U.S. patent number 3,785,801 [Application Number 05/169,791] was granted by the patent office on 1974-01-15 for consolidated composite materials by powder metallurgy.
This patent grant is currently assigned to The International Nickel Company, Inc.. Invention is credited to John Stanwood Benjamin.
United States Patent |
3,785,801 |
Benjamin |
January 15, 1974 |
CONSOLIDATED COMPOSITE MATERIALS BY POWDER METALLURGY
Abstract
Directed to the powder metallurgy production of consolidated
metal products wherein the starting material comprises dense
wrought particles containing at least 15 percent by volume of a
compressively deformable metal with the remainder being one or more
other metals or non-metals with the internal structure of the
particles being non-porous and with the constituents thereof being
intimately united and interdispersed, i.e., mechanically alloyed,
said particles, upon consolidation, yielding metal or cermet
products having unusual properties and capable of compositioinal
characteristics not available as a result of other processing
techniques.
Inventors: |
Benjamin; John Stanwood
(Suffern, NY) |
Assignee: |
The International Nickel Company,
Inc. (New York, NY)
|
Family
ID: |
26865376 |
Appl.
No.: |
05/169,791 |
Filed: |
August 6, 1971 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
|
849133 |
Aug 11, 1969 |
|
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|
|
709700 |
Mar 1, 1968 |
3591362 |
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Current U.S.
Class: |
75/255; 419/1;
419/9; 419/23; 419/32 |
Current CPC
Class: |
C22C
1/1084 (20130101); C22C 32/0026 (20130101); C22C
1/0433 (20130101); B22F 9/04 (20130101); C22C
32/0021 (20130101); C22C 32/0015 (20130101); B22F
2009/043 (20130101) |
Current International
Class: |
C22C
32/00 (20060101); B22F 9/04 (20060101); B22F
9/02 (20060101); C22C 1/04 (20060101); C22C
1/10 (20060101); B22f 009/00 () |
Field of
Search: |
;75/.5BC |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Stallard; W. W.
Attorney, Agent or Firm: Pinel; Maurice L.
Parent Case Text
The present application is a continuation of Ser. No. 849,133,
filed Aug. 11, 1969, now abandoned, which is in turn a
continuation-in-part of U.S. application Ser. No. 709,700 filed
Mar. 1, 1968 now U.S. Pat. No. 3,591,362.
Claims
I claim:
1. A mechanically alloyed composite metal powder, the particles of
which are of substantially saturation hardness, have a plurality of
constituents and have an alloy composition from the group
consisting of platinum with up to about 50% palladium, platinum
with about 3.5 percent to about 40 percent rhodium, platinum with
up to about 35% iridium, platinum with up to about 8% tungsten,
gold alloys containing about 7% to about 30% platinum, about 1% to
13% palladium, about 7% to about 16% silver, about 7% to about 14%
copper, up to about 1% nickel, up to about 2% zinc and the balance
essentially gold, lead-copper alloys, copper-tungsten alloys,
silver-tungsten alloys, copper-chromium alloys, silver-chromium
alloys, copper-molybdenum alloys, silver-molybdenum alloys,
silver-manganese alloys, silver-nickel alloys,
beryllium-molybedenum alloys, silver-platinum alloys, platinum-gold
alloys and zinc-base alloys containing up to about 0.35% lead, up
to about 30% cadmium, up to about 1.5% copper, up to about 1.5%
titanium, up to about 0.1% magnesium and up to 4.5% aluminum, said
particles containing up to about 25%, by volume, of a fine
refractory dispersoid having an average size of less than 1 micron
and said particles being characterized metallographically by an
internal structure comprising said constituents in fragmented form
intimately united together and interdispersed, with the minimum
dimension of said fragments not exceeding about 10 microns.
2. A mechanically alloyed metal powder according to claim 1 having
an alloy composition comprising metal constituents of limited
solubility from the group consisting of copper with about 1% to
about 95% lead, iron with about 1% to about 95% copper, tungsten
with about 2% to about 98% silver, tungsten with about 25% to about
50% copper, copper with about 5% to about 95% chromium, copper with
about 2% to about 98% molybedenum, nickel with about 60% silver and
molybdenum with about 50% beryllium.
3. A mechanically alloyed metal powder according to claim 1 wherein
said dispersoid is a refractory oxide in the amount of about 0.05%
to about 10% by volume and wherein the minimum dimension of said
fragments does not exceed about 3 microns.
Description
This invention relates to metal products and to their production by
powder metallurgy.
When metal products are made by melting, numerous problems arise.
These include the occurrence of dendrites and other forms of
segregation in castings of complex alloys, which lead to
difficulties in working and with non-uniform response to heat
treatment. Brittle segregates impair the ductility of the cast
material. If the segregates are of a very low melting composition
they may lead to the phenomenon known as "hot shortness" severly
limiting the permissible hot working range, and even when working
is possible segregated regions persist in elongated form which give
rise to anisotropic properties and other disadvantages.
These problems may to some extent be overcome by the techniques of
powder metallurgy, which is also the most convenient way of
producing dispersion-strengthened metals and alloys and other
products consisting of finely divided immiscible constituents.
Nevertheless, powder metallurgy presents other problems of its
own.
Since the possibility of homogenization is limited to that which
can be brought about by sintering, thermal diffusion in the solid
state and localized melting, a starting material is required that
contains the constituents in a finely divided and uniformly
distributed condition. Thus, in making an alloy from a mixture of
elemental powders the powders must be very fine, e.g., 25 or 10 or
even 3 microns or less in size, so that the alloy can be rendered
homogeneous by diffusion in a reasonably short time, and such
powders tend to be pyrophoric and to pick up impurities, such as
oxygen from the atmosphere, which contaminate and adversely affect
products made from them. Mechanically mixed powders of different
densities also tend to segregate on storage and handling of the
mixture, leading to non-uniformity in products made from the
mixture.
To avoid the need for mechanical mixing, pre-alloyed powders may be
used, for example, those made by atomisation from a molten bath of
the alloy, but these are expensive, difficult to obtain with
controlled particle size, and may even contain substantial
dendritic segregation.
Similar difficulties arise in making dispersion-strengthened metals
and alloys by consolidating mechanical mixtures of the
constituents. Here, especially fine metal powders are desirable,
with the associated risk of contamination, and there are also the
further problems that the refractory dispersoid particles tend to
flocculate owing to static electrical charges and that constituents
of different densities tend to segregate on storage and handling of
the mixture. Flocculation and segregation both lead to
non-uniformity of the final wrought product owing to the formation
of stringers of dispersoid particles and adjacent areas
impoverished in the dispersoid.
Such stringers and associated defects are deleterious to structural
elements used under stress, particularly at high temperatures. The
impoverished regions do not contribute significantly to the
strength of the product, and a body in which the impoverished areas
constitute more than 10 percent by volume will be significantly
weaker than one without such defects. In addition, the gross
concentrations of refractory particles within the stringers
themselves provide sites for stress concentration and can be an
important factor in causing failure at elevated temperatures,
especially by fatigue.
Non-mechanical processes of producing mixtures of metal and
non-metal particles for consolidation include the internal
oxidation process, in which a powder, e.g., nickel or copper
containing a reactive solute element such as aluminium, silicon,
titanium, zirconium or thorium, is selectively oxidised to form
fine refractory oxide particles dispersed through the metal matrix.
This process also requires fine metal particles; is generally
limited to simple binary alloy systems; and furthermore is
difficult to apply to chromium-containing nickel-base alloys and
stainless steels without oxidising the chromium. Thus, this method
is generally only applicable to simple systems such as NI-Al,
Cu-Al, Ni-Th or Cu-Si, where the free energy of formation of the
oxide of the matrix metal is up to 80,000 calories/gram atom of
oxygen. If however the whole of the alloy powder is first oxidised
and then selectively reduced to leave the refractory oxide it is
difficult to reduce the matrix oxide completely, particularly if it
includes oxides of such metals as chromium, aluminium and
titanium.
Various wet techniques have also been proposed for the production
of dispersion-hardened metals and alloys. The ignition surface
coating process involves coating metal or alloy powders with a
decomposable salt of the intended refractory oxide dispersoid by
mixing the particles with a solution of the salt and evaporating
the liquid. Thus, nickel powder may be mixed with a solution of
thorium nitrate in alcohol. The coated powder is then heated in an
inert or reducing atmoshpere to convert the salt to the
corresponding oxide, as particles which coat the surface of the
metal particles. Here again, the need for fine metal powders in
order to achieve close spacing of the dispersoid particles
introduces the risk of contamination; care must be taken to avoid
pyrophoric combustion of the powder when it is treated to decompose
the salt; and segregation may occur since the last of the liquid to
evaporate tends to be very rich in the salt. Microstructures of
wrought metal products produced by this method tend to show
stringers of dispersed oxide.
In the selective oxide reduction process an intimate mixture of
metal oxides, one of which is reducible while the other provides
the dispersed oxide phase, is made, for example, by
co-precipitating the hydrates of the metals, converting them to
oxides, and selectively reducing the matrix metal oxide to metal.
The resulting powders can be extremely fine and pyrophoric and,
therefore, highly susceptible to contamination. This and other wet
methods present difficult materials handling problems, tend to be
messy, and are usually costly.
It has been proposed in U.K. Specification No. 821,336 to employ,
as starting materials for powder metallurgical processes, powders
comprising composite particles consisting of a high-melting point,
hard refractory material and a ductile metal, the particles of one
constituent being coated by the other. The methods of making such
particles described include the chemical or vapour phase deposition
of metal on the refractory particles, and the production on
particles of the ductile metal of a surface layer of a metal
forming a refractory oxide which is then oxidised. Similar
particles result from the conventional ball-milling of mixtures of
a ductile metal and a refractory oxide, e.g., mixtures of nickel
and thoria, for prolonged periods at the usual ball-to-powder
ratios, e.g., up to 3:1. All composite powders of this type have
the disadvantage that the particle size of the metal core of the
particle is essentially that of the initial powder used and that
this relatively coarse structure is carried over into wrought
products made from the powder, leading to stringers of dispersoid
and associated dispersoid-free areas.
In making powder-metallurgical products from metals normally
immiscible in the liquid and/or solid, e.g., iron and copper, a
skeleton sintered from powder of one metal may be infiltrated with
the other molten metal, or a mixture of the two metal powders may
be sintered. Whichever method is used, the distribution of the
copper is limited either by the size of the pores in the skeleton
or by relative size of the starting powders. The presence of a
liquid phase during the infiltration or sintering also tends to
cause microsegregation.
The present invention overcomes these various difficulties and
provides consolidated metal products having a very high degree of
microstructural uniformity and isotropy and substantially free from
segregation and stringers.
Objects and advantages of the invention will become apparent from
the following description and the accompanying drawing in
which:
FIG. 1 is a schematic representation of an attritor of the stirred
ball mill type capable of providing agitation milling to produce
composite powders for use in accordance with the invention;
FIG. 2 is a reproduction of a photomicrograph taken at 100
diameters showing in longitudinal section a microstructure of a
dispersion-strengthened superalloy provided in accordance with the
invention after an anneal at 2,250.degree.F. for 4 hours in argon;
and
FIG. 3 is a reproduction of an electron photomicrograph taken at
10,000 diameters of a surface replica of a dispersion-strengthened
superalloy shown in FIG. 2;
FIG. 4 is an electron transmission photomicrograph taken at 100,000
diameters showing the structure of another dispersion-strengthened
superalloy provided in accordance with the invention.
Broadly stated, the invention contemplates the production of
consolidated metal products characterised by a high degree of
microstructural uniformity and substantially devoid of segregation
and stringers by consolidation, e.g., by hot extrusion, hot
pressing, forging, etc., unique composite wrought metal particles
containing at least 15 percent by volume of a deformable metal with
the remainder being a metal or a non-metal, said particles having
an interdispersed, mechanically alloyed internal structure.
A non-dispersion strengthened product is to be regarded as
substantially free from stringers or segregation if it contains
less than 10 volume percent of stringers or of regions exceeding 25
microns in minimum dimension in which there is a significant
composition fluctuation from the mean, that is to say, a deviation
in composition exceeding 10 percent of the mean content of the
segregated alloying element. The boundaries of a segregated region
are taken to lie where the composition deviation from the mean is
one-half of the maximum deviation in that region. Regions of
composition deviation of less than 25 microns in minimum dimension
are not regarded as segregated regions. Preferably, the minimum
dimension of the stringer or region of compositional fluctuation
does not exceed 10 microns. Preferably, also the proportion of
stringers or of segregated regions is less than 5 volume percent.
Compositional variations on the scale discussed above may, for
example, be detected and measured by electron microprobe
examination.
The products are advantageously made, according to the invention,
by the consolidation of special composite powders. These powders
and methods for their production are described and claimed in U.S.
application No. 709,700, now U.S. Pat. No. 3,591,362.
The powders used consist of wrought composite particles having a
cohesive, non-porous internal structure made up of two or more
intimately united and inter-dispersed constituents, at least one
constituent, amounting to at least 15 percent by volume of the
particles, being a compressively deformable metal, and the
composite particles individually having substantially the
composition of the powder. The internal structure of the composite
particles may be regarded as a mechanical alloy.
