U.S. patent application number 10/830208 was filed with the patent office on 2005-10-27 for binary rhenium alloys.
This patent application is currently assigned to Rhenium Alloys, Inc.. Invention is credited to Guthman, Clifford L., Leonhardt, Todd A..
Application Number | 20050238522 10/830208 |
Document ID | / |
Family ID | 35136632 |
Filed Date | 2005-10-27 |
United States Patent
Application |
20050238522 |
Kind Code |
A1 |
Leonhardt, Todd A. ; et
al. |
October 27, 2005 |
Binary rhenium alloys
Abstract
Rhenium-tungsten alloys including rhenium and from about 0.025%
to less than about 10% by weight tungsten. The rhenium-tungsten
alloys are formed by a process that includes coating rhenium metal
powders with a liquid including a tungsten compound, drying the
coated rhenium powder, compressing the dried coated powder to form
a compact, and then sintering the compact to form the
rhenium-tungsten alloy. The rhenium-tungsten alloys according to
the invention exhibit mechanical properties that are superior to
high-purity rhenium metal without a loss in ductility.
Inventors: |
Leonhardt, Todd A.; (Medina,
OH) ; Guthman, Clifford L.; (Amherst, OH) |
Correspondence
Address: |
RANKIN, HILL, PORTER & CLARK, LLP
925 EUCLID AVENUE, SUITE 700
CLEVELAND
OH
44115-1405
US
|
Assignee: |
Rhenium Alloys, Inc.
Elyria
OH
|
Family ID: |
35136632 |
Appl. No.: |
10/830208 |
Filed: |
April 22, 2004 |
Current U.S.
Class: |
419/28 ; 419/29;
419/35; 420/433 |
Current CPC
Class: |
B22F 2998/10 20130101;
B22F 1/025 20130101; C22C 27/00 20130101; B22F 3/02 20130101; B22F
3/10 20130101; B22F 1/02 20130101; C22C 1/04 20130101; B22F 2998/10
20130101 |
Class at
Publication: |
419/028 ;
419/029; 419/035; 420/433 |
International
Class: |
B22F 003/12 |
Claims
What is claimed is:
1. An alloy consisting essentially of rhenium and from about 0.025%
up to about 10% by weight tungsten, the alloy exhibiting a room
temperature tensile strength in excess of 150 Ksi and an elongation
of 25% or greater as measured in accordance with ASTM E8-03.
2. The alloy according to claim 1 consisting essentially of rhenium
and from about 0.025% to about 5% by weight tungsten.
3. The alloy according to claim 1 consisting essentially of rhenium
and from about 0.05% to about 2.5% by weight tungsten.
4. The alloy according to claim 1 consisting essentially of rhenium
and from about 0.06% to about 1.25% by weight tungsten.
5. An alloy consisting essentially of rhenium and from about 0.025%
up to about 10% by weight tungsten formed by a process comprising:
coating a metal powder consisting essentially of rhenium with a
liquid comprising a tungsten compound; drying the coated metal
powder; compressing the coated metal powder to form a compact; and
sintering the compact to form the alloy.
6. The alloy according to claim 5 consisting essentially of rhenium
and from about 0.025% to about 5% by weight tungsten.
7. The alloy according to claim 5 consisting essentially of rhenium
and from about 0.05% to about 2.5% by weight tungsten.
8. The alloy according to claim 5 consisting essentially of rhenium
and from about 0.06% to about 1.25% by weight tungsten.
9. A method comprising: coating a metal powder consisting
essentially of rhenium with a liquid comprising a tungsten
compound; drying the coated rhenium powder; compressing the coated
powder to form a compact; and sintering the compact to form an
alloy consisting essentially of rhenium and from about 0.025% up to
about 10% by weight tungsten.
10. The method according to claim 9 wherein the alloy consists
essentially of rhenium and from about 0.025% to about 5% by weight
tungsten.
11. The method according to claim 9 consisting essentially of
rhenium and from about 0.05% to about 2.5% by weight tungsten.
12. The method according to claim 9 consisting essentially of
rhenium and from about 0.06% to about 1.25% by weight tungsten.
13. The method according to claim 9 wherein the liquid comprises
ammonium metatungstate.
