U.S. patent number 3,729,794 [Application Number 05/074,962] was granted by the patent office on 1973-05-01 for fibered metal powders.
This patent grant is currently assigned to Norton Company. Invention is credited to Richard W. Douglass.
United States Patent |
3,729,794 |
Douglass |
May 1, 1973 |
**Please see images for:
( Certificate of Correction ) ** |
FIBERED METAL POWDERS
Abstract
Refractory metal powder compacts are sintered and impregnated
with a softer metal. The compacts are reduced to rod, wire or
sheet. In the process fine fibers of the metal powder are
formed.
Inventors: |
Douglass; Richard W. (Needham,
MA) |
Assignee: |
Norton Company (Worcester,
MA)
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Family
ID: |
22122692 |
Appl.
No.: |
05/074,962 |
Filed: |
September 24, 1970 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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807129 |
Mar 13, 1969 |
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626773 |
Mar 29, 1967 |
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Current U.S.
Class: |
428/567; 75/229;
419/4; 428/605; 428/608; 428/661; 419/24; 422/311; 428/614;
29/419.1; 75/950; 419/27; 428/606; 428/611; 428/674 |
Current CPC
Class: |
C22C
47/08 (20130101); B22F 3/002 (20130101); B22F
3/1134 (20130101); B22F 2998/00 (20130101); Y10T
428/12812 (20150115); Y10T 29/49801 (20150115); Y10T
428/12465 (20150115); Y10S 75/95 (20130101); Y10T
428/12486 (20150115); B22F 2998/00 (20130101); Y10T
428/12431 (20150115); Y10T 428/1216 (20150115); Y10T
428/12424 (20150115); Y10T 428/12444 (20150115); Y10T
428/12903 (20150115) |
Current International
Class: |
C22C
47/08 (20060101); B22F 3/00 (20060101); C22C
47/00 (20060101); B22f 007/00 () |
Field of
Search: |
;29/182,182.1
;75/DIG.1,200,214,201 |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
Lund et al., "International Journal of Powder Met" Vol. 2, No. 3,
1966..
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Primary Examiner: Quarforth; Carl D.
Assistant Examiner: Schafer; R. E.
Parent Case Text
This application is a continuation-in-part of application Ser. No.
807,129, filed Mar. 13, 1969, which is a continuation of
application Ser. No. 626,773, filed Mar. 29, 1967, now
abandoned.
Other related copending applications are Ser. No. 59,555 filed July
30, 1970, Ser. No. 869,404 filed Mar. 13, 1969, as a division of
626,773, Ser. No. 839024 filed July 3, 1969 as a division and
continuation-in-part of Ser. No. 626,773 and 807,129 and 869,404,
and Ser. No. 196,812 filed 8 Nov. 1971 as a division of said Ser.
No. 839,024.
Claims
What is claimed is:
1. An elongated composite material comprising a fibrous reinforcing
component of a first metal in a matrix of a second metal, said
first metal being a refractory metal in elongated fiber form with
an average length of at least 0.025 centimeters and said
reinforcing component comprising an elongated felt bundle of said
fibers axially oriented in the direction of the long dimension of
the fibers, the fibers being interconnected to each other be
metallurgically bonded cross-links spaced along the fiber lengths,
said second metal comprising a metal which is compatible with said
first metal.
2. The composite material of claim 1 wherein said fibers were
cold-work strengthened to the point that the elongated composite
has a tensile strength at least equal to an equivalent volume and
cross-section of an elongated member of the first metal alone.
3. The composite material of claim 1 wherein the fibers have an
average diameter of less than 0.00025 centimeters.
4. The composite material of claim 1 as produced by forming a
powder metallurgy compact of the first metal with sintered bonds
between powders and interconnected open space within the compact,
inpregnating a compatible matrix metal in molten form into the open
space to form a matrix for the first metal cooling the molten phase
to solid, mechanically working the impregnated compact to an
elongated form and fibering the powders while so doing.
5. The composite material of claim 4 wherein said second metal is
the originally impregnated matrix metal.
6. The composite material of claim 4 as produced by removing the
originally impregnated matrix metal after elongation and
substituting said second metal therefor through impregnation of the
fiber bundle with said second metal.