The constituents of the composite particles, other than the
deformable metal, may be other metals or non-metals, including
refractory oxides and other hard phases useful for
dispersion-strengthening alloys. The term metal in this
specification and claims is to be understood as including
alloys.
The average spacing between the sub-particles of the constituents
inter-dispersed in the composite particles should be as small as
possible in order to facilitate thermal diffusion of
inter-diffusible constituents when they are heated to promote
alloying. Advantageously, it does not exceed 10 microns and
preferably, especially in the case of dispersion-strengthened
products, does not exceed 3 microns or even 1 micron, and it may be
much less than 1 micron, while the composite particles conveniently
average from 20 to 200 microns in size, though larger particles may
be used where it is possible to make them with a fine enough
internal structure, and smaller particles can be used when the
systems involved are sufficiently noble to avoid pyrophorocity.
It will be appreciated that the advantage of using such wrought
composite particles to form consolidated powder metallurgy products
arises from the fact that the particles act as building blocks for
the final structure, the high degree of uniformity of each of the
composite particles being carried forward and maintained in the
final wrought product. Conversely, the use of inhomogeneous
composite particles containing dispersoids for making consolidated
products will not lead to homogeneous products. The spacing between
the constituents in the product will of course depend on the amount
of reduction occurring during the consolidation, and the spacing
will generally be less than in the powder particles.
Spacings less than 3 microns or even 1 micron, preferably very much
smaller, are particularly advantageous in the case of powders
containing refractory dispersoids.
The powder particles are advantageously in a heavily work-hardened
condition, as this accelerates alloying of constituents by thermal
diffusion on heating, and facilitates hot deformation as, for
instance, hot extrusion for consolidation of a confined mass of
powder particles. This is believed to be due to the very fine grain
structure resulting from a coalescence of the work-hardened
structure upon heating for hot deformation.
The powder may be made, according to our previous application, by
subjecting a mixture consisting of at least 15 percent by volume of
a compressively deformable metal powder with one or more other
metal or non-metal powders to dry, high energy impact milling,
suitably in a stirred attritor ball mill, sufficiently energetic
and sufficiently prolonged to reduce the particles of deformable
metal to less than half, and preferably to less than one-fifth or
even one-tenth of their original thickness and to comminute and
bond together the constituents of the mixture to form composite,
non-porous wrought particles having a cohesive inter-dispersed
internal structure. To produce the desired structure the milling
may be continued, under conditions in which work-hardening occurs,
at least until the hardness of the composite particles has been
increased by half the difference between the base hardness and the
constant saturation hardness reached on prolonged milling. During
energetic dry milling composite particles are repeatedly fractured
and reformed by cold working, with a progressive increase in the
uniformity of the composition of the particles and the refinement
of their internal structure. Advantageously, the powder is milled
to saturation hardness, and preferably milling is continued beyond
this point until the structure has been refined to the desired
extent. Milling beyond the point of saturation hardness is
particularly desirable in the case of complex alloys, since these
attain saturation hardness while their structure is less uniform
than in the case of unalloyed metals, owing to the hardening effect
of other hard constituents, e.g., fragments of master alloys.
The composite particles thus comprise comminuted fragments of the
initial metal particles welded or metallurgically bonded together,
the minimum dimension of the fragments being usually less than
one-fifth and preferably less than one-tenth of the average
dimension of the initial product from which the fragment was
derived. Refractory particles included in the initial powder became
distributed throughout the individual composite particles in a fine
state of dispersion approximately equal to the minimum dimension of
the fragments. Thus, the average distance between the refractory
particles in the composite particles is much less than the
dimension of the initial metal particles, and is advantageously
less than 1 micron, and down to 0.5 micron or less. In such
particles there are essentially no islands or areas in the
composite particles free from dispersoid.
Dry, high energy impact milling may suitably be performed in a
stirred attritor ball mill comprising an axially vertical
stationary cylinder containing a charge of balls and having a
rotatable agitator shaft located coaxially of the mill with spaced
agitator arms extending substantially horizontally from it and
serving to maintain the bulk of the ball-charge in continuous
relative motion. Such a mill is described in Perry's "Chemical
Engineer's Handbook," Fourth Edition, 1963, at page 8-26, and is
shown diagrammatically in FIG. 1 of the accompanying drawings,
which shows in partial section an upright cylinder 13 surrounded by
a cooling jacket 14 having inlet and outlet ports 15 and 16
respectively for circulating water or other coolant. A shaft 17 is
coaxially supported within the cylinder by means not shown and has
horizontally extending arms 18, 19 and 20 integral with it. The
mill is charged with balls 21 to a depth sufficient to bury at
least some of the arms.
The milling time t required to produce a satisfactory dispersion;
the agitator speed W (in r.p.m.); the radius, r, of the cylinder
(in cm.) and the volume ratio R of balls to powder are related by
the expression:
1/t = K W.sup.3 r.sup.2 R
where K is a constant depending upon the system involved. Thus,
once a set of satisfactory conditions has been established in one
mill of this type, other sets of satisfactory conditions for this
and other similar mills may be predicted by use of the foregoing
expression.
Except where it is otherwise specified, the dry impact milling
referred to in each of the examples in this specification was
performed in a water cooled mill of this type. The rate of milling
specified in r.p.m., is the rate of rotation of the agitator.
Unless otherwise specified the mill was sealed to prevent access of
air during milling other than that initially present.
Other mills that can be used include vibratory ball mills,
high-speed shaker mills and planetary ball mills. Whatever type of
mill is employed, the balls or other attritive elements must be
hard and tough enough to compress the deformable metal and are
preferably of metal or cermet, e.g., steel, stainless steel, nickel
or tungsten carbide; of small diameter relative to the mill; and of
essentially uniform size. For further details of the production of
the powders, reference should be made to U.S. application No.
709,700.
The composite powders may have an extraordinarily wide range of
compositions, and may be used to produce a correspondingly wide
variety of composite products. The compositions include a very wide
range of metal systems, corresponding to both simple binary and
more complex alloys, provided that they include a compressively
deformable metal.
The simple alloys include those based on lead, zinc, aluminium and
magnesium, copper, nickel, cobalt, iron and the refractory metals.
More complex alloys include the well-known heat-resistant alloys,
e.g., those based on nickel-chromium, cobalt-chromium, and
iron-chromium systems containing one or more alloying additions
such as molybdenum, tungsten, niobium, tantalum, aluminium,
titanium, silicon, zirconium and the like, with or without
non-metals such as carbon and boron.
Dispersion-hardened wrought alloys, both simple and complex, may be
produced from composite powders having uniform dispersions of a
hard refractory compound phase. The refractory compounds include
oxides, carbides, nitrides, borides of such refractory metals as
thorium, yttrium, zirconium, hafnium, titanium and even such
refractory oxides as those of silicon, aluminium, cerium, uranium,
magnesium, calcium, beryllium and the rare earth oxide mixture,
didymia. The refractory oxides generally useful as dispersed phases
are those whose negative free energy of formation per gram atom of
oxygen at about 25.degree.C., is at least about 90,000 calories and
whose melting point is at least that of the matrix. The proportion
of hard phases may be sufficient to produce cermet compositions so
long as sufficient ductile metal is present to provide a host
matrix for the hard phase or dispersoid. Where only dispersion
strengthening of wrought compositions is desired, as in high
temperature alloys, the amount of dispersoid may range from 0.05
percent to 25 percent by volume and, more advantageously, from 0.05
percent to 5 percent or 10 percent by volume.
The process of the invention is also particularly useful in
producing wrought products from metal systems whose components have
limited or even substantially no mutual solubility in the liquid
state and/or solid state, for example, lead or iron with copper,
tungsten with copper or silicon, and chromium with copper. It is
particularly to be noted that because the constitution of the
composite powders is that of an extremely fine-structured
mechanical alloy, their compositions and thus that of the products
made from them is not limited by normal practical considerations
using melting techniques or conventional powder metallurgical
techniques and that the substantial absence of segregation in the
products leads in many cases to a remarkable improvement in
workability as compared with cast alloys of the same composition.
Many novel and advantageous alloy compositions thus become
available in wrought forms.
The numerous advantages of the use of the wrought composite
particles for making consolidated powder-metallurgy metal products
include the protection of reactive components such as chromium,
aluminium and titanium from oxidation by their incorporation into
and shielding by the matrix of the deformable metal. The composite
particles also combine the advantages of a coarse powder, including
storage with minimum contamination, ease of out-gassing for canned
extrusion, non-pyrophoric properties, good flow characteristics and
high apparent density, with an extremely intimate and fine
dispersion of the constituents in each particle.
Consolidation of the composite powder to metal products may be
effected by any suitable process of mechanical working, including
extrusion in a sealed can, forging, rolling and hot pressing. The
working temperature will, or course, depend on the nature of the
composition concerned. During the heating of the particles to the
temperature used for working, any homogenisation and annealing of
the particles which can occur will generally take place, but
further heat-treatment may be performed subsequently if desired. It
is generally desirable to de-gas the powder as far as practical
before working is carried out.
Some of the various types of wrought products of the invention will
now be considered in more detail.
Superalloys
Complex nickel, cobalt or iron-base high-temperature alloys
(commonly called superalloys) that contain chromium and are
rendered age-hardenable by such alloying elements as niobium,
titanium and aluminium and/or are solid-solution hardened by
molybdenum or tungsten, tend to suffer from segregation on casting,
particularly at high contents of the alloying element. This leads
to a non-uniform age-hardening response and to hot-working
difficulties. If powder metallurgy techniques or blending of
elemental or partially pre-alloyed powders is resorted to, it is
found that chromium tends to be oxidised and aluminium and titanium
tend to be lost by oxidation, so that they are no longer available
for age-hardening, and other disadvantages such as segregation also
occurs that have already been mentioned.
Further difficulties arose in the attempt to apply
dispersion-strengthening to superalloys owing to the ready
formation of stringers of dispersoid, resulting in substantial
areas within the alloy which were depleted of dispersoid.
Manufacture of superalloys by consolidation of wrought composite
powders according to the invention facilitates the avoidance of
segregation in standard superalloy compositions; enables the
content of alloying elements for age-hardening or solid solution
hardening to be increased; and enables dispersion-strengthened
superalloys to be readily produced. The resulting wrought products
have a microstructure that is substantially uniform throughout, are
substantially free from segregation, primary gamma prime phase and
stringers, and have a uniform distribution of
precipitation-hardening phases as indicated by transmittion
transmission photomicrographs. They may be dispersion-strengthened
by any of the wide variety of refractory oxides, carbides, nitrides
and borides disclosed in more detail hereinbefore.
It has been noted, quite surprisingly, that bodies produced by hot
working of consolidated mechanically alloyed powders can be worked
to a much greater extent than conventionally produced bodies of the
same composition as the matrix alloy. This is seen in reduced
temperatures required for comparable amounts of hot deformation,
reduced working pressures and greater permissible amounts of
working strain.
Broadly speaking, the alloys have a melting point of at least
1093.degree.C. and contain from 4 to 65 percent by weight of
chromium, at least 1% in total of one or more of niobium, aluminium
and titanium, preferably 0.2% to 15% aluminium (e.g., 0.5% to
6.5%), and 0.2% to 25% titanium (e.g., 0.5% to 6.5%), 0 to 40%
molybdenum, 0 to 40% tungsten, 0 to 20% niobium, 0 to 30% tantalum,
0 to 2% vanadium, up to 15% manganese, up to 2% carbon, up to 1%
silicon, up to 1% boron, up to 2% zirconium, and up to 0.5%
magnesium, the balance (at least 25%) being essentially iron,
nickel, or cobalt with or without dispersion-strengthening
constituents, such as yttria, lanthana, alumina, thoria, etc., in
amounts from 0.05% to 10% and preferably 0.05% to 10% by volume of
the total composition.
Superalloys with which the invention is particularly concerned
include those falling within the range 5 to 35% chromium, 0.5% to
8% aluminium, 0.5% to 10% titanium, up to 12% molybdenum, up to 20%
tungsten, up to 8% niobium, up to 10% tantalum, up to 2% vanadium,
up to 2% manganese, up to 1% carbon, up to 1.5% silicon, up to 0.1%
boron, up to 1% zirconium, up to 2% hafnium, up to 0.3% magnesium,
up to 45% iron, up to 10% by volume of a dispersoid which is
advantageously thoria, yttria, lanthana, ceria, or rare earth oxide
mixtures, such as didymia, may suitably be present in amounts of at
least 0.2%, preferably 0.5 to 5% by volume, the balance (at least
40%) being one or both of nickel and cobalt. Some specific examples
of superalloy compositions which may be produced with or without a
dispersoid are set forth in Table I.
