation to take a
cross-sectional area reduction of between 20 percent and 40
percent.
9. The process according to claim 1 wherein the workpiece is formed
of nickel powder particles in the size range of 0.5 to 10 microns
and containing from about 0.2 to about 4.0 percent by volume
submicron thoria particles.
10. The process according to claim 1 wherein the workpiece is
formed of finely divided cobalt particles containing 0.2 to 4.0
percent by volume submicron thoria particles.
11. The process according to claim 1 including an additional step
in which the heat treated workpiece is subjected to a secondary hot
working operation with the temperature of the workpiece being
maintained at least as high as the temperature employed for the
final stage of the initial hot working operation.
12. The process according to claim 11 wherein the additional hot
working step is effected by hot rolling to take a reduction up to
80 percent.
13. A process for fabricating wrought dispersion strengthened
nickel-chromium alloy compositions having improved isotropic high
temperature strength characteristics which comprises forming a
compacted billet from a powder composition comprising nickel, from
10 to 35 percent chromium and from about 0.2-4.0 percent by volume
uniformly distributed discrete, submicron refractory oxide
particles, sintering the said billet at a temperature between
1,100.degree. C. and 1,350.degree. C. to provide a coherent
workpiece, hot working said workpiece to effect a cross-sectional
area reduction sufficient to consolidate the billet to
substantially full density and to take at least a 15 percent
cross-sectional area reduction of the consolidated billet,
maintaining the temperature of said workpiece below its melting
point but above about 1,200.degree. C. during said hot working
operation to cause dynamic recrystallization to occur in the
workpiece microstructure during said hot working, and heat treating
the hot worked workpiece at a temperature between 1,200.degree. F.
and 1,370.degree. F. for a sufficient time to cause
recrystallization and development of large, equi-axed grains within
the size range of 50-100 microns average diameter.
14. The process according to claim 13 wherein the coherent
workpiece is sheathed in mild steel sheet prior to hot working.
15. The process according to claim 13 wherein hot working is
conducted to effect a cross-sectional area reduction of the
consolidated workpiece of between 20 percent and 40 percent.
16. The process according to claim 13 including the additional step
of hot working the heat treated workpiece at a temperature between
1,100.degree. C. and 1,315.degree. C. to take a cross-sectional
area reduction of up to 80 percent.
17. The process according to claim 13 wherein the compacted billet
is formed from a blended mixture of finely divided nickel powder,
chromium powder and refractory oxide particles and the billet is
sintered in an atmosphere of hydrogen having a dew point below
about -45.degree. C. for a sufficient period of time to reduce
oxygen in excess of that combined with the refractory oxide
constituent to below about 0.1 percent by weight.
18. The process according to claim 13 wherein said billet is formed
from a powder composition comprising finely divided pre-alloyed
nickel-chromium alloy-refractory oxide particles.
19. The process according to claim 13 wherein said powder
composition contains about 20 percent by weight chromium and from
about 0.2 to about 4.0 percent thoria.
Description
This invention is concerned with dispersion strengthened nickel and
cobalt and alloys of these metals with each other and with
chromium. More particularly, it is directed to a process for
producing such materials in a form which is characterized by
improved isotropic high temperature strength properties, and to the
products of such process.
It is known that the high temperature service characteristics of
metals and particularly of nickel and nickel base alloys can be
substantially improved by dispersion strengthening. Dispersion
strengthening involves the provision within a matrix metal or alloy
of a large number of discrete, uniformly disseminated, sub-micron
sized refractory particles. These dispersed particles, which
preferably are refractory oxide particles such as thoria, function
to stabilize the matrix microstructure at elevated temperature
thereby increasing its tensile strength and stress-to-rupture life
at high temperatures. Numerous methods are known for fabricating
such dispersion strengthened metals and alloys by powder metallurgy
techniques which include the compacting, sintering and hot and/or
cold working of powder compositions containing the desired metal
constituents and uniformly dispersed refractory oxide
particles.
It is also known that the microstructure of such dispersion
strengthened metals or alloys strongly influences their strength
characteristics and, further, that for optimum high temperature
strength properties, it is desirable for such materials to have a
coarse-grained microstructure rather than a fine-grained structure.
In addition, it is known that the character of the microstructure
is determined to a large extent by the manner in which the material
is fabricated. For example, U.S. Pat. Nos. 3,368,883 and 3,388,010
describe two known procedures for fabricating dispersion modified
nickel and/or cobalt alloys from powder compositions and the
characteristic microstructures which are developed in the products
by such procedures. Although these known processes may be utilized
to produce dispersion strengthened metals and alloys having
relatively coarse grained microstructures and improved high
temperature service characteristics, they are subject to a number
of problems which greatly diminish their utility for any practical
commercial operation. Firstly, it is found that these processes are
very sensitive to the chemical and physical character of the powder
composition used as the starting material. With starting materials
in which there is a very efficient dissemination of discrete
refractory oxide particles within the optimum 5-30 millimicron size
range, the prior methods do not consistently develop the desired
coarse grained structure in the products with the result that
relatively poor high temperature strength properties may be
obtained despite the fact that refractory oxide particle size and
spacing may be within the optimum ranges. This difficulty is
believed to be due, in part at least, to the fact that the high
temperature stability of the metal and alloy products which have
optimum refractory oxide particle size and distribution is such
that recrystallization and development of coarse grains cannot be
achieved under the conditions of the prior processes or, at best,
can only be achieved to a limited degree.
