U.S. patent number 3,815,224 [Application Number 05/151,111] was granted by the patent office on 1974-06-11 for method of manufacturing a ductile superconductive material.
This patent grant is currently assigned to The United States of American as represented by the United States Atomic. Invention is credited to Earl R. Parker, Milton R. Pickus, Victor F. Zackay.
United States Patent |
3,815,224 |
Pickus , et al. |
June 11, 1974 |
METHOD OF MANUFACTURING A DUCTILE SUPERCONDUCTIVE MATERIAL
Abstract
A ductile superconductive material and method for manufacturing
same, which basically may utilize any porous metal or its hydride
with a melting point substantially higher than that of the
infiltrating metal that will form a superconductive compound when
reacted with the infiltrating metal. The superconductive material
is made from a porous strip or tape of niobium or vanadium for
example, infiltrated with tin, aluminum, antimony, antiomony, or
gallium, for example, and treated in a manner so as to contain
interconnecting filaments of the superconducting phase Nb.sub.3 Sn,
Nb.sub.3 A1, Nb.sub.3 (A1,Ge), Nb.sub.3 Sb, or V.sub.3 Ga, for
example. The novel manufacturing process, which is relatively
simple and inexpensive provides a method of producing a new and
useful end product capable of a broad superconductive range due to
the amount of reaction of the infiltrated material with the porous
material. The novel process may be utilized in either batch or
continuous operational applications.
Inventors: |
Pickus; Milton R. (Oakland,
CA), Parker; Earl R. (Oakland, CA), Zackay; Victor F.
(Berkeley, CA) |
Assignee: |
The United States of American as
represented by the United States Atomic (Washington,
DC)
|
Family
ID: |
22537360 |
Appl.
No.: |
05/151,111 |
Filed: |
June 8, 1971 |
Current U.S.
Class: |
29/599;
257/E39.006; 75/245; 419/27; 419/29; 428/567; 505/821; 505/921;
174/125.1; 419/28; 419/47; 428/930; 505/823; 505/919 |
Current CPC
Class: |
H01L
39/12 (20130101); C22C 1/0475 (20130101); H01L
39/2409 (20130101); Y10S 505/919 (20130101); Y10S
505/821 (20130101); Y10T 29/49014 (20150115); Y10S
505/921 (20130101); Y10S 428/93 (20130101); Y10T
428/1216 (20150115); Y10S 505/823 (20130101) |
Current International
Class: |
H01L
39/12 (20060101); H01L 39/24 (20060101); C22C
1/04 (20060101); H01v 011/00 (); B22f 003/24 () |
Field of
Search: |
;29/599,420,420.5,182.1,192R,194,197,198,183.5,191,191.2,191.4,191.6
;174/126CP,DIG.6 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Lanham; Charles W.
Assistant Examiner: Reiley, III; D. C.
Attorney, Agent or Firm: Anderson; Roland A.
Claims
What we claim is:
1. A method for manufacturing a ductile superconductive material
containing interconnecting filaments of a superconducting phase
which in the bulk has a critical field in excess of 100 kilogauss
including the steps of: forming a porous metallic strip having a
network of interconnecting pores from material selected from the
group consisting of niobium and vanadium; sintering the thus formed
porous metallic strip; infiltrating into interconnecting pores of
the porous metallic strip a metallic material selected from the
group consisting of tin, aluminum, germanium, antimony, gallium,
and mixtures thereof by passing the metallic strip through a molten
bath of the metallic material wherein the metallic material
infiltrates into and substantially fills the pores of the metallic
strip; reducing the thickness of the thus infiltrated porous
metallic strip up to about 75 percent by passing the strip through
a thickness reducing mechanism; and diffusion heat treating the
thus infiltrated metallic strip thereby creating interconnecting
filament of a superconducting phase of a compound formed by the
reaction of the porous metallic strip and the infiltrated metallic
material.
2. The method defined in claim 1, wherein the step of forming the
metallic strip is accomplished by compacting finely powdered
metallic material into a strip.
