U.S. patent number 3,779,714 [Application Number 05/217,506] was granted by the patent office on 1973-12-18 for dispersion strengthening of metals by internal oxidation.
This patent grant is currently assigned to SCM Corporation. Invention is credited to Erhard Klar, Anil V. Nadkarni.
United States Patent |
3,779,714 |
Nadkarni , et al. |
December 18, 1973 |
**Please see images for:
( Certificate of Correction ) ** |
DISPERSION STRENGTHENING OF METALS BY INTERNAL OXIDATION
Abstract
Disclosed are methods and compositions for forming
dispersion-strengthened metal products by the in situ internal
oxidation of an alloy powder of a solute metal in a matrix metal.
The matrix metal is relatively noble with respect to the solute
metal so that the solute metal will be preferentially oxidized. The
oxidant for the internal oxidation of said alloy powder is a
mixture of a heat-reducible (i.e., reducible by the solute metal
with heat) metal oxide (the metal moiety of which is different or
the same as the matrix metal that is present in the alloy) present
in proportion sufficient for substantial oxidation of all of said
solute metal to solute metal oxide; and a hard, refractory metal
oxide (the metal moiety of which is different from or the same as
the solute metal present in the alloy). The alloy powder and the
oxidant are intimately mixed and heated in an inert atmosphere for
internal oxidation. Upon internal oxidation, the composite residue
of spent oxidant comprises an in situ heat-reduced metal intimately
associated with the refractory metal oxide, and such residue is
coalesced with the rest of the mass by hot working.
Inventors: |
Nadkarni; Anil V. (Glen Burnie,
MD), Klar; Erhard (Pikesville, MD) |
Assignee: |
SCM Corporation (Cleveland,
OH)
|
Family
ID: |
22811370 |
Appl.
No.: |
05/217,506 |
Filed: |
January 13, 1972 |
Current U.S.
Class: |
75/234; 75/235;
75/354; 75/956; 419/23; 75/252; 75/951; 419/19 |
Current CPC
Class: |
C22C
1/1078 (20130101); Y10S 75/951 (20130101); Y10S
75/956 (20130101) |
Current International
Class: |
C22C
1/10 (20060101); B22f 007/00 (); B23p 003/00 () |
Field of
Search: |
;29/181.5,191.2
;75/206,211,.5BC |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
|
|
|
|
|
|
|
932,460 |
|
Jul 1963 |
|
GB |
|
919,052 |
|
Feb 1963 |
|
GB |
|
669,315 |
|
Aug 1963 |
|
CA |
|
Primary Examiner: Quarforth; Carl D.
Assistant Examiner: Schafer; R. E.
Claims
Having thus described the invention, what is claimed is:
1. A process for dispersion-strengthening of metal by internal
oxidation comprising:
providing a powdered alloy having an average particle size of less
than 300 microns comprising a matrix metal and a solute metal, said
matrix metal having a negative free energy of oxide formation at
25.degree.C. of up to 70 kilocalories per gram atom of oxygen, said
solute material having a negative free energy of oxide formation
exceeding the negative free energy of oxide formation of said
matrix material by at least about 60 kilocalories per gram atom of
oxygen at 25.degree.C.;
providing an oxidant comprising an intimate interspersion of in
situ heat-reducible metal oxide and a finely divided hand
refractory metal oxide, said heat-reducible metal oxide having a
negative free energy of formation at 25.degree.C. of up to 70
kilocalories per gram atom of oxygen, said refractory metal oxide
having a negative free energy of formation exceeding the negative
free energy of formation of said heat-reducible metal oxide by at
least about 60 kilocalories per gram atom of oxygen at
25.degree.C.;
combining into an intimate mixture at least about 0.1 weight parts
of said oxidant per 100 weight parts of said alloy, said oxidant
having the heat-reducible metal oxide present in at least
stoichiometric proportion for complete internal oxidation of all of
said solute metal in said alloy;
internally oxidizing said alloy mixed with said oxidant by heating
to oxidize the solute metal of said alloy and to form a residue of
said oxidant; and
thermally coalescing said internally oxidized alloy and said
oxidant residue into dispersion-strengthened metal stock.
2. The process of claim 1 wherein the ratio of the average particle
diameter of the alloy particles to the average particle diameter of
the oxidant particles is at least about 2:1.
3. The process of claim 1 wherein the metal moiety of said in situ
heat-reducible metal oxide is the same metal as said matrix
metal.
4. The process of claim 3 wherein the metal moiety of said hard,
refractory metal oxide is the same metal as said solute metal.
5. The process of claim 4 wherein the metal moiety of said
heat-reducible metal oxide and the metal moiety of said hard,
refractory metal oxide are in substantially the same proportion as
the proportion of matrix metal and solute metal in said alloy.
6. The process of claim 1 wherein said solute metal is present in
said alloy in the proportion of 0.01 to 5 percent by weight of said
alloy.
7. The process of claim 1 wherein said powdered alloy has an
average particle size of less than about 150 microns.
8. The process of claim 7 wherein said powdered alloy has an
average particle size of less than about 44 microns.
9. The process of claim 6 wherein the ratio of the average particle
diameter of the alloy particles to the average particle diameter of
the oxidant particles is between about 5:1 and about 30:1.
10. The process of claim 1 wherein said matrix metal is copper and
said solute metal is aluminum.
11. The process of claim 5 wherein said matrix metal is copper and
said solute metal is aluminum.
12. The process of claim 1 wherein about 0.1 to 10 weight parts of
said oxidant are mixed with 100 weight parts of alloy.
13. The process of claim 1 including the step of reducing said
alloy mixed with said oxidant with reducing gas after the step of
internally oxidizing the same.