A further and more serious disadvantage of the prior art processes
and the products produced by them is that even with those materials
in which recrystallization and grain growth is achieved, the grains
are generally elongated or fibrous with their long axes extending
in substantially the same direction. Although dispersion
strengthened materials having this type of grain configuration and
orientation may exhibit excellent high temperature service
characteristics compared to conventional super alloys, the strength
properties are highly directional with the strength in a direction
transverse to the long axes of the grains being substantially less
and, in many cases, less than one-half the strength in the
direction of the long axes of the grains.
The problem of anisotropy in the strength properties can be
diminished to some extent by cross-working the material during
fabrication. That is, the material can be worked, for example, by
hot rolling, first in one direction then rotated 90.degree. and
worked again in a direction transverse to the direction of previous
working. However, this procedure is, at best, inefficient in the
fabrication of relatively small wrought shapes and it is generally
impractical for fabrication of large sheets of dispersion
strengthened metal or alloy.
A principal object of this invention, therefore, is to provide a
simple, efficient method for producing wrought dispersion
strengthened compositions having a matrix formed of nickel or
cobalt or alloys of these metals with each other and/or with
chromium which have excellent high temperature service
characteristics and which do not exhibit anisotropy. A further
object of the invention is to provide a method for fabricating such
materials from powder metallurgy compositions which consistently
develops in the product a novel microstructure which is
characterized by coarse, equi-axed grains.
These and other objects of the invention are achieved by a
surprisingly simple fabricating procedure in which a workpiece
formed from a powder composition containing the desired metal or
metals and uniformly dispersed refractory oxide particles and
having certain essential microstructural qualities is hot worked
and annealed under conditions which are controlled to induce growth
of large equi-axed grains in the workpiece matrix during the
primary working and annealing operations.
More specifically, the present invention involves a process for
producing wrought dispersion strengthened nickel, cobalt and alloys
of these metals with each other and with chromium which involves
first providing a workpiece formed from a powder composition
containing uniformly dispersed submicron refractory oxides and one
or more of said metals in the proportions desired in the final
wrought product. The workpiece may be a sintered, non-dense billet
formed from such powder composition or it may be a densified body
formed from such a billet. However, it is essential that the
starting workpiece have a very fine grained microstructure, that
is, a substantial proportion of grains must be below 30 microns and
preferably below 10 microns in size. According to the invention,
this workpiece is hot worked to effect a cross-sectional area
reduction at least sufficient to ensure consolidation of the
workpiece to substantially full density and to effect a reduction
in cross-sectional area of the densified workpiece of at least 15
percent. The hot working temperature is maintained below the
melting temperature of the workpiece matrix but not lower than the
dynamic recrystallization temperature thereof at least while
effecting the final 15 percent reduction in cross-sectional area of
the fully dense workpiece. The hot worked workpiece is then heat
treated at a temperature below its melting point but sufficiently
high and for a period of time sufficient to cause recrystallization
of the metallic matrix and growth of large, equi-axed grains.
According to another aspect of the invention, this coarse grained
primary product may be subjected to secondary working operations to
effect further reductions in cross-sectional area, e.g., to form a
thin gauge sheet material, under conditions which are controlled to
preserve the coarse grains developed in the primary fabrication
procedure of the invention. That is, secondary working conditions
which result in secondary recrystallization or new grain growth are
specifically avoided such that while the geometry of the original
large grains may be altered in working, their volumes remain
substantially unchanged. The secondary working may involve hot or
cold working or various combinations of both hot and cold working
with the precise conditions of working operations for any specific
material depending on the matrix composition. The products of both
the primary and secondary working procedures of the invention are
characterized by a coarse-grained microstructure and an absence or
substantial absence of anisotropy in the high temperature strength
properties even though the material is worked undirectionally in
all working operations.
In the drawings:
FIG. 1 is a drawing prepared from a photomicrograph of a section of
dispersion strengthened nickel-chromium alloy produced in
accordance with the invention, magnification 250X; and
FIG. 2 is a drawing prepared from a photomicrograph of a section of
dispersion strengthened nickel-chromium alloy produced in
accordance with test 3, Example 1, magnification 250X.
In practice, the method of the present invention is applied
directly to a sintered, non-dense billet formed from a metal powder
composition containing the desired metal and refractory oxide
constituents or, alternatively, to a densified body formed from
such billet by any methods which ensure a fine-grained
microstructure in the densified body matrix.
Suitable powder metallurgical compositions for billet forming and
the manner of preparation of such compositions are well known in
the art and in themselves form no part of the present invention.
However, to obtain optimum results from the practice of the present
invention, there are a number of general considerations which are
applicable to the billet forming powders regardless of their exact
source or manner of preparation.
