U.S. patent number 3,737,824 [Application Number 05/280,031] was granted by the patent office on 1973-06-05 for twisted multifilament superconductor.
This patent grant is currently assigned to The United States of America as represented by the Administrator of the. Invention is credited to Willard D. Coles.
United States Patent |
3,737,824 |
Coles |
June 5, 1973 |
TWISTED MULTIFILAMENT SUPERCONDUCTOR
Abstract
Masking selected portions of a ribbon and forming an
intermetallic compounds on the unmasked portions by a controlled
diffusion reaction produces a twisted filamentary structure. The
masking material prohibits the formation of superconductive
material on predetermined areas of the substrate.
Inventors: |
Coles; Willard D. (Fairview
Park, OH) |
Assignee: |
The United States of America as
represented by the Administrator of the (Washington,
DC)
|
Family
ID: |
23071338 |
Appl.
No.: |
05/280,031 |
Filed: |
August 11, 1972 |
Current U.S.
Class: |
336/200; 29/599;
336/DIG.1; 505/920; 216/101; 216/106; 216/48; 174/125.1; 424/DIG.8;
505/887 |
Current CPC
Class: |
H01L
39/2409 (20130101); Y10S 505/887 (20130101); Y10T
29/49014 (20150115); Y10S 336/01 (20130101); Y10S
424/08 (20130101); Y10S 505/92 (20130101) |
Current International
Class: |
H01L
39/24 (20060101); H01v 011/06 () |
Field of
Search: |
;174/DIG.6,15C,126R,126CP ;336/200,DIG.1 ;335/216 ;29/599
;156/18 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Primary Examiner: Goldberg; E. A.
Claims
What is claimed is:
1. A method of making a twisted multifilament superconductor
comprising the steps of
masking predetermined portions of a substrate to form a twisted
configuration about said substrate, and
forming a filament of a superconductive compound on said substrate
between the masked portions.
2. A method of making a twisted multifilament superconductor as
claimed in claim 1 wherein the superconductive compound filament is
formed by diffusion reaction.
3. A method of making a twisted multifilament superconductor as
claimed in claim 1 wherein the substrate is masked by
coating the substrate with an intermediate masking material,
removing said intermediate masking material in predetermined
regions to expose the portions of the substrate to be masked,
and
forming a mask in said regions by oxidizing the exposed substrate
material therein.
4. A method of making a twisted multifilament superconductor as
claimed in claim 3 wherein the mask is formed in the predetermined
regions by heating the substrate after the intermediate masking
material has been removed in the predetermined regions.
5. A method of making a twisted multifilament superconductor as
claimed in claim 3 wherein the predetermined portions of the
intermediate masking material are removed by a photo resist
process.
6. A method of making a twisted multifilament superconductor as
claimed in claim 5 wherein the predetermined portions of the
intermediate masking material are removed by
covering the intermediate masking material with a photo resist
material,
selectively exposing the photo resist material to light through
masks that form continuous paths across the faces of the substrate
and around the edges thereof,
developing the photo resist material to remove the same in said
predetermined regions and provide a protective coating over said
intermediate masking material in regions where the filament is to
be formed, and
applying an etchant to the covered substrate to remove the
intermediate masking material in said predetermined regions where
said photo resist material has been removed.
7. A superconductive ribbon comprising
a flexible substrate,
a superconductive compound in the form of filaments twisted about
said substrate to form filamentary current paths, and
a mask between said filaments to support the same.
8. A superconductive ribbon as claimed in claim 7 wherein each
twisted multifilament is an intermetallic compound of the substrate
material formed by diffusion reaction.
9. A superconductive ribbon as claimed in claim 8 wherein the
substrate is niobium.
10. A superconductive ribbon as claimed in claim 9 wherein the
superconductive compound is Nb.sub.3 Sn.
Description
ORIGIN OF THE INVENTION
The invention described herein was made by employees of the United
States Government and may be manufactured and used by or for the
Government for governmental purposes without the payment of any
royalties thereon or therefor.