14. The method according to claim 9 further comprising cold rolling
the sintered compact.
15. The method according to claim 9 further comprising annealing
the sintered compact.
16. A wire formed of an alloy consisting essentially of rhenium and
from about 0.025% up to about 10% by weight tungsten.
17. The wire according to claim 16 wherein the alloy consists
essentially of rhenium and from about 0.025% to about 5% by weight
tungsten.
18. The wire according to claim 16 wherein the alloy consists
essentially of rhenium and from about 0.05% to about 2.5% by weight
tungsten.
19. The wire according to claim 16 wherein the alloy consists
essentially of rhenium and from about 0.06% to about 1.25% by
weight tungsten.
20. A method of forming an alloy consisting essentially of rhenium
and from about 0.025% up to about 10% by weight tungsten
comprising: providing a precipitate comprising a rhenium compound
and a tungsten compound; compressing the precipitate to form a
compact; and sintering the compact to form the alloy.
21. An alloy consisting essentially of rhenium and from about
0.025% up to about 10% by weight of a metal selected from the group
consisting of tungsten, molybdenum, tantalum, iridium, ruthenium
and osmium, the alloy formed by a process comprising: coating a
metal powder consisting essentially of rhenium with a liquid
comprising a compound selected from the group consisting of
tungsten, molybdenum, tantalum, iridium, ruthenium and osmium;
drying the coated metal powder; compressing the coated metal powder
to form a compact; and sintering the compact to form the alloy.
22. A method comprising: coating a metal powder consisting
essentially of rhenium with a liquid comprising a compound selected
from the group consisting of tungsten, molybdenum, tantalum,
iridium, ruthenium and osmium; drying the coated rhenium powder;
compressing the coated powder to form a compact; and sintering the
compact to form an alloy consisting essentially of rhenium and from
about 0.025% up to about 10% by weight of a metal selected from the
group consisting of selected from the group consisting of tungsten,
molybdenum, tantalum, iridium, ruthenium and osmium.
23. A method of forming an alloy consisting essentially of rhenium
and from about 0.025% up to about 10% by weight of a metal selected
from the group consisting of tungsten, molybdenum, tantalum,
iridium, ruthenium and osmium, the method comprising: providing a
precipitate comprising a rhenium compound and a compound comprising
a metal selected from the group consisting of tungsten, molybdenum,
tantalum, iridium, ruthenium and osmium; compressing the
precipitate to form a compact; and sintering the compact to form
the alloy.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of Invention
[0002] The present invention relates to a process of forming
rhenium-tungsten alloys that exhibit exceptional mechanical
properties and rhenium-tungsten alloys formed according to the
process.
[0003] 2. Description of Related Art
[0004] Rhenium has a very high melting point (mp 3180.degree. C.),
no known ductile to brittle transition temperature, excellent
chemical resistance and high electrical resistivity over a wide
temperature range. It is sold in the form of foil, sheet, plate,
ribbon, wire, rod and powders for use in a variety of applications,
particularly in the lighting and aerospace industry.
[0005] Rhenium is derived primarily from the roasting of molybdenum
concentrates generated in the copper mining industry. During the
roasting of molybdenite, rhenium is oxidized and carried off in the
flue gases. These gases are scrubbed to remove the rhenium, which
is then recovered in solution using an ion exchange process. The
rhenium solution is then treated and neutralized with ammonium
hydroxide to precipitate ammonium perrhenate. Ammonium perrhenate
can be reduced in a hydrogen atmosphere to form rhenium metal
powder. The rhenium metal powder can be compacted and sintered to
form high-purity rhenium metal.
[0006] Depending upon the raw material source and processing
techniques employed, high-purity rhenium metal will typically have
a rhenium content of from about 99.8% to 99.9999% by weight (on a
metallic content basis). The most common trace contaminant in
high-purity rhenium metal is molybdenum, but traces of other
elements are sometimes also observed in high-purity rhenium
metal.
[0007] High-purity rhenium metal has a maximum room temperature
tensile strength of about 140 Ksi, as tested in accordance with the
ASTM E8-03 standard. Inter-granular separation has been observed in
samples of high-purity rhenium metal during processing and
mechanical testing. High-purity rhenium metal appears to fail in
such testing at the grain boundaries.