The refractory oxide constituent of the powder composition must be
a thermally stable material having a melting point appreciably
higher than the metal or alloy which is to comprise the matrix of
the final wrought product; it must have low solubility in the
matrix and it must be substantially nonreactive with the matrix at
normal and elevated temperatures. Refractory oxides which satisfy
the foregoing criteria are well known in the art. Two refractory
oxides which are preferred for purposes of the present invention
are yttria and thoria. Other suitable oxides are calcia, magnesia,
zirconia, silica, berylia, hafnia, alumina, titania, uranium
dioxide and oxides of rare earth metals such as samarium, cerium
and lanthanum. The refractory oxide constituent must be in a very
finely divided, discrete form. The particles should be less than
100 millimicrons in size and preferably in the size range of 5 to
30 millimicrons. Thoria is a preferred refractory oxide for these
compositions because of its high melting point, high temperature
stability and ready availability in the preferred size range. The
amount of refractory oxide can vary from a trace to 30 percent by
volume or more depending on the type of oxide employed and the
properties desired in the end product. Normally, the refractory
oxide constituent will comprise from about 0.2 to about 4.0 percent
by volume of the densified metal or alloy product.
The refractory oxide constituent may be simply mixed with the metal
powder constituents of the powder composition such as by wet or dry
mechanical blending. For example, thoria, in the form of a
colloidal aquasol can be mixed directly with very fine nickel,
cobalt and/or chromium powders and the combined constituents
mechanically blended such as by ball milling to produce a uniform
mixture. Also, thoria may be formed in situ on the metal powder
particles by mixing them with thorium nitrate then calcining the
thorium nitrate to thoria. However, it is generally preferred to
utilize composite metal-refractory oxide powders in which submicron
refractory oxide particles are integrally associated with metal
powder particles. Use of such composite metal-refractory oxide
powders prevents segregation of the refractory oxide constituents
during handling of the powder and facilitates the obtaining of
uniform inter-particle spacing of the refractory oxide phase in the
matrix in the final wrought product, which is an essential
characteristic for maximum improvement in high temperature strength
properties.
Methods are known by which a particularly suitable type of
nickel-refractory oxide powder can be produced. For example,
Canadian Pat. No. 768,268 describes an economic and efficient
method for producing nickel-refractory oxide powders which are
comprised of very fine, irregular-shaped nickel particles, about
0.5 to 10 microns in size having sub-micron refractory oxide
particles firmly attached in the surfaces thereof. These powders
are particularly suitable as a starting material because of their
small particle size which ensures that sintered billets prepared
from the powders have the fine grained microstructure necessary in
the starting material for the process of the invention.
For chromium containing alloy compositions, the chromium content of
the billet-forming powder composition can be provided as a finely
divided powder physically mixed with nickel and/or cobalt powder or
it can be provided in the form of a pre-alloyed powder. When
chromium powder, as such, is utilized in the powder composition, it
should be protected from exposure to air so as to minimize nitrogen
and oxygen contamination. A combined content of oxygen and nitrogen
of less than 1.0 percent by weight is desirable. A particle size
smaller than 200 mesh standard Tyler screen and preferably less
than 325 mesh should be used. Chromium powders meeting the
specifications are available from commercial sources. It is
preferred, however, to provide the chromium content of the powder
composition in a pre-alloyed nickel-chromium-refractory oxide
powder which is substantially free from oxides other than those
present in the refractory oxide constituent. Copending U.S.
application Ser. No. 813,214, now U.S. Pat. No. 3,716,357 describes
a method for producing nickel-chromium alloy-refractory oxide
powders having physical characteristics similar to the
nickel-refractory oxide powders referred to hereinabove.
The relative amounts of nickel, cobalt and/or chromium provided in
the powder composition will, of course, depend on the composition
desired for the matrix of the final product. In the case of powder
compositions for preparing nickel-chromium alloys, the chromium
content of the powder composition may vary from about 10 to about
35 percent by weight and preferably is about 20 percent by weight.
Other typical matrix compositions which may be advantageously
utilized include 75 cobalt-25 nickel and 55 cobalt-25 nickel-20
chromium.
The powder composition is formed into a billet suitable for
purposes of the present invention by any of the static or isostatic
powder compacting methods commonly employed in the powder
metallurgy art. Preferably, an elongated billet of about 50-90
percent theoretical density is formed. In order to give it
sufficient handling strength, the billet preferably is sintered at
an elevated temperature. The precise conditions of this sintering
step will vary depending on the nature of the powder composition
from which the billet was formed. For example, in the case where
the powder composition contains non-alloyed chromium powder, it
normally will also contain chromium oxide. For optimum results,
these oxides must be removed in the sintering step. This is done by
sintering at a temperature in the range of 1,100.degree.C. to
1,350.degree.C. in a flowing atmosphere of pure dry hydrogen having
dew point below about -45.degree.C., preferably below about
-75.degree.C. Sintering is continued for a sufficient period of
time to reduce oxygen in excess of that combined with the
refractory oxide constituent to below about 0.1 percent by weight
and preferably below about 0.01 percent by weight.