7. The product of claim 1 wherein the fibers comprise niobium
stannide and the matrix comprises copper.
8. The product of claim 1 wherein the fibers comprise tantalum and
the matrix comprises copper.
9. The product of claim 1 wherein the fibers comprise molybdenum
and the matrix comprises copper.
10. The product of claim 1 wherein the fibers comprise tungsten and
the matrix comprises copper.
11. The product of claim 1 wherein the felt has a swollen
arrangement to exhibit a density of less than half of the
theoretical density of the metal.
12. The product of claim 1 wherein the felt has a compact
arrangement with a density over half of the theoretical density of
the metal.
Description
The present invention relates to composites reinforced by metal
fibers particularly the class of hard metals having high strength
and high temperature use capability (having at least 50 percent
room temperature strength at 500.degree.C and is distinctly
advantageous as applied to refractory metals and of extraordinarily
small diameter which may be on the order of a micron or less, while
having continuous length of several times diameter and as high as
ten inches.
BACKGROUND
Metal felts and fine metal wires or fibers or filaments used in
such felts 8re known in the art as indicated in U.S. Pat. Nos.
2,903,787 and 3,178,280. These felts are made from standard cold
reduced metal wires which are limited to minimum diameters on the
order of 0.001 - 0.10 inches or less by the inherent
vulnerabilities of standard drawing processes or from shavings from
metal blocks which are characterized by many surface defects. Much
finer wires can be made by extrusion as indicated in U.S. Pat., No.
3,199,331 to Allen. But production by this process is substantially
limited as a practical matter to low melting metals and alloys
(e.g., tin). Other prior art of interest is Buehler, U.S. Pat. No.
3,124,455 and the Speidel, Levi and Wulff work cited below.
The present invention involves as a principa object the production
of metal fibers of sub-micron size by a new process which is
capable of being used with high temperature metals such as
tantalum.
It is a further object of the invention to provide an economical
method of making metal fibers on the order of 10 microns or less,
and preferably sub-micron, in diameter with a single series of
processing steps; i.e., free of the expensive supplementary or
recycling processing involved, for instance, inSpeidel, U.S. Pat.
3,256,118, Levi, U.S. Pat. No. 3,029,496 and Wulff, January 1966
Journal of Applied Physics, p. 5.
It is a further object of the invention to provide work hardened
fibers by a production process free of the need for intermediate
anneals as required in the above patents of Allen and Levy, and for
use in composites providing a high degree of work hardening in
final product form, with or without a final low anneal for stress
relief of the matrix only.
Other objects, features and advantages of the present invention
will in part be obvious and will in part appear hereinafter.
DESCRIPTION
The invention is now described with respect to typical specific
embodiments thereof and with reference to the accompanying drawings
wherein:
FIG. 1 is a block diagram of the process of the invention.
FIG. 2 is a copy of a photomicrograph of a composite according to
the invention.
FIG. 3 is a copy of a photomicropraph of a metal felt according to
the invention.
FIGS. 4-10 are copies of photomicrographs of a composite according
to the invention.
The fibers of the invention are made and used by the following
process described with reference to FIG. 1 which is a block diagram
of the process. First, powders of the metal to be fibered are
obtained. The metal may be any of the refractory metals (as
elements, alloys or compounds) including tantalum, niobium,
molybdenum, tungsten, chromium, beryllium, magnesium oxide,
titanium hydride and fabricable aluminides and silicides. The
invention would also be of particular utility and distinctly
advantageous benefit in fibering other hard metal elements,
compounds or alloys which have softening temperatures in excess of
about 1,000.degree.C. The starting powder size is variable
dependinG upon subsequent processing and reactivity of the powders.
The invention has been practiced successfully for instance with
tantalum powders as large as minus 100 mesh and as small as a few
microns diameter. The powder is consolidated into a compact by
pressing and sintering or sintering ina mold. Then a melt of a
second metal is provided in vacuum or inert atmosphere and the
powder compact of the first metal is impregnated by eipping in the
melt. During both the sintering and impregnating steps the compact
is degassed and purified to enhance its wettability and
ductility.