BRIEF SUMMARY OF THE INVENTION
[0008] The present invention provides a process of forming
rhenium-tungsten alloys consisting essentially of rhenium and from
about 0.025% (250 ppm) to less than about 10% by weight tungsten.
The process according to the invention comprises coating rhenium
metal powder with a liquid comprising a tungsten compound, drying
the coated rhenium powder and then sintering the dried coated
rhenium powder to obtain the rhenium-tungsten alloy. Alternatively,
a liquid comprising a rhenium compound can be contacted with a
liquid comprising a tungsten compound to form a mixture, which is
then treated with a precipitating agent. The precipitate is then
dried and sintered to obtain a rhenium-tungsten alloy.
[0009] Rhenium-tungsten alloys formed in accordance with the
methods of the invention exhibit improved mechanical properties at
all temperature ranges as compared to high-purity rhenium, without
exhibiting a loss in ductility. The presence of the relatively
small amount of tungsten in the rhenium-tungsten alloys according
to the invention appears to produce an alloy having a substantially
smaller grain structure than that which is observed in high-purity
rhenium metal. This smaller grain structure is believed to improve
the mechanical properties of the rhenium-tungsten alloys, which
also improves its processability.
[0010] The foregoing and other features of the invention are
hereinafter more fully described and particularly pointed out in
the claims, the following description setting forth in detail
certain illustrative embodiments of the invention, these being
indicative, however, of but a few of the various ways in which the
principles of the present invention may be employed.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] FIG. 1 is a photomicrograph showing the grain structure of a
rhenium-tungsten alloy according to the invention.
[0012] FIG. 2 is a photomicrograph showing the grain structure of
high purity rhenium metal.
[0013] FIG. 3 is a photograph showing the edge of a sheet of cold
rolled rhenium and the edge of a sheet of a cold rolled
rhenium-tungsten alloy.
[0014] FIG. 4 is a graph showing the longitudinal tensile
stress-strain response of a cold rolled rhenium-tungsten alloy
according to the invention at 70.degree. F. in comparison to that
of cold rolled high-purity rhenium metal at the same
temperature.
[0015] FIG. 5 is a graph showing the longitudinal tensile
stress-strain response of a cold rolled rhenium-tungsten alloy
according to the invention at 2500.degree. F. in comparison to that
of cold rolled high-purity rhenium metal at the same
temperature.
[0016] FIG. 6 is a graph showing the longitudinal tensile
stress-strain response of a cold rolled rhenium-tungsten alloy
according to the invention at 3500.degree. F. in comparison to that
of cold rolled high-purity rhenium metal at the same
temperature.
DETAILED DESCRIPTION OF THE INVENTION
[0017] In accordance with the method of the invention, rhenium
powder is contacted with a liquid comprising a tungsten compound
under mixing conditions sufficient to evenly distribute the liquid
throughout the rhenium powder and thereby wet all of the rhenium
powder particles. The rhenium powder used in the invention can be
of any particle size and shape, but preferably is minus 200 mesh
rhenium flake powder. The rhenium powder is preferably very pure,
such as the 99.9999% purity rhenium powder sold by Rhenium Alloys,
Inc. of Elyria, Ohio, but other less pure rhenium powders can be
used. Typical trace contaminants found in rhenium powders include
molybdenum and/or potassium.
[0018] Ammonium metatungstate, which is soluble in water, is the
preferred tungsten compound for use in the invention, but other
compounds (typically tungsten salts) can be used such as, for
example, ammonium paratungstate, which is also soluble in water.
Ammonium metatungstate is a solid at typical room temperatures
(.about.22.5.degree. C.), but can be effectively combined with
rhenium powder in the form of a dilute aqueous solution.
[0019] No surfactants are generally needed in order to obtain good
wetting. The concentration of the tungsten compound in water or
other solvent is not critical, but should be adjusted such that
only enough water is used to completely wet all of the rhenium
powder. Mechanical blending is sufficient to obtain a homogeneous
distribution of the liquid comprising the tungsten compound and the
rhenium powder.