The process of the invention may be, and preferably is, applied
directly to the sintered, non-dense billet. Alternatively, the
billet may first be consolidated to full density and worked,
provided the working conditions employed produce a fine grained
microstructure in the densified and worked material. By "fine
grained microstructure" is meant a structure which consists of a
substantial proportion of grains whose greatest diameter is less
than 30 microns and preferably less than 10 microns.
According to the invention, where the starting material is a
sintered non-dense billet, it is hot worked to consolidate it to
100 percent density and to effect a cross-sectional area reduction
of the fully densified body of at least 15 percent and preferably
between about 20 percent and 40 percent. For example, a 60 percent
dense sintered billet must be worked so as to effect at least a 40
percent overall reduction in cross-sectional area to fully densify
the billet and at least a 15 percent reduction of the fully
densified body. Working may be effected by any of the conventional
processes such as extrusion, swaging, drawing and forging but
preferably it is by rolling and, in the present description, unless
the contrary is indicated, all references to working will mean
working by a rolling operation. The required degree of working may
be effected by taking a single large reduction in cross-sectional
area or a plurality of smaller reductions.
It is essenial, according to the invention, that at least the final
15 percent reduction in cross-sectional area of the fully densified
body be carried out at a temperature below its melting temperature
but no lower than the minimum temperature at which dynamic
recrystallization occurs in the densified body microstructure while
said final reduction is being effected. Such "dynamic
recrystallization" occurs in the workpiece microstructure during
the hot working of the workpiece in the following manner. As the
grains reach a critical degree of deformation, new grains form and
then grow as in the regular recrystallization mechanism. However,
because of the continuing deformation of the workpiece, these new
grains reach a point of critical strain again and the whole process
of grain nucleation and grain growth takes place again and then
again and again as long as the hot working is continued at a
sufficiently high temperature. This dynamic recrystallization
process terminates upon termination of the hot working operation
with the grains at various different stages of recrystallization.
That is, the microstructure at this point is not completely
recrystallized but is what is termed a "mixed grain structure."
The minimum temperature at which dynamic recrystallization will
occur in the dispersion strengthened metals and alloys contemplated
by the present invention will depend primarily on the regular
recrystallization temperature of the material and to a lesser
extent on the rate and degree of deformation during the working
operation. In general, the minimum dynamic recrystallization
temperature of the materials of the invention may be as much as
150.degree. C below the regular recrystallization temperature of
the materials although in most cases it will not be more than
40.degree. C below the regular recrystallization temperature.
Preferably, the hot working operation of the invention is conducted
at temperatures above the minimum dynamic recrystallization
temperature and, more preferably, it is conducted at or above the
regular recrystallization temperature. The specific regular
recrystallization temperature of any given dispersion modified
metal or alloy material contemplated by the present invention and
thus the preferred hot working temperature for that particular
material will depend on the chemistry of the matrix and the
refractory oxide content, particle size and particle spacing or
distribution. Accordingly, there is no specific preferred hot
working temperature which is applicable to all compositions.
However, in general, for materials containing about 0.2 - 4.0
volume percent of uniformly disseminated 5 - 30 millimicron
refractory oxide particles and having a matrix formed of nickel or
an alloy of nickel and cobalt with each other or with chromium, the
recrystallization temperature will be within the range of
1,200.degree. - 1,370.degree. C. For materials having a matrix
formed of cobalt, the recrystallization temperature will be between
about 1,250.degree. and 1,425.degree. C. There is no critical upper
limit on the working temperature except that it must be below the
melting temperature of the material since melting results in an
agglomeration of the dispersed oxide phase with an accompanying
loss of high temperature strength properties.
As noted hereinabove, it is essential only that at least the final
15 percent reduction in cross-sectional area be effected at a
temperature at or above the minimum temperature at which
recrystallization occurs in the workpiece microstructure while such
final reduction is being effected. Thus, in the processing of the
billet prior to the hot working step of the invention, it may be
consolidated to full density and worked at temperatures below the
minimum dynamic recrystallization temperature of the material
provided that the product of such preliminary working has a
fine-grained microstructure.
Since usually there is no particular advantage in consolidating and
initially working the non-dense sintered billet at temperatures
below the minimum temperature required for the hot working
operation of the invention, the preferred procedure in the practice
of the invention is to both densify and work the non-dense billet
the required amount at a temperature well above the specified
minimum. This normally can be accomplished in a single
reduction.
Inasmuch as the temperature of the workpiece during the hot working
operation is critical, it is desirable, in order to obtain uniform
properties throughout the workpiece cross-section, that the
workpiece temperature be maintained at or above the required
minimum across its entire section during the hot working operation.
This can be done by heating the faces of the work rolls or other
working tools which contact the workpiece surface. However, a more
practical and economic procedure, it has been found, is to cover
the surfaces of the workpiece which contact the work tool surfaces
with a mild steel sheath at least about 0.04 inch in thickness. The
sheath, which is heated with the billet prior to hot working, acts
as a barrier or buffer against the temperature differential of the
workpiece and the work tools ensuring uniform temperature over the
workpiece cross-section during the hot working operation. The mild
steel sheath can be readily removed from the billet after hot
working by conventional acid pickling procedures.