3. The method defined in claim 1, wherein the step of forming the
metallic strip is accomplished by compacting hydrides of selected
metallic material into a strip, the hydrides decomposing to form
the porous metallic strip during the sintering step.
4. The method defined in claim 1, wherein the step of diffusion
heat treating the thus infiltrated metallic strip is accomplished
by passing same through a diffusion heat treating furnace wherein
at least a portion of the metallic material is reacted with the
porous metallic strip.
5. The method defined in claim 1, additionally including the step
of collecting the diffusion heat treated metallic strip by rolling
same on a collecting apparatus.
6. The method defined in claim 1, wherein the step of forming the
porous metallic strip is accomplished by containing niobium powder
of a particle size in the range of -100 to -400 mesh, and directing
the thus contained niobium powder through a compacting roller
apparatus forming a continuous "green" strip of porous niobium.
7. The method defined in claim 6, wherein the step of sintering is
accomplished by passing the porous niobium strip through a
sintering furnace having an atmosphere selected from the group
consisting of vacuum and inert gas, a temperature in the range of
1,850.degree.C to 2,250.degree.C, and for a time period of about 3
minutes.
8. The method defined in claim 6, wherein the step of infiltrating
the porous niobium strip is accomplished by passing the strip
through a bath of molten tin having a temperature range of
500.degree.C to 1000.degree.C and for a time period ranging from
less than 1 minute to about 3 minutes.
9. The method defined in claim 7, wherein the step of thickness
reduction of the tin-infiltrated strip is accomplished by passing
the strip through a rolling apparatus whereby the thickness of the
strip is reduced in the order of up to 75 percent.
10. The method defined in claim 9, wherein the step of diffusion
heat treating the tin-infiltrated strip is accomplished by
directing the strip through a diffusion heat treating furnace
having a temperature in the range of 925.degree.C to 1,075.degree.C
for a time period varying from less than 1 minute to several hours
depending on the amount of infiltrated tin to be converted to
Nb.sub.3 Sn.
11. The method defined in claim 1, wherein the porous metallic
strip constitutes a porous niobium strip, wherein the step of
infiltrating the niobium strip is accomplished by directing the
strip through a molten bath selected from the group consisting of
tin, aluminum, antimony, germanium and mixtures thereof, and
wherein the diffusion heat treating of the infiltrated niobium
strip creates a superconductive material containing interconnected
filaments of a superconducting phase selected from the group
consisting of Nb.sub.3 Sn, Nb.sub.3 Al, Nb.sub.3 (Al,Ge), and
Nb.sub.3 Sb.
12. The method defined in claim 1, wherein the porous metallic
strip constitutes a porous vanadium strip, wherein the step of
infiltrating the vanadium strip is accomplished by directing the
strip through a molten bath, selected from the group consisting of
gallium, aluminum, germanium, and mixtures thereof, and wherein the
diffusion heat treating of the infiltrated vanadium strip creates a
superconductive material containing interconnected filaments of
superconducting phase selected from the group consisting of V.sub.3
Ga, V.sub.3 Al, and V.sub.3 (Al,Ge).
13. The method defined in claim 1, wherein the step of diffusion
heat treating is accomplished by coiling the thus infiltrated
strip, and subjecting the thus coiled strip to a diffusion heating
means.
Description
BACKGROUND OF THE INVENTION
The invention described herein was made in the course of, or under
Contract No. W--7405--ENG--48, with the United States Atomic Energy
Commission.
This invention relates to superconductive material, and more
particularly to an improved superconductive material and method of
manufacturing.
When cooled to extremely low temperature, certain metals and alloys
lose their resistance to the passage of an electric current and are
then called superconductors. Once a flow of current has been
started in a superconductor, it will continue in a closed circuit
indefinitely, even after the source of the current is removed.
An electromagnet with the exciting current carried by coils of a
superconducting material would function with little or no power
expenditure except that required to maintain the necessary low
temperature. The problem in the construction of such
superconducting magnets of appreciable size has been the difficulty
of producing wire with satisfactory physical and mechanical
properties at a reasonable cost. In recent years, certain metallic
compounds (alloys) of niobium, e.g., with tin, titanium, or
zirconium, have been developed for fabrication into superconducting
wires. While the prior art efforts have resulted in substantially
improving the state of the art of superconductive materials, the
prior processes have been complicated and expensive, thus
illustrating a need in this field for an effective superconductive
material that can be manufactured by a relatively simple and
inexpensive process.