TABLE I
__________________________________________________________________________
Nominal Composition Wt% Alloy No. C Mn Si Cr Ni Co Mo W Cb Fe Ti Al
B Zr Other
__________________________________________________________________________
1 0.12 -- -- 12.5 bal. -- 4.2 -- 2.0 -- 0.8 6.1 0.012 0.10 -- 2
0.10 -- -- 8.0 bal. 10.0 6.0 -- -- -- 1.0 6.0 0.015 0.10 4.0 Ta 3
0.15 -- -- 15.5 bal. -- 5.0 -- -- 4.5 2.5 3.5 0.05 -- -- 4 0.12
0.10 0.30 15.0 bal. 28.5 3.7 -- -- 0.7 2.2 3.0 -- -- -- 5 0.04 0.55
0.20 15.0 bal. -- -- -- -- 6.5 2.4 0.6 -- -- -- 6 0.18 -- -- 10.0
bal. 15.0 3.0 -- -- -- 4.7 5.5 0.014 0.06 1.0 V 7 0.09 -- -- 19.0
bal. 11.0 10.0 -- -- -- 3.1 1.5 0.005 -- -- 8 0.07 -- -- 19.0 bal.
19.0 4.2 -- -- -- 3.0 3.0 0.007 0.05 -- 9 0.38 1.20 0.40 20.0 20.0
bal. 4.0 4.0 4.0 4.0 -- -- -- -- -- 10 0.45 0.25 0.25 21.0 -- bal.
-- 11.0 2.0 2.0 -- -- -- -- -- 11 0.05 0.10 0.10 12.5 42.5 -- 5.7
-- -- bal. 2.8 0.2 0.015 -- -- 12 0.04 0.90 0.80 13.5 26.0 -- 2.7
-- -- bal. 1.7 0.1 0.005 -- -- 13 0.15 1.50 0.50 21.0 20.0 20.0 3.0
2.5 1.0 bal. -- -- -- -- 0.15 N 14 0.05 0.25 0.25 21.5 61.0 -- 9.0
-- 3.65 25.0 0.2 0.2 -- -- -- 15 0.05 -- -- 25.0 -- -- 10.0 -- --
-- -- -- -- -- 0.015 Mg, 0.013 Ce 16 0.1 -- -- 15.0 bal. 15.0 4.0
-- -- -- 4.0 5.0 -- -- --
__________________________________________________________________________
The stable refractory compound particles may be maintained as fine
as possible, for example, below 0.5 microns in size. A particle
size range recognized as being particularly useful in the
production of dispersion-strengthened systems is 10 Angstroms to
1,000 Angstroms (0.001 to 0.1 micron).
The heavy cold work imparted to the composite metal particles
produced by milling the high-melting metals to produce superalloy
compositions is particularly advantageous. It increases effective
diffusion coefficients in the product powder and this factor, along
with the intimate mixture in the product powder of metal fragments
from the initial components to provide small interdiffusion
distances, promotes rapid homogenisation and alloying of the
product powder upon heating to homogenising temperatures and
improves hot workability as explained hereinbefore. The foregoing
factors are of particular value in the production of powder
metallurgy articles having rather complex alloy matrices. Some
examples will now be given:
EXAMPLE I
A powder mixture consisting, by weight, of 14.9% of a powdered
Ni-Ti-Al master alloy containing Ni 72.93%, Ti 16.72%, Al 7.75%, Fe
1.55%, Cu 0.62%, C 0.033%, Al.sub.2 O.sub.3 0.05%, TiO.sub.2
0.036%; 62.25% of carbonyl nickel powder of particle size 5-7
microns; 19.8% of chromium powder of particle size less than 74
microns; and 3.05% of thoria of particle size 0.04 micron, was
preblended and 1,300 g. of it was dry impact milled under argon for
48 hours in an attritor mill at a ball-to-powder ratio of 17:1,
running at 176 r.p.m. The product consisted of composite powder
particles exhibiting excellent inter-dispersion of the ingredients
within the individual particles and having a striated structure
under a magnification of .times.750. The analysis of the powder was
Ni 73.86%, Cr 19.3%, Ti 2.16%, Al 1.19%, C 0.017%, Cu less than
0.05%, ThO.sub.2 2.93%, Al.sub.2 O.sub.3 0.015%, TiO.sub.2 0.013%.
The amount of other impurities was negligible.
After removal of some coarse particles larger than 350 microns, the
powder having a particle size range of 45 to 350 microns was
extruded to bar in a stainless steel can after degassing under
vacuum (2 .times. 10.sup..sup.-5 mm Hg) at 350.degree.C. using an
extrusion ratio of 16:1 and a temperature of 1,175.degree.C. The
extruded bar contained a fine and uniform dispersion of thoria
particles of average size 0.04 micron with an inter-particle
spacing of less than 1 micron, free from stringers, and had a
hardness of 275 Vickers. Solution-heating for 16 hours at
1,200.degree.C. reduced the hardness to 235 Vickers, while
subsequent aging for 16 hours at 705.degree.C. brought about
precipitation-hardening, the hardness increasing to 356
Vickers.
By comparison, wrought alloys having substantially the same matrix
composition, produced by conventional melting techniques, had a
hardness of 200-250 Vickers after annealing, which was raised to
290-320 Vickers by a similar aging treatment.
EXAMPLE II
A mixture consisting, by weight, of 39.5% of a powdered master
alloy of particle size less than 43 microns and containing 67.69%
Ni, 8.95% Mo, 5.70% Nb, 15.44% Al, 1.77% Ti, 0.053% C, 0.06% Zr and
0.01% B; 45.74% of carbonyl nickel powder of particle size 5
microns; 11.64% of chromium powder of particle size less than 74
microns; and 3.12% of thoria of particle size 0.04 microns, was dry
milled for 48 hours in air in an attritor mill at a ball-to-powder
ratio of 29:1 by volume and a speed of 176 r.p.m. Microscopic
examination of the powder revealed that the constituents had
intimately united together to form composite metal powder particles
which showed excellent inter-dispersion of the ingredients.
A portion of the powder product, after removal of coarse particles
larger than 350 microns was extruded to bar in a stainless steel
can (after degassing under vacuum at 425.degree.C.), using an
extrusion ratio of 16:1 and a temperature of 1,200.degree.C. The
resulting bar had the analysed composition: C 0.07%, Cr 10.40%, Mo
3.00%, Nb 1.60%, Al 5.20%, Ti 0.65%, B 0.007%, Zr 0.03%, ThO.sub.2
3.20%, Al.sub.2 O.sub.3 0.38%, TiO.sub.2 0.018%, Cr.sub.2 O.sub.3
0.016%, Ni balance. The Al.sub.2 O.sub.3 was present as an intimate
dispersion and the proportion of the extraneous oxides, TiO.sub.2
and Cr.sub.2 O.sub.3 was thus very low.
Portions of the extruded bar were heated to 1,240.degree.C. for 4
hours in argon to solution-treat the alloy, increase its grain size
and complete the homogenisation of the structure, and then
furnace-cooled to allow precipitation-hardening to occur. The grain
structure of the alloy after this treatment is shown at a
magnification of .times.100 in FIG. 2 of the drawings. It will be
noted that the grain structure is elongated in the direction of
extrusion. On examination by electron microscopy after this
treatment the alloy was observed to contain both a gamma prime
precipitation-hardening phase and an intimate dispersion of thoria
particles of average size 0.05 micron, with an inter-particle
spacing of less than 1 micron. The fine structure under the
electron microscope at 10,000 diameters is shown in FIG. 3 of the
drawings.
The high-temperature properties of the alloy after heat-treatment
are set forth in Table II.
TABLE II ______________________________________ Test Yield Strength
Tensile Elongation R.A. Temp. 0.2% offset Strength % % (.degree.C.)
(kg/mm.sup.2) (kg/mm.sup.2) ______________________________________
760 69.6 79.0 7.5 10.0 982 19.3 24.9 11.0 8.0 1093 7.5 8.2 9.0 24.5
______________________________________
The improvement brought about by the dispersion of thoria in the
alloy is shown by comparison of the stress-rupture properties of
the heat-treated alloy with those of a cast, precipitation-hardened
high-temperature alloy (Alloy 713) containing no thoria and having
a composition similar to that of the matrix of the
thoria-containing alloy, namely Ni 74.84%, Cr 12.0%, Mo 4.5%, Nb
2.0%, Ti 0.6%, Al 5.9%, C 0.05%, Zr 0.1%, B 0.01%. These properties
are compared in Table III in terms of the stress at which the
alloys exhibited lives of 100 and 1,000 hours at
1,093.degree.C.
TABLE III ______________________________________ Life Stress for
indicated life (kg/mm.sup.2) Alloy Hours ThO.sub.2 -containing
alloy 713 ______________________________________ 100 6.0 4.5 1000
5.4 2.9 ______________________________________
EXAMPLE III
An 8.5 kg. powder charge of 1,550 parts of a nickel master alloy
containing 7% aluminium, 14% titanium and 9% didymium (a rare earth
metal mixture containing 50% lanthanum with neodymium and
praseodymium and other rare earth metals) ground to pass a 74
micron screen; 1,800 parts of chromium powder smaller than 74
microns; 20.4 parts of Ni-Zr master alloy, 3.87 parts of Ni-B
master alloy; and 5,241 parts of carbonyl nickel powder was dry
impact milled in a 38 litre attritor mill containing 189 kg. of 6.3
mm. nickel pellets for 40 hours at an agitator speed of 132 r.p.m.
The product was screened through a 350 micron sieve and packed into
an 8.9 cm. diameter steel can, which was sealed without evacuation,
soaked at 1,038.degree.C. and extruded to round bar 1.9 cm.
diameter. The powder became consolidated by upsetting within the
container prior to extrusion and good hot workability was evident
from the fact that extrusion was possible at the relatively low
temperature of 1,038.degree.C. The extruded bar was subjected to
heat treatment comprising heating 2 hours at 1,275.degree.C.
followed by heating 7 hours at 1,080.degree.C. and then for 16
hours at 705.degree.C. A coarse grain structure elongated in the
extrusion direction was present. The extruded bar was characterized
by a finely-divided and well-distributed dispersion of rare earth
metal oxides, principally lanthana resulting from internal
oxidation by reaction of extremely finely-divided rare earth metal
and oxygen present in the milled powder.
The stress rupture properties of the heat treated bar were very
good as illustrated by data set forth in the following Table IV,
indicating a very uniform dispersion of fine refractory oxide
particles.
TABLE IV ______________________________________ Test Stress Time to
Elongation Reduction Temp. (kg/mm.sup.2) rupture (%) in area
(.degree.C) (Hrs.) ______________________________________ 1038 12.7
1.5 8.0 11.6 1038 11.2 472.7 4.0 6.0 1038 9.8 389.7 2.7 3.9 760
35.2 16.3 2.7 3.9 760 28.1 193.1 4.4 7.0
______________________________________
This example illustrates a special feature of the invention whereby
dispersion-strengthened metals may be produced using as a starting
material a powder having distributed therethrough on a micro-scale
a metal whose oxide has a high heat of formation at 25.degree.C.
exceeding 90 kg. cal. per gram atom of oxygen. Said metal becomes
oxidised in situ by oxygen available in limited supply in the
powder by virtue of the very short diffusion distances involved,
with the result that the resulting oxide is very fine and is well
distributed in the resulting consolidated shape wherein the oxide
is an effective dispersion strengthener.
EXAMPLE IV
A further 8.5 kilogram powder charge containing about 1,490 parts
of a Ni-17%, Ti-8.5%, Al master alloy ground to less than 75
microns, 2,000 parts of chromium smaller than 75 microns, 1,330
parts of fine carbonyl nickel powders premixed with 10%, by weight,
of fine yttria (400 A) in a Waring blender, 24.8 parts of a Ni-Zr
master alloy smaller than 75 microns, 3.9 parts of a Ni-B master
alloy smaller than 75 microns and 5,290 parts of carbonyl Ni powder
was milled for 40 hours in a 38 litre attritor mill containing 180
kg of 6.3 mm. nickel pellets at 132 r.p.m. The product powder was
screened through a 350 micron screen and packed into a 8.9 cm.
diameter steel can. The can was evacuated to less than
10.sup..sup.-4 mm. of mercury pressure at 425.degree.C. and sealed
by welding. The sealed, evacuated can was heated to 1,093.degree.C.
and extruded to 15.5 mm. diameter bar. The extruded bar was heated
in argon 2 hours at 1,275.degree.C., then at 1,080.degree.C. for 7
hours and cooled in air. It was then heated for 16 hours at
705.degree.C. and again air cooled. A desirable coarse grain
2.46elongated in the extrusion direction resulted. The bar
contained 0.061% C, 0.92% soluble Al, 2,46% soluble Ti, 20.4% Cr,
0.029% soluble Zr, 0.005% B, 1.22% Y.sub.2 O.sub.3 and 0.37%
Al.sub.2 O.sub.3.
Specimens of the extruded, heat treated bar were subjected to
stress-rupture testing with the excellent results set forth in the
following Table V.