According to the invention, the hot worked material, after removal
of the mild steel sheath if necessary, is heat treated at an
elevated temperature above the recrystallization temperature of the
material but below the melting temperature for a time sufficient to
cause recrystallization of the matrix metal or alloy and growth of
large equi-axed grains. This heat treating or annealing step may be
conducted in a protective atmosphere such as a hydrogen atmosphere
if the material has a tendency to oxidize at the heat treatment
temperature, but for highly oxidation resistant material, such as
nickel-chromium alloys, this is not essential. The minimum
annealing temperature in any specific case depends on the matrix
composition, the amount of energy stored in the workpiece during
the hot working operation and the nature of the oxide dispersion,
i.e., the dispersoid content and size and spatial distributions. In
general, the optimum annealing temperature for all the dispersion
modified compositions contemplated by the present invention is
between about 1,200.degree. C. and 1,425.degree. C. and preferably
is about 1,350.degree. C. At this temperature, complete
recrystallization of the matrix metal or alloy and growth of large
equi-axed grains is obtained in a very short time, i.e., less than
1 hour in most cases.
The hot worked-annealed products of the invention have a
distinctive, novel microstructure which differs fundamentally from
the microstructure of the prior art materials of the same general
composition. For example, the dispersion strengthened nickel and
cobalt base alloys described in U.S. Pat. Nos. 3,388,010 an
3,494,807, respectively, are characterized by elongated grains in
the case of the first patent and grains laminar in shape in the
plane of the sheet in the case of the second patent. These
characteristic grain structures result from recrystallizing
material which has a very high level of residual stress which, in
turn, results from the fact that the material is hot worked before
being recrystallized at temperatures below that at which any
recrystallization occurs. The materials of the present invention,
on the other hand, are not worked prior to recrystallization at a
temperature above that at which recrystallization occurs in the
material during working. As a result, the material passed to the
high temperature recrystallizing step is essentially stress free.
When this material is recrystallized the new grains grow randomly
in all directions rather than along particularly aligned axes as is
the case with the prior art material. More specifically, the
microstructure of the hot-worked-annealed products of the present
invention is characterized by large grains which are defined by
irregular grain boundaries and which are generally equi-axed. The
term "generally equi-axed" as used herein means that the geometry
of the grains is such that the ratio of the diameter of a sphere
inscribed within any grain to the diameter of a sphere
circumscribed about the same grain is not less than about 0.2 and
preferably not less than 0.4 as measured from the ratio of the
diameters of the inscribed and circumscribed circles in a random
planar section of the material. Although worked unidirectionally,
these materials exhibit excellent high temperature strength
properties not only in the direction of working but in the
direction transverse thereto. Actual grain sizes in the products of
the invention will vary depending on the matrix composition and the
precise conditions employed in the hot working and heat treating
steps but, in general, the grains are within the broad size range
of 50- 1,000 microns average diameter and in the preferred
compositions they are in the range of about 125-250 microns average
diameter (as determined by the method described in Example 1). The
preferred materials contain about 0.2 to about 4.0 percent of
uniformly dispersed, discrete refractory oxide particles,
preferably thoria, in the 5-30 millimicron size range.
These materials from the primary hot working annealing operations
of the invention may be used as such in applications where high
temperature serviceability is required but, in most cases, further
or secondary working will be necessary to produce products of the
desired dimensions and shape. According to the invention, it is
important that any such secondary working be carried out in a
manner which does not break down or cause refinement of the coarse
grained structure which has been developed in the primary products
by the hot working-anneal procedure just described. There are known
cold working procedures which can be used for secondary working
such as those described in U.S. Pat. Nos. 3,366,515 and 3,159,908.
The method of this latter patent may, in appropriate cases, be
employed in the secondary working of materials in which the matrix
consists of nickel or cobalt but it cannot be applied to nickel
and/or cobalt-chromium alloys without causing break-down of the
coarse grained microstructure with accompanying loss of desired
high temperature strength properties. The process of U.S. Pat. No.
3,366,515 can be employed for secondary working of all compositions
contemplated by the present invention. However, inasmuch as it
requires use of relatively small cross-sectional area reductions
followed by intermediate anneals, particularly when applied to
nickel-chromium alloys, the method has economic drawbacks where a
relatively large total reduction in cross-sectional area is
required in the secondary working operation in order to produce a
product having the desired gauge. According to a modification of
the present invention, a secondary working method is provided which
is applicable to all the metal and alloy compositions contemplated
by the present invention and also which can be used to particular
advantage when relatively large reductions in cross-sectional area
are desired in the secondary working operation. According to the
invention, the secondary working is carried out at a temperature at
least as high as the primary working temperature discussed
hereinabove and generally in the range of 1,100.degree. -
1,315.degree. C. to take a cross-sectional area reduction of up to
about 80 percent and preferably about 65 percent. One or more such
high temperature reductions may be taken with the material
preferably being subjected to heat treatment after the final
reduction to relieve residual stresses. Normally, about 1 hour at a
temperature between 1,315.degree. C. and 1,370.degree. C. is
sufficient for this purpose. It is important to note that virtually
no recrystallization or new grain growth occur in the final heat
treatment step provided the secondary working has been conducted at
the elevated temperature as indicated above. Preferably the same
care should be taken in the secondary working as in the primary
working to ensure that the workpiece remains above the minimum
temperature across its section during the working operation. Thus,
the workpiece preferably should be sheathed in mild steel for the
secondary operation in the same manner as previously described for
the primary working.