[0020] The use of a liquid comprising a tungsten compound is
necessary in order to obtain homogenous distribution of the
tungsten material throughout the bulk of rhenium powder. It is not
possible to obtain as even and as homogeneous a distribution of
tungsten throughout the bulk of the rhenium powder by mixing
tungsten powder with the rhenium powder. It is very difficult to
form a homogeneous mixture of dry tungsten powders and rhenium
powders due to differences in density and particle morphology.
However, a liquid comprising a tungsten compound can be evenly
distributed on the surface of rhenium powders, which leads to
excellent homogeneity upon drying.
[0021] Once the rhenium powder has been completely wetted with the
liquid comprising the tungsten compound, the coated rhenium powder
must be dried. The method of drying is not critical, and drying can
be accomplished by any conventional means. The bulk of the coated
rhenium powder can be heated without additional mixing or, more
preferably, the coated rhenium powder can be dried as it is being
tumbled or mixed. Depending upon the drying method employed, some
particle agglomeration may be observed. Agglomerated particles can
be ground into usable powder after the drying step without
disturbing or upsetting the homogeneous distribution of the
materials.
[0022] The dried coated rhenium metal powder is then compacted into
any desired shape. The material can be used to form products via
near-net shape powder metallurgy. The material can also be
consolidated using cold isostatic pressing or die compaction, which
is well known. The compaction conditions used with the dried coated
rhenium metal powders are the same as used in conventional powder
metallurgy for high purity rhenium.
[0023] Compaction of the dried coated rhenium metal powder results
in the formation of a green compact. Preferably, the green compact
is pre-sintered to reduce any oxides that may be present, to reduce
the tungsten compound to tungsten metal, and also provides some
diffusion of the rhenium and tungsten. Pre-sintering times and
temperatures are not critical, but pre-sintering at temperatures
above 1,500.degree. C. for periods of greater than twelve hours
appear to provide the best results.
[0024] The pre-sintered compact is then sintered at a temperature
of greater than about 2,200.degree. C. in a reducing atmosphere or,
less preferably, in a vacuum. Sintering times should be kept at a
minimum, with a sintering time of six hours typically being
sufficient. Longer sintering times and higher sintering
temperatures tend to produce rhenium-tungsten alloys with a larger
grain structure, which is not desirable for some applications
because it tends to reduce the mechanical properties of the
resulting alloy.
[0025] After sintering, the resulting alloy can be, but need not
be, further treated in the same manner as high-purity rhenium
metal. Typical additional treatment steps include, for example, hot
isostatic pressing (HIP), cold-rolling, swaging and other cold
forming processes. The rhenium-tungsten alloys according to the
invention can be formed into final products using near-net shape
powder metallurgy, or into foils, sheets, plates, bars, rods, wires
and ribbons using conventional processing techniques and
equipment.
[0026] The method of the invention has heretofore been described as
a solid-liquid method, wherein solid particles of rhenium are
coated with a liquid comprising a tungsten compound. While this is
the preferred method, it is also possible to form rhenium-tungsten
alloys of the present invention via a liquid-liquid method. In the
liquid-liquid method, a liquid comprising a rhenium compound such
as perrhenic acid is mixed with a liquid comprising a tungsten
compound such as ammonium metatungstate to obtain a mixture. A
precipitating agent such as ammonium hydroxide is added to the
mixture to precipitate co-rhenium/tungsten salts. The
co-rhenium/tungsten salts can then be co-reduced to form a powder
that is suitable for compaction and consolidation as previously
described above.
[0027] The addition of a relatively small amount of tungsten to the
rhenium surprisingly resulted in the formation of an alloy having a
finer grained microstructure than that of high-purity rhenium
metal. The finer grain structure is believed to be one of the
reasons why the rhenium-tungsten alloys according to the invention
exhibit improved mechanical properties as compared to high purity
rhenium metal. For example, rhenium alloyed according to the
invention with 5% tungsten by weight (Re5% W) had a room
temperature tensile strength of 184 Ksi with 31% elongation, as
tested in accordance with the ASTM E8-03 standard. Rhenium alloyed
with 2.5% tungsten by weight (Re2.5% W) had a room temperature
tensile strength of 181 Ksi with 37% elongation. And, rhenium
alloyed with 1% tungsten by weight (Re1% W) had a room temperature
tensile strength of 171 Ksi with 44% elongation. These mechanical
properties exceed that of high-purity rhenium, which has a room
temperature tensile strength of 140 Ksi and an elongation of
36%.