14. A dispersion-strengthened metal produced by internally
oxidizing a mixture of 100 weight parts of a powdered alloy with at
least about 0.1 weight parts of an oxidant, said powdered alloy
having an average particle size of less than 300 microns and
comprising a relatively noble matrix metal having a negative free
energy of oxide formation at 25.degree.C. of up to 70 kilocalories
per gram atom of oxygen and a solute metal having a negative free
energy of oxide formation exceeding that of said matrix metal by at
least about 60 kilocalories per gram atom of oxygen at
25.degree.C., said oxidant comprising an intimate mixture of
heat-reducible metal oxide having a negative free energy of
formation at 25.degree.C. of up to 70 kilocalories per gram atom of
oxygen and finely divided refractory metal oxide having a negative
free energy of formation exceeding the negative free energy of
formation of said heat-reducible metal oxide by at least about 60
kilocalories per gram atom of oxygen at 25.degree.C., said
heat-reducible metal oxide present in at least stoichiometric
proportions for complete oxidation of all of said solute metal in
said alloy, comprising: a dispersion-strengthened metal mixture of
oxidized solute metal, relatively noble matrix metal, residue of
heat-reducible metal oxide, and hard refractory metal oxide, said
mixture adapted to be thermally coalesced whereby said hard
refractory metal oxide dispersion strengthens said residue of
heat-reducible metal oxide to form dispersion-strengthened metal
stock.
15. The dispersion-strengthened metal mixture in claim 14 wherein
said metal mixture is thermally coalesced and said residue of
heat-reducible metal oxide is dispersion strengthened by said hard
refractory metal oxide.
16. The dispersion-strengthened metal in claim 14 produced by
internally oxidizing a mixture of 100 weight parts of said powdered
alloy with from about 0.1 to 10 weight parts of said oxidant, and
said metal moiety of said residue of heat-reducible metal oxide is
the same moiety as said relatively noble matrix metal.
17. The dispersion-strengthened metal in claim 16 wherein the metal
moiety of said hard refractory metal oxide is the same metal moiety
as said oxidized solute metal.
18. The dispersion-strengthened metal in claim 16 wherein the metal
moiety of said relatively noble matrix metal is copper and the
metal moiety of said oxidized solute metal is aluminum.
Description
The present invention relates to dispersion strengthening of
ductile matrix metals by the in situ formation of a hard,
refractory oxide phase therein by the technique known as internal
oxidation. Dispersion-strengthened metal products such as copper
dispersion strengthened with aluminum oxide have many commercial
and industrial uses where high temperature strength and high
electrical conductivity and/or heat conductivity are desired or
required. Such uses include frictional brake parts such as linings,
facings, drums and the like and other machine parts for frictional
applications; contact points for resistance welding electrodes;
electrodes generally, electrical switches and electrical switch
gears, transistor assemblies, wires for solderless connections,
wires for electrical motors and many other related applications.
Dispersion-strengthened products of this invention are useful in
the above and other applications.
In the past, it has been recognized that strength and hardness can
be imparted to a solid solution alloy of a ductile matrix metal,
having relatively low negative heat or free energy of oxide
formation, and a solute metal having a relatively high negative
heat or free energy of oxide formation, by heating the alloy under
oxidizing conditions so as to preferentially oxidize the solute
metal to cause the in situ precipitation of hard, refractory solute
metal oxide particles in the matrix metal without substantial
oxidation of the matrix metal. This technique is known as the in
situ internal oxidation of the solute metal to the solute metal
oxide or more simply "internal oxidation". In internal oxidation,
the matrix metal is relatively noble compared to the solute metal
so that the solute metal will be preferentially oxidized.
In the past, attempts have been made to dispersion strengthen
alloys by internal oxidation in various ways. For instance, U. S.
Pat. No. 3,026,200 shows the surface oxidation of alloy powder
followed by a heat treatment in an inert atmosphere to diffuse the
oxygen from the surface of the alloy and to preferentially oxidize
the solute metal to solute metal oxide within the alloy. This
method requires the precise control of the conditions for oxidation
of the alloy powder.
U. S. Pat. No. 3,399,086 discloses the internal oxidation of
copper-aluminum alloy in plate or strip form using copper oxide as
the oxidant, through an oxidation-reduction chemical mechanism. The
copper oxide is reduced and gives up its oxygen for the
preferential oxidation of the alloyed aluminum to form dispersed
particles of aluminum oxide dispersed within the copper matrix.
Internal oxidation of alloy powder is not discussed, so the problem
of oxidant powder removal from alloy powder is not a factor.
U. S. Pat. No. 3,184,835 discusses the internal oxidation of
copper-beryllium or copper-aluminum alloys wherein the oxidant is a
sintered and milled (110 mesh) mixture consisting of 50 percent
copper oxide and 50 percent aluminum oxide. The use of the sintered
mixture as the oxidant is said to minimize adhesion of the oxidant
residue to the internally oxidized alloy. The sintered oxidant
residue is physically separated from the internally oxidized alloy
powder before the powder is formed into a dispersion-strengthened
metal product.
U. S. Pat. No. 3,179,515 discloses the internal oxidation of alloys
by surface oxidizing a powdered alloy and then diffusing the oxygen
into the powder particles to preferentially oxidize the solute
metal to solute metal oxide. This patent shows that internal
oxidation can be achieved by treating the alloy powder at a
controlled partial pressure of oxygen at which copper does not
readily oxidize whereas the solute metal is oxidized mainly by
diffusion of oxygen into the alloy. Particle size and surface
parameters of the solute metal oxide are said to be critical to
product performance.
British Patent 654,962 shows a method of internally oxidizing
silver, copper and/or nickel alloys containing solute metal by
oxygen diffusion to increase the hardness of the alloy by more than
30 percent.
All of these prior art methods either require a delicate control
over the partial pressure of oxygen during internal oxidation or
the removal of oxidant residue after the internal oxidation
reaction is complete. When an oxidizing gas is used as an oxidant,
elaborate processing and control equipment must be provided and
maintained. When the oxidant is an oxide of the matrix metal or
another metal the reduced oxide metal often sinters during the
oxidizing reaction and produces agglomerates that must be separated
and removed before the metal powder can be further processed.
Furthermore, any oxidant residue that remains in the internally
oxidized powder in these prior art processes forms defects due to
compositional variations when said metal shapes are eventually
formed. The present invention provides a unique solution to this
problem in providing for the complete assimilation of the oxidant
residue into metal articles formed from the internally oxidized
alloy powder.
The above and other advantages will be more easily understood from
the following description and drawings wherein
FIGS. 1, 2 and 3 are graphs showing how the electrical
conductivity, ultimate tensile strength and hardness vary with
composition and annealing treatment according to the present
invention.