Like the products of the primary hot working-annealing operation,
the products of the hot and/or cold secondary working operations
are characterized by a coarse grained microstructure and a
substantial absence of anisotropy in strength properties even where
all working has been in one direction. It is believed that this is
because the size, configuration and orientation of the grains of
the primary material of the invention are such that even after
unidirectional secondary working, the geometrical grain shape
requirements for strength in the direction transverse to the
working direction are still satisfied. For example, in the case
where the secondary working consists in hot and/or cold rolling to
produce thin gauge sheet, the rolling operation may tend to flatten
the large equi-axed grains of the primary material but the geometry
and size of these grains, which have a pancake-like shape, is
sufficient to ensure that the transverse width of the grains is
sufficient to satisfy the geometric requirements for high strength
in the direction transverse to the direction of the working as well
as in the direction of the working.
The material from the secondary hot working operation of the
invention may advantageously be given a final finishing reduction
or reductions, if necessary, by the method of U.S. Pat. No.
3,366,515.
The invention is further described and illustrated with reference
to the following Examples.
EXAMPLE 1
Nickel-thoria powder was prepared in accordance with the procedure
described in Example 1 of Canadian Pat. No. 786,268. The powder
product, after being deoxidized by heating in a dry hydrogen
atmosphere for 15 minutes at 815.degree. C. had the following
characteristics: Fisher No. - 1.4; apparent density -- 1.5
gm/cm.sup.3 ; thoria content -- 2.7 percent by weight; size
distribution -- 90 percent minus 10 microns. 2,000 grams of this
nickel-thoria powder were blended with 500 grams of chromium
powder. The chromium powder, which had a Fisher No. of 8, was
prepared by air classifying commercial grade minus 325 mesh
chromium powder to remove the coarse fraction. The blended powders
were statically compacted into a plurality of 60 gram, 1.25 by 2.4
inch billets in a double-acting compacting die using a 33 tons per
square inch compacting pressure. The billets were sintered for 30
hours at 1,100.degree. C. in a pure, dry hydrogen atmosphere having
a dew point of -90.degree. C. Diffusion alloying of the nickel and
chromium took place during this sintering operation.
The sintered billets, which had a density of about 60 percent
theoretical density, were sandwiched in mild steel sheaths 0.045
inch thick, heated in a hydrogen atmosphere and given a single 65
percent hot rolling reduction at temperatures between 925.degree.
C. and 1,200.degree. C. to consolidate the billets to full density
and effect a 40 percent cross-sectional area reduction of the dense
billets. Each billet was held for 15 minutes at its respective
rolling temperature before rolling. After hot rolling, the steel
sheath was removed by pickling in nitric acid and the strips were
annealed for 16 hours at 1,350.degree. C. The strips were tensile
tested at 1,150.degree. C. and examined metallographically. The
results which are set out in the following Table I clearly show the
improvement in high temperature tensile strength that is obtained
by the process of the invention. (Test 1). The characteristic
microstructures of the products of Test 1 and Test 3 are shown in
FIGS. 1 and 2, respectively. The microstructure of the high
strength product of the invention shown in FIG. 1 is characterized
by large, generally equi-axed grains defined by irregular grain
boundaries. The grains are randomly oriented and of generally
uniform average size. The material shown in FIG. 2, on the other
hand, has a microstructure characterized by very small equi-axed
grains and relatively poor high temperature strength. The
microstructure of the material of Test 2 had substantially the same
appearance as that of Test 3 except that the grains were slightly
coarser.
TABLE I ______________________________________ Test Hot Rolling
Conditions Grain UTS at No. Overall Temperature size **
1150.degree.C. Reduction % .degree.C. microns psi *
______________________________________ 1 65 1200 200 12,000 2 65
1050 35 8,400 3 65 925 15 5,800
______________________________________
*The indicated results are strengths in the direction of rolling;
transverse tensile strength of the product of Test 1 was 11,600
p.s.i.