SUMMARY OF THE INVENTION:
The present invention provides a ductile and effective
superconductive material that can be produced relatively simply and
inexpensively by either batch or continuous production. Basically
the invention involves the forming of a porous strip or tape from
niobium or vanadium powder, for example, sintering the strip,
infiltrating tin, aluminum, germanium, antimony, or gallium, for
example, into the pores of the niobium or vanadium strip, and
diffusion heating treating the infiltrated strip forming
interconnecting filaments of the superconducting phase Nb.sub.3 Sn,
Nb.sub.3 Al, Nb.sub.3 (Al,Ge), Nb.sub.3 Sb or V.sub.3 Ga, for
example, throughout the strip. The amount of the superconducting
phase is varied by controlling the time and temperature of the heat
treatment. Also, the novel process may include reduction of the
infiltrated strip, such as by rolling, prior to the diffusion heat
treatment which has a significant effect on the conversion of the
infiltrate to the superconducting phase during the subsequent heat
treatment thereof. Hydrides of the metals, e.g., niobium hydride
can be used in place of the element. The hydrides decompose to form
the porous metal during the sintering process.
Therefore, it is an object of the invention to provide a
superconductive material and method for manufacturing same.
A further object of the invention is to provide a ductile
superconducting material containing interconnected filaments of a
superconducting phase throuhout the material.
Another object of the invention is to provide a process for
manufacturing a superconductive material containing interconnected
filaments of Nb.sub.3 Sn, Nb.sub.3 Al, Nb.sub.3 (Al,Ge), Nb.sub.3
Sb or V.sub.3 Ga.
Another object of the invention is to provide a method of
manufacturing a superconducting material which includes forming a
strip of porous niobium from niobium powder, infiltrating the
porous strip with tin, aluminum, aluminum-germanium, or antimony,
and selectively treating the infiltrated niobium strip to form
interconnecting filaments of the superconducting phase Nb.sub.3 Sn,
Nb.sub.3 (Al,Ge), or Nb.sub.3 Sb throughout the strip.
Other objects of the invention will become readily apparent from
the following description and accompanying drawing.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is a schematic illustration of an apparatus for carrying out
the operational sequence in a continuous method for making
superconductive material in accordance with the invention; and
FIGS. 2-4, illustrate typical structures of the niobium-tin
(Nb.sub.3 Sn) embodiment of the inventive superconductive material
in various stages of processing in accordance with the
invention.
DESCRIPTION OF THE INVENTION
While the following description is directed primarily to the
niobium-tin (Nb.sub.3 Sn) embodiment for purposes of illustration,
it is not intended that the greater detailed description of this
embodiment limit the invention to this specific embodiment in that,
as pointed out above and as set forth in greater detail
hereinbelow, that the invention can be carried out with other
superconductive compound such as niobium-aluminum-germanium,
Nb.sub.3 (Al,Ge); niobium-aluminum, Nb.sub.3 Al; niobium-antimony,
Nb.sub.3 Sb; and vanadium-gallium, V.sub.3 Ga. While efforts
conducted thus far to verify the invention have been directed to
the above-mentioned compounds, it is currently believed that the
porous base metal of the strip may be any porous metal with a
melting point substantially higher than that of the infiltrating
metal that will form a superconductive compound when reacted with
the infiltrating metal.
Referring now to FIG. 1 wherein an embodiment of an apparatus is
illustrated schematically for carrying out the operational sequence
for manufacturing the niobium-tin (Nb.sub.3 Sn) embodiment of the
superconducting material as partially illustrated in FIGS. 2-4.
While the illustrated process is of the continuous type, it may be
modified for batch type production if desired.