In achieving the objects of the present invention, one feature
provides for the internal oxidation of solute metal to solute metal
oxide in a powdered alloy of a matrix metal and solute metal
wherein the matrix metal has a negative free energy of oxide
formation per gram atom of oxygen at 25.degree.C. ranging up to 70
kilocalories per gram atom of oxygen at 25.degree.C.; and the
negative free energy of formation of said solute metal oxide
exceeds the negative free energy of formation of said matrix metal
oxide by at least 60 kilocalories per gram atom of oxygen at
25.degree.C. in the presence of and in intimate admixture with an
oxidant comprising a pulverulent, in situ, heat-reducible metal
oxide having a negative free energy of oxide formation per gram
atom of oxygen ranging up to 70 kilocalories per gram atom of
oxygen at 25.degree.C. in intimate interspersion with discrete
particles of hard, refractory metal oxide, the negative free energy
of formation of said hard, refractory metal oxide exceeding the
negative free energy of formation of said heat-reducible metal
oxide by at least 60 kilocalories per gram atom of oxygen at
25.degree.C. The heat-reducible metal oxide can contain the same or
different metal moiety that is present as the matrix metal in the
alloy. Similarly, the hard, refractory metal oxide that is present
in a proportion and particle size adapted for dispersion
strenghtening the oxidant residue resulting from internal oxidation
can be the same or different metal oxide that results from the
internal oxidation of the solute metal to the solute metal oxide in
the alloy.
The pulverulent, in situ heat-reducible metal oxide in the oxidant
is in substantial stoichiometric proportion for internal oxidation
of all the solute metal to solute metal oxide in said alloy. After
internal oxidation, the oxidant residue comprises uniformly
distributed agglomerates consisting of particles of in situ reduced
metal and particles of hard, refractory metal oxide. The oxidant
residue is in intimate mixture with the particles of internally
oxidized alloy powder which after internal oxidation comprises
matrix metal containing dispersed particles of refractory oxide.
According to this present technique, the oxidant is neither
presintered nor is the oxidant residue separated from the
internally oxidized alloy powder as in U. S. Pat. No. 3,184,835.
When the internally oxidized alloy powder and the oxidant residue
are eventually consolidated by hot working to form a solid metal
workpiece, the oxidant residue itself dispersion strengthens to
form an integral part of the resulting workpiece.
Preferably, the in situ heat-reducible metal oxide in the oxidant
contains the same metal moiety as the matrix metal in the alloy
powder; and preferably, the hard, refractory metal oxide in the
oxidant contains the same metal moiety as the solute metal in the
alloy powder. In one particular commercially important embodiment
of this preferred practice, the oxidant contains substantially the
same proportion of matrix metal moiety and solute metal moiety as
are present in the alloy powder. Thus upon eventual coalescense of
the internally oxidized mixture of alloy and oxidant residue into a
workpiece, the oxidant residue itself is of substantially the same
composition as the internally oxidized alloy and becomes dispersion
strengthened therewith.
Another feature of the present invention resides in a metal powder
composition based upon an alloy of matrix metal and solute metal
about 0.01 to 5 percent by weight, adapted for coalescense upon hot
working to form dispersion-strengthened metal articles, said
composition comprising particles of internally oxidized alloy of a
matrix metal whose oxide has a negative free energy of formation at
25.degree.C. ranging up to about 70 kilocalories per gram atom of
oxygen, the matrix metal having dispersed substantially uniformly
throughout by internal oxidation fine particles of a hard,
refractory solute metal oxide, the negative free energy of
formation of said solute metal oxide exceeding the negative free
energy of oxide formation of said matrix metal by at least 60
kilocalories per gram atom of oxygen at 25.degree.C., said
particles of internally oxidized alloy being blended with an
oxidant residue mixture comprising discrete particles of in situ
heat-reduced metal having a negative free energy of oxide formation
at 25.degree.C. ranging up to 70 kilocalories per gram atom of
oxygen and discrete particles of hard, refractory metal oxide
having a negative free energy of oxide formation exceeding the
negative free energy of formation of said heat-reduced metal by at
least 60 kilocalories per gram atom of oxygen at 25.degree.C.
Preferably, the heat-reduced metal oxide in the oxidant residue is
of the same metal moiety as the matrix metal in the internally
oxidized alloy. Most preferably, the proportion of matrix metal and
hard, refractory metal oxide in said oxidant residue is
substantially the same as the proportion of matrix metal and solute
metal oxide in said internally oxidized alloy.
The matrix metals in the alloy and in situ, heat-reduced metal in
the oxidant residue are defined broadly as those metals having a
melting point of at least about 200.degree.C. and whose oxides have
a negative free energy of formation at 25.degree.C. of from 0 to 70
kilocalories per gram atom of oxygen. Suitable metals of this class
for practicing the present invention include the following:
Approximate negative free energy of formation of Matrix metal
Heat-reducible oxide at 25.degree.C. in kilo- and in situ metal and
calories per gram heat-reduced metal matrix metal atom of oxygen
oxide Iron FeO 59 Fe.sub.2 O.sub.3 60 Cobalt CoO 52 Nickel NiO 51
Copper Cu.sub.2 O 35 CuO 32 Cadmium CdO 55 Thallium Tl.sub.2 O 40
Germanium GeO.sub.2 58 SnO 60 SnO .sub.2 62 Lead PbO 45 Antimony
Sb.sub.2 O.sub.3 45 Bismuth Bi.sub.2 O.sub.3 40 Molybdenum
MoO.sub.2 60 MoO.sub.3 54 Tungsten WO.sub.2 60 WO.sub.3 59 Rhenium
ReO.sub.3 45 Indium In.sub.2 O.sub. 3 65 Silver Ag.sub.2 O 3 Gold
Au.sub.2 O 0 Ruthenium RuO.sub.2 25 Palladium PdO 15 Osmium
OsO.sub.4 20 Platinum PtO 0 Rhodium Rh.sub.2 O.sub.3 17
in the above table, matrix metal of the alloys and in situ
heat-reduced metal of the oxidant residue are shown to be of the
same class of metals. Similarly, the corresponding heat-reducible
metal oxides in the oxidant and matrix metal oxides are listed as
the same class of metal oxides.
In practicing the present invention, a matrix metal and a solute
metal are alloyed by conventional techniques such as melting the
metals under inert or reducting conditions. The matrix metal of the
alloy can be a single matrix metal of a combination of two or more
matrix metals which themselves form an alloy. Accordingly, the term
"matrix metal" includes a plurality of matrix metals so alloyed.