**Several methods can be used to measure the grain size of wrought
metal products. The grain sizes in Examples 1 - 8 were measured
using conventional metallographic techniques, counting the number
of train boundaries, N, per unit of length, intersecting a straight
line and obtaining grain size from the equation d = 3/2N. This
method is based on the following considerations:
The number of intercepting grain boundaries per unit length can be
directly related to the surface area to volume ratio of the
individual grains which, in turn, can be related to the average
grain diameter if spherical or cubic grains are assumed. It has
been shown that N = 1/2 S/V where S and V are surface area and
volume of the grain respectively. If it is assumed that all of the
grains are cubic of a side equal to d, then with close packing:
N = 1/2 6d.sup.2 /d.sup.3 (2)
Alternatively, if it is assumed that all of the grains are
spherical and of a diameter d, then with close packing:
N = 1/2 4 .pi. (3/2).sup.2 /4/3 .pi. (d/2).sup.3 (4)
Thus, the relation of N to d is similar for cubic and spherical
grains and clearly suggests that for equi-axed grains N is
inversely proportional to average grain diameter. However, in order
to relate N to an average grain diameter, the surface area S in the
equation N = 1/2 S/V must be considered as the exterior surface
area of two grain surfaces, the interior and exterior grain
surfaces, and the exterior surface area is one-half that used in
equations (1) and (3). Equations (2) and (4) would then become: N =
3/2d or d = 3/2N.
EXAMPLE 2
Material from Test 1 and Test 3 of Example 1 was resheathed in mild
steel and given a second hot rolling reduction of 50 percent at
1,200.degree. C. The sheaths were pickled from the strips and the
strips were then annealed at 1,350.degree. C. for 16 hours. The
strips were examined metallographically and tensile tested at
1,150.degree. C. The results are shown in Table II.
TABLE II ______________________________________ Overall
Temperature, Reduction,% .degree.C. Grain UTS at Test 1 2 1 2
Size** 1150.degree.C. No. Hot Hot Hot Hot microns psi Roll Roll
Roll Roll ______________________________________ 1 65 50 1200 1200
150 11,400 2 65 50 925 1200 100 10,200
______________________________________
The results in Table Ii show that a strong, coarse grained
structure can be developed in fully dense, fine grained material
which has been consolidated and worked at temperatures below the
minimum hot working temperature of the invention. For example, the
grain size of the material which had been consolidated and hot
rolled at 925.degree. C. (Test 2) was increased from 15 to 100
microns and 1,150.degree. C. tensile strength increased from 5,800
to 10,200 p.s.i. by the hot working-annealing procedure of the
invention. On the other hand, the grain size and strength of the
coarse grained material (Test 1) was essentially unaffected by the
second hot working-annealing treatment.
EXAMPLE 3
A series of sintered, 60 percent dense billets prepared as
described in Example 1 was sheathed, preheated to 1,200.degree. C.
and then hot rolled at reductions that ranged between 40 percent to
80 percent. The sheating was removed from each sample and the
strips were annealed at 1,350.degree. C. for 16 hours. The strips
were examined micrographically and tensile tested at 1,150.degree.
C. The results, which are set out in Table III, show that
preferably about 30-40 percent, cross-sectional area reduction is
required for development of large grains and optimum high
temperature tensile strength in the dispersion strengthened
nickel-chromium alloy product.
TABLE III ______________________________________ Test Overall Dense
Billet Grain Size** UTS at No. Reduction Reduction % microns
1150.degree.C. % psi ______________________________________ 1 40 0
35 7,000 2 50 12 50 7,400 3 60 30 200 11,000 4 65 40 200 12,000 5
75 58 200 11,000 6 80 67 200 11,800
______________________________________
EXAMPLE 4
A series of 60 percent dense sintered billets made in accordance
with the procedure of Example 1 was sheathed and hot rolled at
1,200.degree. C. to take a 70 percent overall reduction. The
sheaths were removed by pickling and the strips annealed for
various time periods at different temperatures as shown in Table
IV.
TABLE IV ______________________________________ Annealing
Conditions Ultimate Tensile Strength at 1100.degree.C.
______________________________________ As hot rolled 2,800 1/2 hour
at 1100.degree.C. 2,600 16 hours at 1100.degree.C. 3,100 16 hours
at 1200.degree.C. 5,500 1 hour at 1350.degree.C. 11,700 1 hour at
1375.degree.C. 13,900 ______________________________________
These results illustrate the necessity of a sufficiently high
anneal temperature to cause the recrystallization and grain growth
necessary for good high temperature strength. It can also be noted
that at the higher temperatures, recrystallization and grain growth
are achieved very rapidly.
EXAMPLE 5
A series of 60 percent dense sintered billets produced in
accordance with the procedure of Example 1 was sheathed in mild
steel, preheated 15 minutes at 1,200.degree. C. in purified
hydrogen and hot rolled at 1,200.degree. C. to take a 70 percent
overall reduction. The billets were then given a variety of
secondary rolling reductions at different rolling temperatures. The
resulting strips were pickled to remove the sheaths and then
annealed at 1,350.degree. C. for 16 hours. The strips were tensile
tested at 1,150.degree. C. and the results are shown in Table
V.