BACKGROUND OF THE INVENTION
This invention is directed to a twisted multifilament intermetallic
compound superconductive ribbon or tape. The invention is
particularly concerned with producing such a material by
controlling a diffusion reaction process.
Existing technology has provided commercially available, flexible,
superconductive ribbon in the form of a substrate material having a
brittle superconductive intermetallic compound, such as Nb.sub.3 Sn
or V.sub.3 Ga, formed on the substrate by various means. These
intermetallic compounds have the desirable characteristic of
remaining in the superconductive state to higher values of magnetic
field strength, temperature, and current densities than most other
superconductive materials. However, thin sections are required to
achieve the desired flexibility without damage because the compound
is very brittle.
All known superconductors are subject to instabilities in their
performance characteristics which limit their usefulness, unless
certain steps are taken to reduce or eliminate these instabilities.
The provision of a low resistance, high thermal conductance
material in parallel and in intimate contact with the
superconductor has been adequate for large, low current density
applications. Other solutions are necessary for higher current
density applications, such as very high field strength magnets.
The instabilities arise from magnetic flux penetrations called
"flux jumps" which occur when the magnetic field strength at the
superconductor forces shielded or pinned flux to move into or
within the superconductor. These flux jumps are accompanied by
local reversions to the resistive state. The severity of the effect
is not solely determined by the value of the useful or "transport"
current which must pass through the resistive region. It also
depends on the value of the magnetization current, an induced
circulating current, which may approach the critical current
density.
Nontwisted current-sheet superconductors are subject to
instabilities resulting from magnetization currents. The severity
of the instability is strongly dependent on the rate of change of
magnetic field at the conductor. Nontwisted current-sheet
superconductors are totally unsuitable for alternating current
applications.
For ductile superconductive alloys, such as NbTi, stability is
achieved by dividing the superconductor into many fine filaments
embedded in a copper matrix and then twisting the resulting
composite conductor. The twist reduces the magnetization current
loop path, and if sufficiently short twist pitches are used, the
transport current can be made the limiting factor.
Thin ribbons or tapes of a superconductive material, such as
Nb.sub.3 Sn or V.sub.3 Ga, present a different problem. A twisted
Nb.sub.3 Sn filamentary structure has been produced in the form of
cabled strands and suggested as strands in a matrix material.
However, these methods cannot produce the desired flexibility of
the conductor because of the extreme brittleness of the
intermetallic compound. Winding of the unreacted niobium and tin
materials and then reacting at high temperatures to form a compound
in place has been used. However, this procedure suffers from the
disadvantages of requiring high temperature insulation and results
in a product that cannot be unwound or repaired. Winding of
conductor shapes other than thin ribbon results in excessive
tensile stresses in the outer fibers of the conductor. This tends
to destroy the brittle Nb.sub.3 Sn. The tensile stresses result
from the difference in circumferential distance traversed by the
outer and inner fibers of the conductor.
Removal of the superconductor to form filaments has been utilized
in the prior art. However, this is a slow process, and it leaves
unsupported edges of Nb.sub.3 Sn. Also the removal operation may
damage adjacent sections of the material.
SUMMARY OF THE INVENTION
These problems have been solved by the present invention wherein
the superconductor is divided and the current path twisted without
physically distorting the ribbon. Prior to producing the
superconductive compound a mask is formed on the base ribbon to
selectively prevent the formation of the superconductive compound
on predetermined portions of this substrate. The masked portions
form the boundaries defining the filamentary structure and the
twist characteristic. Subsequent diffusion reaction of the
unprotected regions of the base ribbon and the other reaction
constituents produces the superconductive compound only in the
desired current path pattern.
OBJECTS OF THE INVENTION
It is, therefor, an object of the present invention to provide
twisted filamentary current paths of a superconductive material
without inherently placing tensile strains on a brittle
material.
Another object of the invention is to form twisted filamentary
current paths of superconductive intermetallic compounds having
improved stability in that they are less susceptible to transition
to the normal state than nontwisted and nonfilamentary
intermetallic compounds.