Similarly, the solute metal includes a single solute metal or a
combination of two or more solute metals which form solid solution
alloys with the matrix metal. The alloy composition comprises 0.01
percent to about 5 weight percent of the solute metal with the
balance of the alloy being matrix metal with or without other
conventional additives in minor proportions to improve abrasion
resistance, hardness, conductivity and other selected
properties.
The alloy is then comminuted by atomization or other conventional
size reduction techniques such as grinding or ball milling to form
a particulate alloy having an average particle size of less than
about 300 microns, usually less than about 150 microns and
preferably less than about 44 microns.
Optionally, the comminuted alloy powder is then annealed according
to conventional procedures to increase the grain size since one of
the problems associated with internal oxidation of alloys is the
tendency for the solute metal oxide to concentrate at the powder
grain boundaries. This is undesirable because it can cause early
failure under stress at these grain boundaries. It is, therefore,
often desirable to reduce the grain boundary area in the alloy
powder; and this is done by annealing the powder to form a larger
grain size of at least about ASTM Grain Size Number 6 as measured
by ASTM Test E-112. For copper-aluminum alloys which are one of the
more commercially important embodiments of the present invention,
annealing treatment at 1,600.degree.F. for one hour in an inert
atmosphere such as argon produces grain size of at least about ASTM
Grain Size Number 6 by ASTM Test E-112.
The oxidant for internally oxidizing the above alloy powder is a
mixture of an in situ heat-reducible metal oxide (this term
includes materials capable of providing such metal oxide under
internal oxidation conditions) and a hard, refractory metal oxide.
The heat reducible metal oxide in the oxidant is in substantially
stoichiometric proportion for internally oxidizing all of the
solute metal in said alloy.
In any particular combination of matrix metal and solute metal in
the alloy to be internally oxidized, the matrix metal must be
relatively noble with respect to the solute metal so that the
solute metal will be preferentially oxidized. This is achieved by
selecting the solute metal such that its negative free energy of
oxide formation at 25.degree.C. is at least 60 kilocalories per
gram of oxygen greater than the negative free energy of formation
of the oxide of the matrix metal at 25.degree.C. Generally, such
solute metals have a negative free energy of oxide formation per
gram atom of oxygen of over 80 kilocalories and generally over 120
kilocalories. The approximate negative values of free energy of
formation of several suitable solute metal oxides at 25.degree.C.
are:
Approximate negative free Solute metal energy of formation of oxide
and oxide at 25.degree.C. in kilo- hard, refractory calories per
gram Solute metal metal oxide atom of oxygen Silicon SiO.sub.2 96
Titanium TiO.sub.2 101 Zirconium ZrO.sub.2 122 Aluminum Al.sub.2
O.sub.3 126 Beryllium BeO 139 Thorium ThO.sub.2 146 Chromium
Cr.sub.2 O.sub.3 83 Magnesium MgO 136 Manganese MnO 87 Niobium
Nb.sub.2 O.sub.5 85 Tantalum Ta.sub.2 O.sub.5 92 Vanadium VO 99
in the above table, the solute metal oxide in the alloy and hard,
refractory metal oxide in the oxidant are shown to be the same
class of metal oxides.
The metal moiety of the heat-reducible metal oxide in the oxidant
preferably is the same metal as matrix metal present in the alloy
to be internally oxidized, although the heat-reducible metal oxide
moiety can be different to achieve specific performance
requirements in the final product.
For instance, alloy matrix metal/oxidant heat-reducible metal oxide
combinations include:
Oxidant Heat-Reducible Alloy Matrix Metal Metal Oxide copper cobalt
oxide, nickel oxide, copper oxide nickel cobalt oxide, nickel
oxide, copper oxide cobalt cobalt oxide, nickel oxide, copper
oxide
Similarly, the hard, refractory metal oxide in the oxidant
preferably is the same as the solute metal oxide formed in the
alloy during internal oxidation of the alloy, although the
refractory metal oxide in the oxidant can be different from the
solute metal oxide in the internally oxidized alloy.
For instance, solute metal oxide/oxidant hard, refractory metal
oxide combinations include:
Oxidant Hard, Refractory Alloy Solute Metal Oxide Metal Oxide
Al.sub.2 O.sub.3 Al.sub.2 O.sub.3, BeO, ZrO.sub.2, ThO.sub.2 BeO
Al.sub.2 O.sub.3, BeO, ZrO.sub.2, ThO.sub.2 ZrO.sub.2 Al.sub.2
O.sub.3, BeO, ZrO.sub.2, ThO.sub.2 ThO.sub.2 Al.sub.2 O.sub.3, BeO,
ZrO.sub.2, ThO.sub.2
to achieve the proper proportion of oxidant, about 0.1 to about 10
parts by weight of oxidant are employed per 100 parts of alloy to
be internally oxidized. The exact proportions depend on the solute
metal to be oxidized, its concentration in alloy and oxygen content
of oxidant.
In a commercially important embodiment, the matrix metal is copper
and the solute metal is aluminum in the alloy; and the oxidant
contains copper oxide as the in situ, heat-reducible metal oxide
and aluminum oxide as the hard, refractory metal oxide. The copper
oxide in the oxidant is present in substantially stoichiometric
proportions for internally oxidizing all of the aluminum metal to
aluminum oxide in the alloy powder. During internal oxidation of
the preferred embodiment, the in situ, heat-reducible copper oxide
in the oxidant gives up its oxygen to the aluminum metal in the
alloy. This reduces the copper oxide to copper in the oxidant which
by virtue of its intimate mixture with aluminum oxide in the
oxidant becomes dispersion strengthened during subsequent
coalescense upon hot working. The stoichiometry of the oxidant is
predetermined so that the composition of the oxidant residue and
internally oxidized alloy are substantially identical after
internal oxidation. This represents a substantial advance over the
prior art techniques where matrix metal oxide alone is used as the
oxidant and reverts to matrix metal which must be removed, or where
the mixture of matrix metal oxide and refractory oxide, because of
unfavorable particle size and homogeneity, does not produce
acceptable properties.
The ratio of the average particle size diameters of the alloy
particles to the oxidant particles should be at least about 2:1 and
usually between about 5:1 and about 30:1 or even higher if
practical to provide desirable inter-particle contacts for
efficient chemical reaction and to maximize the homogeneity of the
final product. This particle size differential permits the oxidant
particle to surround the alloy particle thus providing for
sufficient solid-state reaction during the internal oxidation
period. Generally the oxidant particles are micron or submicron in
particle size.