The second metal may be any of aluminum, copper, nickel, Woods
metal, tin, indium, mercury, or any other metal which meets the
following criteria with respect to the first metal under the
conditions of impregnation:
1. readily wet the skeleton structure of the sintered compact of
the first metal.
2. not alloy extensively with the first metal.
3. have similar hardness and fabrication characteristics to the
extent necessary for co-working.
4. be easily removable from the compact by chemical or thermal
means.
The impregnated compact is then worked down to an this process the
adjacent particles of hard metal in the compact begin to form long
fibers within the matrix of the second metal.
At this point, the rod or cylinder or plate may be used or
fabricated into a useful product in any of tht following ways:
A-1. Removing the matrix metal and
a. using directly as a filter or with further fabrication as a
capacitor
b. separating out individual fibers
c. re-impregnating the fibered article
A-2. Using the rod directly as a composite structural element
B- Rolling the rod to sheet prior to (1) or (2) above
C- Drawing the rod to wire prior to (1) or (2) above
D- Heating the rod for diffusion reaction between the hard metal
fibers and the matrix prior to (1) or (2) above.
Several permutations of the foregoing can be made. For instance a
rod can be drawn for several passes before rolling. A wire or sheet
can be heated for diffusion reaction. Similarly a re-impregnated
article can be used as a composite, with or without a diffusion
reaction, or re-leached. With diffusion reactions, fibers of alloys
or compounds can be formed even though such alloys are too brittle
to be fibered directly. Another alternative in the scope of the
invention is to form a loose fiber bundle or separate fiber (a or b
above) and expose it to an oxidizing or nitriding atmosphere. In
this way fibers of aluminum oxide or aluminum nitride can be made
for use in reinforced composite structures. Also fibers of tantalum
or niobium nitride can be made for use as superconductors. In these
applications it is of special interest that the fiber diameters are
so small as to favor the formation of the above compounds in single
crystal form which is especially desirable.
The fibers of the invention are characterized in that each fiber is
derived from a single powder particle and its length is dependent
on the degree of diameter reduction. For instance, an 8 micron
diameter powder particle fibered to 0.1 microns diameter will have
a length of about 1 inch, a 30 micron diameter particle fibered to
0.1 microns diameter will have a length of about 70 inches. Further
cold working to finer fiber diameters would increase the length. In
most applications of the invention, useful fibers will have a
length of 10 times the diameter of the fiber or longer (as high as
10.sup.6 times for extreme cases).
The felts of the invention are characterized by substantial
cross-linking by metallurgical bonds between tangentially
contacting fibers corresponding in part to the bonds between
powders in the original powder compact skeleton and corresponding
in part to new bonds formed during cold working the impregnated
compact down to an elongated article, the new bonds being
essentially an extension or stretching out of the old bonds.
FIG. 2 shows longitudinal section photomicrograph of a composite in
the form of a wire of 0.039 inch diameter at 133 times
magnification. The composite has elongated reinforcing tantalum
fibers in a matrix of copper. The starting material for the fibered
metal was coarse melting grade powder minus 12 and plus 60 mesh
pressed at 18,000 psi and sintered at 2,300.degree.C for one hour
to produce a compact of 61 percent density.
FIG. 3 shows a longitudinal section photomicrograph of a tantalum
metal felt, encapsulated in a molding resin for microscope
examination, at 266 times magnification. The tantalum was made from
nominal 8 micron diameter powders (minus 100 mesh and plus 5
microns) which was consolidated to a compact of about 50 percent
density and then impregnated with copper and then swaged to rod and
rolled to sheet after which the copper was leached out in a nitric
acid bath. Upon leaching the metal felt ballooned up to several
times its original volume.
Fibers obtained from rod or wire are found to be essentially
circular in cross-section and fibers obtained from sheet are found
to be rectangular in cross-section. The term "diameter" as used
herein refers to diameter of a circle or width of a rectangle.
The practice of the invention is further illustrated by the
following non-limiting Examples.