A hopper 10 containing finely powdered niobium 11, for example, of
particle sizes ranging from -100 mesh to -400 mesh, is mounted
above a compacting roller mechanism indicated at 12 which, when
rotated in the direction indicated by the arrows, produces a
"green" strip or tape 13 of porous niobium, the interconnected
pores being indicated after filling with tin at 13' in FIG. 2. For
example, with the compacting roller mechanism 12 having 2 inch
diameter rolls and a roll gap of 0.012 inch, a "green" strip 13
having a thickness of .apprxeq. 0.015 inch is produced. The "green"
strip 13 is passed through a sintering furnace 14 having, for
example, either vacuum or an inert gas atmosphere, a temperature in
the range of 1,950.degree.-2,250.degree.C, for a time of about 3
minutes, for example, for a thin strip. The sintered strip
indicated at 13-1 coming out of the furnace 14 has interconnected
pores and a porosity which can be controlled over a considerable
range. By way of specific example: Density = 6.71 GMS/cm.sup.3 =
78.3 percent of theoretical density .congruent. 21.7 percent
porosity. Sintered strip 13-1 is passed through a molten tin bath
15 having direction changing rollers 16 and 17 around which the
strip 13 passes, where the porous niobium is infiltrated (pores
filled) with tin producing a tin infiltrated strip indicated at
13-2 (see FIG. 2), the tin filled pores being indicated by legend.
For example, the molten tin bath temperature is in the
500.degree.-1,000.degree.C range, and the immersion time of the
strip 13-1 in bath 15 is in the range of a few seconds to several
minutes. As tin infiltrated strip 13-2 emerges from bath 15 it
passes over a direction changing roller 18 and through a thickness
reduction rolling mechanism generally indicated at 19 wherein a
cold reduction of the tin infiltrated strip indicated at 13-3 is
accomplished due to the strip being ductile (see FIG. 3), the
interconnected tin filaments shown by legend in FIG. 3. Reductions
in thickness of the order of 75 percent, for example, presents no
problem. However the cold reduction operation is optional depending
on the desired thickness of the strip and the heat treating of the
strip as described hereinafter. The thus rolled tin infiltrated
strip 13-3 is then passed through a diffusion heat treating furnace
20 wherein the tin is converted to Nb.sub.3 Sn (See FIG. 4), and
the converted strip now indicated at 13-4 is rolled or reeled on a
take-up spool apparatus 21 or other suitable collecting mechanism.
The diffusion temperature of the strip in the furnace 20 may be up
to about 1,100.degree.C with a preferred range of 925.degree.C to
1,075.degree.C, with a time at that temperature being from less
than 1 minute to several hours. As pointed out above, the desired
superconducting phase is Nb.sub.3 Sn. By controlling the amount of
prior deformation, the time and temperature of heat treatment, part
or all of the infiltrated tin may be converted to Nb.sub.3 Sn.
If desired, the diffusion heat treatment of the tin infiltrated
strip 13-3 may be accomplished by passing the strip through a bath
or molten tin instead of furnace 20.
Also, if desired the diffusion heat treating operation can be
carried out as a separate process. The infiltrated strip 13-3 can
be coiled directly on the reel 21, and subsequently heated in an
inert atmosphere or vacuum to produce the superconductive phase as
above described. This would be a desirable modification of the
above described process for materials that must be heated for long
periods of time at low temperatures to produce the superconductive
phase. An example of this is V.sub.3 Al.
By way of example, with no prior cold reduction of the
tin-infiltrated niobium strip, a heat treatment of 2 hours at
975.degree.C (ductility: nil) results in appreciable amounts of
unreacted tin; while with a prior reduction in thickness of 75
percent, a heat treatment for only 1 minute at 1,000.degree.C
(ductility: can be formed around a 3/8 inch diameter mandrel)
results in conversion of a major portion of tin to Nb.sub.3 Sn.
To illustrate the advantages of the inventive superconductive
material, current density tests have been conducted to determine
the current carrying capacity of specific strips of the material.