TABLE V ______________________________________ Secondary Test
Working Conditions Grain UTS at 1150.degree.C. No. Reduction
Temperature size** psi % .degree.C. microns Longi- Trans- tudinal
verse ______________________________________ 1 20 1200 300 12,000
11,700 2 40 1200 150 12,600 12,000 3 56 1200 50 11,300 11,500 4 50
1050 25 9,100 -- 5 50 1000 20 8,400 -- 6 20 900 40 10,200 -- 7 30
900 20 8,200 -- 8 42 900 15 6,800 -- 9 20 20 30 9,100 -- 10 30 20
15 8,000 -- 11 40 20 10 6,000 -- 12 56 20 5 5,500 -- 13 63 20 3.5
4,700 -- ______________________________________
The results in Table V show that at temperatures below
1,200.degree. C. and 1,150.degree. C. UTS decreased with decreased
secondary working temperature. The results also indicate that at
ambient and other low working temperatures, the secondary working
reductions adversely affect the 1,150.degree. C. UTS values unless
the degree of reduction is small (less than 20 percent).
EXAMPLE 6
This example illustrates the use of hot extrusion as the working
method. Nickel thoria powder prepared in accordance with the
procedure of Example 1 in Canadian Pat. No. 786,268 was de-oxidized
by heating in a dry hydrogen atmosphere at 815.degree. C. for 15
minutes. The powder had a Fisher No. of 1.4, apparent density of
1.5, thoria content 2.5 percent by volume and was 90 percent minus
10 microns in size. 4 parts of this nickel thoria powder were
blended with 1 part of minus 325 mesh commercial grade chromium
powder. The blended powders were isostatically compacted into a 3
inch diameter billet using a 30,000 p.s.i. compacting pressure. The
billet was sintered for 40 hours at 1,200.degree. C. in pure dry
hydrogen, canned in mild steel and then hot evacuated to less than
1 micron Hg at 1,100.degree. C. before sealing. The billet was
extruded at 1,200.degree. C. using an extrusion ratio of 15:1. The
resulting bar was tensile tested at 1,150.degree. C. in the as
extruded condition and following an annealing treatment of 16 hours
at 1,350.degree. C. In the as extruded condition the ultimate
tensile strength at 1,150.degree. C. was 1,100 p.s.i. After
annealing, the tensile strength was 10,200 p.s.i. The bar was also
examined metallographically for grain size. The as extruded bar had
no distinct grain structure; after annealing, the bar had a large,
equi-axed grain structure with average individual grain diameters
of about 125 microns.
EXAMPLE 7
A de-oxidized nickel-thoria powder which had a Fisher No. of 1.0,
an apparent density of 0.8 and thoria content of 2.5 percent by
weight was compacted into 100 gram billets measuring 1 .times. 3
inches. The billets were sintered at 1,200.degree. C. or 2 hours in
purified hydrogen atmosphere. Each billet was given a 50 percent
overall thickness reduction at 1,100.degree. C. The hot rolled
billets were then given a second consecutive 50 percent overall hot
rolling reduction using the same conditions. The hot rolled billets
were annealed at 1,350.degree. C. for one-haLf hour in purified
hydrogen atmosphere, then given a series of cold roll anneal
cycles. The amount of reduction per cycle was either 10, 20, 30 or
70 and the intermediate anneals were for one-half hour at
1,200.degree. C. All rolling was unidirectional. The 1,100.degree.
C. UTS of the resulting samples is given in Table VII.
TABLE VII ______________________________________ Fabrication
Procedure Hot Rolling Cold Overall 1100.degree.C. UTS Schedule
Rolling Cold psi Schedule Rolling Longi- Trans- Reduction tudinal
verse ______________________________________ 2.times.50 as Hot Roll
None 0 5,400 2.times.50 plus Anneal None 0 14,300 14,400 2.times.50
plus Anneal 1.times.70% 70% 20,400 20,200 2.times.50 plus Anneal
4.times.30% 76% 24,100 23,500 2.times.50 plus Anneal 7.times.20%
79% 23,800 22,200 2.times.50 plus Anneal 13.times.10% 75% 26,200
26,200 ______________________________________
The results in Table VII show the strengthening affect of the high
temperature anneal after hot working and also show that the high
temperature UTS of the primary material can be substantially
increased by cold working and, further, that strength properties
were isotropic despite the fact that all working was in one
direction.
EXAMPLE 8
A finely divided cobalt-thoria powder was prepared by ball milling
1 micron cobalt powder with 3.5 percent by weight thoria added in
the form of a thoria sol containing thoria particles in the size
range of 5 to 50 millimicrons. The ball mill material was
de-oxidized by heating in a dry hydrogen atmosphere for 15 minutes
at 815.degree. C. and was formed into a 60 gram compact by
compacting in a double acting die at 33 tons per square inch. The
compact was sintered for 2 hours at 1,200.degree. C. in a dry
hydrogen atmosphere. The sintered billet was fabricated by a
procedure consisting of two consecutive 50 percent hot rolling
reductions at 1,100.degree. C. The resulting hot worked material
had an ultimate tensile strength at 1,100.degree. C. of 3,900
p.s.i. This material was then annealed at 1,450.degree. C. for 1
hour. The annealed material had an ultimate tensile strength at
1,100.degree. C. of 12,000 p.s.i. The grain size of the hot rolled
material, as determined by the procedure outlined in Example 1, was
20 microns. The grain size of the annealed material was 1,000
microns.
* * * * *