TABLE V ______________________________________ Temp. Stress Life to
Elongation Reduction (.degree.C.) (kg/mm.sup.2) rupture- (%) in
area (hrs.) (%) ______________________________________ 1038 12.7
5.8 3.2 9.0 1038 11.5 70.9 4.0 9.4 1038 11.2 393.6 2.7 1.6 927 17.6
7.1 6.2 10.5 927 15.8 117.4 5.3 11.6 760 35.2 4.0 7.2 20.5 760 28.1
131.3 6.4 21.5 760 28.1 53.3 10.0 19.1
______________________________________
In addition, the yttriated material was found to be markedly more
resistant to sulfidation corrosion resulting from exposure at
927.degree.C. to a fused salt bath containing, by weight, 90%
sodium sulfate and 10% sodium chloride than the non-dispersion
strengthened base alloy. Similarly, the yttriated material was
markedly more resistant than the non-dispersion strengthened base
alloy in a cyclic oxidation test at 1,093.degree.C. in flowing air
wherein the specimens were cycled to room temperature every 24
hours. In particular, the yttriated material was much more
resistant to subsurface penetration than was the standard material
in these tests.
FIG. 4 is a transmission electron photomicrograph taken at 100,000
diameters from the yttriated material of this example. The fine,
substantially uniform distribution of finely divided dispersoid
(yttria and alumina) as indicated by reference character G, and a
substantially uniform distribution of gamma prime phase as
indicated by reference character H in FIG. 4. Somewhat larger MC
metal carbides indicated by reference character J are also evident
in FIG. 4. FIG. 4 demonstrates the absence of segregation which
characterizes materials of this invention.
EXAMPLE V
Composite alloy powders having the composition of a conventional
nickel base superalloy containing 10% Cr, 3% Mo, 15% Co, 5.5% Al,
4.7% Ti, 1% V, 0.18% C, 0.06% Zr, 0.014% B, balance Ni, were
produced by mechanical alloying. A mixture of 441 g. of Cr powder
(less than 150 microns), 134 g. of Mo powder (less than 44
microns), 663 g. of Co powder (less than 44 microns), 1,005 g. of
carbonyl Ni powder, 7.6 g. of graphite powder, 1,050 g. of less
than 75 micron powder of a Ni-15.96% Al-3.68% Ti master alloy, 932
g. of less than 75 micron powder of a Ni-9.08% Al-17.5% Ti master
alloy, 71 g. of a less than 150 micron powder of a Ni-65% V master
alloy, 12 g. of a less than 75 micron powder of a Ni-28% Zr- 14.5%
Al master alloy and 3.3 g. of a less than 75 micron powder of a
Ni-18% B master alloy were placed in a high energy horizontal ball
mill of 15 litres capacity having a stationary tank and a driven
horizontal shaft provided with multiple agitator arms extending at
right angle therefrom, and processed at 220 r.p.m. with 90 kg. of
9.5 mm. steel balls. A nitrogen atmosphere was maintained in the
mill. Two batches were processed for 16 hours, one for 8 hours and
one for 4 hours.
The internal powder structure of the batches processed for 16 hours
was observed to be substantially homogeneous with the majority of
the ingredient fragments within the composite particles being below
1 micron in size. In contrast, the structures of the 8 hour and 4
hour batches were progressively less homogeneous although all had
substantially the same overall composite particle size
distributions.
3,066 g. of one of the 16 hour batches, sieved to pass through a
350 micron screen was packed in a 8.9 cm. diameter mild steel can
and evacuated to less than 10.sup..sup.-4 mm of mercury pressure at
425.degree.C. through a stainless steel tube provided for that
purpose. The can was sealed by fusion welding the tube and
consolidated by hot extruding to 2.5 cm. diameter bar at
1,177.degree.C. The extrusion was accomplished with no difficulty,
requiring less than two-thirds of the capacity of the press and
moving at a ram speed of from 33 to 61 cm. per second. This, in
spite of the fact that the composition as normally produced, is not
readily hot workable and must be precision cast to final shape.
The results of hardness tests performed on samples of this
extrusion in the as extruded condition and after two annealing
treatments are given in Table VI.
TABLE VI ______________________________________ Hardness Condition
Rc ______________________________________ As extruded 48 2 hours at
1243.degree.C. 42.5 2 hours at 1266.degree.C. 40.5
______________________________________
Wrought, Dispersion-Strengthened Electrical Heating Elements
Heat-resistant alloys for electrical heating elements, comprising
one or both of iron and nickel alloyed with one or both of chromium
and aluminium, suffer from segregation when made by casting.
Soaking to homogenise the structure leads to little improvement and
may result in grain coarsening, with adverse effects on
forgeability, extrusion and rolling. In particular, certain
well-known alloys which contain both aluminium and chromium,
together with nickel or iron or both, are brittle at room
temperature although soft at elevated temperatures. One such alloy
contains 67% iron, 25% chromium, 5% aluminium and 3% cobalt and
another 55% iron, 37.5% chromium and 7.5% aluminium. These two
alloys exhibit excellent resistance to oxidation and corrosion at
elevated operating temperatures of about 1,200-1,300.degree.C., but
tend to creep and lose their shape during service as electrical
resistance elements.
These disadvantages are overcome by the wrought,
dispersion-hardened electrical heating alloys provided by the
invention which are characterized throughout by compositional
uniformity (i.e., freedom from segregates) and by a high degree of
dispersion uniformity and absence of stringers and attendant
dispersoid free regions.
Broadly speaking, the alloys concerned are those containing at
least 10% in all of one or both of chromium and aluminium, the
chromium content not exceeding 40% and the aluminium content not
exceeding 34%, and from 0 to 5% silicon, the balance of the alloy
(apart from impurities) being at least 50% in all of one or more of
iron (5% to 75%), cobalt (up to 15%) and nickel (5% to 80%), and
including from 0.05% to 25% by volume (based on the total
composition) of a refractory compound dispersoid. Generally, the
alloys have an electrical resistance of at least 100
microhms/cm.sup.3.
Advantageously, the chromium content is from 15 to 40%, the cobalt
content does not exceed 10%, the aluminium content does not exceed
32%, the sum of the iron, cobalt and nickel content is from 50 to
80% and the dispersoid content is from 0.05 to 10 volume percent of
the total composition.
A composition range particularly desirable for electrical heating
alloys contains 15-40% chromium, 3-20% aluminium, balance iron,
with from 0.05 to 5 volume percent of dispersoid.
Dispersoids that are particularly useful are yttria, lanthana,
thoria and the rare earth mixture didymium, in sizes less than 1
micron and preferably less than 0.1 micron. Oxides of zirconium,
titanium, and beryllium and carbides, nitrides and borides of all
the metals set forth above may also be used. Generally speaking,
suitable refractory oxides are those of metals whose negative free
energy of formation of the oxide per gram atom of oxygen at
25.degree.C. is at least 90,000 calories and whose melting point is
at least 1,300.degree.C.
Specific examples of alloys that may be dispersion-strengthened by
the invention are set forth in Table VII below:
TABLE VII
__________________________________________________________________________
Alloy Resistance No. Microhms/cm.sup.3 Nominal Composition at
20.degree.C. % Cr % Al % Fe % Ni % Others
__________________________________________________________________________
17 1387 23 5 72 -- -- 18 1662 37.5 7.5 55 -- -- 19 1379 20 5 73.5
-- 1.5 Si 20 1163 20 -- 8.5 68 2 Si 21 1122 16 -- 22.5 60 1.5 Si 22
-- 25 5 67 -- 3 Co 23 -- 15 5 -- 80 -- 24 -- 20 4 -- 76 -- 25 -- 15
5 5 75 -- 26 -- -- 15 Bal. -- -- 27 1013 20 -- 43.5 35 1.5 Si 28 --
-- 31.5 -- 68.5 -- 29 -- 20 -- -- 80 --
__________________________________________________________________________
Some examples will now be given:
EXAMPLE VI
An iron-aluminium alloy dispersion-strengthened with Al.sub.2
O.sub.3 is made from composite powder produced by dry impact
milling a charge of 65 micron sponge iron and an Fe-Al master alloy
crushed to powder smaller than 74 microns in the appropriate
proportions with 3 volume percent of 0.03 micron gamma alumina
using a 20:1 ball-to-powder ratio and 6 mm. nickel balls and an
agitator speed of 175 r.p.m. Milling for 45 hours produced a highly
cold-worked powder of which the particles comprised a substantially
homogeneous inter-dispersion of all the ingredients. The powder was
vacuum packed in a mild steel can which was welded shut, heated to
1,093.degree.C. and extruded at a ratio of 16:1. After removal of
the can material, the extruded bar was hot- and cold-worked to
ribbon and wire for use as electrical heating elements.
EXAMPLE VII
In producing a wrought dispersion-strengthened electrical heating
alloy containing, by weight, 20% Cr, 5% Al, 1.5% Si and 73.5% iron
with 4 volume percent of Y.sub.2 O.sub.3, 2,300 g. of a brittle
master alloy containing, by weight, 63.25% Fe, 21.7% Al, 6.5% Si
and 8.55% yttrium metal, crushed to particles smaller than 75
microns, was blended with 4,870 g. of 150 micron high-purity sponge
iron and 2,830 g. of 75 micron ferrochrome powder. The mixture was
dry impact milled in a stirred attritor mill of 38 litres capacity
at 180 r.p.m. using 6 mm. hardened steel balls at a ball:powder
ratio of 15:1. Milling for 24 hours gave fully work-hardened
composite powder. After sieving out particles larger than 0.35 mm.,
the powder was vacuum packed and welded shut in a mild steel can
and the assembly heated to 1,093.degree.C. During this heating the
oxygen adventitiously present within the powders combined with the
yttrium metal to produce a fine uniform dispersion of Y.sub.2
O.sub.3 of less than 0.1 micron average particle size. The can was
then extruded at 1,093.degree.C. at an extrusion ratio of 16:1 to
rod, suitable for drawing down to size suitable for electrical
heating elements.
EXAMPLE VIII
To produce a ThO.sub.2 dispersion-strengthened electrical heating
alloy containing Cr 15%, Al 5%, Fe 5% and Ni 75%, a brittle master
alloy containing Al 67%, Fe balance was crushed to particles
smaller than 150 microns. 89.5 g. of the crushed powder was blended
was 68.3 g. of a commercial Cr 70%-Fe 30% powder of particle size
less than 150 microns, 132.2 g. of Cr powder of particle size less
than 75 microns, 900 g. of 5-7 micron Fisher size carbonyl Ni
powder, and sufficient 0.02 micron ThO.sub.2 to give 3 volume
percent ThO.sub.2 in the product. The mixture was dry impact milled
for 50 hours at 185 r.p.m. in a stirred attritor mill of 3.8 litres
capacity using 6 mm. nickel balls at a ball:powder ratio of 18:1.
The composite powder was sieved through a 0.35 mm. mesh screen and
vacuum packed and welded shut in a mild steel can; heated to
1,093.degree.C; and extruded at a ratio of 15:1 to rectangular
section rod. The rod had ThO.sub.2 particles less than 0.02 micron
in size uniformly dispersed through it, which conferred stiffness
and resistance to sagging in use at elevated temperatures.
Other dispersion-strengthened products that can advantageously be
made include dispersion-strengthened nickel, copper, low alloy
steels, maraging steels, zinc-base alloys, the refractory metals
chromium, niobium, tantalum, molybdenum and tungsten and their
alloys, e.g., with up to 50% of other metal, platinum metal-base
alloys and gold-base alloys. Some examples of these will now be
given.
Dispersion-Strengthened Nickel
EXAMPLE IX
A charge consisting of 1,173 g. of carbonyl nickel powder having an
average particle size of 3 to 5 microns and 27 g. of thoria having
a particle size of 0.005 micron was preblended in a high speed food
blender and then dry impact milled in air at room temmerature for
24 hours. The mill contained 3.8 litres of carbonyl nickel balls of
average diameter 6.2 mm., the ball-to-powder ratio being 18:1 by
volume, and was operated at an agitator speed of 176 r.p.m., which
served to maintain substantially all the balls in a highly active
state of mutual collision in which the ratio of the powders to the
dynamic interstitial volume was about 1:18 by volume. The milled
product consisted of composite particles of nickel with thoria
particles very finely and uniformly disseminated through them, and
having saturation hardness of 640 to 650 Vickers. After removal of
the few coarse particles, the powder was placed in a mild steel
extrusion can, degassed under vacuum at 400.degree.C., and then
sealed in the can and extruded to bar at 982.degree.C. at an
extrusion ratio of 16:1. The extruded product consisted of a nickel
matrix with grain size less than 5 microns having a fine, stable,
substantially uniform dispersion of thoria particles less than 0.2
micron and most about 0.02 micron in size.
The properties of the material in the as-extruded condition and
after various amounts of cold swaging are given in the following
table:
TABLE VIII ______________________________________ Test Hot Ultimate
Tensile Strength (kg/mm.sup.2) % R.A.
______________________________________ Temp. As-extruded 40% 61%
75% .degree.C. ______________________________________ 760 13.1 --
-- 26.2 982 7.4 11.5 15.4 18.5 1093 5.3 -- -- 14.7
______________________________________ R.A. = Reduction in area
It will be observed that this very satisfactory structure in the
extruded material, and the associated high level of properties,
were obtained from the composite powder of the invention with an
extrusion ratio of only 16:1.