There are several methods of forming oxidant suitable for the
present invention. In one method, an oxide-forming salt of a
refractory metal is applied to and decomposed on a particle of a
heat-reducible metal oxide in the micron or submicron range. In the
case of the copper-aluminum system, for instance, submicron
cuprous/cupric oxide particles are treated with an aqueous solution
of aluminum nitrate so as to form a uniform coating. The particles
are dried and heated to decompose the aluminum nitrate to form
cuprous/cupric oxide particles having uniform coating of aluminum
oxide thereon. The amount of aluminum nitrate added to the
cuprous/cupric oxide particles is predetermined according to the
aluminum oxide content desired in the final product.
In another method, oxide-forming compounds of refractory metal and
metals of heat-reducible metal oxides are simultaneously
coprecipitated from solution of their salts. In the copper-aluminum
system for example, copper and aluminum hydroxides or carbonates
are precipitated from a solution of their nitrates by adding
ammonium hydroxide or carbonate respectively. The hydroxide and
carbonate salts are then decomposed to their respective oxides by
heating.
In a third method, a physical blend of micron or submicron
particles of heat-reducible metal oxide and refractory oxide
particles can be intimately blended in a blending device to form
the oxidant.
The amounts of such oxidants that are to be added to the alloy are
determined by the stoichiometric amount of oxygen required to
oxidize the solute metal completely. For most applications, this is
in the range of 0.1 to 10 parts oxidant per 100 parts of alloy. The
percent of hard, refractory metal oxide in the oxidant is then
calculated to produce that desired in the oxidant residue which
also equals that desired in the final product.
In the following examples, all parts are parts by weight and all
temperatures are in .degree.F. unless stated otherwise.
EXAMPLE 1
Part A -- Preparation of the Alloy Powder
Electrolytic tough-pitch grade copper rods are melted in an inert
refractory crucible in an induction-heating furnace under reducing
conditions at about 2,300.degree.F. Metallic aluminum shavings are
introduced into the molten copper in the proportion of 0.33 percent
by weight of the resulting molten metallic mass.
The molten solution of aluminum in copper is then super-heated to
2,400.degree.F., atomized through an atomizing aperture in a jet of
nitrogen (alternatively other inert gases or water or stream can be
used as the atomizing fluid) to yield an atomized copper-aluminum
alloy powder which substantially all passes a 100-mesh U. S. Sieve
indicating that the average particle size is less than about 146
microns.
The atomized and screened alloy powder is annealed at a temperature
of about 1,600.degree.F. about an hour in an inert argon atmosphere
to yield a grain size in the annealed powder of at least about ASTM
Grain Size 6 according to ASTM Test E-112. Preferably, the grains
are as large as possible to minimize grain boundary area in the
powder. The alloy powder is then ready for use in combination with
the oxidant.
Part B -- Preparation of the Oxidant
One hundred parts of commercially available cuprous oxide (Cu.sub.2
O) with an average particle size of about 1 to 2 microns is mixed
with 4.1 parts of a 20 percent aqueous solution of AL(NO.sub.3
).sub.3 .sup.. 9H.sub.2 O to form a slurry of cuprous oxide in
aluminum nitrate solution. The solution of aluminum nitrate is
slurried with cuprous oxide particles, and the stirring is
continued with mild heating at 200.degree.F. until the water has
evaporated and the mixture is almost dry. The mixture is then
heated at a temperature of about 500.degree.F. for 1/2 hour to
decompose the aluminum nitrate into aluminum oxide. The resulting
agglomerate is then ground to form fine oxidant powder which passes
a 325-mesh sieve. The resulting oxidant powder comprises 99.44%
Cu.sub.2 O and 0.56% Al.sub.2 O.sub.3 by weight.
Part C -- Preparation of the Internally Oxidizable Alloy
Powder-Oxidant Mixture
The alloy powder of Part A is thoroughly mixed with the oxidant
powder of Part B in the proportion of 2.12 parts of oxidant to 100
parts of alloy powder. The mixing is accomplished in a ball-mill,
although a conventional V-cone blending device can alternatively be
used.
Part D -- Internal Oxidation of the Alloy Powder-Oxidant Mixture to
form the Internally Oxidized Metal Powder Composition
The alloy powder-oxidant mixture of Part C is then charged to an
internal oxidation vessel which is then sealed. The oxidation
vessel is copper or copper-lined steel to avoid contamination of
the alloy powder-oxidant mixture during oxidation.
The alloy powder-oxidant mixture is then brought to a temperature
of about 1,750.degree.F. and maintained at this temperature for
about 30 minutes to effectuate internal oxidation of the alloy
powder. Alternatively, the internal oxidation can be carried out on
a continuous basis using a continuous belt furnace maintained under
an inert atmosphere.
At the end of the 30-minute internal oxidation period,
substantially all of the aluminum in the alloy powder has been
oxidized to Al.sub.2 O.sub.3 and substantially all of the cuprous
oxide in the oxidant has been reduced to metallic copper. The
particles of internally oxidized alloy comprise 99.37 percent by
weight of copper plus minor amounts of impurities and 0.63 percent
by weight of Al.sub.2 O.sub.3. The oxidant residue comprises 99.37
percent copper particles and 0.63% Al.sub.2 O.sub.3 particles. The
overall internally oxidized metal powder composition comprises
98.21 percent internally oxidized alloy powder and 1.79 percent
oxidant residue.
Part E -- Reduction of the Internally Oxidized Metal Powder
Composition
The internally oxidized metal powder composition of Part D is then
placed in a reducing atmosphere of hydrogen at a temperature of
about 1,500.degree.F. for one hour to reduce any residual copper
oxide.
Part F -- Thermal Coalescence or Consolidation of the Internally
Oxidized Metal Powder Composition
The internally oxidized and reduced metal powder composition of
Part E are then charged under an inert argon aatmosphere to a
thin-walled copper can having a diameter of about 7 inches and
equipped with a vent tube. The can and its contents are heated to
about 1,600.degree.F. and the vent tube sealed. Alternatively
instead of using the inert gas atmosphere, the vent tube can be
attached to a vacuum pump; and the can is evacuated while the
temperature of the can is brought to 1,600.degree.F. to remove any
occluded gas from the powder. After evacuation at a pressure of 1
.times. 10.sup..sup.-5 mm of Hg for 60 minutes at 1,600.degree.F.,
the vent tube is sealed and disconnected from the vacuum pump.