[0028] A loss of ductility was observed as the tungsten content of
the alloy approached 10% by weight. Accordingly, an amount of
tungsten less than about 10% by weight preferred in order to obtain
the desired improvements in mechanical strength without losing
ductility. More preferably, the tungsten content of the alloys is
from about 0.025% to about 5% by weight, or about 0.05% to about
2.5% by weight, or about 0.06% to about 1.25% by weight. A
rhenium-tungsten alloy formed according to the present invention
having a tungsten content of about 0.067% by weight is particularly
preferred.
[0029] As noted above, the substantial improvements observed in the
mechanical properties of the alloys according to the invention was
not expected. Several phase diagrams of the binary tungsten-rhenium
system have been published over the years, but none included data
points in the area of present interest. Furthermore, prior art
binary tungsten-rhenium phase diagrams were based upon alloys that
were formed by arc-melting rhenium and tungsten together.
Applicants have found that the desired improvements in mechanical
properties provided by the rhenium-tungsten alloys of the present
invention cannot be obtained by arc-melting the relative amounts of
rhenium and tungsten together to form an alloy. Reasons for this
phenomenon include the difficulty of obtaining good dispersion of
the tungsten throughout the bulk of the rhenium and the formation
of very large grain structures at arc melting temperatures.
[0030] Rhenium-tungsten alloys according to the present invention
can be processed substantially more easily that conventional
high-purity rhenium metal. One particularly desirable processing
improvement is in the area of drawn wire, which is used as
filaments in some lighting applications. Thus, the present
invention provides wire formed of rhenium-tungsten alloys formed in
accordance with the process of the invention.
[0031] In addition to wire, rhenium-tungsten alloys of the present
invention are also suitable for use in the fabrication of rocket
engines, in heat shielding and in element packages for high
temperature furnaces. Other applications include hot valve
assemblies. Rhenium-tungsten alloys according to the invention can
be used in virtually any application where higher strength rhenium
is desired.
[0032] It is believed that rhenium can be alloyed with other metals
such as, for example, molybdenum, tantalum, iridium, ruthenium and
osmium, by coating a metal powder consisting essentially of rhenium
with a liquid comprising a compound of such metals, drying the
coated rhenium powder, compressing the coated powder to form a
compact and sintering the compact to form an alloy. Similarly, it
is believed that rhenium can be alloyed with such metals by
providing a precipitate comprising a rhenium compound and a
compound of such metals, compressing the precipitate to form a
compact and sintering the compact to form the alloy.
[0033] The following examples are intended only to illustrate the
invention and should not be construed as imposing limitations upon
the claims.
EXAMPLE 1
[0034] Six separate 200 gram portions of 99.9999% purity rhenium
powder flakes (-200 mesh) obtained from Rhenium Alloys, Inc. of
Elyria, Ohio were placed into separate beakers marked A, B, C, D, E
and F, respectively. Ammonium metatungstate was dissolved in
deionized distilled water and then added to the beakers labeled A,
B, C, D, E and F, respectively, to provide the final concentration
of tungsten shown in weight percent in Table 1 below. Additional
water was added to each beaker, as necessary, to insure good
wetting of the rhenium powders and good distribution of the
tungsten compound throughout the powders. The contents of each
beaker were stirred together until the liquid coated the powder
particles uniformly. A control sample comprising the 200 grams of
the same rhenium powder and distilled water (no tungsten compound
was added) was placed in a beaker marked Control.
[0035] The beakers containing the wetted powders were placed on a
hot plate and the volatile portion of the liquid was driven off.
Two 80 gram samples were taken from each beaker and die compacted
using a 90 ton hydraulic press to obtain green compacts of about
2.53 inches in length, about 0.61 inches in width and about 0.28
inches in height. The actual density of the compacts was determined
to be about 53% of theoretical density.
[0036] The green compacts were pre-sintered at 1400.degree. C. for
20 minutes. After pre-sintering, the pre-sintered compacts were
about 2.35 inches in length, 0.57 inches in width and about 0.26
inches in height. The actual density of the green compacts was
determined to be 65% of theoretical density.