A further object of the invention is to provide twisted filamentary
current paths that are stable without sacrificing the flexibility
of a ribbon conductor.
Still another object of the invention is to form twisted
filamentary current paths of superconductive intermetallic
compounds having supporting structure between the filaments.
These and other objects of the invention will be apparent from the
specification which follows and from the drawing wherein like
numerals are used throughout to identify like parts.
DESCRIPTION OF THE DRAWING
FIGS. 1 to 6 are sectional views illustrating the fabrication steps
used to produce the superconductive ribbon of the present
invention;
FIG. 7 is a perspective view of a ribbon with masking material
forming twisted filamentary paths; and
FIG. 8 is a perspective view of a twisted filamentary
superconductive ribbon constructed in accordance with the
invention.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now to the drawings there is shown in FIG. 8 a twisted,
multifilament superconductive ribbon of an intermetallic compound
constructed in accordance with the present invention. A flexible
base 10 of a suitable material, such as niobium, forms a substrate.
This substrate is preferably in the form of a ribbon or tape a few
hundredths of a millimeter thick and about 1.25 centimeters
wide.
In order to make the ribbon shown in FIG. 8 the substrate 10 shown
in FIG. 1 is first cleaned of surface impurities. This is
accomplished by degreasing, immersing in an alkali solution,
ultrasonically cleaning, or abrasive cleaning. It is further
contemplated that other forms of cleaning may be utilized.
The substrate 10 is then coated all over with an intermediate
masking material 12, such as copper, as shown in FIG. 2. This may
be accomplished by evaporative coating, plating, roll bonding, or
metallic spraying.
Predetermined portions of the masking material 12 are then
selectively removed to form the inverse of the final mask. Regions
14 in FIG. 4 are exposed base and regions 16 are covered with the
intermediate mask. Removal of the masking material in the regions
14 is preferably accomplished by a photo resist process.
In this process niobium ribbon 10 previously coated with masking
material 12, such as copper or nickel, is additionally coated all
over with suitable photo resist material 18, such as Kodak KPR-3,
as shown in FIG. 2. The photo resist material is dried or baked.
Then it is exposed to light selectively through previously prepared
masks that are properly indexed on each side of the ribbon. In this
manner the masks employed on each side of the ribbon are so
positioned that continuous paths are formed across the faces of the
ribbon and around the ribbon edges.
Development of the photo resist in suitable chemicals selectively
removes the photo resist material leaving a protective coating over
the portions which are not to be etched as shown in FIG. 3. After
again drying or baking the etch resist material to harden it, the
unwanted sections of the masking material 12 are removed in a
suitable etchant, such as ferric chloride, exposing the niobium in
the filament divider regions 14, but leaving the regions 16 covered
with the masking material as shown in FIG. 4.
The final mask is formed on regions 20 of FIGS. 5 and 7 by heating
the substrate 10 in an oxidizing atmosphere to a temperature
between 200.degree. C and 500.degree. C. The temperature is
preferably near 370.degree. C. At this temperature oxides of
niobium form on the exposed niobium base, the photo resist material
18 burns off, and the copper 12 remains. The heating is continued
until an oxide layer forms on the region 14 of FIG. 4 to form the
final mask 20 in FIGS. 5 to 8.
The intermediate mask on region 16 of FIG. 4 may then be removed or
not. If the intermediate mask is copper it need not be removed.
A superconductive filament 22 shown in FIGS. 6 and 8 is then formed
between the masked areas 20 by diffusion reaction. Copper will be
displaced from the region 16 in the process.
By way of example, Nb.sub.3 Sn is formed by such a diffusion
reaction between the exposed niobium ribbon and molten tin at
temperatures between 900.degree. C to 1200.degree. C. The Nb.sub.3
Sn is preferably formed between 930.degree. C and 970.degree. C.
The masking material 20 shields the niobium from the tin and
prevents the formation of the superconductive compound Nb.sub.3 Sn
in the masked regions as shown in FIGS. 6 and 8.