EXAMPLE X
Batches of composite nickel-thoria powder were prepared by dry
impact milling charges of 777.4 g. of carbonyl nickel powder and
22.6 g. of thoria, particle size 100-500 Angstroms, preblended in a
high speed blender, for 24 hours in air at room temperature in the
attritor mill of Example IX, using carbonyl nickel balls of average
diameter 4.5 mm. at a ball-to-powder ratio of 26:1. The agitator
speed was 176 r.p.m. After combining several batches of the product
powder and removal of particles too large to pass a 0.35 mm. mesh
screen, 2,500 g. of the composite powder were sealed in an 8.9 cm.
diameter mild steel can and extruded to 2.2 cm. diameter bar at
982.degree.C. Stress rupture tests at 1,093.degree.C. on specimens
of the bar that had been further cold swaged to 75% reduction in
area gave the following results:
TABLE IX ______________________________________ Stress Life
Elongation (kgf/mm.sup.2) (hours) (%)
______________________________________ 9.14 4.3 -- 8.44 12.5 2.5
7.74 120.1 5.0 ______________________________________
EXAMPLE XI
The strength of a 90% tantalum -- 10% tungsten alloy is increased
by the incorporation of thoria. A mixture of 2,160 g. tantalum and
240 g. tungsten, particle size from 3 to 40 microns, with 28 g. of
0.02 micron ThO.sub.2 (about 2% by volume) was preblended and then
dry impact milled in a nitrogen atmosphere for 40-50 hours at 176
r.p.m., using 1 cm diameter hardened steel shot at a ball:powder
ratio of 2:1 in an attritor mill as described in Example IX. After
48 hours the powder product had reached saturation hardness. After
screening out particles larger than 0.35 mm, the composite powder
was placed in an 8.9 cm. diameter molybdenum can, which was
evacuated, sealed and extruded to 2 cm. diameter at 1,315.degree.C.
The dispersion of thoria in the resulting wrought bar was highly
uniform both longitudinally and transversely.
EXAMPLE XII
In producing dispersion-strengthened niobium, 1,100 g. of 10-50
micron Nb powder was preblended with 26 g. of 0.04 micron thoria
powder, and dry attritor milled in a nitrogen atmosphere at 176
r.p.m. for 48 hours using 6 mm. tool steel balls at a ball:powder
ratio of 18:1. After sieving through a 0.35 mm. screen, the
composite powder was charged into an 8.9 cm. molybdenum can which
was evacuated, sealed, heated to 1,482.degree.C. in hydrogen, and
extruded into 2.5 cm. bar at 1,482.degree.C.
EXAMPLE XIII
Dispersion-hardened tungsten was produced by milling a charge of
2,500 g. of W powder with 27 g. ThO.sub.2 (2% by volume) as in the
preceding example, to give a composite powder which was screened
and extruded in an 8.9 cm. evacuated Mo can, after heating to
1,925.degree.C. in hydrogen, to bar 2.5 cm. in diameter.
Dispersion-Strengthened Low-Alloy Steels
Dispersion-strengthening of low-alloy steels, particularly those
containing molybdenum or vanadium, with or without chromium, having
for example, the composition set out in the following Table,
enables low alloy steels having improved high temperature tensile
and creep strength to be produced.
Low alloy steels which may be produced in accordance with the
invention include steels containing up to 0.8% carbon, at least
0.25% of one or both of Cr up to 5% and Mo up to 5%, from 0 to 2%
V, from 0 to 2% W, from 0 to 5% Ni, from 0 to 2% Si, and from 0 to
2% Mn. Examples of such steels are given in the following Table
X:
TABLE X ______________________________________ Alloy Steel Nominal
Composition By Weight No. % C % Cr % Mo % Fe % Others
______________________________________ 1 0.08 5 0.5 bal. 0.5 Ti 2
0.12 5 0.5 bal. 1.2 Si 3 0.15 -- 0.5 bal. -- 4 0.17 0.5 0.5 bal. --
5 0.12 1 0.5 bal. -- 6 0.13 0.6 0.01 bal. 0.65 Mn 0.018 P 7 0.08
1.25 0.5 bal. 0.06 Zr 8 0.13 2 1.0 bal. -- 9 0.12 2.25 0.5 bal. --
10 0.4 2 0.35 bal. -- 11 0.4 1 -- bal. 0.25 V
______________________________________
EXAMPLE XIV
In producing a dispersion-strengthened low alloy steel containing
2% Cr, 1% Mo and 0.4% C, a brittle master alloy containing 30% Cr,
15% Mo, 5% C, balance Fe was ground to pass a 74 micron screen, and
80 g. were preblended with 1,120 g. of 65 micron sponge iron. This
mixture was dry milled with 30 g. of 0.02 micron ThO.sub.2 as in
the preceding Example. After screening through a 0.35 mm. screen,
the composite powder was placed in an 8.9 cm. mild steel can which
was heated to 400.degree.C., evacuated, quenched under vacuum,
sealed and extruded at 982.degree.C. to 2 cm. diameter rod.
Dispersion-Strengthened Maraging Steel
The recently developed maraging steels, i.e., steels that are
age-hardenable in the martensitic state and have compositions
broadly within the range Ni 10-30%, Ti 0.2-9% and Al up to 5%, such
that (Ti + Al) does not exceed 9%, Co up to 25%, Mo up to 10%, Fe
balance (at least 50%) would benefit from dispersion strengthening.
The rather sluggish diffusivity of molybdenum and other materials
in powder mixtures may be countered by the use of composite powders
in the present invention. Incorporation of a dispersoid in the
powder enables a dispersion-strengthened product to be made by hot
extrusion that has improved strength properties in the range
480-650.degree.C.
Dispersion-Strengthened Zinc-Base Metals
Wrought zinc and zinc alloys, containing, for example, 50% or more
zinc, can be dispersion-strengthened in accordance with the
invention, thus increasing their resistance to creep. Examples of
such alloys include: Pb 0.15-0.35%, Cd 0.15-30%, Zn bal.; Pb
0.005-0.1%, Cu 0.5-1.5%, Ti 0.12-1.5%, Zn bal.; Mg up to 0.025%, Al
0.25-0.6%, Zn bal.; Cu up to 3.5%, Mg 0.02-0.1%, Al 3.5-4.5%, Zn
bal.
EXAMPLE XV
In producing dispersion-strengthened zinc, 1,500 g. of Zn powder
that passes a 150 micron screen was preblended with 25 g. of 0.02
micron gamma alumina and dry impact milled for 50 hours at 180
r.p.m. using a 20:1 ball: powder ratio of hardened steel balls.
After sieving to remove coarse particles larger than 0.35 mm., the
composite powder was cold-pressed to a 6.3 cm. diameter cylinder,
which was sintered for 3 hours at 315.degree.C. in very dry
hydrogen. The sintered billet was machined smooth and consolidated
by extrusion at 177.degree.C. to a 1.6 cm. diameter rod that had a
highly uniform dispersion of Al.sub.2 O.sub.3 particles in both the
longitudinal and transverse directions and was substantially free
from stringers.
Dispersion-Strengthened Platinum Group Metals and Alloys
Dispersion-strengthening of platinum-base metals is particularly
desirable to improve their strength at elevated temperatures, and
alloys that can advantageously be strengthened include Pt with up
to 50% Pd; Pt with 3.5-40% Rh; Pt with up to 35% Ir; Pt with up to
8% W. Examples of dispersion-strengthened Pt-base metals that can
be produced as wrought shapes in accordance with the invention are:
Pt with 2 vol. % of 0.02 micron ThO.sub.2 ; Pt 75%-Rh 25% with 3
vol. % of 0.04 micron yttria; Pt 92%-W 8% with 5 vol.% of 1 micron
Ti carbide; Pt 90%-Pd 10% with 2 vol.% of 0.1 micron ZrO.sub.2.
Dispersion-Strengthened Gold-Base Metals
Gold is quite soft and has low resistance to creep. It can be
hardened by addition of alloying elements, and this method of
hardening can be replaced or supplemented by dispersion-hardening
in accordance with the invention. Gold-based metals that can be
advantageously so hardened include gold alloys, e.g., Au 54-60%, Pt
14-18%, Pd 1-8%, Ag 7-11%, Cu 7-13%, Ni 1% max., Zn 1% max; Au
62-64%, Pt 7-13%, Pd 6% max., Ag 9-16%, Cu 7-14%, Zn 2% max., and
Au 70%-Pt 30%. Volume loadings of up to 10% or more of dispersoids
such as thoria, yttria, alumina and refractory carbides can readily
be produced in wrought gold-base metals.
Dispersion-Strengthened Copper
An example of the dispersion-strengthening of copper to improve its
resistance to creep at elevated temperatures while maintaining high
electrical and thermal conductivity is as follows:
EXAMPLE XVI
A charge of 1,173 g. of 7-10 micron Fisher sub-sieve size Cu powder
and 27 g. of 0.03 micron alumina was dry milled for 30 hours at 176
r.p.m. in the stirred attritor mill of FIG. 1, using 6.5 mm.
hardened steel balls, the ball:powder ratio being 18:1. The
composite powder (after screening) was compacted and sintered in
hydrogen at 850.degree.C. for 1 hour, then vacuum welded into a Cu
can and hot extruded at a ratio of 18:1 at 800.degree.C. to produce
a wrought Cu product substantially free from stringers. The product
after reduction to wire had high electrical and thermal
conductivities together with strength at both ambient and elevated
temperatures substantially above that of pure copper.
Sintered Refractory-Metal Compositions
Sintered refractory-metal materials, such as sintered refractory
carbides, otherwise known as cemented carbides, which are widely
used for cutting or abrasion-resistant tools, oil drilling bits and
dies, consist of 24 percent or more by volume of finely divided
particles of the hard refractory compound and embedded in a matrix
of iron, nickel, cobalt or other ductile metal to form a body of
high hardness and compressive strength. Conventionally, the
sintered body is formed by compacting a mixture of the refractory
compound, e.g., tungsten carbide, and the matrix-forming bonding
metal, in the form of finely-divided powders, and heating the
compact in vacuum or dry hydrogen to bring about liquid phase
sintering.
The preferred binder metal is cobalt, since this dissolves only
about 1 % tungsten carbide at ambient temperatures and therefore
provides a tough matrix. Iron and nickel dissolve more tungsten
carbide and thus form less ductile matrices.
The mixture of tungsten carbide, cobalt, and an organic wax binder
is made by milling the powder for 60 hours or more in a protective
fluid, such as hexane, containing stainless steel balls. During the
milling, part of the cobalt powder is smeared onto the surface of
the carbide particles as a very thin coating.
The microstructure of the compounds, in particular the size of the
carbide particles in the matrix; their distribution; and the
porosity and the quality of the bond between the binder metal and
the carbide particles, are factors which affect the hardness and
strength of the sintered product. The average particle size of
refractory carbides in the sintered product is limited by that of
the starting materials, which is generally from 2 to 10
microns.
This difficulty is overcome, and an extremely finely dispersed
structure of very fine particles of carbide or other refractory
compound is obtained, if the carbide is incorporated into composite
particles inter-dispersed with the binder metal by dry impact
milling in accordance with U.S. application No. 709,700. These
particles are to be distinguished from those resulting from the
conventional blending operation, in which the binder metal is
smeared onto the hard particles as a coating. According to the
invention, sintered refractory compound materials are made by
compacting and sintering composite particles containing finely
divided and inter-dispersed constituents in which the distance
between the constituent sub-particles is advantageously less than
10 microns and preferably less than 2 microns, or even 1 micron.
This may be done in various ways. A body of powder can be
consolidated by hot pressing at an elevated temperature high enough
for sintering to occur; it can be first hot-compacted or
cold-compacted and sintered under non-oxidising conditions; or the
mixture may be extruded in a can, e.g., of steel, and the whole
extruded at a temperature high enough for sintering to occur during
extrusion. The wrought products produced in any of these ways have
a high degree of dispersion uniformity of the hard phase in the
matrix.
The refractory compound, which comprises 30 percent or more by
volume of the composition, may be a carbide, boride or nitride, of
titanium, zirconium, hafnium, chromium, tungsten, molybdenum,
vanadium, columbium, tantalum; silicon carbide, or an oxide of
aluminium, beryllium, a rare earth metal, e.g., cerium, lanthanum,
or yttrium, magnesium, zirconium, titanium, and thorium.
Intermetallic compounds such as aluminides, beryllides or silicides
may be used under conditions in which they retain their
identity.
The matrix-forming binding metal may comprise at least one metal
from the following groups:
a. the iron group metals iron, nickel, cobalt; alloys of these
metals with each other; and alloys of at least one iron group metal
with at least one of the metals chromium, molybdenum, tungsten,
niobium, tantalum, vanadium, titanium, zirconium and hafnium.
b. a metal or alloy of the group silver, copper, and a ductile
metal of the platinum group (e.g., platinum, palladium, rhodium or
ruthenium).
c. aluminium, zinc, lead or alloys thereof.
The matrix-forming binding metals of group b are particularly
useful in the production of wear resistant electrical contact
elements.
The binder alloys of group a include the well known superalloy
compositions capable of being age-hardened at temperatures of about
600.degree. to 1,000.degree.C. These resist softening under
conditions where the cutting tool is used at relatively high
cutting speeds which tend to overheat the cutting edge of the tool.