EXAMPLE 1
A mold was filled with tantalum powder of about 8 micron nominal
diameter (-100 mesh and plus 5 microns) and the powder was sintered
in the mold at 1,500.degree.C for 20 minutes to form a green
compact. Then sintering was completed by removing the compact from
the mold and heating at 2,300.degree.C for 1 hour to complete
consolidation of the powder. The density of the compact was 8.22
gms/cc or 49.5 percent of theoretical density. The compact was
vacuum impregnated with copper by dipping in a molten copper bath
at 1,170.degree.C for 5 minutes under a vacuum of about
10.sup.-.sup.4 torr. The impregnated compact (0.35 inches diameter
by 4 inches long) was enclosed in an iron pipe and then swaged to
0.125 inches diameter. The jacket was removed and the rod was then
further swaged to 0.080 inches diameter. After swaging the rod was
then leached in nitric acid to remove the copper. The leached
compact left a bundle of interwoven tantalum fibers in the form of
a felt.
This metal felt was rinsed and removed from the leach bath. The
felt was anodized and formed into a capacitor anode and tested for
capacitor properties in a wet electrolyte. The formation voltage
was 200 volts and the capacitance was 30.6 microfarads and on a
specific weight basis 6,120 microfarad -- volts per gram. The felt
had a dissipation factor of 32.19 percent making it an over-all
operable capacitor anode.
EXAMPLE 2
Tantalum felts were made as in Example 1 but with the difference
that the compact was rolled to 0.010 inch thich sheet before
leaching. The felt exhibited a vigorous swelling up with a volume
incrtase and density decrease of 5-10 increase during leaching and
floated on the leaching bath. The capacitor formed from the felt at
150 volts had 7,965 microfarad -- volts per gram specific
capacitance.
EXAMPLE 3
Felts were made as in Examples 1 and 2 with the difference that
consolidation of the tantalum powder was accomplished by pressing
at 18,000 psi and then sintering at 2,250.degree.C for one hour and
that some rods were drawn to wire. Densities of 60 - 80 percent of
theoretical were obtained in the original compact. Upon leaching
the final composite article of this type, the felt did not swell
up. However, high values of capacitance were still obtained
indicating substantial formation of new surface as in Examples 1
and 2 (surface enhancement of about 2.5 times).
EXAMPLE 4
Several fibers from the felts of Examples 1 and 2 were encapsulated
in epoxy resin and measured to yield an individual fiber diameter
indication of 0.0002 cm. diameter. The Example 2 fibers were 5 to
10 times as long as the diameter of the fiber; the Example 1 fibers
were continuous over much longer length.
EXAMPLE 5
Several compacts made essentially as in Examples 1 and 2 were
rolled or drawn to the final sizes indicated below for testing of
their composite material properties. These tantalum reinforced
copper composites were in the form of 0.020 inch diameter wire and
as 0.010 inch thick sheet, both as worked and after being heated
(350.degree.C for 1 hour to anneal the copper). The results for
these specimens and for comparison, the properties of tantalum and
copper, per se, are given in Table 1:
TABLE 1
Example 5 Sample Ultimate Tensile Strength a. 0.01-0.020 inch
diameter wire as worked 160,000-195,000 psi b. wire with stress
relief 150,000-172,000 c. sheet, as worked 99,000-127,000 d. sheet,
stress relieved 93,000 e. Pure tantalum, as worked (0.005 and 0.015
inch thick sheet) 104,000-116,000 f. Pure copper, as worked (0.005
and 0.015 inch thick sheet) 59,000-60,500
EXAMPLE 6
A molybdenum -- copper composite was made and tested in the same
manner as the tantalum -- copper composites of Example 5 and formed
into 0.06 and 0.08 in wire which displayed ultimate tensile
strengths of 81,700 and 108,000 psi, respectively.
EXAMPLE 7
Tantalum felts made as in Examples 4 and 2 were tested for tensile
strength after leaching out the copper. The results are in Table
2.
TABLE 2
Example Sample Ultimate Tensile Strength a. 0.01 in sheet 114,700
psi b. 0.04 in wire 90,000 psi EXAMPLE 8 Iron powder of -- 270 mesh
was mold sintered at 800.degree.C for 20 minutes and then finally
sintered at 1,150.degree.C for 1 hour to a density of 3.45 grams
per cc (45 percent theoretical) impregnated as above and worked to
0.025 inch wire and leached to form a fibrous bundle of iron fibers
0.0015 cm diameter, quite continuous and having a surface layer of
copper -- iron alloy overlaid by residual copper but with a
substantial core of pure iron in the fibers.