[0037] The pre-sintered compacts were then sintered in a hydrogen
atmosphere at 2350.degree. C. for four hours to form test bars. The
test bars were allowed to cool to room temperature in the hydrogen
atmosphere. The test bars had a length of about 2.06 inches, a
width of about 0.49 inches and a height of about 0.23 inches. The
actual density of the test bars was about 97.5% of theoretical
density.
[0038] Each of the test bars was then repeatedly cold rolled and
annealed using conventional rhenium metal processing techniques to
form sheets about 0.080 inches thick. The sheets were EDM cut to
form sub-size tensile bars in accordance with the procedures set
forth in the ASTM E8-03 standard. The results of room temperature
tensile testing in accordance with the ASTM E8-03 standard are
reported in Table 1 below (where: "Re %" means weight percent
rhenium; "W %" means weight percent tungsten; "RT TS" means room
temperature (70.degree. F.) tensile strength as measured in
accordance with ASTM E8-03; "RT YS" means room temperature
(70.degree. F.) yield strength as measured in accordance with ASTM
E8-03; and RT Elong % means room temperature (70.degree. F.)
percent elongation as measured in accordance with ASTM E8-03).
1 TABLE 1 Control A B C D E F Re % 100 99.95 99.5 99.0 97.5 95.0
90.0 W % 0 0.05 0.5 1.0 2.5 5.0 10.0 RT TS 140 153 158 171 181 183
181 RT YS 47 77 79 86 94 92 143 RT Elong % 36 49 38 44 33 37 6
[0039] Table 1 shows that the rhenium-tungsten alloys according to
the invention exhibit improved tensile strength and increased the
yield strength as compared to high-purity rhenium, while
maintaining the ductility of the material until the tungsten
content of the allow approaches 10% by weight. FIG. 1 is a
photomicrograph showing that the ASTM E112-96e2 grain size of
tensile bar C (Re1% W) is 7. FIG. 2 is a photomicrograph showing
that the ASTM E112-96e2 grain size of the Control tensile bar is 4.
At all tungsten concentrations, the grain structure of the
rhenium-tungsten alloy according to the invention was much smaller
than that of high-purity rhenium.
[0040] In addition to the improvements in mechanical properties, an
increase in end product yield can be expected because the
rhenium-tungsten alloys produce less edge cracking. FIG. 3 is a
photograph that shows the edges of sheets from which tensile bar F
(top) and tensile bar C (bottom) were cut. Edge cracking is
significantly more pronounced in tensile bar F (top), which was
alloyed with 10% by weight tungsten, than tensile bar C (bottom),
which was alloyed with only 1% by weight tungsten.
EXAMPLE 2
[0041] An 0.080 inch thick sheet of a rhenium-tungsten alloy
containing 1% tungsten by weight (Re1% W) was formed using the
materials and procedures described in Example 1. Tensile bars were
cut from the sheet in accordance with ASTM E8-03 and ASTM E21-03a.
Tensile bars were tested at room temperature (70.degree. F.), at
2500.degree. F. and at 3500.degree. F. FIG. 4 is a graph of the
longitudinal tensile stress-strain response of the Re1% W alloy
(solid line) as compared to that of high-purity rhenium metal
(dashed line) at room temperature. FIG. 5 is a graph of the
longitudinal tensile stress-strain response of the Re1% W alloy
(solid line) as compared to that of high-purity rhenium metal
(dashed line) at 2500.degree. F. FIG. 6 is a graph of the
longitudinal tensile stress-strain response of the Re1% W alloy
(solid line) as compared to that of high-purity rhenium metal
(dashed line) at 3500.degree. F. As shown in the graphs, the Re1% W
alloy exhibited a higher longitudinal tensile stress-strain
response than high-purity rhenium at all three temperatures.
[0042] Additional advantages and modifications will readily occur
to those skilled in the art. Therefore, the invention in its
broader aspects is not limited to the specific details and
illustrative examples shown and described herein. Accordingly,
various modifications may be made without departing from the spirit
or scope of the general inventive concept as defined by the
appended claims and their equivalents.
* * * * *