The sealed can is brought to 1,700.degree.F. and then placed in a
ram-type extrusion press and is extruded to form extrudate in the
shape of cylindrical bar stock having a diameter of about 1.25
inches. This corresponds to an extrusion ratio of about 31:1 (i.e.,
the ratio of the cross-sectional area of the can to the ratio of
the cross-sectional area of the extrudate).
The bar stock comprises about 99.37 percent copper having dispersed
throughout 0.63 percent (or about 1.5 percent by volume) of
Al.sub.2 O.sub.3 particles and has a density of about 99.2 percent
of the theoretical density. The bar stock has an electrical
conductivity of 88% IACS* (*International Annealed Copper Standard
-- A copper wire 1 meter long weighing 1 gram, having a resistance
of 0.15328 ohms. at 20.degree.C. has a conductivity of 100% IACS.
(see Kirk-Othmer: Encyclopedia of Chemical Technology, Second
Edition, Volume VI, Interscience Publishers, Inc. 1965 p. 133).), a
tensile strength of about 72,000 psi, an elongation of 19 percent
using ASTM Test E-8 (for a test specimen 0.16 inch diameter and
0.65 inch gage length) and a Rockwell hardness of about 75 units on
the B scale. All property measurements reported in the example are
conducted at room temperature. The bar stock is substantially
uniform and does not possess the compositional defects that
normally result when the spent oxidant is present in the
dispersion-strengthened workpiece.
The bar stock is suitable for use as is, or it can be cold worked
by swaging, forging, rolling, wire drawing, cold extrusion or cold
drawing to form workpieces having particular tensile strengths
according to conventional cold working techniques.
For instance, when the bar stock is reduced to 50 percent in
cross-sectional area by coldswaging, the tensile strength is 80,000
psi, the elongation is 13 percent and Rockwell B hardness is 84
units and conductivity is 86 percent IACS.
This swaged material with a Rockwell B hardness of 84 units and
prepared by the procedure of Example 1 is annealed along with a
commercial copper-chromium alloy (0.9% Cr) at various temperatures
for 1 hour in argon. The hardness values obtained by annealing in
an annealing furnace for 1 hour at the various temperatures and
cooling to room temperature after annealing at each temperature are
shown in FIG. 1. In another experiment these same two materials are
annealed together at 1,000.degree.F. in argon. At various time
intervals samples are removed from the annealing furnace, cooled at
room temperature and tested for hardness. The results are shown in
FIG. 2. The results shown in FIGS. 1 and 2 show the superior
resistance to softening on heating of the dispersion-strengthened
workpieces of this invention.
EXAMPLE 2
The procedures of Example 1 are repeated except that in Part F the
7 inch diameter copper can is replaced by a 1.25 inch diameter
copper can. The extrusion is carried out at an extrusion ratio of
30:1 yielding a 0.250 inch diameter rod. Such rod has an electrical
conductivity of 86.7% IACS, a tensile strength of about 73,000 psi
and an elongation of 19.8 percent in a gage length of 0.650
inch.
EXAMPLE 3
The material of Part E of Example 1 is fed into a thin-walled
copper can of 1.25 inch diameter and extruded at an extrusion ratio
of 45:1 to yield a rod of 0.206 inch diameter. This rod has an
electrical conductivity of 89% IACS and when swaged and drawn to a
0.010 inch diameter wire and heat treated at 500.degree.C. for 1/2
hour in helium yields an ultimate tensile strength of 84,000 psi,
yield strength of 71,200 psi and an elongation of about 5 percent
in 10 inches.
EXAMPLE 4
The procedures of Example 2 are repeated except that the
compositions of the alloy powder in Part A and the oxidant in Part
B is modified so that the alloy powder and the oxidant each contain
the equivalence of 0.22 weight percent aluminum to produce extruded
copper bar stock containing 0.42 weight percent (or 1 volume
percent) Al.sub.2 O.sub.3.
The electrical conductivity of the bar stock is 91% IACS, the
tensile strength is 70,000 psi, elongation is 21 percent and the
Rockwell B hardness is 68 units. The bar stock is substantially
uniform and does not possess the compositional defects normally
associated with in situ, reduced copper oxide.
EXAMPLE 5
The procedures of Example 2 are repeated except that the
compositions of the alloy powder in Part A and the oxidant in Part
B are modified so that the alloy powder and the oxidant each
contain the equivalence of 0.66 weight percent aluminum to produce
extruded copper bar stock containing 1.26 weight percent (or 1
volume percent) Al.sub.2 O.sub.3.
The electrical conductivity of the bar stock is 78% IACS, the
tensile strength is 85,000 psi, elongation is 19 percent and the
Rockwell B hardness is 89 units. The bar stock is substantially
uniform and does not possess the compositional defects normally
associated with in situ, reduced copper oxide.
FIG. 3 shows a plot of properties against aluminum or aluminum
oxide content of workpieces as extruded in rod form as described in
this Example 5 and the preceding Examples 3 and 4.
EXAMPLE 6
The procedures of Example 1 are repeated except that the alloy
powder of Part A has a particle size passing a U. S. standard sieve
of 80 mesh but is retained on a 325-mesh sieve. On the basis of the
sieves employed, the particle size varies between 44 and 75
microns. The internally oxidized powder is used to compact test
bars at 45 tsi having a size of 0.394 in. .times. 0.394 in. .times.
2.96 in. These test bars are preheated in an atmosphere of 92%
N.sub.2 - 8% H.sub.2 at 1,700.degree.F. for 10 minutes and forged
using a 200 ton drop hammer and a 28 inch vertical drop rather than
extruded as in Example 1, Part F. The resulting drop-forged bars
are 0.35 inch square in cross-section
The bars are then cold forged at room temperature to form 0.31 inch
diameter bars which represents a 38 percent reduction in
cross-section.