EXAMPLE 9
Before leaching, the iron -- copper composite wire of Example 8 was
tested for tensile strength and this was found to be 160,000
psi.
EXAMPLE 10
Leaching experiments were conducted and a solution of 5 parts
ammonium hydroxide in one part hydrogen peroxide was found to be
superior to nitric acid for selectively leaching copper from the
iron to free the iron fibers from the composites.
EXAMPLE 11
A sample of -100/+325 mesh tantalum powder was placed inside of a
sealed rubber tube and was isostatically pressed at 3,000 psi. The
pressed powder bar (1 inch diameter rod) was then vacuum sintered
at 2,200.degree.C for 2 hours to give a theoretical density of 45
percent. The sintered porous powder bar was infiltrated with
superheated copper to give a composite of 1 inch diameter. The
Ta-Cu composite was swaged to 0.2 inch in diameter and was sheared
into 1/4 inch slugs. Copper was then leached out from the cut ends
of the 1/4 inch slugs leaving an array of tantalum fiber ends. The
leached cut ends were then examined microscopically.
FIG. 4 showed a low magnification (29X) photograph of the sheared
end of a fiber tantalum slug FIGS. 5, 6 and 7 were magnified (700X)
photomicrographs of regions A, B and C marked in FIG. 4
respectively. These were taken end-on from a viewing angle of
15.degree. with respect to the rod (slug) axis. FIGS. 8 and 9 were
two different magnifications (670X and 2,650X, respectively; FIG. 9
being a blow-up of the circled area of FIG. 8 - note the
corresponding die marks) of the side surface of the slug. FIG. 10
was an inside longitudinal section view at 530X of the slug located
half a radius distance from center to periphery of the slug.
The slugs were cut from top to bottom of the FIG. 4 view and
ductile failure is apparent at the bottom edge of the slug (region
C). Fibers at or near the slug peripheries are of tobacco-leaf form
reflecting the characteristic twisting of swaging operations. But
fibers below the surface are filamentary in appearance and are
believed to be round in cross-section at the center of the slugs
(note FIGS. 8 and 9 for surface and sub-surface fibers). All
figures (except low magnification FIG. 4) show the essentially
straight axial orientation of the fibers. Interconnections can also
be seen in the side views.
The best mode of using the invention is believed to be selection of
a tantalum - copper pair to produce a tantalum felt suitable for
use as a capacitor anode. In addition to the above indicated
advantages of ease of processing, surface enhancement and work
hardening it is a further useful advantage of the invention that it
may be practiced if desired, with relatively coarse melting grade
tantalum powder in the original compact rather than the
conventional fine grain capacitor grade powder and the desired
surface area increase can be obtained in the fibering p7ocess
rather than in the original processing of the pooder. A further
useful aspect of the invention is the above described feature of
swelling when the original compact is made in low density (40 - 60
percent theoretical) and/or when a high degree of working is put
into the composite. The swelling of the metal felt, when utilized
makes it easier to refill the felt with an anodizing medium and
electrolyte.
The extension to other species of the above advantages and
variations in processing and still other advantages and variations
will be obvious to those skilled in the art from the description
herein. For instance, a niobium - tin pair could be utilized to
4btain interconnected niobium fibers in a tin matrix with a better
degree of interconnection between fibers than is obtainable in the
process of the above described Speidel patent. Then the composite
could be heated for diffusion reaction to form a niobium stannide
superconductor subsequent to which residual tin would be leached
out and replaced with copper by re-impregnation to provide a higher
conductivity matrix for electrical stability of the
superconductor.
A high degree of control of the final product is obtainable. For
instance, use of coarse melt grade powders or low density
consolidation of the original compact (40 - 60 percent) tend to
limit the number of cross-link bonds formed between fibers thereby
enhancing the swelling up of fibers upon leaching the matrix metal
and enhancing the ease of separation of fibers.
For superconductor applications it is particularly desirable to use
a fine grain powder and form the original compact to a higher
density for forming maximum cross-links between fibers. Still other
applications within the scope of the present invention will be
apparent to those skilled in the art when aided by the foregoing
description. The description is therefore intended to be read as
illustrative and not in a limiting sense.
* * * * *