Examples of age-hardenable superalloy compositions are those
falling within the following range by weight: 4% to 65% chromium,
at least 1% in sum of an age hardening element selected from the
group consisting of up to 15% aluminum and up to 25% titanium, up
to 40% molybdenum, up to 20% niobium, up to 40% tungsten, up to 30%
tantalum, up to 2% vanadium, up to 15% manganese, up to 2% carbon,
up to 1% silicon, up to 1% boron, up to 2% zirconium, up to 4%
hafnium and up to 0.5% magnesium, the balance essentially at least
one element from the group consisting of iron, nickel and cobalt
with the sum of these being present in an amount of at least about
25%.
Examples of compositions are as follows:
Co 15-25% with up to 3 wt. percent (TaC + TiC), balance WC;
Co 25-45% with up to 2 wt. percent (TaC + TiC), balance WC;
Co 15-25% with 10-22 wt. percent TiC, balance WC;
Co 15-25% with 18-30% TaC, balance WC;
Ni-Mo alloy 15-50%, TiC 85-50%
The Ni-Mo matrix alloy in the last composition may contain 25-70%,
advantageously 35-60% molybdenum, balance nickel.
The compositions alsoo include the recently-developed heat
resisting metal carbide compositions for high temperature
applications, known as cermets, for example, from 85 to 24 volume
percent, and preferably at least 60 percent, of carbides of
titanium and chromium with the balance nickel or nickel-base alloy
as the binder metal. The carbide phase generally consists
predominantly of TiC with up to 25 percent of Cr carbide.
Some examples will now be given:
EXAMPLE XVII
A powder mixture of 25% of 5-7 micron Co and 75% of 3-5 micron WC
by weight (63 percent WC by volume) is dry impact milled in a
stirred attritor mill of the type shown in FIG. 1 at 185 r.p.m.,
using hardened steel balls at a ball:powder ratio of 25:1 for 50
hours to form a wrought composite powder consisting of particles
having WC particles homogeneously inter-dispersed in a Co matrix.
The WC particles were reduced in size to less than 1 micron. The
powder was consolidated by hot pressing in a graphite die at
1,350.degree.C. for 3 minutes using 35 kg/cm.sup.2 pressure.
EXAMPLE XVIII
To produce a heat- and oxidation-resistant TiC/Ni 80-Cr 20 alloy
cermet composition, a mixture of 1,240 g. of 5-7 microns TiC
particles, 448 g. of 4-8 micron carbonyl Ni and 112 g. of Cr powder
smaller than 75 microns was dry impact milled in a stirred attritor
mill of the type shown in FIG. 1 at 180 r.p.m. for 50 hours, using
6 mm. hardened steel balls at a ball:powder ratio of 20:1 to
produce a wrought composite powder in which the particles comprised
uniformly inter-dispersed Ni, Cr and TiC.
EXAMPLE XIX
This is an example of the production of a sintered electric contact
material containing 50% Ag and 50% WC, by weight, (40% WC by
volume).
A composite powder was made by dry milling 1,000 g. of Ag of
particle size below 75 microns and 1,000 g. of 5-7 microns WC
powder, using an attritor mill containing hardened steel balls at a
ball:powder ratio of 18:1, and operating at 185 r.p.m. for 45
hours. The WC particles were reduced by the milling to less than 1
micron in size. The powder is then screened to remove particles
coarser than 100 microns and then hot pressed into shapes for
electrical contacts in a graphite die by exerting a pressure of 35
kg/cm.sup.2 for three minutes at a temperature slightly above the
melting point of silver, e.g., at 980.degree.C.
An example of another composition that can be made by similar
techniques is a titanium carbide composition (79 vol.%, 65 wt.%
TiC) containing 35% by weight of a 50-50 nickel-molybdenum alloy as
binder.
Metal Systems of Limited Solubility
Metal systems comprising two or more metal constituents having
limited mutual solubility in the liquid and/or the solid state,
i.e., that are immiscible or only partly miscible, tend to
segregate or separate on solidification if it is attempted to make
them by melting. Infiltration of one molten metal into a solid
skeleton of the other, e.g., copper into iron, or compacting
mixtures of the respective powders followed by liquid phase
sintering, also lead to non-uniform segregated microstructures,
subject to the limitations imposed by the particle sizes of the
powders employed.
Consolidated metal products of these systems can readily be made
from appropriate composite powders by the invention, with a highly
refined internal structure substantially free from segregation,
lakes, pools or dendritic coring.
Examples of binary systems of limited solubility include:
lead-copper, copper-iron, copper-tungsten, silver-tungsten,
copper-chromium, silver-chromium, copper-molybdenum,
silver-molybdenum, silver-manganese, silver-nickel, platinum-gold,
beryllium-molybdenum, and silver-platinum. The invention is also
applicable to limited solubility metal systems containing three or
more elements, e.g., copper-nickel-chromium.
Examples of composition ranges that may be produced are: Cu with
1-95% Pb; Fe with 1-95% Cu; W with 5-95% Cu; W with 2-98% Ag; and
Cu with 5-95% Cr.
EXAMPLE XX
This is an example of the production of a composite iron-copper
powder containing Fe 80%, Cu 20 %.
Hydrogen-reduced copper, particle size less than 45 microns, and
sponge iron, particle size less than 150 microns, were dry impact
milled in air in a 50 c.c. capacity high speed shaker mill operated
at 1,200 cycles per minute, which produced composite metal
particles in a very short period of time compared with the attritor
mill of FIG. 1. The mill was charged with 10 g. of powder and 45 g.
of 6.2 mm. nickle balls to give a ball-to-powder ratio of 4.5:1 and
a ratio of dynamic interstitial volume to powder volume of
41:1.
Milling for 30 minutes produced composite particles of hardness of
353 Vickers and average size 135 microns, with a fine, uniform
striated structure, the average spacing between striations being
about 1 micron.
Consolidation by compacting in a steel tube which was vacuum
sealed, followed by hot forging at 982.degree.C. to full density
gave a highly uniform wrought product.
EXAMPLE XXI
This is an example of the production of a limited-solubility 50%
copper -- 50% lead product.
Equal volumes of lead filings and hydrogen-reduced copper, particle
size less than 45 microns, were milled in the shaker mill of the
preceding example at a ball-to-powder ratio of 4:1. After 10
minutes the product particles had a hardness of 34.6 Vickers and a
particle size of 100-200 microns and, after 30 minutes, 69.5
Vickers and 100-150 microns. In each case the individual composite
particles contained the two elements substantially uniformly
inter-dispersed, the particle spacing being about 5 microns after
10 minutes and about 1 micron after 30 minutes. The structure did
not exhibit striations. This is believed to be due to the fact that
lead, which has a melting point of about 600.degree.K, is
self-annealing when worked at ambient temperatures.
Because of the large amount of lead present, the composite powder
can be cold deformed, e.g., by cold extrusion or cold pressing in a
die, into any desired shape, for example, an anti-friction bearing
element.
By a similar technique, highly uniform wrought products of the
components 50% Ag-50% W for electrical contact materials; 25%-50%
Cu/75%-50% W; 80% Au-20% Pb; 50%-95% Pt/50-5% Ag; and 50-95%
Pb/50-5% Au may be obtained. In a like manner, compositions within
the liquid immiscibility range of 6-63% Cu in the Cu-Cr system,
e.g., Cu 70%-Cr 30%; within the immiscibility range of the Cu-Mo
system, e.g., from 2-98% Cu, balance Mo can be produced,
Silver-nickel compositions suitable for electric contact
applications, including Ag 60%-Ni 40%, may be produced, as may
beryllium-molybdenum compositions including Be 50%-Mo 50%.
Beryllium powder may have a thin oxide coating because of its
propensity to surface oxidation. This oxide may be used to provide
dispersion-strengthening in the final product.
Dispersion-Strengthened Stainless Steel
Stainless steel alloys are particularly prone to segregation when
cast into ingots, making the ingots difficult to forge. Thus, the
rather slow solidification of large ingots leads to the formation
of large dendrites, large, non-uniformly distributed grains, and
composition segregates along the length and across the width of the
ingots. Prolonged soaking at high temperatures in an attempt to
homogenize the metallurgical structure of the ingot generally
effects little improvement, and may even cause further grain
coarsening, with further adverse effects on hot forgeability,
extrusion, or rolling. This tendency to segregation also leads to
non-uniform precipitation-hardening response in steels containing
hardening constituents. The production of stainless steel by
conventional techniques of power metallurgy suffers from the
disadvantages already discussed in general above, particularly that
of oxidation of the more reactive alloying elements, e.g.,
chromium, and such precipitation hardeners as aluminium and
titanium during processing, and, in the case of dispersion-hardened
compositions, the formation of stringers.
One advantageous class of products of the present invention is that
comprising wrought dispersion strengthened stainless steels
characterized by a high degree of uniformity of composition and, in
the case of precipitation-hardening compositions, hardening
response, together with freedom from segregation and stringers.
This is readily achieved by the use of composite particles of the
corresponding composition produced by high energy impact milling to
saturation hardness and beyond as described hereinbefore, according
to U.S. application No. 790,700, since these composite particles
are both statistically and internally substantially uniform.
Stainless steels which can be produced in accordance with the
invention may have compositions ranging, by weight, from 4% to 30%
chromium, from 0 to 35% nickel, up to 10% manganese, and up to 1.0%
carbon, together with from 0.5% to 25%, e.g., 0.05% to 10%, by
volume of a dispersoid of a refractory compound, the balance, apart
from inpurities and incidental ingredients, being iron in an amount
of at least 45%. It will be understood that here, as elsewhere in
the specification, the percentages of the constituents other than
the dispersoid, refer to the composition of the alloy matrix.
More preferably, the steels contain from 8% to 30% chromium, up to
20% nickel, up to 5% manganese and up to 0.25% and more preferably,
up to 0.15% carbon together with from 0.05% to 10% by volume of a
dispersoid of a refractory compound and the iron content is at
least 55%.
As will be appreciated, the stainless steel compositions may
contain other alloying additions, e.g., up to 5% silicon, up to 5%
molybdenum, up to 8% tungsten, up to 2% aluminium, up to 2%
titanium, up to 2% niobium/tantalum, up to 7% copper.
Precipitation-hardenable stainless steels include those containing
at least 0.2% by weight of one or more of aluminium up to 2%,
titanium up to 2%, niobium up to 2% and copper up to 7%. These
steels may also contain up to 0.4% phosphorous and up to 0.3%
nitrogen. Preferred amounts of dispersoid range from about 0.05 to
5 volume per cent at sizes below one micron.
Impurities and incidental ingredients that may be present include
some sulphur and/or selenium for free machining, etc.
Examples of the types of stainless steel that can be produced in
accordance with the invention are given in the XI. Table Xi.
TABLE XI
__________________________________________________________________________
AISI Nominal Composition Type % C % Mn % Si % Cr % Ni Others 1
Austenitic Steels
__________________________________________________________________________
201 0.15 max 5.50-7.50 1.0 max 16-18 3.5-5.5 0.25N max 202 0.15 max
7.5 - 10 1.0 max 17-19 4-6 0.25N max 301 0.15 max 2.0 max 1.0 max
16-18 6 - 8 -- 302 0.15 max 2.0 max 1.0 max 17-19 8 - 10 -- 303
0.15 max 2.0 max 1.0 max 17-19 8 - 10 0.15 min S 308 0.08 max 2.0
max 1.0 max 19-21 10 - 12 -- 309 0.20 max 2.0 max 1.0 max 22-24 12
- 15 -- 314 0.25 max 2.0 max 2.0-3.0 23-26 19 - 22 -- 316 0.08 max
2.0 max 1.0 max 16-18 10 - 14 2.0-3.0 Mo 321 0.08 max 2.0 max 1.0
max 17-19 9 - 12 5.times.C min Ti 347 0.08 max 2.0 max 1.0 max
17-19 9 - 13 10.times.C min
__________________________________________________________________________
Nb/Ta MARTENSITIC STEEL
__________________________________________________________________________
403 0.15 max 1.0 max 0.5 max 11.5-13 -- -- 414 0.15 max 1.0 max 1.0
max 11.5-13.5 1.25-2.5 -- 431 0.20 max 1.0 max 1.0 max 15-17
1.25-2.5 -- 440B 0.75-0.95 1.0 max 1.0 max 16-18 -- 0.75 Mo max
440C 0.95-1.2 1.0 max 1.0 max 16-18 -- 0.75 Mo max 501 0.1 max 1.0
max 1.0 max 4-6 -- 0.04-0.65 Mo
__________________________________________________________________________
Nominal Composition
__________________________________________________________________________
405 0.08 max 1.0 max 1.0 max 11.5-14.5 -- 0.1-0.3 Al 430 0.12 max
1.0 max 1.0 max 14-18 -- -- 430F 0.12 max 1.25 max 1.0 max 14-18 --
0.15 S min 446 0.2 max 1.5 max 1.0 max 23-27 -- 0.25 N max
__________________________________________________________________________
Nonstandard Grades
__________________________________________________________________________
AISI Type % C % Mn % Si % Cr % Ni Others
__________________________________________________________________________
316 F O.6 1.5 0.5 18 13 2.25 Mo 0.13P, 0.15S 418 1.17 0.4 0.3 12.75
2.0 3.0 W Stain- less W 0.07 0.5 0.5 16.75 6.75 0.8 Ti 0.2 Al 17-4
PH 0.04 0.4 0.5 16.50 4.25 0.25 Nb 3.6 Cu 17-7PH 0.07 0.7 0.4 17.0
7.0 1.15 Al PH 15-7 0.07 0.7 0.4 15.0 7.0 1.15 Al Mo 2.25 Mo 17-10P
1.12 0.75 0.5 17.0 10.5 0.28 P
__________________________________________________________________________
To produce the wrought, dispersion-strengthened stainless steel
product, a batch of the wrought, composite, mechanically alloyed,
dense metal particles of the appropriate composition and preferably
having an average size such that the surface area per unit volume
of particles is not more than 6,000 cm.sup.2 /cm.sup.3 of
particles, i.e., substantially free from particles smaller than 5
microns is hot-consolidated to a wrought metal shape. This may
conveniently be effected by hot extrusion of the powder sealed in a
metal can, e.g., of mild steel.