The resulting test bars have a Vicker's hardness (at 15 gram load)
of 149 Kg/mm.sup.2, a tensile strength of 67,700 psi and an
elongation of 4.3 percent. The test samples are then annealed for 1
hour at 1,500.degree.F. in argon after which the Vicker's hardness
is 139 Kg/mm.sup.2, tensile strength is 60,200 psi with an
elongation of 5.7 percent.
EXAMPLE 7
The procedures of EXAMPLE 6 are repeated except that the alloy
powder has a particle size passing a U. S. standard sieve of 325
mesh. This means that the average particle is less than 44 microns.
The test sample has a Vicker's hardness of 153 Kg/mm.sup.2, a
tensile strength of 75,600 psi and an elongation of 6.2 percent.
After annealing in argon at 1,500.degree.F. for 1 hour, the
Vicker's hardness is 153 Kg/mm.sup.2, the tensile strength is
68,000 psi and the elongation is 8.8 percent.
Examples 6 and 7 illustrate that the smaller alloy particles after
internal oxidation produce better hardness, higher tensile strength
and better elongation properties in the dispersion-strengthened
product.
Examples 8 through 17 further illustrate the dispersion
strengthening of matrix metals with various solute metal oxides by
internal oxidation. Where solubility permits, the solute metal
concentration in the alloy is selected to provide approximately 5
percent by volume of the solute metal oxide. In cases where the
solubility of the solute metal is not sufficient to provide 5
percent by volume of the solute metal oxide, the solute metal
concentration in the alloy is adjusted to maximum solubility at
room temperature. In all of the following Examples 8 through 21,
the alloy powder passes through a U. S. standard sieve of 100 mesh,
the pulverulent oxidant is an intimate interspersion of the stated
metal oxides having an average particle size of about 1 to 5
microns and the alloy powder-oxidant mixture is internally oxidized
by the method described in Parts D, E and F of Example 1. In the
metal oxides presented in the following examples, copper is at a
valence of 1, nickel is at a valence of 2, iron is at a valence of
3, silver is at a valence of 1, zirconium is at a valence of 4,
molybdenum is at a valence of 6 and beryllium and magnesium are at
a valence of 2.
EXAMPLE 8
Dispersion-strengthened metal bar stock is formed by the
above-described method by oxidizing 100 parts of a powdered alloy
of 98.87 percent copper and 1.13 percent aluminum with 9.38 parts
of pulverulent oxidant comprising 9.2 parts of copper oxide and
0.18 parts of aluminum oxide. The resulting dispersion-strengthened
bar stock has increased tensile strength and hardness at elevated
temperatures or after annealing as compared to bar stock of a
similar copper-aluminum alloy which has not been internally
oxidized. Furthermore, the dispersion-strengthened bar stock does
not have the disadvantages that normally result from compositional
variations when the spent oxidant is present in the
dispersion-strengthened workpiece.
EXAMPLE 9
Dispersion-strengthened metal bar stock is formed by the
above-described method by oxidizing 100 parts of a powdered alloy
of 99.37 percent copper and 0.63 percent beryllium with 10.26 parts
of pulverulent oxidant comprising 10.10 parts of copper oxide and
0.16 parts beryllium oxide. The resulting dispersion-strengthened
bar stock has increased tensile strength and hardness at elevated
temperatures or after annealing as compared to bar stock of a
similar copper-beryllium alloy which has not been internally
oxidized. Furthermore, the dispersion-strengthened bar stock does
not have the disadvantages that normally result from compositional
variations when the spent oxidant is present in the
dispersion-strenghtened workpiece.
EXAMPLE 10
Dispersion-strengthened metal bar stock is formed by the
above-described method by oxidizing 100 parts of a powdered alloy
of 99.90 percent copper and 0.10 percent zirconium with 0.319 parts
of pulverulent oxidant comprising 0.318 parts of copper oxide and
0.001 parts of zirconium oxide. The resulting
dispersion-strengthened bar stock has increased tensile strength
and hardness at elevated temperatures or after annealing as
compared to bar stock of a similar copper-zirconium alloy which has
not been internally oxidized. Furthermore, the
dispersion-strengthened bar stock does not have the disadvantages
that normally result from compositional variations when the spent
oxidant is present in the dispersion-strengthened workpiece.
EXAMPLE 11
Dispersion-strengthened metal bar stock is formed by the
above-described method by oxidizing 100 parts of a powdered alloy
of 98.86 percent nickel and 1.14 percent aluminum with 4.76 parts
of pulverulent oxidant comprising 4.68 parts of nickel oxide and
0.08 parts of aluminum oxide. The resulting dispersion-strengthened
bar stock has increased tensile strength and hardness at elevated
temperatures or after annealing as compared to bar stock of a
similar nickel-aluminum alloy which has not been internally
oxidized. Furthermore, the dispersion-strengthened bar stock does
not have the disadvantages that normally result from compositional
variations when the spent oxidant is present in the
dispersion-strengthened workpiece.
EXAMPLE 12
Dispersion-strengthened metal bar stock is formed by the
above-described method by oxidizing 100 parts of a powdered alloy
of 99.8 nickel and 0.2 percent beryllium with 1.687 parts of
pulverulent oxidant comprising 1.680 parts of nickel oxide and
0.007 parts of beryllium oxide. The resulting
dispersion-strengthened bar stock has increased tensile strength
and hardness at elevated temperatures or after annealing as
compared to bar stock of similar nickel-beryllium alloy which has
not been internally oxidized. Furthermore, the
dispersion-strengthened bar stock does not have the disadvantages
that normally result from compositional variations when the spent
oxidant is present in the dispersion-strengthened workpiece.
EXAMPLE 13
Dispersion-strengthened metal bar stock is formed by the
above-described method by oxidizing 100 parts of a a powdered alloy
of 99.8 percent nickel and 0.2 percent zirconium with 0.328 parts
of pulverulent oxidant comprising 0.327 parts of nickel oxide and
0.001 parts of zirconium oxide. The resulting
dispersion-strengthened bar stock has increased tensile strength
and hardness at elevated temperatures or after annealing as
compared to bar stock of similar nickel-zirconium alloy which has
not been internally oxidized. Furthermore, the
dispersion-strengthened bar stock does not have the disadvantages
that normally result from compositional variations when the spent
oxidant is present in the dispersion-strengthened workpiece.