The etchant resistant material also may be selectively applied by a
suitably indexed printing process. In this manner only the desired
masked regions on each side and edge of the coated ribbon have
etchant resistant material applied.
Similarly, uncoated niobium ribbon may be masked with a plating
resist material using a photo resist or printing process. The
ribbon is then selectively plated in the unmasked sections of the
ribbon. After removal of the plating resist to expose the bare
niobium, the niobium oxide mask is formed. Then the diffusion
reaction process is again used to form the Nb.sub.3 Sn
superconductive compound.
In order to better illustrate the features of the invention a
length of twisted multifilament niobium tin superconductive ribbon
was made in accordance with the invention. Niobium ribbon 0.025
millimeters thick by 1.25 centimeters wide was cleaned in a sodium
hydroxide solution for 10 minutes. The ribbon was then rinsed in
distilled water and coated with a very thin film of copper in a
vacuum chamber in which copper was evaporated and deposited on all
surfaces of the niobium. This eliminates hydrogen contamination
between the copper and the niobium.
The thinly copper coated strip was electroplated with copper to a
copper thickness of about approximately 0.006 mm, rinsed, dried,
and spray-coated on both sides and edges with Kodak KPR photo
resist material. This was then air dried for 10 minutes and oven
dried at 170.degree. F for 10 minutes.
Previously prepared photographic film masks with approximately 10
lines per inch and with an opaque line to transparent spacing width
ratio of approximately 1:3 were placed on each side of the ribbon
with opposite slopes as viewed from one side. They were indexed to
match opaque to opaque and transparent to transparent at the edges
of the ribbon sandwiched between them. Thin transparent sheets,
such as Lucite, were placed on each side of the sandwich array to
prevent inadvertent misalignment. Exposure times of 5 1/2 minutes
were used on each side. This relatively long exposure time was
required because the KPR is most sensitive in the near ultraviolet
part of the spectrum and the added Lucite adsorbs ultraviolet
light. After exposure, the ribbon was placed in Kodak photo resist
developer for 2 1/2 minutes, rinsed, air dried for 10 minutes, and
oven dried at a temperature of 170.degree. F for 10 minutes.
The intermediate mask was formed by chemically etching away the
unprotected copper to expose the niobium. The final mask of niobium
oxide was formed by heating the ribbon in air to a temperature of
370.degree. C for 5 minutes. A light chemical etch in dilute nitric
acid removed any remaining photo etch resist material and copper
oxide. The niobium oxide is a very stable compound and was
unaffected.
The ribbon was suspended from a stainless steel rod in a Vycor tube
which extended into a vertical furnace. The tube contained a
tantalum crucible in the form of a tube with one closed end. A
chromel-alumel thermocouple was attached to the outside of the
Vycor tube. At the top end of the Vycor tube, out of the furnace, a
transition to metal tubing was made, and in this section provision
was made for attaching a vacuum pump, gage, and argon gas supply.
In addition, a sliding seal arrangement enabled vertical movement
of the ribbon into and out of the furnace.
The apparatus was assembled, purged with argon gas, and pumped out
several times to reduce contaminating residual gas levels. The
apparatus was then pumped down to the low micron range of 5-10.mu.
. The furnace was then turned on, and when the thermocouple
indicated a temperature of 970.degree. C had been reached, the
ribbon was lowered into the tantalum crucible containing the molten
tin, allowed to remain in the tin for 1 1/2 minutes, and withdrawn
to just above the tin for an additional 1 1/2 minutes still in the
high temperature region of the furnace. The ribbon was then
withdrawn from the hot section of the tube and the furnace shut
off.
After cooling to room temperature, the ribbon was removed from the
apparatus and tested for superconductive properties. Tests
indicated the transition temperature was greater than 17.95.degree.
K and the critical current at 0.6 telsa is 150 amperes.
Metallographic examination showed no traces of copper
remaining.
While the preferred embodiment of the invention has been shown and
described it is contemplated that various modifications may be made
without departing from the spirit of the invention or the scope of
the subjoined claims.
* * * * *