Annealing of the heavily cold-worked powder takes place during
heating in the can to the extrusion temperature.
Two examples of the production of stainless steels will now be
given:
EXAMPLE XXII
A mixture comprising, by weight, 27.2% of powdered low-carbon
ferrochrome, particle size 44-74 microns, containing Cr 70%, Si
1.01%, SiO.sub.2 1.35%, Cr.sub.2 O.sub.3 0.54%, Fe balance; 62.8%
of high purity sponge iron powder, particle size less than 150
microns; and 10% of carbonyl nickel powder, average particle size
3-5 microns, was milled in a stirred attritor mill of the type
shown in FIG. 1 operated at 176 r.p.m. at a ball-to-powder ratio of
24:1 in two batches, the first for 16 hours and the second for 48
hours. Each product consisted of composite particles of average
size 125-135 microns, the particles milled for 48 hours having a
much finer and more homogeneous microstructure. The hardness of the
power as-produced and after various heat-treatments is shown in
Table V, which shows that the hardness of the 48-hour powder was
retained to a greater extent on heating.
TABLE XII ______________________________________ Milled 16 hours
Milled 48 hours ______________________________________
Heat-treatment Hardness (Vickers)
______________________________________ As milled 785 794 30
mins./982.degree.C. 381 523 30 mins./1066.degree.C. 324 409 1
hour/1204.degree.C. -- 200-220
______________________________________
After heating for 30 minutes at 1,066.degree.C. the internal
structure of the 48-hour particles was homogeneous, and compacting
at 56.2 kg/mm.sup.2 gave a compact having density of 74% of the
true density and a green strength of 76.2 kg/cm.sup.2. The initial
hardness of the particles was remarkably high compared with the
hardness of 233 Vickers of a commercial atomised stainless steel
powder.
EXAMPLE XXIII
Another stainless steel composition was produced by dry milling a
mix containing 84 g. of carbonyl nickel powder of an average
particle size 3-5 microns, 341 g. of high purity ferrochrome powder
(0.1% SiO.sub.2, 70% Cr, balance Fe), average particle size 120
microns and 763 g. of high purity sponge iron powder (0.032%
carbon, 0.115% silica) of particle size less than 150 microns for
40 hours in air in an attritor mill, run at 176 r.p.m. with a
ball-to-powder ratio of 18:1 by volume. The resulting composite
particles had an average particle size of 85 microns. Extrusion of
the product, vacuum-sealed in a mild steel can, to rod at an
extrusion ratio of 12.5:1 at 1,038.degree.C., gave a product
analysing Ni 9%, soluble Cr 20%, Si 0.09%, Cr.sub.2 O.sub.3 2.15%,
Fe balance, which contained a finely divided grayish dispersoid
uniformly distributed therein. The dispersoid is believed to have
been chromium oxide. At room temperature, the material exhibited a
tensile strength of 137.5 kg/mm.sup.2, a yield strength (0.2%
offset) of 121.0 kg/mm.sup.2, an elongation of 7.5%, a reduction in
area of 29% and a modulus of elasticity of 18.8 .times. 10.sup.3
kg/mm.sup.2. The material had a Vickers hardness of 421 and was
very slightly ferromagnetic.
After heating for 90 hours at 1,093.degree.C. it was non-magnetic
and had a Vickers hardness of 390, and at 650.degree.C. it had a
stress-rupture life of 44.9 hours with 2.5% elongation under a
stress of 24.6 kg/mm.sup.2. At 816.degree.C. and 7 kg/mm.sup.2 load
sample was unbroken after 70 hours.
The properties clearly demonstrated this material was
dispersion-strengthened.
EXAMPLE XXIV
In producing a dispersion-strengthened, precipitation hardenable,
wrought stainless steel product of the 17-7 PH type containing, by
weight, 0.07% C, 0.7% Mn, 0.4% Si, 17% Cr, 7% Ni, 1.15% Al, and
2.5% zirconia, the balance, apart from impurities, being Fe, the
following starting materials are employed: (a) low carbon
ferrochrome containing about 70% chromium and some silicon of
particle size 44-75 microns; (b) high purity sponge iron of
particle size less than 150 microns; (c) carbonyl nickel powder of
about 3 to 5 microns average size; (d) ferroaluminium containing
about 65% aluminium and zirconia of about 400 Angstroms average
size. A 900 gram batch proportioned to yield the foregoing
composition is placed in the attritor mill as described
hereinbefore and dry impact milled in a nitrogen atmosphere for 48
hours at 176 r.p.m. using a 3.8 litre volume of nickel pellets in
size at a ball-to-powder ratio of 24:1. After the 48-hour milling
the composite particles were of optimum uniformity, and were of
about 100 microns average particle size.
After removal from the mill, and passing through a 177 micron
screen, the poweder was vacuum sealed by welding in a mild steel
can. The canned powder was then heated for 1.5 hours to
1,038.degree.C., and extruded to rod at an extrusion ratio of 16:1,
the extruded material having approximately the nominal composition
of 17-7 PH stainless, except for the presence of a highly uniform
dispersion of finely divided zirconia (about 400 Angstroms in
average size). The extruded rod is solution annealed at
1,200.degree.C., reheated at about 760.degree.C. for 11/2 hours,
air cooled and again reheated at 565.degree.C. for 11/2 hours and
cooled. Thus, the steel is strengthened using the two-fold effect
of dispersion-strengthening and precipitation hardening.
A special group of two-phase stainless steels is now known which
are compositionally adjusted to provide a micro-structure
containing ferrite and either martensite or austenite. These steels
contain 2%, preferably 4.5% to 8% or 12% nickel, 18%, preferably
23% to 28% or even 35%, chromium, up to 1.5% titanium, up to 1%
vanadium, balance essentialy iron. It is found that powder mixtures
of powders proportioned to yield such steels milled to saturation
hardness and beyond in a high energy impact mill, e.g., an
attritor, exhibit exceptionally fine two-phase structures when hot
consolidated by extrusion or hot forging of the canned powders at
temperatures in the range of e.g., 1,700.degree.F. to
2,000.degree.F. Such fine-structured or microduplex structural
consolidated materials exhibit superplasticity at elevated
temperatures.
High Carbon Tool Steels
High carbon tool steels are particularly prone to segrgation during
solidification of the ingot when made by melting methods, with the
formation of large dendrites and of segregates or aggregates of
carbide. The carbides are brittle and adversely affect the
ductility of the ingot, but the segregates or aggregates may, with
difficulty, be dispersed to a limited extent by mechanical working
of the ingot. Even so, the carbide tends to be distributed in the
forged or hot-worked product as elongated stringers in the
driection of working, with areas between them impoverished in
carbides.
It is also difficult to obtain good composition homogeneity by
solid state diffusion at elevated temperatures when powder
metallurgy methods are used, since such alloying ingredients as
chromium, tungsten, and molybdenum diffuse only sluggishly in the
powder condition.
The use of a composite powder produced by dry high energy milling
of starting powder mixtures proportioned to provide a high carbon
tool steel composition as the starting material for the powder
metallurgical production of high speed tool steels enables the
production of wrought high carbon tool steel characterized by a
substantially uniform dispersion of finely divided carbides; and
substantial freedom from carbide segregates and aggregates. The
degree of uniformity of the structure depends on the uniformity,
bot statistical and internal, of the composite particles. The
increased rate of diffusion and alloying resulting from the high
degree of cold work in the composite particles is particularly
advantageous in overcoming the sluggish diffusion tendencies of the
alloying elements.
Broadly speaking, the tool steels of the invention contain from
0.7% to 4%, e.g., 0.9 to 3.5 %, carbon, and at least 0.1%,
advantageously at least 1%, of at least one of the alloying
elements chromium, vanadium, tugsten and molybdenum, up to 2%
silicon, up to 2% manganese, up to 5% nickel and up to 15% cobalt,
the balance (at least 40%), apart from impurities being iron.
The alloying elements may advantageously be present in the ranges
3% to 15% chromium, up to 10% or 20% vanadium, up to 25% tungsten
and up to 12% molybdenum. A particularly useful CR-V-W tool steel
composition is one containing Cr 3 to 9%, V 0.3 to 10%, W 1 to 25%,
Mo 0 to 10%, Fe balance. A particular advantage of the invention is
that carbide formers such as tantaluum, niobium, hafnium, zirconium
and titanium can be added in amounts up to 15% and well distributed
in the form of carbides in the resulting tool steel composition.
Examples of specific alloys that may be made are give in the
following table XIII, the balance of each composition being
iron.
TABLE XIII
__________________________________________________________________________
Nominal Composition % by Weight Type Steel C Mn Si Cr Ni V W Mo Co
__________________________________________________________________________
Chromium 0.85-1.0 0.6-0.8 0.1-0.4 0.15-0.3 -- -- -- -- --
__________________________________________________________________________
Chromium- Molybdenum 0.9-1.25 0.3-0.7 0.1-0.4 1.1-1.5 ' -- --
0.3-0.5 --
__________________________________________________________________________
2 Tungsten- Finishing Steel 1.25-1.40 0.1-0.4 0.1-0.5 0.2-0.4 -- --
3.25-4.0 0.2-0.4 --
__________________________________________________________________________
Semihigh Speed 1.15-1.25 0.1-0.4 0.1-0.4 3.75-4.25 -- 3-3.3 --
4.0-4.5 -- Steels 1.35-1.45 0.1-0.4 0.1-0.4 3.75-4.25 -- 3.9-4.4 --
4.0-4.5 -- 1.05-1.15 0.1-0.4 0.1-0.4 3.75-4.25 -- 3.75-4.25 2.3-2.7
2.4-2.8 --
__________________________________________________________________________
Air-Hardening Die Steels 0.9-1.05 0.4-0.85 0.1-0.4 4.75-5.25 --
0.15-0.5 -- 0.9-1.15 --
__________________________________________________________________________
High Carbon, High 1.4-1.6 0.2-0.4 0.1-0.4 11.5-12.5 -- 0.2-1.0 --
0.7-0.9 -- Chromium Die 2.1-2.3 0.2-0.4 0.1-0.4 11.5-12.5 --
0.2-0.8 -- 0.7-0.9 -- Steels 2.0-2.2 0.2-0.4 0.7-1.0 11.5-12.5 --
-- 0.6- 0.9 -- --
__________________________________________________________________________
Wear Resistant 2.15-2.5 0.3-0.8 0.3-0.8 5-5.5 -- 3.75-5.0 0.95-1.3
0.8-1.3 -- Die Steels 2.1-2.3 0.3-0.5 0.1-0.4 3.75-4.25 -- 3.75-5.0
-- -- --
__________________________________________________________________________
Chromium Nickel 0.9-1.1 0.03-0.5 0.1-0.4 0.5-0.8 1.2-1.6 -- -- --
--
__________________________________________________________________________
Tungsten Types 0.8-0.85 0.1-0.4 0.1-0.4 4-4.25 -- 2-2.15 18-18.5
0.5-0.75 -- 0.95-0.98 0.1-0.4 0.1-0.4 4-4.25 -- 2-2.15 18-18.5
0.5-0.75 -- 0.97-1.03 0.1-0.4 0.1-0.4 3.75-4.25 -- 2.8-3.2
13.5-14.5 0.65-0.85 --
__________________________________________________________________________
Tungsten-Cobalt Types 0.7-0.75 0.1-0.4 0.1-0.4 4-4.5 -- 1.0-1.25
18-19 0.6-0.8 4.75-5.25 1.5-1.6 0.1-0.4 0.1-0.4 4.5-4.75 --
4.75-5.0 12.5-13.5 0.4-0.6 4.75-5.25 0.75-0.85 0.1-0.4 0.1-0.4
4.0-4.5 -- 1.6--- 18.75-20.5 0.6-0.8 11.5-12.25
__________________________________________________________________________
Molybdenum Types 0.78-0.85 0.1-0.4 0.1-0.4 3.75-4.0 -- 1-1.25
1.5-1.65 8-9 -- 0.97-1.03 0.1-0.4 0.1-0.4 3.75-4.0 -- 1.9-2.1
1.5-1.75 8.5-8.75 --
__________________________________________________________________________
Molybdenum- Cobalt Types 0.8-0.85 0.1-0.4 0.1-0.4 3.75-4.25 --
1.1-1.4 1.5-1.8 8.25-8.5 4.75-5.25 0.87-0.93 0.1-0.4 0.1-0.4
3.5-4.0 -- 1.85-2.25 1.3-1.6 8.45-8.95 8-8.5
__________________________________________________________________________
Tungsten- Molybdenum Types 1.0-1.1 0.1-0.4 0.1-0.4 4-4.25 --
2.4-2.55 6-6.25 5.7-6.25 -- 1.25-1.3 0.1-0.4 0.1-0.4 4.25-4.5 --
3.75-4.25 5.5-6.0 4.5-4.75 --
__________________________________________________________________________
Tungsten- Molybdenum-Cobalt Types 1.5 1.6 0.1-0.4 0.1-0.4 4.0-4.75
-- 4.75-5.25 6.25-6.75 3.0-5.0 4.75-5.25
__________________________________________________________________________
Self-Hardening -Type 2.25 1.5 0.25 2.0 -- -- 11.0 -- --
__________________________________________________________________________
Special Wear- Resistant Ore Steel 3.25 0.3 0.3 1.0 -- 12.0 -- 1.0
--
__________________________________________________________________________
Besides the dispersion strengthening of the tool steels that
results from the presence of the extremely finely dispersed
carbides, other dispersoids may be incorporated in the composite
powder used to form the steels, and thereby in the steels
themselves, in an amount of 0.05 to 25%, preferably not more than
10%.