EXAMPLE 14
Dispersion-strengthened metal bar stock is formed by the
above-described method by oxidizing 100 parts of a powdered alloy
of 98.72 percent iron and 1.28 percent aluminum with 3,864 parts of
pulverulent oxidant comprising 3.800 parts of iron oxide and 0.065
parts of aluminum oxide. The resulting dispersion-strengthened bar
stock has increased tensile strength and hardness at elevated
temperatures or after annealing as compared to bar stock of a
similar iron-aluminum alloy which has not been internally oxidized.
Furthermore, the dispersion-strengthened bar stock does not have
the disadvantages that normally result from compositional
variations when the spent oxidant is present in the
dispersion-strengthened workpiece.
EXAMPLE 15
Dispersion-strengthened metal bar stock is formed by the
above-described method by oxidizing 100 parts of a powdered alloy
of 99.55 percent iron and 0.45 percent beryllium with 2.724 parts
of pulverulent oxidant comprising 2.700 parts of iron oxide and
0.024 parts of beryllium oxide. The resulting
dispersion-strengthened bar stock has increased tensile strength
and hardness at elevated temperatures or after annealing as
compared to bar stock of a similar iron-beryllium alloy which has
not been internally oxidized. Furthermore, the
dispersion-strengthed bar stock does not have the disadvantages
that normally result from compositional variations when the spent
oxidant is present in the dispersion-strengthened workpiece.
EXAMPLE 16
Dispersion-strengthened metal bar stock is formed by the
above-described method by oxidizing 100 parts of a powdered alloy
of 99.04 percent silver and 0.96% aluminum with 12.70 parts of
pulverulent oxidant comprising 12.48 parts of silver oxide and 0.22
parts of aluminum oxide. The resulting dispersion-strengthened bar
stock has increased tensile strength and hardness at elevated
temperatures or after annealing as compared to bar stock of a
similar silver-aluminum alloy which has not been internally
oxidized. Furthermore, the dispersion-strengthened bar stock does
not have the disadvantages that normally result from compositional
variations when the spent oxidant is present in the
dispersion-strengthened workpiece.
EXAMPLE 17
Dispersion-strengthened metal bar stock is formed by the
above-described method by oxidizing 100 parts of a powdered alloy
of 98.84 percent silver and 1.16 percent magnesium with 11.30 parts
of pulverulent oxidant comprising 11.10 parts of silver oxide and
0.20 parts of magnesium oxide. The resulting
dispersion-strengthened bar stock has increased tensile strength
and hardness at elevated temperatures and after annealing as
compared to bar stock of a similar silver-magnesium alloy which has
not been internally oxidized. Furthermore, the
dispersion-strengthened bar stock does not have the disadvantages
that noramally result from compositional variations when the spent
oxidant is present in the dispersion-strengthened workpiece.
Examples 18 and 19 illustrate the dispersion strengthening of
alloys of matrix metals (rather than a single matrix metal) by
internal oxidation using the method of Examples 8 through 17.
EXAMPLE 18
Dispersion-strengthened metal bar stock is formed by the
above-described method by oxidizing 100 parts of a powdered alloy
of 72,54% copper, 26.33 percent nickel and 1.13 percent aluminum
with 4.75 parts of pulverulent oxidant comprising 4.67 parts of
nickel oxide and 0.08 parts of aluminum oxide. The matrix
composition of the resulting dispersion-strengthened bar stock is
70.6 percent copper metal and 29.4 percent nickel metal. The
resulting dispersion-strengthened bar stock has increased tensile
strength and hardness at elevated temperatures or after annealing
as compared to bar stock of a similar copper-nickel-aluminum alloy
which has not been internally oxidized. Furthermore, the
dispersion-strengthened bar stock does not have the disadvantages
that normally result from compositional variations when the spent
oxidant is present in the dispersion-strengthened workpiece.
EXAMPLE 19
Dispersion-strengthened metal bar stock is formed by the
above-described method by oxidizing 100 parts of a powdered alloy
of 60.00 percent nickel, 19.55 percent molybdenum, 20.00 percent
iron and 0.45 percent aluminum with 1.207 parts of pulverulent
oxidant comprising 1.200 parts of molybdenum oxide and 0.007 parts
of aluminum oxide. The matrix composition of the resulting
dispersion-strengthened bar stock is 59.5 percent nickel metal,
21.0 percent molybdenum metal and 19.5 percent iron metal. The
resulting dispersion-strengthened bar stock has increased tensile
strength and hardness at elevated temperatures or after annealing
as compared to bar stock of a similar
nickel-molybdenum-iron-aluminum alloy which has not been internally
oxidized. Furthermore, the dispersion-strengthened bar stock does
not have the disadvantages that normally result from compositional
variations when the spent oxidant is present in the
dispersion-strengthened workpiece.
Examples 20 and 21 illustrate the dispersion strengthening of alloy
of matrix metals and solute metals with an oxidant containing a
hard, refractory oxide that is different from the solute metal
oxide.
EXAMPLE 20
Dispersion-strengthened metal bar stock is formed by the
above-described method by oxidizing 100 parts of a powdered alloy
of 98.87 percent copper and 1.13 percent aluminum with 9.34 parts
of pulverulent oxidant comprising 9.20 parts of copper oxide and
0.14 parts of beryllium oxide. The resulting
dispersion-strengthened bar stock has increased tensile strength
and hardness at elevated temperatures or after annealing as
compared to bar stock of a similar copper-aluminum alloy which has
not been internally oxidized. Furthermore, the
dispersion-strengthened bar stock does not have the disadvantages
that normally result from compositional variations when the spent
oxidant is present in the dispersion-strengthened workpiece,
although the dispersed oxides are dissimilar.
EXAMPLE 21
Dispersion-strengthened metal bar stock is formed by the
above-described method by oxidizing 100 parts of a powdered alloy
of 99.8 percent nickel and 0.2 percent zirconium with 0.329 parts
of pulverulent oxidant comprising 0.327 parts of nickel oxide and
0.002 parts of aluminum oxide. The resulting
dispersion-strengthened bar stock has increased tensile strength
and hardness at elevated temperatures or after annealing as
compared to the bar stock of similar nickel-zirconium alloy which
has not been internally oxidized. Furthermore, the
dispersion-strengthened bar stock does not have the disadvantages
that normally result from compositional variations when the spent
oxidant is present in the dispersion-strengthened workpiece,
although the dispersed oxides are dissimilar.
* * * * *