However, it should be noted that the current density will vary with
different materials and process variables such as the porosity of
the strip (which determines the maximum amount of infiltrate that
can be infiltrated into the strip), the amount of reduction of the
infiltrated strip, and the heat diffusion time and temperature
which determine the amount of reaction between the porous strip and
the infiltrate, and thus determines the critical current required
to drive the material from a superconductive state to a normal
state. By way of example only, niobium powder of -270 mesh was
rolled into a strip, sintered, infiltrated with tin, reduced about
75 percent forming a strip having a cross-section of 0.004 inch by
0.055 inch, and diffusion heat treated in accordance with the
invention. The thus formed strip of Nb.sub.3 Sn was wound on a
mandrel and tested for critical current density by placing the coil
in a variable magnetic field and varying the amount of current
passed through the coil. The tests were conducted in magnetic field
settings of 15KG, 20KG, and 50KG. To determine the amount of
current flow through the coil required to drive the coil normal
voltage readings across the coil were taken. A detectable voltage
reading indicated the start of the transition to the normal state.
For example, with the coil as above described, the tests showed the
starting of the transition to normal as being 8.7 .times. 10.sup.4,
7.0 .times. 10.sup.4 and 3.1 .times. 10.sup.4 amps. per sq. cm. for
the 15, 20 and 50KG magnetic fields respectively. The cross-section
utilized to determine the above amps/sq. cm. values is the cross
section of the ribbon or strip. In this specific test the volume
fraction of Nb.sub.3 Sn in the strip was estimated to be about 7
percent. Accordingly, it is readily apparent that by increasing the
volume fraction of the Nb.sub.3 Sn by the processing variables
indicated above, the current carrying capacity of the strip would
be substantially increased.
After the completion of the above current density test the strip
was reverse wound on the mandrel, and retested with the result that
there was no substantial reduction in the current carrying
capacity. This clearly verifies the ductility of the inventive
superconductive material.
As pointed out above, the inventive superconductive material is not
limited to the niobium-tin (Nb.sub.3 Sn) embodiment set forth
above, other embodiments manufacturable by the inventive process
will be briefly described hereinafter to more fully illustrate the
novel concept.
For the binary niobium-aluminum (Nb.sub.3 Al) embodiment, the
molten bath 15 contains aluminum at about 800.degree.C with good
infiltration of the aluminum into the niobium strip being obtained
in less than 1 minute, the remainder of the process being the same
as above described.
In the ternary niobium-aluminum-germanium--Nb.sub.3 (Al,Ge) --
embodiment, an aluminum-germanium eutectic (approximately 53
percent by weight of germanium) having a melting point of
424.degree.C was used as the infiltrate in the molten bath 15, with
the molten eutectic being maintained at a temperature of about
700.degree.C, and with an immersion time of the niobium strip in
the bath being about 30 seconds. This gave good infiltration into
the porous niobium, the remainder of the process being carried out
as described above.
In the vanadium-gallium (V.sub.3 Ga) embodiment, vanadium powder is
rolled, as above described, to produce a porous vanadium strip
which is thereafter sintered in furnace 14 and passed through
molten bath 15 where gallium is maintained at a temperature in the
range of about 100.degree.C, since gallium melts at 30.degree.C,
the thus gallium-infiltrated vanadium strip being processed as
described above with respect to the niobium-tin-embodiment as
carried out by the FIG. 1 apparatus.
As also pointed out above, the amount of reaction of the infiltrate
with the porous metal is related to the time and temperature of the
diffusion processing step, the times and temperatures being
established by series of tests.
It has thus been shown that the present invention provides a
ductile and effective superconductive material formed from a porous
infiltrated metal strip having interconnected filaments of a
superconducting phase produced by a relatively simple and
inexpensive process wherein the amount of infiltrated metal
converted into the superconducting phase is controlled by the
amount of deformation, and the time and temperature of the
diffusion heat treatment. Thus, this invention has greatly advanced
the state of the art.
While a particular apparatus and operation sequence has been
illustrated for producing the novel superconductive material, it is
not intended to limit the method of manufacture to the specifically
disclosed operational sequence of the illustrated apparatus as
modifications and changes will become apparent to those skilled in
the art, and it is intended to cover in the appended claims all
such modifications and changes as come within the spirit and scope
of the invention.
* * * * *