In making the steels, composite powder of the desired composition
may be hot consolidated to a wrought metal shape, e.g., by vacuum
packing a charge of the particles into a mild steel can which is
then heated to 425.degree.C. under vacuum, quenched under vacuum,
welded shut, followed by hot extrusion, usually at a temperature of
about 815.degree.C., or more, e.g., 1,038.degree.C. to
1,260.degree.C. Homogenisation and annealing can be accomplished
during the heating of canned powders prior to extrusion.
Some examples of the production of wrought tool steels by the
invention are as follows:
EXAMPLE XXV
In producing a complex high-carbon tool steel containing 20%
tungsten, 12% cobalt, 4% chromium, 2% vanadium, 0.8% carbon,
balance iron, a blend is made of 28.6 g. of 70% V-30% Fe master
alloy of particle size less than 150 microns; 57.2 g. of a 70%
Cr-30% Fe master alloy of particle size less than 150 microns; 200
g. of 10 micron W powder; 120 g. of cobalt powder of particle size
less than 44 microns; 8.0 g. of graphite flakes of particle size
less than 150 microns; and 586.2 g. of 65 micron sponge Fe powder.
This mixture is dry impact milled in an attritor mill of the type
shown in FIG. 1, for 40-50 hours at 180 r.p.m. using 6.2 mm.
hardened steel balls at a ball:powder ratio of 20:1. The composite
powder thus produced had a microstructure comprising a
substantially homogeneous inter-dispersion of all the constituents.
After vacuum-sealing in a mild steel can, the powder was extruded
at 1,175.degree.C. at a ratio of 16:1 to a wrought bar free from
carbide dendrites, segregates and aggregates.
The complex high speed steel product is hardened by heating to a
temperature of 1290.degree.C. for 5-10 mins. followed by oil
quenching to room temperature, the cooled steel being thereafter
subjected to double tempering by heating to a temperature of
565.degree.C. for about 2 hours, air-cooling and re-heating to
565.degree.C. for an additional 2-hour period.
EXAMPLE XXVI
A wrought high carbon steel containing 0.85% C, 0.2% Cr, 0.7% Mn,
0.3% Si, balance iron, was produced as follows. A brittle high
carbon master alloy containing 4.25% C, 1% Cr, 3.5% Mn, 1.5% Si,
balance iron, was chill-cast and crushed to particles smaller than
75 microns. The resulting powder (400 g.) was mixed and uniformly
blended with 1600 g. of 65 micron high purity sponge iron powder,
and the mixture was dry impact milled as in Example XXV using 6.2
mm hardened steel balls at a ball-to-powder ratio of 18:1 and an
agitator speed of 175 r.p.m. for 45 hours to obtain a highly
cold-worked composite metal powder having a substantially
homogenous interdispersion of all of the alloying constituents. The
composite powder was vacuum packed in a mild steel can which was
welded shut, heated to 1095.degree.C. and then hot-extruded to a
round rod at an extrusion ratio of 16:1.This steel, which was free
from carbide segregates and aggregates, was hardened by oil
quenching from an austenitizing temperature of 788.degree.C.,
followed by tempering at a temperature of 177.degree.C.
EXAMPLE XXVII
To make a wrought semi-high speed steel composition having the
composition: 1.2% C, 4% Cr, 3% V, 4% Mo, 0.3% Mn, 0.3% Si, balance
iron, a brittle high-carbon master alloy containing 4.8% C, 16% Cr,
12% V, 12% Mo, 1.2% Mn, 1.2% Si, balance iron, was chill cast and
then crushed to particles smaller than 75 microns. 400 g. of this
powder were mixed with 1200 g. of high purity 65 micron sponge iron
powder and the mixture was dry impact milled as in Example XXV for
48 hours at 175 r.p.m. using 6.3 mm. hardened steel balls at a
ball-to-powder ratio of 18:1 by volume. The highly cold-worked
composite metal powder thus obtained had a microstructure
comprising a substantially homogeneous interdispersion of all of
the alloying constituents and was used to make wrought tool steel
shapes by hot extrusion at 1,095.degree.C. in a mild steel can
which was evacuated and welded shut. Square rod was produced at an
extrusion ratio of 15:1. A tool made from the rod may be heat
treated by quenching from 1,232.degree.C. in oil and then tempering
(secondary hardening) by heating to 538.degree.C. and holding for 1
hour with good response.
EXAMPLE XXVIII
In producing a wrought high-C high-speed steel containing 2.5% C,
4.0% Cr, 2.5% Mo, 5.0% Co, 7.0% V, 6.0% W, balance Fe, a blend was
first made of 112.5 g. of graphite flakes, 432 g. of a 70% V -- 30%
Fe master alloy powder, 180 g. of Cr powder, all smaller than 150
microns, 113 g. of Mo powder and 225 g. of Co powder bulk smaller
than 45 microns, 270 g. of 10 microns W powder and 3191 g. of 65
micron sponge iron powder. This blend was dry impact milled for 15
hours in a horizontal stirred ball mill containing 91 kg. of
hardened steel balls at an impeller speed of 245 r.p.m. in a
nitrogen atmosphere, to give a highly cold-worked composite metal
powder having a microstructure comprising a substantially
homogeneous interdispersion of all the alloying elements.
The powder was vacuum packed in a mild steel can which was welded
shut and extruded to rod at 1,093.degree.C. at an extrusion ratio
of 16:1.The extruded bar had the remarkably high hardness of 62.5
Rc. A tool was made from this bar was hardened by heating slowly to
870.degree.C, then heated to 1205.degree.C, held for 5 minutes and
oil-quenched. After double-tempering by heating twice for 2 hours
at 538.degree.C. and air-cooling, the hardness was as high as 67
Rc.
The structure of this complex high carbon steel was exceptionally
fine and uniform containing less than about 5 percent by volume of
segregated regions exceeding 10 microns in size. The microstructure
of this very high carbon tool steel was strikingly finer and much
less segregated than that of conventional tool steels at much lower
carbon and other alloy contents.
In producing products containing dispersed oxides, the composite
particles employed in the process need not contain the oxide
finally desired. Instead, composite particles may be used
containing constituents that react when subsequently heated to form
refractory oxides or other refractory phases not initially present.
Thus, composite particles may be made having intimately distributed
therethrough metals that form stable refractory oxides, for
example, yttrium, lanthanum, cerium, thorium, chromium, silicon,
aluminum, beryllium or rare earth metal mixtures such as didymium,
together with a less stable oxide of another metal, e.g., nickel
oxide, and other alloying constituents. Alternatively the oxygen
may be added as adsorbed oxygen or gaseous oxygen in the milling
atmosphere which becomes adsorbed and mechanically alloyed with the
solid constituents of the powder mix. Such powders can then be
consolidated and heated to permit oxidation of the metal having the
stable oxide by diffusion of oxygen from the less stable oxide or
metastable mechanically alloyed oxygen. By controlling the
effective interdiffusion distance over which the oxygen would be
required to travel to less than 1 micron and even to less than 0.5
micron, the refractory oxide particles can be produced in a very
fine state of dispersion by heating for only a short time. The
process may advantageously be used to make nickel or
nickel-containing alloys dispersion strengthened with lanthana,
yttria, thoria, etc., from composite particles containing the
corresponding metal and mechanically alloyed oxygen. If more than
one oxidisable metal is present, the process may be controlled by
limiting the oxygen supply to the amount necessary to oxidize only
the metal with the most stable oxide.
The following example illustrates the use of this procedure to make
a nickel alloy dispersion strengthened with alumina.
EXAMPLE XXIX
A mixture of 781 g. of carbonyl nickel powder of particle size 3-5
microns; 44 g. of nickel oxide (Ni0) particle size less than 44
microns; and 75 g. of an 80% Ni -- 20% Al master alloy powder,
particle size less than 44 microns is dry milled in a nitrogen
atmosphere for 48 hours in the mill of Example I at a
ball-to-powder ratio of 22:1 and 176 r.p.m. The composite particles
formed, after removal of a small coarse fraction, are vacuum
sealed, in a mild steel can. The sealed can is then heated at
982.degree.C. for 2 hours to allow the constituents in the
composite metal particles to diffuse into each other and to allow
the oxygen of the nickel oxide to react with the aluminum and
convert a stoichiometric portion of it to Al.sub.2 0.sub.3, which
is formed as a fine dispersion throughout the alloy. The heated can
is then extruded with an extrusion ratio of 16:1.
Two compatible constituents may also be combined in the same alloy
by separating them with a third mutually compatible constituent,
the two incompatible constituents being introduced in successive
milling operations. Bearing in mind that harder or less ductile
constituents will tend to become dispersed within softer or more
ductile constituents, many combinations of constituents may be
utilized in a hierarchy. Such a hierarchical composite may be
combined with one or more other hierarchical composite in a common
matrix. In this way, novel structures may be produced which cannot
be made in any other way.
A hierarchical process of this kind is illustrated in the following
example.
EXAMPLE XXX
A charge consisting of 50% by volume of 5 microns tungsten powder
and 50% by volume of zirconium oxide powder having a particle size
of 0.03 micron was dry milled in a high speed laboratory shaker
mill for about three hours. A composite powder comprising zirconia
distributed through a tungsten matrix was produced. Forty volume
percent of this powder was then mixed with 60% of carbonyl nickel
powder having an average particle size of 3 to 5 microns and the
mixture was again dry milled in the high speed shaker mill for a
total of 2 hours. Hard tungsten-zirconia powder particles were
comminuted and distributed in the product powder as a finely
dispersed phase. The resulting relatively coarse product powder
contained by volume 20% zirconium, 20% tungsten and 60% nickel in
hierarchical relation with minimal contact between zirconia and
nickel.
It is to be understood that in the foregoing examples wherein a
dispersion-strengthened product, e.g., a dispersion-strengthened
superalloy or stainless steel, was produced, the product contained
less than 10%, by volume, of segregated regions exceeding 3 microns
in size and more usually such regions did not exceed 1 micron or
even 0.5 micron in size.
Other wrought metal systems that are advantageously produced by the
invention include the following:
1. compositions that are difficult to make because of the low
boiling point of one of the constituents, e.g., alloys including
lithium such as Ni-1% Li, for purposes requiring corrosion
resistance; systems including boron such as nickel-boron
compositions and boron-containing steels such as 18-8 Cr-Ni or AISI
Type 347 steels with boron.
2. compositions in which one component is highly reactive e.g.,
rare earth metal compositions such as RCo.sub.5 for permanent
magnets, where R is a rare earth metal such as cerium or samarium.
The rare earth metals react readily with the refractory linings of
crucibles used for melting, so that levitation melting or
consumable arc melting into a cooled metal mould is normally
employed, leading to an undesirably large grain size.
3. Iron-silicon alloys for transformer laminations, e.g., Fe/5-7%
Si with or without up to 10% Ni to improve magnetic properties.
The invention is particularly applicable to those deformable metals
having an absolute melting point of over 600.degree.K. and, more
preferably, over 1,000.degree.K., as such metals are capable of
being heavily worked with the milling process. With regard to lower
melting metals, which tend to be self-annealing under heavy working
conditions at substantially ambient temperature, these can be
processed with other metals at ambient temperatures to produce
useful wrought composite metal powder. On the other hand, where the
need calls for it, such metals can be processed at below their
recrystallization temperature by working at substantially below
ambient temperatures to thereby achieve a substantially steady
state balance between the welding and grinding factors.
Although the present invention has been described in conjunction
with preferred embodiments, it is to be understood that
modifications and variations may be resorted to without departing
from the spirit and scope of the invention, as those skilled in the
art will readily understand. Such modifications and variations are
considered to be within the purview and scope of the invention and
appended claims.
* * * * *